R Gourdon

M Jean

Marc Lancelin

M Gérard Scorletti
email: gerard.scorletti@ec-lyon.fr

M Obadia

Dcm

% O C n H 2n+1 1. O OAc AcO AcO

Keywords:

RESUME 6

), le glucopyranoside de méthyle est d'abord protégé en 4,6 par un acétal benzylidene, puis la monobenzylation conduit à un mélange des deux produits possibles ayant soit OH-2 soit OH-3 comme seule position libre.

Celle-ci peut être alors éthérifiée par réaction avec les 1,2-epoxyalkanes en présence de DMAP et de DABCO dans le DMSO. Après purification par chromatographie sur colonne de gel de silice, les produits ont été traités avec l'acide p-toluène sulfonique pour couper le 4,6acétal, puis débenzylés par hydrogénolyse en présence de palladium sur charbon. Cette séquence a été appliquée à partir des époxydes en C8, C10, C12, C14 et C16, et les produits finaux correspondants ont été purifiés et parfaitement caractérisés. Rappelons que chaque composé est en fait un mélange de deux isomères au niveau de l'OH sur la chaine éther, dans un rapport 1 :1 comme démontré par la RMN du carbone 13.

O O BnO

OMe OH

Acknowledgement

Three years ago, I packed my luggage and took the plane from Shanghai to Paris. I was nervous at that time. I seldom travelled abroad and rarely on my own, even in China. I had a very basic knowledge of the French language and I didn't know whether I could express myself correctly. When I landed at the airport, after the long queue to show my passport to the officer, he replied in French "Merci". At this moment I finally realized that I had arrived in France. Now I am on the stage to finish all my work here, looking backwards and finding that this three-year experience is a big treasure in my life, which in fact is accompanied with a lot of help from known or unknown people. I will firstly express my appreciation to my supervisor, Dr. Yves QUENEAU, Directeur de Recherche CNRS à l'INSA de Lyon, who kindly accepted me as the PhD student in the lab. He helped me, from the very first day when picking me up at the rail station in Lyon, waiting for me with my name written in Chinese on a paper. He also showed me all along my thesis how it is important to be strict and curious in science, always thinking about new aspect of the subject, and inspiring me a lot on my work. Thanks to his generous help, I could gradually establish my sense as a glycochemist.

Dr. Stéphane CHAMBERT, Maitre de Conférences à l'INSA de Lyon, who accompanies with my bench work for all these years, has been very patient and kind on me. His suggestions were very helpful to pull me out of the problems I had met with in my experiments. He was always very kind to receive me although I kept bothering him. I am also very happy that we have spent a great time in the CANOE during the drifting in Ardèche. His precious piloting helped us finish the drifting with a lot of fun. I also thank Prof. Jacques AUGE, from Université de Cergy-Pontoise and Prof. Grahame MACKENZIE, from University of Hull, for spending time on examining my manuscript. As well as to Prof. Bruno ANDRIOLETTI, from Université Claude Bernard-Lyon 1, who accepted the additional task to be president of the jury for my defense.

I would like to thank to Prof. John GOODBY, Dr. Stephen COWLING and the fellows in the lab for their warm welcome at the University of York, where I have spent two fruitful weeks discussing the subject of glycolipidic liquid crystal with them. There I have learned how wide the field of liquid crystalline materials which I found fascinating was.

I also owe my thank to Dr. David GUEYRARD, Prof. Peter GOEKJIAN, from LCO-2 in Lyon 1 and Dr. Olivier MARCILLAT, Prof. René BUCHET from ODMB in Lyon 1 for their kind advice on developing the glycoprobes along with the fluorescence tests of them.

Many thanks to my colleagues in the lab who have accompanied with me for these years. Their help from many aspects has made my life in the lab full of happiness. Particular thanks to Dr. Nuno XAVIER and Dr. Madan SINGH for their kind guide around Lyon when I just arrived, and Dr. Mohamad SABBAH for his delicious Lebanese flavor which I quite miss right now, and Dr. Sebastien REDON for his kind invitation to the rugby match which was excellent. I will also thank Lucie GRAND for her super French courses where I got a lot of progress. I am also grateful to Professor DOUTHEAU, then to Professor POPOWYCZ, for the kind interest they have expressed to my work and to myself.

Particular thanks to China Scholarship Committee (CSC), who supported my life in France so that I could have a better life condition and undergo my research calmly. I also thank my friends in Lyon with whom I spent the unforgettable period on travelling around, cooking, sporting and so on.

To close this little piece, I have to say I owe a lot to my parents and my family. Thanks to their backing and comprehension, I could come to France and proceed on my subject without much care. You are the best.

非常感谢!!

INTRODUCTION

Les amphiphiles à base de glucides représentent une importante classe de molécules non seulement parce qu'ils sont largement présents dans la Nature (glycolipides) mais aussi du fait de leur propriétés physico-chimiques liées à leur aptitude à l'auto-assemblage et l'autoorganisation. Ces propriétés sont aussi celles qui donnent aux amphiphiles glucidiques leur intérêt industriel, avec par exemple des tensioactifs tels que les esters de saccharose et les alkylpolyglycosides.

Les glycolipides sont largement distribués dans les membranes, et participent à de nombreux mécanismes biologiques. Compte tenu du caractère organisé de la membrane cellulaire, l'aptitude physicochimique des glycolipides à établir ou s'insérer dans des édifices supramoléculaires est nécessairement un paramètre clé dans leur possibilité de remplir leur rôle biologique. L'état physique en question est celui de cristal liquide, aussi dénommé le quatrième état de la Nature (avec l'état solide, l'état liquide et l'état gazeux), et c'est ce qui donne son importance au domaine des cristaux liquides glucidiques.

Par le processus d'auto-assemblage et/ou d'auto-organisation, ces molécules s'associent pour former les mésophases possédant l'état cristal liquide. De tels amphiphiles peuvent former des phases thermotropes (état pur) ou lyotropes (en présence d'eau). La formation des phases thermotropes dépend beaucoup de la structure des molécules, alors que pour les phases lyotropes, c'est surtout la concentration dans l'eau qui est le paramètre le plus important. Les forces qui conduisent à l'établissement de ces phases sont notamment les interactions polaires (liaisons hydrogène) et les interactions hydrophobes (liaisons de van der Waals). Des phases lamellaires, hexagonales, cubiques sont communément observées.

Les paramètres qui orientent vers telle ou telle géométrie de phase sont notamment les surfaces de section respectives des têtes polaires sucre et des chaines hydrophobes, la balance hydrophile-lipophile globale de la molécule, et les éléments qui affectent la forme de la molécule tels que le degré de substitution ou la position de la chaine hydrophobe sur le sucre.

Notre laboratoire s'est impliqué dans le domaine des cristaux liquides glycoamphiphiliques depuis plusieurs années, dans le cadre d'une collaboration avec le Professeur John Goodby à l'Université de York, et précédemment, à l'Université de Hull au Royaume-Uni, impliquant aussi le Professeur Grahame Mackenzie. L'objectif était en particulier d'apporter des éléments sur la relation entre la structure des molécules et leurs propriétés, grâce à la conception et la synthèse de diverses familles d'amphiphiles glucidiques. Le travail présenté dans cette thèse est une nouvelle contribution à ce thème de recherche collaboratif qui vise à une meilleure compréhension des aspects moléculaires des processus d'auto-assemblage et auto-organisation des amphiphiles glucidiques.

Dans ce travail, on a développé deux nouvelles familles de molécules : une série de n-O-(2hydroxylalkyl)--D-glucopyranosides de méthyle (1) et une série de glucostéroides (2) comportant un motif espaceur de type alkyle et pouvant présenter une deuxième substitution par une chaîne hydrophobe en position O-2 (figure 1).

La première famille (1) est une série d'hydroxyalkylethers de l'-D-glucoside de méthyle possédant des chaines alkyle de différentes longueurs, monosubstitutués sur l'une des 4 positions disponibles sur le squelette sucre. Les comportements thermotrope et lyotrope de ces produits ont été étudiés. Après nos travaux qui avaient porté sur un système disaccharidique (saccharose), et qui avaient mis en évidence l'influence des interactions entre les deux parties du disaccharide lui-même, l'objectif avec cette nouvelle série monosaccharidique était d'établir des relations structure-propriété liées exclusivement à la position de la chaine et à ces conséquences sur la compétition entre liaisons hydrogène inter-et intra-moléculaires.

Le cholestérol est un des lipides les plus fréquemment rencontrés, notamment au sein des membranes, où il coexiste avec d'autres types de lipides et glycolipides. De nombreuses molécules possédant un sucre et un stéroïde comme éléments structuraux principaux existent également dans la Nature. Malgré cette occurrence, la physicochimie des amphiphiles glycostéroidiques a été relativement peu étudiée, et en particulier le comportement cristal liquide. C'est ce qui nous a guidés dans la conception de la deuxième famille de dérivés étudiés dans ce travail, mettant à profit une stratégie de synthèse basée sur l'utilisation de synthons bicyclolactoniques (CMGLs), développée dans notre laboratoire.

Comme illustré dans la figure 1, les glycostéroides (2) qui ont été préparés sont en fait constitués de quatre éléments, le sucre, le stéroïde, un espaceur de type alkyle de Pour la dernière série substituée en O-6, OH-6 est d'abord protégé par un groupe trityle.

Puis, les autres groupes hydroxy sont benzylés et le trityle est déprotégé en conditions acides. Le produit résultant est alors éthérifié avec les 1, 2-epoxyalkanes puis les groupes benzyles sont hydrogénolysés (Figure 5). Les propriétés thermotropes de ces éthers ont été étudiées par microscopie optique polarisée et par calorimétrie différentielles (DSC). Les phases lamellaires (smectiques) de type Sm A* sont l'unique type de phase observé pour toute la famille de molécules, ce qui signifie que les tailles respectives de la partie sucre et de la partie aliphatique est de l'ordre de 1 :1 pour ce système. La longueur de chaine C12 est la limite à partir de laquelle les molécules sont capables de former les mésophases. Pour les séries qui ont les chaines les plus longues (14 et 16), les températures de transition entre la phase organisée et le liquide isotrope (clearing point) varient avec la position de la chaine, diminuant quand la chaine est déplacée de O-2 vers O-6. Pour la série en C12, les températures de transition sont plus irrégulières, avec le composé substitué en O-3 était ayant la plus haute température de transition, et aucune mésophase observée pour de dérivé en O-4. Les études de modélisation moléculaires et l'analyse des enthalpies et entropies de transition de phase, permettent d'interpréter les variations de comportement en termes de capacité des différents groupes hydroxyéther de s'associer de manière intramoléculaire avec les autres OH du motif sucre, ce qui modifie donc la compétition entre liaisons intra et intermoléculaires des têtes polaires entre elles.

Les propriétés lyotropes ont été aussi étudiées, montrant successivement, quand on augmente la quantité d'eau, des phases lamellaires, cubiques puis hexagonales, comme il est attendu pour ce type de molécules.

Glucostéroides

Pour la famille de glucostéroïdes, on a utilisé les synthons carboxymethyl glycosyl lactones (CMGL) pour attacher la partie sucre au système. Il a été montré que ces synthons, qui ont été développés par notre groupe, peuvent être facilement ouverts par divers types de nucléophiles, notamment possédant une fonction amine. L'ouverture de la lactone conduit à l'obtention d'un OH libre sur position 2 qui peut être alors sélectivement fonctionnalisé. Cette méthode a permis d'obtenir divers types de pseudo glycoconjugués, tels que des pseudodisaccharides, des glycosondes fluorescentes, des monomères pour polymérisation, etc. Notamment, des travaux préliminaires avaient permis d'obtenir des composés dans lesquels un stéroïde et le sucre étaient couplés directement, mais ces produits étaient quasiment incapables de former des mesophases. C'est pourquoi on s'est intéressé dans cette thèse à une nouvelle gamme de glycostéroides comportant un espaceur entre la partie sucre et la partie stéroïde. La substitution en position 2 a ensuite conduit à de nouveaux bolaphiles. La séquence synthétique est illustrée dans la figure 6. Les propriétés liquides cristallines de ces produits ont été étudiées. En premier lieu, il ressort que les températures de transition entre la phase liquide cristalline et le liquide isotrope décroit à mesure que la longueur de l'espaceur entre le sucre et le cholestérol augmente, en raison de la plus grande flexibilité que cela apporte dans le système.

Pour ce qui concerne l'effet de la variation de la longueur de la chaine latérale en O-2, quand cette chaine est courte, on observe des phases lamellaires (Sm A*) indiquant un équilibre entre les tailles relatives de la tête sucre et de la partie hydrophobe (quand cette chaine latérale passe de C4 à C12, on observe une diminution du clearing point). Dès la chaine latérale est en C14 ou plus longue, une autre mésophase se forme, identifiée comme colonnaire (hexagonale), avec augmentation de la température de transition vers le liquide isotrope, signalant une stabilisation de la phase hexagonale à mesure que la chaine latérale augmente en taille. L'analyse par modélisation moléculaire indique que dans ces cas, les molécules adoptent une forme de coin (wedge-shape), expliquant la préférence de l'architecture hexagonale au niveau supramoléculaire. Les mésophases Sm A* sont observées clairement dans la série avec espaceur en C4, elles persistent déjà moins dans le cas de la série avec espaceur en C6, alors que pour la série avec espaceur en C8, seule la phase hexagonale est observée, sans passer par la phase SmA*. Toutes ces variations de comportement illustrent les divers types d'interactions qui existent entre le cholestérol et la chaine latérale, et ce en fonction de la flexibilité du système apportée par un espaceur plus ou moins long.

Glycosondes fluorescentes

A la fin de cette thèse, nous avons abordé brièvement la synthèse, par la voie CMGL,

General introduction

Carbohydrate-based amphiphiles are important molecules not only because they are widely distributed in nature (glycolipids), but also because they often behave as materials which

show specific physicochemical properties due to their self-assembling and self-organizing ability. The mesophases shown by these amphiphiles were observed in the early age of glycochemistry, but this liquid crystalline behavior was recognized as one of their major properties only many years later. Nowadays, it is believed that this liquid crystalline state, referred to as the fourth state of matter, has some relationships with the biological properties shown by glycolipids. Also, glycoamphiphilicity is a basis for developing biobased surfactants having interest in industry or biology. This is why our laboratory has been involved in this topic for several years, in particular trying to provide information of the structure-property relationships by designing and synthesizing various series of sugar-based amphiphiles. This has been the object of collaboration with the group of Pr. J. Goodby at the University of York, and prior to this, at the University of Hull.

The work achieved in this thesis which relates to two new families of glycoamphiphiles is a new contribution to this collaborative project dedicated to understanding better the molecular aspects of the self-organisation of carbohydrate-based amphiphiles.

The first family is a series of monosubstituted hydroxyalkylethers of -methyl-D-glucoside (1 shown in Fig. 1) having alkyl chains of different lengths at one of four possible positions on the sugar backbone. The liquid crystalline study of these compounds was performed in terms of thermotropic and lyotropic aspects. After some previous work on a disaccharidic system (sucrose), the present study on monosaccharidic ethers aimed at establishing some structure-property relationships that would not relate to the intersaccharidic interactions (as it happened in the disaccharidic series), but only to the positioning of the chain and the resulting balance between intermolecular and intramolecular hydrogen bonding.

Among key lipidic compounds is cholesterol. Despite the extremely important presence of cholesterol in supramolacular biological systems and the numerous natural products which possess a sugar and a steroid as their main building blocks, very little has been reported about glycoseroidic amphiphiles, notably in terms of liquid crystalline behavior. This has In this document, a bibliographic section is firstly given, illustrating the basic aspects of amphiphilicity, followed by focus on glycoamphiphiles and more specifically on carbohydratebased liquid crystals. Also, the scope of the CMGL synthon strategy is rapidly overviewed.

In the second "result and discussion" part, is described the synthesis and the study of the liquid crystalline properties of the two series of new carbohydrate-based amphiphiles above mentioned. Also in this part, it is included a short chapter dealing with some preliminary work In the final part of this thesis, we will document the experimental section, including the experimental procedures, spectroscopic and physical data, and the references.

Chapter 1

Carbohydrate based amphiphiles

Introduction

An amphiphilic molecule is constructed by two blocks with different affinities, where one affinity, hydrophilic head, is towards the water and the other, hydrophobic tail, towards the organic solvent, as illustrated in Fig. 1.1. The hydrophilic head could be charged, such as those bearing a sulfate ion (anionic amphiphiles) or quaternary ammonium ion (cationic amphiphiles), or uncharged, such as those involving a carbohydrate moiety (nonionic type).

The hydrophobic tail could be a long straight chain or branched alkyl groups with the chain length ranging from 8 to 22 carbon atoms with possible unsaturations, like those coming from vegetable oils, or alkyl substituted aromatic groups, or polymeric blocks, etc. [START_REF] Myers | Surfactant Science and Technology[END_REF] Fig. 1.1: Schematic illustration of an amphiphilic molecule Among properties of amphiphiles there is the ability to self-assemble and self-organize through specific interactions between polar heads, on one hand, and between non polar tails,

Hydrophilic head

Hydrophobic tails on the other hand, either in solution (formation of micelles) or as pure materials forming liquid crystalline assemblies.

In this section, after a short basic overview on surfactants, we will focus on those who possess a carbohydrate moiety, and develop particularly the specific field of liquid crystalline glycolipids.

Surfactants

General aspects

Surfactants are used in every corner in daily life. Fig. 1.2 shows surfactant market demand in the US in 2007. [START_REF]Surfactants-A Market Opportunity Study Update[END_REF] Although the detergents and industrial areas remain two predominant parts in surfactant consumptions, some other applications, like cosmetics, [START_REF] Inami | Surfactant-induced Itching and the Involvement of Histamine Released from Keratinocytes[END_REF] oil recovery process, [START_REF] Satpute | Biosurfactants, bioemulsifiers and exopolysaccharides from marine microorganisms[END_REF][START_REF] Pruthi | Novel sucrose lipid produced by Serratia marcescens and its application in enhanced oil recovery[END_REF] medicine, [START_REF] Szűts | Sucrose esters as natural surfactants in drug delivery systems-A mini-review[END_REF][START_REF] Lowe | Liquid Crystalline Materials for Biological Applications[END_REF][START_REF] Pierre | Liposomal systems as drug delivery vehicles for dermal and transdermal applications[END_REF] have seen rapid development recently. Special uses are also explored. [START_REF] Ziyatdinova | Application of surfactants in voltammetric analysis[END_REF][START_REF] Tkalya | The use of surfactants for dispersing carbon nanotubes and graphene to make conductive nanocomposites[END_REF] Fig. 1.3 shows a more detailed diversity of applications of surfactants. [START_REF] Myers | Surfactant Science and Technology[END_REF] Referring to requirements for surfactant performance, besides some traditional ones, like stability, foaming power, detergency, solubility, etc, other more specific properties have been emphasized, like toxicity, skin irritability, and environmental performance. The requirements of some important applications are listed in Table 1.1. [START_REF] Myers | Surfactant Science and Technology[END_REF] These diverse functionalities may in turn demand for diverse chemical building blocks and synthetic strategies.

Fig. 1.2: US surfactants market demand in 2007 [START_REF]Surfactants-A Market Opportunity Study Update[END_REF] 0,50 0,10 0,11 0,29

Household detergents

Alimental industry

Personal care

Industrial use

Fig. 1.3: Some important surfactant applications [START_REF] Myers | Surfactant Science and Technology[END_REF] Application Characteristics

Detergency

Low CMC, good salt and pH stability, biodegradability, desirable foaming properties

Emulsification

Chemical stability, adsorption at surfaces

Mineral flotation

Proper adsorption characteristics on the ore(s) of interest, low cost

Petroleum recovery

Proper wetting of oil-bearing formations, microemulsion formation and solubilization properties, ease of emulsion breaking after oil recovery

Pharmaceuticals

Biocompatibility, low toxicity, proper emulsifying properties

Lubrication

Chemical stability, adsorption at surface Table 1.1: Typical characteristics for surfactants that must be evaluated for various applications [START_REF] Myers | Surfactant Science and Technology[END_REF] Soaps are a kind of surfactant that have been involved in human`s history for a long time. In China, the first record of manufacturing soap is in the Song Dynasty. At that time, people smashed the seeds from Gleditsia sinensis, mixed with some perfume to form spherical pieces of matter, and sold to be used for personal care. In western history, the Phoenicians were the first to be documented to sell the alkali metal soaps as early as 600 BC. The Romans developed the manufacture process, which is, however, generally considered to be from the Celts or some Mediterranean culture. [START_REF] Myers | Surfactant Science and Technology[END_REF] In the modern time, with the development of science and technology, people began to think about using chemical synthetic methods to design and manufacture useful surfactants. The early example was the short-chain alkylnaphthalene sulfonates, created by the Germans, during the World War I, showing a good wetting property. Then the surfactant industry has seen a rapid growth that new surfactants emerged one after another, like long-chain alkyl alcohol sodium sulfates, long-chain alkylaryl sulfonates, alkylbenzene sulfonates (ABS), and linear alkylbenzene sulfonates (LABS). They are widely used in routine life at present. [START_REF] Myers | Surfactant Science and Technology[END_REF] Nowadays, the ecological harmony has become an important issue in the world, as well as the as limitation of fossil fuel reserves, an alternative resource to replace the petrochemical feedstocks must be identified. Thus the oleochemical feedstocks and a variety of other renewable substrates have been of increasing interest as feedstocks for surfactant production. Some research revealed that if the petro-originated surfactants were replaced by renewable surfactants, the resulting reduction of CO 2 emission generated from the production and utilization of surfactants could be up to 37%. [START_REF] Dornburg | Comparing the Land Requirements, Energy Savings, and Greenhouse Gas Emissions Reduction of Biobased Polymers and Bioenergy[END_REF] Meanwhile, some unique properties directed by oleochemical feedstocks, like versatile self-assembling and biochemical properties, have been found one after another, providing some very interesting applications in ecological and biological fields.

Classification and applications

Surfactants may be classified in several ways, either in terms of properties (emulsifier, wetting agent…) or in terms of structure, in particular with respect to the type of hydrophilic moiety, as it is done below. [START_REF] Myers | Surfactant Science and Technology[END_REF] 1.

ANIONIC SURFACTANTS

As the only available for thousands of years, the anionic surfactants are the kind received most attention. In 2012, the production of anionic surfactants in European Union is 1.219 million tons, nearly half in whole surfactant industry. [START_REF]CESIO statistics[END_REF] The major head group of this class could be constructed by the alkali carboxylates or soaps, sulfates, sulfonates, and phosphates, as shown in

CATIONIC SURFACTANTS

There are two types of cationic surfactants based on the nitrogen-containing group, the first is the alkyl nitrogen compounds, as shown in Fig. 1.4, and the second is the heterocyclic amine surfactants, as shown in Fig. 1.5. groups, X could be halide, sulfate, acetate, etc)

C n H 2n+1 NHR 2 + X - C n H 2n+1 NR 3 + X - C n H 2n+1 N  R 2 O 
N + R X - N + R X - R N N R 2 R 1 R 3 X - + O N + R 1 R 2 X -

N-alkylpyridinium salts Salts of alkyl-substituted pyridines

Imidazolinium derivatives Morpholinium salts

Fig. 1.5: Schematic representatives of heterocylic amino compounds (R is H or lowmolecular -weight alkyl groups, X could be halide, sulfate, acetate, etc)

They are used as fabric softeners in textile industry, modifiers for controlling the surface tribological properties in the mineral flotation process, are also extremely important.

NONIONIC SURFACTANTS

Different from two types above with the head group charged, the nonionic surfactants are the neutral kinds driven by hydrogen bondings (H-bondings) between the polar groups with the solvent, particularly the water. These materials have some advantages such as lower sensitivity to the electrolytes and pH, and easy designed properties. The most widely produced and used non ionic surfactants are based on polyoxyethylene (POE). The general formula for this type is:

RX(CH 2 CH 2 O) n H X = O, N, functional group n > 6
Fig. 1.6: Formula of polyoxyethelene For these compounds, a characteristic is the inverse temperature-solubility relationship, that is to say, when the temperature increases, the solubility of the molecule in the water decreases. This phenomenon is mainly due to the change of hydrogen bonding interactions between the molecules and the water.

Another source in this category is the derivatives of polyols, in which renewable hydrophilic moieties are included, for example, glycerol or carbohydrates. Due to their low toxicity and biocompatibility, they are found use in foods and food emulsions, pharmaceuticals, cosmetics, and agricultural applications of pesticides and herbicides. A more extended discussion on the carbohydrate-based amphiphiles is given in the next section.

Carbohydrate Based amphiphiles

Introduction

Sugar-based amphiphiles rank high among compounds that are designed according to the principles of green chemistry. [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] The raw materials for producing sugar-based amphiphiles, such as monosaccharides, disaccharides are abundant in the nature and of easy access, for example for sucrose, by crystallization from concentrated sugarcane or sugar beet juice. [] Though plenty of methods have been tried out to bind the carbohydrate moiety to the hydrophobic tails, in the industrial point of view, such as price and quality, only a few carbohydrates derived surfactants could be brought into commercial. Thus, more convenient and economically acceptable manufacturing procedures in industrial scale are still under research. Nowadays, the best-known carbohydrate based surfactants are alkyl polyglycosides (APGs), sorbitan esters, and sucrose esters. [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF][START_REF] Foley | Derivation and synthesis of renewable surfactants[END_REF][START_REF] Queneau | Recent progress in the synthesis of carbohydrate-based amphiphilic materials: the examples of sucrose and isomaltulose[END_REF][START_REF] Holmberg | Natural surfactants. Current Opinion in Colloid &amp[END_REF] Table 1.3 shows a survey on the production volume and cost of three big families in the carbohydrate surfactants, exhibiting comparative counterparts towards the petroleum based surfactants in the industrial perspective. [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] Source: Lichtentaler, F. W., Methods and Reagents for Green Chemistry, Wiley-Interscience, 2007. (Price here could only be indications) Table 1.3: Availability of Carbohydrate Raw Materials [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] Another rich resource of carbohydrate amphiphiles is found in the natural organisms, [START_REF] Marchant | Microbial biosurfactants: challenges and opportunities for future exploitation[END_REF][START_REF] Marchant | Biosurfactants: a sustainable replacement for chemical surfactants?[END_REF][START_REF] Kitamoto | Self-assembling properties of glycolipid biosurfactants and their potential applications[END_REF][START_REF] Kitamoto | Functions and potential applications of glycolipid biosurfactants -from energy-saving materials to gene delivery carriers[END_REF] these glycolipids, the biological name of carbohydrate amphiphiles, are known to play key roles in immune and endocrine systems, fertilization, brain development, prevation of pathogenesis and blood clotting. [START_REF] Hakomori | The glycosynapse[END_REF][START_REF] Yu | Membrane glycolipids in stem cells[END_REF] The glycolipid biosurfactants discovered as the metabolic compounds from fermentation of microorganisms are also found very important in some specific domains. Owing to their biocompatibility and some ecological advantages, they were firstly considered as the alternatives to chemical surfactants, but as their unique properties explored recently and optimized conditions for large scale manufacturing, they will be seen in great growth in the cosmetic, medical domains. [START_REF] Kitamoto | Self-assembling properties of glycolipid biosurfactants and their potential applications[END_REF] Some examples will be shown in the following sections.

Self-assembling and self-organizing mechanism is considered as the main theory to explain the formation of liquid crystals, [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF][START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF][START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF][START_REF] Vill | Carbohydrate liquid crystals: structure-property relationship of thermotropic and lyotropic glycolipids[END_REF] gelators, [START_REF] Gronwald | Gelators for organic liquids based on self-assembly: a new facet of supramolecular and combinatorial chemistry[END_REF][START_REF] Capicciotti | Potent inhibition of ice recrystallization by low molecular weight carbohydrate-based surfactants and hydrogelators[END_REF][START_REF] Trivedi | Noncovalent syntheses of supramolecular organo gelators[END_REF][START_REF] Buerkle | Nonionic surfactant-induced stabilization and tailorability of sugar-amphiphile hydrogels[END_REF] and nanotubes [START_REF] Zhang | Host-guest interactions mediated nano-assemblies using cyclodextrincontaining hydrophilic polymers and their biomedical applications[END_REF][START_REF] Diaz-Moscoso | Mannosylcoated nanocomplexes from amphiphilic cyclodextrins and pDNA for site-specific gene delivery[END_REF][START_REF] Assali | Improved Non-Covalent Biofunctionalization of Multi-Walled Carbon Nanotubes Using Carbohydrate Amphiphiles with a Butterfly-Like Polyaromatic Tail[END_REF] by the carbohydrate amphiphiles. The resulting supramolecules will exhibit some interesting properties as not possible for the individual molecules. Some pioneering work will be described, too.

Industrial manufacturing carbohydrate surfactants for consumer products 1.3.2.1 Sorbitan esters

Known under the trade name of Span TM (sorbitan alkanoates) and Tween TM (ethoxylated sorbitan alkanoates), [START_REF] Holmberg | Natural surfactants. Current Opinion in Colloid &amp[END_REF] the sorbitan esters find main applications in pharmaceuticals, [START_REF] Lawrence | Microemulsion-based media as novel drug delivery systems[END_REF] cosmetic products, [START_REF] Hill | Sugar-based surfactants for consumer products and technical applications[END_REF] latex polymerization. [START_REF] Hernandezbarajas | Inverse-emulsion polymerization of acrylamide using block copolymeric surfactants: Mechanism, kinetics and modelling[END_REF][START_REF] Omidian | Polymerization of sodium acrylate in inverse-suspension stabilized by sorbitan fatty esters[END_REF] There are two main processes to fabricate the sorbitan esters: batch and continuous processes. Both processes employ the acid (NaH 2 PO 3 or p-TSA) as catalyst. [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] Since the easy-controlled conditions for continuous process, the appearance of resulting product would be better. [START_REF] Stockburger | Process for preparing sorbitan esters[END_REF] Scheme 1.1 shows the general process of continuous process.

Sucrose esters

The only commercially available surfactants using sucrose as the polar head are the sucrose esters, which are found in the food emulsification, personal care and pharmaceutical domains. Because of multifunctionalities as three primary alcohols, five secondary alcohols, and two anomeric carbons on the sucrose matrix, [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF][START_REF] Queneau | Recent progress in the synthesis of carbohydrate-based amphiphilic materials: the examples of sucrose and isomaltulose[END_REF] it is difficult to control the degrees of substitution: 255 distinct possible isomers with varying degrees of substitution can be obtained from acylation with a single fatty acid. However, due to rapid acyl group migration towards primary positions, [START_REF] Molinier | Self-organizing properties of monosubstituted sucrose fatty acid esters: The effects of chain length and unsaturation[END_REF] fatty chains are essentially found at the primary position in the final products.

Early condensed process was performed in DMSO or DMF, [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF][START_REF] Foley | Derivation and synthesis of renewable surfactants[END_REF][START_REF] Queneau | Recent progress in the synthesis of carbohydrate-based amphiphilic materials: the examples of sucrose and isomaltulose[END_REF] in which the sucrose could be dissolved, with K 2 CO 3 as the basic catalyst, shown in Scheme 1.2. But the problematic removal of solvent made it not easy to conduct, so an important know-how has been developed to have this reaction optimized for industrial production, for example, transesterification and solvent-free process. These methods have been proved to have a good yield and facile workup.

Alkyl polyglucosides (APGs)

APGs are the most extensively studied carbohydrate based surfactants. [START_REF] Rybinski | Alkyl Polyglycosides-Properties and Applications of a new Class of Surfactants[END_REF] As the starting materials are from fatty alcohol and glucose or starch, they are the first commercial series to offer a variety of properties based on the green chemistry concept. [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] The synthesis method is known as the Fischer glycosydation reaction. Currently, the industrial available processes are the direct glycosydation and double alcohol exchange. [START_REF] Foley | Derivation and synthesis of renewable surfactants[END_REF] The double alcohol exchange process employs short chain alcohol, like butanol, as reagent to convert glucose into Oalkylglucoside at the first step, which is the solvent in the following transglycosidation with long chain fatty alcohol (C8~C16), as shown in Scheme 1.3. This process is not as popular as direct glycosydation since the latter process could save time and control the selectivity. An alternative is enzymatic synthesis, using -glucosidase as catalyst which yields only the anomer though such processes are less easy to be used in large scale syntheses. APGs are widely used as the liquid dishwashing agents and personal care products for C12/14 series, cleaners for hard surface and industrial cleaning for C8/10 series. [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF]

Glycolipids and glycolipid biosurfactants 1.3.3.1 Biologically occurring carbohydrate amphiphilesglycolipids

Glycolipids are widely found in the cell membranes. [START_REF] Yu | Membrane glycolipids in stem cells[END_REF] The most common seen glycolipids in the organisms are glycosphingolipids (GSLs), glycoglycerolipids (GGLs) and glycosyl phosphopolyprenols (GPPPs). [START_REF] Mannock | Thermotropic and lyotropic phase properties of glycolipid diastereomers: role of headgroup and interfacial interactions in determining phase behaviour[END_REF] Among them, GSLs and GGLs are those which are the most studied. GSLs are widely distributed in the eukaryotes, some prokaryotes and viruses, [START_REF] Hakomori | Structure and function of glycosphingolipids and sphingolipids: Recollections and future trends[END_REF][START_REF] Degroote | The cell biology of glycosphingolipids[END_REF] containing a hydrophobic ceramide anchor N-acylsphingosine and a hydrophilic head group composed of sugars, which could be sorted into three subgroups: cerebrosides, globosides, and gangliosides. [START_REF] Goodby | Liquid crystals and life[END_REF] Since many important biological behaviors like cell-cell recognition, [START_REF] Queneau | Recent progress in the synthesis of carbohydrate-based amphiphilic materials: the examples of sucrose and isomaltulose[END_REF][START_REF] Khatun | Modulation of the neurotensin solution structure in the presence of ganglioside GM1 bicelle[END_REF][START_REF] Smith | Sphingolipid Metabolism and Signaling Minireview Series[END_REF] membrane transport, [START_REF] Lingwood | Lipid Rafts As a Membrane-Organizing Principle[END_REF][START_REF] Fujita | Nanoscale Analysis of Glycolipid Distribution in the Cell Membrane[END_REF][START_REF] Michel | Lipid rafts in health and disease[END_REF][START_REF] Staubach | Lipid rafts: signaling and sorting platforms of cells and their roles in cancer[END_REF][START_REF] Brown | Structure and Function of Sphingolipid-and Cholesterol-rich Membrane Rafts[END_REF] are related to the activity of this species, thousands of studies have been dedicated to this type of glycolipids. It was found that absence or a too low level of GSLs may cause some physiological problems. [START_REF] Degroote | The cell biology of glycosphingolipids[END_REF] GM1 (Fig. 1.7), a kind of GSLs, is found to one of important components forming a microdomain, "lipid raft", in the membranes for selective membrane transport. [START_REF] Lingwood | Lipid Rafts As a Membrane-Organizing Principle[END_REF][START_REF] Michel | Lipid rafts in health and disease[END_REF][START_REF] Staubach | Lipid rafts: signaling and sorting platforms of cells and their roles in cancer[END_REF][START_REF] Brown | Structure and Function of Sphingolipid-and Cholesterol-rich Membrane Rafts[END_REF][START_REF] Danielsen | Lipid raft organization and function in the small intestinal brush border[END_REF][START_REF] London | Structure and Function of Sphingolipid-and Cholesterol-rich Membrane Rafts[END_REF] cyanobacteria. [START_REF] Hölzl | Structure and function of glycoglycerolipids in plants and bacteria[END_REF][START_REF] Mannock | The thermotropic phase behaviour and phase structure of a homologous series of racemic βd-galactosyl dialkylglycerols studied by differential scanning calorimetry and X-ray diffraction[END_REF] Monogalactosyl-and digalactosyl-diacylglycerol (MGDG and DGDG) are two major glycoglycerolipids found. The DGDGs are found to play a crucial role in plant growth, thylakoid function and protein import into chloropalsts. [START_REF] Popova | Effects of the sugar headgroup of a glycoglycerolipid on the phase behavior of phospholipid model membranes in the dry state[END_REF][START_REF] Mannock | The physical properties of glycosyl diacylglycerols. Calorimetric, X-ray diffraction and Fourier transform spectroscopic studies of a homologous series of 1,2-di-O-acyl-3-O-(β-d-galactopyranosyl)-sn-glycerols[END_REF] One of this kind of compound digalactosyldiacylglycerol mono-estolides, isolated from oat seeds, is shown in Digalactosyldiacylglycerol mono-estolides were reported in oat kernels [START_REF] Hamberg | Isolation and structure of a new galactolipid from oat seeds[END_REF] Other glycolipids like steroid glycosides (SGs) are also found in many plants and fungi, some animals and bacteria. [START_REF] Grille | The functions of steryl glycosides come to those who wait: Recent advances in plants, fungi, bacteria and animals[END_REF] Some of SGs are considered as an active component in Chinese traditional medicine. [START_REF] Ikeda | Synthesis of neosaponins having an α-lrhamnopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-d-glucopyranosyl glyco-linkage[END_REF][START_REF] Yu | Assembly of Naturally Occurring Glycosides, Evolved Tactics, and Glycosylation Methods[END_REF][START_REF] Ekholm | Synthesis of a Small Library of Estradiol-Based Glycosteroid Mimics Containing a Modified D-Ring[END_REF] One such example, 3, 16, 17-trihydroxycholest-5-en-22-one 16-

O-(2-O-4-methoxybenzoyl--D-xylopyranosyl)-(1 → 3)-(2-O-acetyl--l-arabinopyranoside), 1,
(OSW-1) is illustrated in Fig. 1.9. [START_REF] Zhou | OSW-1: a Natural Compound With Potent Anticancer Activity and a Novel Mechanism of Action[END_REF] It was found in bulbs of Ornithogalum saudersiae, which showed high antitumor activities. Acyl steryl glycosides (ASG) are usually referred to the SGs where a monoglycoside conjugates with sterol in 3-O position while an additional acyl long fatty chain attached in the position 6 of a glycoside. [START_REF] Schrick | Steryl Glucoside and Acyl Steryl Glucoside Analysis of Arabidopsis Seeds by Electrospray Ionization Tandem Mass Spectrometry[END_REF] For most compounds of this kind, they are found in plants, while two kinds of cholesteryl glucosides were just reported recently from some bacteria: one is the cholesteryl 6-O-acyl--D-galactopyranoside (BbGL-I), [START_REF] Ben-Menachem | A newly discovered cholesteryl galactoside from Borrelia burgdorferi[END_REF] , 3, which is from Borrelia burgdorferi. Accompanied with another glycolipid 1, 2-di-O-acyl-3-O--Dgalactopyranosyl-sn-glycerol (BbGL-II), they were found to have activities towards Lyme disease; the other kind is cholesteryl 6'-O-acyl--glucopyranoside (-CAG), 2, which is from H. pylori. [START_REF] Mcgee | Cholesterol Enhances Helicobacter pylori Resistance to Antibiotics and LL-37[END_REF][START_REF] Kawakubo | Natural Antibiotic Function of a Human Gastric Mucin Against Helicobacter pylon Infection[END_REF] It is thought to be synthesized by the taking up cholesterol from the stomach cells to couple with glucose moiety via a bacterial glucosyltransferase, Hp0421, the resulting compounds of which are further enzymatically acylated. [START_REF] Grille | The functions of steryl glycosides come to those who wait: Recent advances in plants, fungi, bacteria and animals[END_REF] surfactants [START_REF] Morita | Production of glycolipid biosurfactants by basidiomycetous yeasts[END_REF] Another source for the glycolipids relies on the fermentation of microorganisms. Up to now, the glycolipid biosurfactant categories include the mannosylerithritol lipids (MELs) mainly from the genus Pseudozyma, [START_REF] Morita | Identification of <i>Pseudozyma graminicola</i> CBS 10092 as a Producer of Glycolipid Biosurfactants, Mannosylerythritol Lipids[END_REF] sophorolipids from the genus Candida, [START_REF] Van Bogaert | Microbial synthesis of sophorolipids[END_REF] rhamnolipids from the genus Pseudomonas aeruginosa, [START_REF] Henkel | Rhamnolipids as biosurfactants from renewable resources: Concepts for next-generation rhamnolipid production[END_REF] trehalose lipids from the genus Rhodococcus , [START_REF] Franzetti | Production and applications of trehalose lipid biosurfactants[END_REF] succinoyl trehalose lipids, cellobiose lipids, and oligosaccharide lipids. The Fig. 1.10 shows the general structure of each glycolipids. They could be produced from some renewable resources and even waste materials, like the byproducts of biodiesel production. [START_REF] Henkel | Rhamnolipids as biosurfactants from renewable resources: Concepts for next-generation rhamnolipid production[END_REF] For example, RL-1 and -2, two kinds of rhamonlipid, could be produced from vegetable oils, like soybean oil, or corn oil. As the development of biological technology, the yield of some types could surpass 100g l -1 , like MELs and rhamnolipids, though that for some other glycolipid surfactants is still less. Another problematic issue in the industrial scale is the downstream processing since the isolation of the products is not economic. [START_REF] Marchant | Microbial biosurfactants: challenges and opportunities for future exploitation[END_REF] In the traditional surfactant domain, studies showed that these biosurfactants could reduce the surface tension of water from 72 mN/m to less than 25 mN/m. Further comparison showed that STL-1, a kind of trehalose lipid, is highly efficient with a low critical micelle concentration (CMC) at 5.6×10 -6 M, which reduces the tension to 19 mN/m. [START_REF] Kitamoto | Self-assembling properties of glycolipid biosurfactants and their potential applications[END_REF] Extensive applications of this kind could be found in the food additive industry, [START_REF] Haesendonck | Rhamnolipids in bakery products[END_REF] enhancing hydrocarbon degradation [START_REF] Marchant | Microbial biosurfactants: challenges and opportunities for future exploitation[END_REF][START_REF] Kitamoto | Functions and potential applications of glycolipid biosurfactants -from energy-saving materials to gene delivery carriers[END_REF][START_REF] Franzetti | Production and applications of trehalose lipid biosurfactants[END_REF][START_REF] Pacwa-Plociniczak | Environmental Applications of Biosurfactants: Recent Advances[END_REF][START_REF] Rahman | The Potential of Bacterial Isolates for Emulsification with a Range of Hydrocarbons[END_REF] formation and disruption of biofilm, [START_REF] Dusane | Rhamnolipid mediated disruption of marine Bacillus pumilus biofilms[END_REF] nanotechnologies, [START_REF] Lo | Sophorolipids-induced cellulase production in cocultures of Hypocrea jecorina Rut C30 and Candida bombicola[END_REF][START_REF] Singh | A direct method for the preparation of glycolipid-metal nanoparticle conjugates: sophorolipids as reducing and capping agents for the synthesis of water re-dispersible silver nanoparticles and their antibacterial activity[END_REF][START_REF] Baccile | Sophorolipids: a yeast-derived glycolipid as greener structure directing agents for self-assembled nanomaterials[END_REF] gene transfection, [START_REF] Morita | Production of glycolipid biosurfactants by basidiomycetous yeasts[END_REF][START_REF] Inoh | Rapid delivery of small interfering RNA by biosurfactant MEL-A-containing liposomes[END_REF][START_REF] Fukuoka | The diastereomers of mannosylerythritol lipids have different interfacial properties and aqueous phase behavior, reflecting the erythritol configuration[END_REF] enhancing oil recovery. [START_REF] Yan | Oil recovery from refinery oily sludge using a rhamnolipid biosurfactant-producing Pseudomonas[END_REF][START_REF] Banat | Microbial biosurfactants production, applications and future potential[END_REF] One interesting application involving such glycolipids is towards wound healing, as some researches indicated that the additions of rhamnolipids may help the recovery in the treatments of burns and ulcers. [START_REF] Piljac | Successful Treatment of Chronic Decubitus Ulcer with 0.1% Dirhamnolipid Ointment[END_REF][START_REF] Stipcevic | Enhanced healing of full-thickness burn wounds using dirhamnolipid[END_REF]

HO

Supramolecular systems

Self assembling and self organizing properties of glycolipids have attracted intense attention.

In such systems, non-covalent interactions drive these units to cluster together to form supramolecular moieties. The forces vary in strength from hydrogen-bonding, CH- stacking to weak van der Waals attractions.

Hydrogel and organogels

Low molecular weight gelators (LMWGs) are an interesting family of small molecules which could form reversible supramolecular gels to immobilize the organic fluids. The resulting soft matters could be used in the field of drug delivery [START_REF] Vintiloiu | Organogels and their use in drug delivery -A review[END_REF][START_REF] Gao | Preparation and gelling properties of sugar-contained low-molecular-mass gelators: Combination of cholesterol and linear glucose[END_REF][START_REF] Gao | Enzyme-Instructed Molecular Selfassembly Confers Nanofibers and a Supramolecular Hydrogel of Taxol Derivative[END_REF] , enzyme immobilization [START_REF] Li | Gelator-polysaccharide hybrid hydrogel for selective and controllable dye release[END_REF][START_REF] Iwanaga | Application of organogels as oral controlled release formulations of hydrophilic drugs[END_REF] , etc.. A recent study showed that the galactoside amphiphile shown in Fig. 1.11, was very effective to make gelation of various organic liquids, fuel oils, vegetable oils. Interestingly, it also showed selective affinity towards organic phase against aqueous phase, as it could gel the organic liquid, fuel oils in the mixture with water. In addition to this, it was found to remove crystal violet as efficiency up to 97%, found to be very useful for the water purification. [START_REF] Mukherjee | Phase selective carbohydrate gelator[END_REF]

Modified nanotubes

The carbon nanotubes (CNTs) have a wide range of biomedical applications, [START_REF] Feng | Self-assembly of sugar-based amphiphile on carbon nanotubes for protein adsorption[END_REF] including biosensing, [START_REF] Bhattacharya | Pronounced Hydrogel Formation by the Self-Assembled Aggregates of N-Alkyl Disaccharide Amphiphiles[END_REF] imaging, [START_REF] Cherukuri | Near-Infrared Fluorescence Microscopy of Single-Walled Carbon Nanotubes in Phagocytic Cells[END_REF] drug delivery and specifically targeting and killing of cancer cells. [START_REF] Chakravarty | Thermal ablation of tumor cells with antibodyfunctionalized single-walled carbon nanotubes[END_REF] However, their poor solubility in most solvents, above all water, has hindered the CNTs from practical uses. Thus some modifications on the CNTs sidewalls introduced by covalent and non-covalent bonds have been developed. [96] The non-covalent method is preferred as the covalent method may disrupt the -network in the CNTs leading to the loss of electrical, mechanical and biosensing properties. [START_REF] Tsyboulski | Self-Assembling Peptide Coatings Designed for Highly Luminescent Suspension of Single-Walled Carbon Nanotubes[END_REF] In addition, the  stacking strategy proved itself as an efficient method to combine the functionalities onto the surface of carbon nanotubes.

One such example was carried out by Assali, M. et al.. [START_REF] Assali | Improved Non-Covalent Biofunctionalization of Multi-Walled Carbon Nanotubes Using Carbohydrate Amphiphiles with a Butterfly-Like Polyaromatic Tail[END_REF] The compounds have shown a stronger interaction with the multi-walled carbon nanotubes (MWCNTs) comparing with that baring the conventional pyrene as an anchor group. By the test of affinity towards Arachis hypogeal (peanut) lectin, compound 4 showed a positive action, while compound 5 was negative, demonstrating the selectivity of ligand-lectin interactions simulating the situation of glycoconjugates on a cell membrane, shown in Fig. 1.12. absence of binding of PNA to mannose coated nanoglycoarrays MWCNT-Tbf-PEG-Man-9. [START_REF] Assali | Improved Non-Covalent Biofunctionalization of Multi-Walled Carbon Nanotubes Using Carbohydrate Amphiphiles with a Butterfly-Like Polyaromatic Tail[END_REF] 1.

Liquid crystals

Another consequence of the self-assembling and self-organizing properties of carbohydratebased amphiphiles is their ability to exist in the physical state of liquid crystal. Lamellar, columnar, cubic mesophases are three main liquid crystalline behaviors for carbohydratebased amphiphiles in a pure state, while in the solution state, a sequence of mesophases will be observed according to the concentration. An extensive discussion on the carbohydratebased liquid crystal materials is given in the next section.

Carbohydrate-based liquid crystals 1.4.1 Introduction

"Carbohydrates are remarkable as a source of mesogens." [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] Commented by Jeffrey G. A., who was respected as a pioneer in the field of carbohydrate-based liquid crystal, as there are not only a great variety of carbohydrate moiety itself, but also the versatility of possibilities to access to polyfunctionality and adjustable degree of polymerization from mono-, di-to oligoand polymer. On the other hand, a growing knowledge on the mechanism of carbohydratebased amphiphiles in their biological activities makes people think that their physical state like liquid crystal should be argued as a factor responsible for these functionalities, too. [START_REF] Corti | Self-assembly in glycolipids[END_REF] For example, the disease caused by tubercle bacteria, was believed to have connections with "Cord factor" appearance of extracted materials under the microscope, which was actually related to their lyotropic liquid crystalline behaviors. [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF] The first synthesized carbohydrate derivative observed to show liquid crystalline behavior was hexadecyl -D-glucoside 6 (Fig. 1.13), which was prepared by E. Fischer et al. around 1911. In their report, the unusual melting behavior of this compound as it softened near 78 o C and finally melted to the fluid at around 145 o C confused them. [START_REF] Van Doren | Mesogenic sugars. From aldoses to liquid crystals and surfactants[END_REF] A similar melting pattern was observed on a same polar head with longer aliphatic chain, named ceryl -Dglucopyranoside 7 (Fig. 1.13) two years later. [100] It was not until 1938 that people began to realize this "double melting" behavior was due to the ability of alkyl -D-glucopyranoside to exhibit liquid crystalline behavior. [101] Besides the synthetic sugar derivatives, the natureoccurred glycolipids are also found to exhibit liquid crystalline phases. For instance, the 6, 6`dimycolic ester of trehalose 8 (Fig. 1.13), which possesses immunostimulant properties and antitumour activity in cluster, exhibits a thermotropic cubic liquid crystal phase. [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF] But in many cases, these experiments are taken in the aqueous condition, since the functionalities of glycolipids are more related to the water atmosphere. For example, the MEL-A mentioned above was observed to show sponge, bicontinuous cubic, and lamellar phases according to different concentrations. Today, as thousands of works contributed in this area, the mesogenic behavior has been regarded as a common property of sugar amphiphilic derivatives. [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] 1.

Mesophase behavior based on the structure of the glycolipids

There are plenty of reviews dealing with the carbohydrate-based thermotropic and lyotropic liquid crystalline behaviors. [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF][START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF][START_REF] Vill | Carbohydrate liquid crystals: structure-property relationship of thermotropic and lyotropic glycolipids[END_REF][START_REF] Van Doren | Mesogenic sugars. From aldoses to liquid crystals and surfactants[END_REF]100,[103][104][105] An early point of view towards these behaviors relies on the microphase separation caused by the fact of amphiphilic structure, owing to the different melting behaviors and affinities of sugar head and hydrophobic tails. [START_REF] Corti | Self-assembly in glycolipids[END_REF]103] Nowadays, based on the more broadened category of amphiphilic carbohydrate derivatives, a modern attitude to examine these mesophases is the self assembling and self organizing mechanism, [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF] which could be expressed in the terms that the units in the system communicate with each other to found some ordered state under certain conditions. [106] This mechanism could be used to explain the mesomorphic behaviors and to predict the possibilities of mesophases formed by amphiphiles, as shown in Fig. 1.14. Waals attractions, where the H-bondings is caused by the interactions of sugar head and others are by those of hydrophobic tails. In the traditional view of the requirements for mesogens, the structure of carbohydrate-based amphiphilic molecules seems to be softer than the rod-like mesogen in monophilic systems. However, with the fact that the hydroxyl groups of sugar head could be packed together via the intermolecular H-bondings to form the hard core moiety as the benzyl groups do in the monophilic system, and a flexible counterpart provided by the self-assembly of hydrophobic tails, the mesophases could be induced in the carbohydrate-base amphiphilic system.

At this point, according to the competition between the hydrophilic and hydrophobic parts during the self-assembling and self-organizing process, a tendency to form the layer or to create the curvature to bend into other dimensions will affect the packing strategy, which will be eventually observed in the different types of mesophases. Normally, this tendency could be examined in terms of comparing the relative sizes of cross-sectional area of head group to aliphatic chains and the resulting curvature, which refers to the molecular structure and interactions with outer environment.

The effect of molecular structure could be seen in the thermotropic liquid crystalline behaviors, since it is tested in the pure state of compound. According to the structure of compound, they may show 1D, 2D, 3D molecular topology as will be shown in the following discussions, thus the possible connections between structure and performance could be built up.

In low curvature occasion, as the carbohydrate derivatives own competitive amounts of sugar heads and hydrophobic tails, a lamellar mesophase is preferred. In this case, the relative sizes of hydrophilic to hydrophobic parts in this system are nearly equal, leading to a rod-like topological structure. These calamitic mesogens then aggregate paralleling to each other to form the layers where the head groups self-assemble together via the intermolecular Hbondings. These mesophases possess high viscosity, since the closely packing of layers.

Normally, the lamellar mesophases observed by the glycolipids are Sm A*, where the average of the long molecular axes parallels to normal (n) of layers, as shown A in Fig. 1.15 .

A typical defect texture is shown B in Fig. 1.15 under transmission optical microscope, which

shows the elliptical and hyperbolic lines. Some models of the possible packing styles were proposed to support the experimental results in Fig. 1.16. The difference between these two models is whether the H-bondings or van der Waals attractions devote more to the stabilization of mesophases. As indicated in this figure, in the first model the H-bondings are more important whereas in the second the hydrophobic parts stay inside the bilayer, the mesophases are more stabilized by the interactions of fatty chains. In the case of the carbohydrate-based amphiphiles showing regular and small changes in transition temperatures, the second model would be preferred. This might be due to the sensitivity of H-bonding towards the increase of thermal energy than the van der Waals forces. phase; [103] B: Typical defect image of lamellar phases (Sm A*) under light polarized microscope [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF] Fig. 1.16: Proposed models for lamellar phases: A) the sugar heads stay inside of the bilayer, the dashed lines stand for static H-bondings; B) the hydrophobic chains stay inside, the dotted lines represent optimum van der Waals attractions [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] If the ratios of relative sizes lean to either hydrophilic or hydrophobic fraction, for instance, two sugar heads to one aliphatic chain or for an inverse construction, a wedge-shape topology of molecule will be created (A, Fig. 1.17). Thus, assembling of these compounds will lead to disc-like supra-structures or a lamellar structure formed by inserting alternatively, B, Fig. 1.17. For glycolipids, the disc-like supra-structure is preferred. And the resulting disc- Fig. 1.17: Illustration of molecular structure (A) and the packing type for hexagonal mesophases (B) [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF] Fig. 1.18: Schematic representation of packing style of hexagonal phases [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF][START_REF] Van Doren | Mesogenic sugars. From aldoses to liquid crystals and surfactants[END_REF] Cubic phases are less commonly observed in pure state of these amphiphiles. These phases are shown when the molecular topology has a conical or bowlic shape, which will require the molecular structure to be highly unbalanced to hydrophilic or hydrophobic part, as illustrated in Fig. 1.19. These cones pack together to form objects, like micelles, possessing curvature

A B Lamellar

Disc-like in three dimensions. The organization of this type of compounds will form a cubic array, which expresses the discontinuous cubic phases. Cubic phases are highly viscous and they don`t show the birefringent property under the transmission light microscope, however, which makes its identification very problematic. Thus, a supplementary dyeing technology or X-ray diffraction experiment is needed to study these mesophases. (down) [START_REF] Goodby | Thermotropic liquid crystalline glycolipids[END_REF]105] The effect of molecular structure on the lyotropic behaviors of amphiphiles could still be seen, but the effect of outer environment, in most cases the water, plays a key role in the formation of mesophases. The curvature here will change rapidly according to concentration as well as temperature, as a result a sequence of phases could be observed. For example, the alkyl -D-glucopyranoside, [107] with one single thermotropic phase as lamellar, shows a sequence of mesophases in aqueous conditions, shown in Fig. 1.20. [107] In addition, some rare phases which could not be observed in pure state can be observed under lyotropic conditions, like nematic, cholesteric and blue phase. This is because these phases are very sensitive to small modifications of the curvature which are easier to provoke by modification of solvation than by modifying the structure of the molecules.

Bowlic structure

From the discussion above, a schematic representation of relationship between curvature and mesophase type could be drawn, as shown in Fig. 1.21. In the following section, these models will be detailed into the discussion of different effects on the formation of mesophases. Here we will mainly talk about the molecular structural diversities in the study of thermotropic liquid crystalline behaviors, in which we are more interested in our studies.

Hydrophilic/hydrophobic balance

The hydrophilic/hydrophobic balance (or hydrophilic/lipophilic, HLB) plays a core role in surfactant performances of amphiphiles, and it is also an important factor in the liquid crystalline behaviors. It could be examined in terms of ratio of head groups to tails and the degree of substitution.

Many systematic studies employed a gradual increase of the number of methylene groups to study the effect of HLB on the liquid crystalline behavior. For example, the thermotropic liquid crystalline behaviors of alkyl -D-glucopyranosides, [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] shown in Fig. 1.22, were found an increase of clearing point as the chain length increased. By summarizing the data obtained from these systematic observations, a general tendency of transition temperatures depending on the aliphatic chains could be drawn, [109] Interestingly, the odd-even effects were found their influence on the clearing point, as shown in the 6-O-alkyl-D-galactitols system, Fig. 1.24. [110] The reason for this phenomenon is still unknown. On the other hand, this effect is obvious on the system with shorter aliphatic chain.

Fig. 1.24: The transition temperatures of 6-O-alkyl-D-galactitols as function of chain length [110] The effect of the degree of substitution has been discussed in the previous section. Here we will examine some examples. The psychosine, (1--D-galactosphingosine), exhibits the Sm A* phase, [START_REF] Goodby | Liquid crystals and life[END_REF] but if a second long chain was attached on the amine group, like palmitoyl, stearoyl, oleoyl and nervonoyl galactocerebrosides, [111] they show thermotropic columnar phases (Fig. 1.25). The chemical structures and liquid-crystalline properties of psychosine and its cerebrosides derivatives [111] Some of the glycolipids consisting of triple substituted aliphatic chain show double mesophases during heating process. Like compound O--D-galactopyranosyl-tri-O-alkyl pentaerythritols, [108] it was composed of three aliphatic chains and one galactose head. Its shown in Table 1.4. At low temperature, the energy is not enough for the aliphatic chain to move, they are more restricted to vibrate within a certain space; thus the topology of this compound is wedge-like, a columnar phase was expected to adopt, the mesogenic units selforganize into a cylindrical columnar arrangement. When the temperature goes up, the chains could take up more dynamical motion, they were much expanded at this time. As a result, the compound showed a conical shape, which was able to support the formation of the cubic mesophase.

53

CHAPTER 1

Location of substitution

For the non-cyclic system, the family of x-O-dodecyl-(D or L)-xylitols was tested as the dodecyl chain moved from position 1 to 3. The melting and clearing points increased as the order of position 1 < 2, 4 < 3, sequentially, see Table 1.5. [112] The explanation to this behavior could be as the dodecyl chain moved from outer position inward, the ratio of the crosssectional area of hydrophilic to hydrophobic part increased, increasing the curvature during the formation of mesophase. Another reason is that the flexibility of compound reduced as the motion of aliphatic chain was disturbed by the steric hindrance. An example of study on the sucrose showed that the location of substituent may eventually change the molecular topology shape, thus two kinds of mesophases were observed. [113] The thermotropic liquid crystalline behaviors of this family were shown in Table 1

Compound

Orientation of hydroxyl groups

As the carbohydrate units are full of chiral centers, one could expect cholesteric mesophases to show up in this category like monophilic chiral compounds do. However, so far these mesophases induced by the orientation of hydroxyl groups on the sugar head have not been observed yet. In many cases, the effect of chirality in the category could be regarded as the effect of conformation of hydroxyl groups on the sugar moiety. But still, the data obtained is confusing.

For some systems, this effect on clearing point is not significant. For example, in the noncyclic polyol with mono-aliphatic chain system, the compound 9 and 10, 11 and 12 (Fig. But for some systems, the conformation of hydroxyl group will change the cross-sectional area of hydrophilic moiety, influencing the packing style of molecules; thus, a different mesophase will be observed. A study was conducted on the 4'-N, Ndidodecylaminophenylazo) phenyl as the hydrophobic tail coupling with different sugar heads, gluocopyranoside, galactopyranoside, lactose, xylopyranoside, and mannopyranoside, [114] in which the glucose derivative showed columnar mesophases whereas galatose and mannose derivatives showed lamellar phases, no mesophases observed for the other two series. Compared the structures of these amphiphiles showing the mesophases, the hydroxyl groups are all in equatorial position for glucose while there is one of the hydroxyl groups stands in the axial position for the others. Thus, the head group of 14 is smaller than the others, resulting in a larger relative size of hydrophobic to that of sugar head. In consequence, the topological shape of glucose derivative is more wedge-like, inducing a rectangular columnar, as shown in Fig. 1.29.

Other effects

The configuration of the head group may see its effect in the thermotropic transition behavior of homologue, e.g. the -and -octyl D-glucopyranoside and furanoside. [115] Fig. 1.30 showed that clearing point of this array followed this order -pyranoside > -pyranoside > - furanoside > -furanoside. But this pattern is not universal, since the formation of liquid crystal phases depends strongly on balance of hydrophilic and hydrophobic parts, the order could not be easily obeyed in other sugar systems. [115] Besides the effect of molecular nature on the packing process, small modifications on the structure may have impact, too. One example of this kind is the linkage between the carbohydrate matrix and the hydrophobic part. [116] The comparison work was carried out on the mono-substituted xylitol system with linkage of ether, thioether ester and amide, respectively. The transition temperatures of these molecules as a function of alkyl chain length are shown in Fig. 1.31, where it was found the efficiency of these functional groups to stabilize the mesophases was shown as the order of RS->RCOO->RO-.

Methods to identify the liquid crystalline behavior 1.4.3.1 Polarized optical microscopy (POM)

For most of liquid crystalline materials, they possess a birefringent property, meaning that if the polarized light enters these materials the orientation of light wave will be change, thus some exotic images which are the reflection of the defects occurring during the formation of mesophases could be observed. This method which was found by Friedel in 1922 [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] is the most widely used in identifying the type of liquid crystalline phases. The images, Fig. shown) [START_REF] Molinier | Self-organizing properties of monosubstituted sucrose fatty acid esters: The effects of chain length and unsaturation[END_REF] Fig. 1.34: Fan-like region defects texture of columnar phases [117] Fig. 1.35: Transition from cubic to columnar phases, [108] where the cubic phases were black and the normal of columnar phases could be seen as the long rang of extension of long rod

Differential scanning calorimetry (DSC)

DSC is another useful tool to identify the transition temperatures. Since this method is very sensitive to the heat absorption and emission, it gives a more precise data for the transition temperatures, with accuracy close to 0.01°C. In addition, by measuring heat absorption and emission, it also allows to calculate the corresponding transition enthalpies ΔH and entropies ΔS. Melting point and clearing point are normally reported from the first heating cycle, as possible hysteresis during the test can occur. In some cases, some transitions like crystalcrystal which were not seen under the polarized light microscope can be identified here.

X-ray diffraction spectroscopy (XRD)

When unclear or insufficient information is provided by microscopy when identifying the type of mesophase, X-ray diffraction can be used as a supplementary means, as it could give some information by providing diagnostic diffraction patterns. [118] The relation between the first reflections for different liquid crystalline phases could be shown as below:

Cubic: 1:1/√2:1/√3:1/√4:1/√5:1/√6:1/√8... Lamellar: 1:1/2:1/3:1/4...

Hexagonal: 1:1/√3:1/√4:1/√7...

Conclusion

In this section, we briefly described the carbohydrate-based liquid crystals, their selfassembling and self-organizing properties and the effects that induce different formations of mesophases. The intermolecular H-bondings and the relative cross-sectional area of sugar heads to aliphatic tails are considered as two essential factors that govern the formation of mesophases. Van der Waals and other types of interactions also contribute to the stability of such mesophases. Though carbohydrates are chiral molecules, no cholesteric phases, like chiral smectic, chiral discotic, have been yet discovered in the family of carbohydrate surfactants. Elaboration of more complex systems involving sugar and lipidic moieties can still enrich the field of carbohydrate based liquid crystals.

Such studies contribute to the understanding of the relationships between structures and properties, which eventually can provide insights in their possible roles in some biological processes.

Chapter 2

Carbohydrate Bicyclic Lactones and Their Applications

Introduction

During the last decade, our group has been involved in developing a new synthon based on glycosyl lactones, namely carboxymethyl glycosyl lactones (CMGLs). Over the years, we have widened the scope of this synthetic strategy and applied it to several intermediates towards functional compounds such as probes for fluorescent imaging, monomers for polymerization, mesogens for carbohydrate liquid crystals, pseudoglycoconjugates and so on.

These efforts proved it to be a general and useful way to couple carbohydrate moieties with other specific systems. What follows aims at reviewing briefly the field of carbohydrate lactones with a focus on bicyclic ones.

Carbohydrate-based lactones are interesting compounds which have been used in many fields and a topic for several reviews. [119][120][121][122][123][124] Monocyclic and bicyclic lactones are two main streams in the carbohydrate derived lactones.

The former ones are found to be in 1,4-() or 1,5-() configurations. In the latter system, the lactones could be fused or linked to the sugar moiety. Both families contain -unsaturated examples.

Monocyclic lactones, or aldonolactones, from the carbohydrate resources are usually prepared by the selective oxidation on the anomeric hydroxyl group. The resulting and lactones, under certain conditions, could be reversed, Fig. 2.1. Using traditional method, for example, oxidized by bromine, the majority of resulting lactones will be aldono-1,4-lactones (lactones), which are thermodynamic more stable, except for D-glucose. In order to obtain the 1,5-lactones as major products, some efforts have been carried out. By using the Schvo`s catalytic system, where dimeric ruthenium complex [(C 4 Ph 4 CO)(CO) 2 Ru] 2 , 18, as catalyst, cyclohexanone as hydrogen acceptor, the selectivity ratio in -Dgalactonolactone reached 93%, whereas the -D-mannonolactone reached to 94%. [125] Scheme 2.1 and Table 2 Whereas a similar system, where [RuH 2 (PPh 3 ) 4 ] as catalyst and benzalacetone (trans-4phenylbut-3-en-2-one) as hydrogen acceptor, showed a reversed results. In this condition, aldono-1,4-lactones were the major products, where even for the D-gluocose, no -lactone was obtained. Table 2.2: Results obtained from a variety of sugars and protected sugars in this condition [126] Another method by the ring-closed reaction of dihydroxyenoate was achieved. In this method, 2, 4-hexadienoates were employed as the starting materials, of which the second double bond was dihydroxylation by Sharpless AD-mix reagents, followed by either direct ringclosed reaction to obtain the -L-galactonolactone or further protected to obtain the -Lgalactonolactone, as shown in Scheme 2.3. [127,128] The microorganisms are also employed to produce to aldonolactones. For example, the -Dgluconolactone could be largely manufactured by oxidation of glucose associated by the enzymes form bacteria of Pseudomonas and fungi of Asperigillus niger. [129] In this case, a lactonase enzyme is also needed for preventing further opening of lactone (Scheme 2.4). 23 [131] and 24; [132] fused C-branched lactones 25 [133] and 26 [134] ; lactonized carboxyalkyl ether 27 and 28, [135] and the CMGLs. The synthesis and the uses of this latter family are further detailed in the next section.

Synthesis of the CMGLs

The interest of our group for this topic originated from some work on the reactivity of sucrose.

Looking for new oxidation products by reaction with hydrogen peroxide and sodium tungstate, a clean and efficient method already applied to the preparation of adipic acid from cyclohexene via cylohehane diol, the low stability of sucrose in acidic conditions appeared as an absolute drawback. However, we knew that isomaltulose, (6--D-glucopyranosyl-Dfructofuranose), was significantly more stable under acidic conditions and we switched to this other substrate, also a cheap and available sugar interesting starting material for sucrochemistry, obtained by bioconversion from sucrose. It was found that the oxidation of isomaltulose could lead to a glucopyranoside derived carboxylate, which was identified as carboxymethyl -D-glucopyranoside (-CMG) (Scheme 2.5). [136,137] Scheme 2.5: Synthesis for -CMGL 29 originated from palatinose or trehalose Various parameters affecting this oxidation reaction were studied. The results showed that the pH value was essential. In the case of palatinose, at high pH, the yield of -CMG was very low, below 15%; but when the reaction took place at pH 2, the reaction took less time and the yield was improved up to 35%. The effect of catalyst was investigated, too. The presence of sodium tungstate (Na 2 WO 4 ) would shorten the reaction time, but increasing amount of tungstate was not found to help increase the yield of -CMG. The result obtained from trehalulose was better, where the yield of -CMG could be up to 59% based on recovery of starting material. However, thehalulose is not as available. Despite the modest yield of this reaction, it appeared as a simple and direct method compared to multistep selective construction by classical glycosylation sequences.

In the next step, the obtained -CMG was subjected to the reaction with acetic anhydride in pyridine, and underwent ring-closure. A possible mechanism of this step is proposed in To examine the factors affecting the oxidation of the disaccharides and optimize the conditions for increasing the yield of lactones, a close supervision on each step was carried out. [138] By monitoring the resulting byproducts, the study showed that a stable pH value at 4 where the glycosidic linkage was stable for preventing the hydrolysis to glucose and higher temperature for complete oxidation of the fructose moiety were needed. Since the obtained lactone was sensitive to the conditions, careful handling was needed for storage and use.

Before purification by silica gel column chromatography, the residue was washed by ammonium chloride solution and dried over the sodium sulfate (Na 2 SO 4 ) carefully. After gaining the pure compound, a precipitation in pentane was needed to yield a white solid which could be stored at 4 o C for months. Different protecting groups, like chloroacetyl, pivaloyl and benzoyl, were used to yield the corresponding -CMGLs with more or less stable protecting groups, as shown in Fig. glycosides which were oxidized by sodium periodate (NaIO 4 ) using ruthenium trichloride (RuCl 3 ) as catalyst, followed by treating the resulting product with triethylamine (TEA) to yield corresponding CMG residue. [139] The ring closed reaction was also carried out with acetic anhydride in pyridine. The whole procedure is shown in Scheme 2.8. An alternative oxidation can be ozonolysis to the aldehyde which is further oxidized in the presence of sodium chlorite (NaClO 2 ) to the carboxylic acid. This method offers a more straightforward sequence to the desired lactones, without purifying the intermediates. The procedure is shown in Scheme 2.9. A Koenigs-Knorr-type reaction was tried to obtain the lactones with benzyl groups protected.

O OAc R 1 AcO O AcO R 2 O OAc R 1 AcO O R 2 O O O OAc R 1 AcO R 2 O O O Glucose or Galactose O OH R 1 HO O HO R 2 O -HNEt 3 + O 1.
[29] R 1 = OAc, R 2 = H [30] R 1 = H, R 2 = OAc [31] R 1 = OH, R 2 = H [32] R 1 = H, R 2 = OH [33] R 1 = OAc, R 2 = H [34] R 1 = H, R 2 = OAc [35] R 1 = OAc, R 2 = H [36] R 1 = H, R 2 = OAc
These lactones are less stable than the acetylated ones, however. For the  conformation, the procedure went through a orthoester strategy to yield the resulting OH-2 free compounds with benzyl groups protected in 3, 4, 6 position, which followed by the same route of previous ozonolysis process, shown in Scheme 2.10. A modified option is based on an anomeric alkylation with tert-butyl bromoacetate, which proved to be very convenient and general in terms of starting carbohydrate (Scheme 2.12). [140] Firstly, the peracetylated glucopyranoside was treated with NH 2 NH 3 OAc to deprotect the anomeric OH, which was further reacted with tert-butyl bromoacetate in the presence of K 2 CO 3 to yield the acetal ether 48. At this stage, the  and  anomers were obtained. The  anomer was preferred with the ratio :  = 6.1: 1. After, the tert-butyl group was selectively removed by TFA to the carboxymethyl acid. The lactones were obtained in the same ring-closed conditions as described. This procedure was applied on other monoand di-saccharides and proved to be successful. (Table 2. Table 2.3 List of sugars formed CMGLs [140] The conditions for starting from fully unprotected sugars were also studied. The glucose, mannose, N-acetyl glucosamine, maltose, and lactose were treated with NaH in DMF (Scheme 2.13). The yield was low compared with the corresponding acetylated ones, but the reaction showed preference towards  conformation, as shown in

Ac 2 O, pyridine

[39] R 1 = OAc, R 2 = H [40] R 1 = H, R 2 = OAc [41] R 1 = OAc, R 2 = H [42] R 1 = H, R 2 = OAc [43] R 1 = OBn, R 2 = H [44] R 1 = H, R 2 = OBn [45] R 1 = OBn, R 2 = H [46] R 1 = H, R 2 =

Construction and applications of conjugates obtained from

CMGLs

The lactones are known to be readily opened by nucleophiles, such as amines and alcohols.

Via this strategy, pseudo disaccharides, sugar amino acids, surfactants and monomers and so on can be prepared. Using these bicyclic lactones, since the attack by nucleophiles would not affect the sugar ring, the opening of lactone ring offers a convenient method for conserving the cyclic pyranose or furanose skeleton into the target molecules, which could be useful for bringing some biological function or at least some biocompatibility.

At first, this research started with amino acids, and simple alcohols, amines. With alcohols, the reaction can be either promoted by acid or base catalysis. The reaction was applied to a great variety of alcohols, Scheme 2.13. However, the newly created ester function is just as unstable as other acetyl groups on the sugar, therefore making difficult subsequent deprotection of adducts without cleaving as well the new connection. Using chloroacteyl protected lactones, selective de protection of the sugar could be achieved. Scheme 2.14: Reactions of lactones 33 and 55 with alcohols [137] The reaction proved to be much more general and useful using amines as nucleophiles. The results showed that with amines the obtained yields were much higher than alcohols with a short reaction time, and the resulting compounds were stable which could be further deacetylated to yield the glucopyranoside derivatives. Scheme 2.16: Reactions of -CMGL with amino acids [137] Some pseudodisaccharides of glucose-glucose, glucose-galactose, and glucose-uridine were formed by the amide linkage by ring-opening of -CMGL. [141] The yields of final product were 72% 56, 72% 57, and 60% 58, respectively, as shown in Fig. Scheme 2.17: An example of applications in 'click' chemistry [139] In the field of biological applications, the CMGLs were used to couple sugars with some hydrophobic functional groups to improve their solubility in water along with biological compatibility. For example, compound 68 was synthesized as a photosensitizer in the field of photodynamic therapy (PDT) [142] and fluorescent probes 69, 70 showed a good an affinity towards membranes, as shown in Fig. 2.6. [143] Fig. 2.6: Chemical structures of -CMG amide probes [142,143] By further oxidation at O-2 after lactone opening, a series of -unsaturated carbonyl compounds derived from the CMGLs were synthesized. [144] Their structures were shown in Fig. 2.7. Among them, the compounds bearing dodecyl chain show the activity in the antifungal and antibacterial tests, and interestingly compound 73 showed a low toxicity while its -isomer 76 was toxic. CMGLs [144] "Living" polymerization using monomers arising from -CMGL derivatives has also been explored. [145] The obtained monomers 88 and 89 (Scheme 2.18) show a good ability to form the polymers via the reversible addition fragmentation chain transfer (RAFT) polymerization.

They also showed a great trend in the "living" polymerization, as indicated in the size exclusion chromatography (SEC) spectra that the elution volume continued to grow. Scheme 2.19: Polymerization of monomer 89 and post modification by CuAAC reaction [145] The possibility of trying polymerizations through this strategy was also studied by introducing both the azido and alkynyl groups on the glucosyl matrix. [146] The monomers were derived from -and -CMGLs, whose structures were shown in Scheme 2.19. The polymerization of these monomers was performed in the DMSO-d 6, monitored by 1 HNMR. They all showed a good ability to polymerize, and an example of polymerization of monomer 91 is shown in The long time interest of the collaborative project gathering the teams in Lyon, Hull then York in the field of carbohydrate based liquid crystals led us to explore the application of the glucoconjugates prepared by CMGLs strategy in this area. In order to study the effect of relative cross-sectional areas of sugar head to aliphatic tails on the thermotropic liquid crystalline behavior, glucopyranoside derivatives of a series of aliphatic amines (C6, C8, C10, C12, C14, C16) and aminocholesterol, amino steroid with  and  conformations were prepared. [147] (× 100) [147] For steroidal series, structures of which were shown in Fig 2 .9. Unlike the systems with the fatty chain, the steroid moieties are bulky and rigid units, thus the transition temperature for two cholestanyl compounds are very high while no mesophases were observed on the cholesteryl derivatives, since the double bonds brought more rigidity to the system compared to the cholestanyl mimics.

Conclusion

Carbohydrate-based lactones are important synthons not only in the aspect of their easy way to be introduced into the systems, but also in some special abilities they could bring, like chirality, biocompatibility and water solubility and so on. The CMGLs were found to be a useful type of synthons with various preparations, with versatile sources of sugars, and with wide applications. At this point, in this study, the simplest monosaccharide glucopyranose was chosen; and, as to prevent conformational variations due to anomeric equilibrium, the system was locked as a methyl -glucoside throughout the study. The hydrophobic reagents used were 1,2epoxyalkanes with alkyl chain length from 8 to 16 carbon atoms. As a matter of comparison, two compounds having simple linear alkyl chains of 8 and 12 carbons atoms at the position 6 were also prepared.

Some of the compounds in this series were synthesized by Mr. Madan Kumar Singh during his post-doc stay in the laboratory.

Synthesis procedure

The general scheme for the preparation of the desired monosubstituted hydroxyalkylethers is shown in Scheme

Synthesis of methyl 2-O-(2-hydroxyalkyl)--Dglucopyranosides

The method we adapted for the OH-2 compound is by J. Xue et al.. [148] In this method, the methyl -D-glucopyranoside was firstly reacted with benzaldehyde dimethylacetal and catalytic amount of camphorsulfonic acid in acetonitrile to get the methyl 4,6-O-benzylidene--D-glucopyranoside, then the diol OH-2-OH-3 was monobenzylated via the intermediate tin acetal obtained by reaction with dibutyltin oxide, using benzyl bromide and tetrabutylammonium iodide in toluene, as shown in Scheme 3.2. The resulting product was a mixture of ethers at O-2 and O-3 compounds. The major product 96, which has its OH-2 free, was obtained in 42% yield, and easily separated by chromatography. As the resulting compounds are amphiphilic, a mixture of CDCl 3 and MeOD at the ratio of 9 to 1 was used to dissolve them. Fig. 3.4 shows the [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR spectrum of methyl 2-O-(2hydroxydodecyl)--D-glucopyranoside 97c. It is observed that some peaks appear as pairs of two peaks. The reason is that the etherification product is a mixture of two epimers, because the configurations of the hydroxyl group resulting from the epoxy ring opening reaction either upside or downside, as indicated in the Scheme 3.4. Separation of these two epimers was not feasible in view of the very close R f on the thin layer chromatography (TLC). According to this [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR, their proportion in the two products was close to 1:1, showing that the chance of forming the two isomers was equal. Through the whole series of compounds studied, the same thing was observed and the ratios of the two isomers in these series were nearly the same. Thus, the mesomorphic behaviors of these compounds were studied as the state of mixture at this hydroxyalkylether position.

Synthesis of methyl 3-O-(2-hydroxyalkyl)--Dglucopyrano-sides

For methyl 3-O-(2-hydroxyalkyl)--D-glucopyranosides, the method introduced by Murphy et al. was used. [149] An intermediate in the previous synthesis, methyl 4,6-O-benzylidene--D- glucopyranoside, was also used as starting material. It was reacted with benzyl bromide (BnBr), tetrabutylammonium iodide (TBAI) and aqueous NaOH in DCM at room temperature, as shown in Scheme 3.5. Again both regioisomers were obtained, but this time, the product with OH-3 free was the major one.

C 2' -H 2' C 2 -H 2 H 8a C 2' C 2 C 8 -H 8 C 8' -H 8' H 8b C 2 -H 8b C 2' -H 8'

Synthesis of methyl 4-O-(2-hydroxyalkyl)--Dglucopyranosides

The synthetic sequence toward this series was adapted from T. Nobuo et al.. [150]

H 3 -H 2 H 1 -H 2 H 3 -H 4 C 4 -H 4 C 2 -H 2 C 3 -H 3 -CH 2 Ph

Synthesis of methyl 6-O-(2-hydroxyalkyl)--Dglucopyranosides

In this procedure, the methyl -D-glucopyranoside was reacted with triphenylmethyl chloride (TrCl), which shows a preference for reacting with primary alcohols. [151] The obtained The resulting products 106a, 106b were examined by NMR, and their structure was confirmed by comparison with the data reported in literature. [152][153][154] C 6' -H

Study on the thermotropic liquid crystalline behavior of the methyl glucoside hydroxyalkyl ethers

The studies of thermotropic liquid crystalline behavior were carried out in collaboration of J.

W. Goodby's group in the University of York. They were examined in three aspects: the mesophases, the transition temperature, the transition H and S. The methods using for the tests were polarized light microscopy and differential scanning calorimetry (DSC). Since the mesophases were very characteristic in all series and easily identified with microscopy, the X-ray diffraction (XRD) was not used.

DSC and polarized light microscopy results of these ether compounds

The DSC tests were performed at the scan rate of 10 o C min -1 , and the heating and cooling processes were repeated twice. In this series, the shortest aliphatic chain with 8 carbon atoms was not observed to form a mesophase. It was found to form a glassy state at -5.4 o C and melt into liquid at higher temperature. The formation of glassy state, which is a typical state of sugar, indicates that intermolecular H-bondings of the head groups are the main interactions in this system. As the chain extended to 10 and 12 carbon atoms, the crystalline state appeared whereas the glassy state could still be seen at low temperatures, which were higher than the shortest C8 chain. This behavior suggests that as the increase of hydrophobic proportion in the system, the van der Waals interactions of the hydrocarbon chain began to compete with the intermolecular H-bondings. Eventually, with the longer aliphatic chains of 14 and 16 carbon atoms, the glassy state was replaced by the crystalline state. And a new heat absorbing peak was observed, which indicated a mesophase was formed between the crystalline state and isotropic liquid.

This result fits with the results observed by transmission polarized light microscopy as the Smectic A* (Sm A*) phase. The compounds of all the series bearing longer chain were found to show this mesophase, indicating that the topological shape of these molecules is rod-like. this defect is due to the fact that the aligning of the molecules was perpendicular to the plane of the microscope slide. That is because of hydroxyl groups of glucoside head preferring to interact with the glass surface while the aliphatic chain didn`t. Combining the results from the DSC experiments and observations from transmission light microscopy, the following tables (Table 3.1 to Table 3.5) summarize the thermotropic behaviors of these series. The melting points and the clearing points are recorded in the first heating and first cooling section, since these temperatures are sensitive to thermal history of sample and possibility of decomposition during the heating. [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] For example, the melting points of methyl 3-O-(2-hydroxydodecyl)--D-glucopyranosides 99c in the first heating was 32.7 o C while that in the second heating was 12.9 o C. This is due to the fact that the crystal melting in the first heating is from the solution whereas the crystal in the second heating is from the crystallization in the bulk sample which follows a different energetical and structural mechanism. The clearing points of some compounds are in the brackets, which is because these transition temperatures were observed during the cooling process. Comparing these two distant results, the additional hydroxyl group may have a relatively stronger impact on the shorter aliphatic to the longer ones. This result may be due to the hydrophilic/ hydrophobic balance of the system. In the case of regular aliphatic chain, the number of carbon atoms of 8 was enough to be competitive to the H-bondings induced by the glucoside head group; but for the family with the additional hydroxyl group, the hydrophilic/ hydrophobic balance at this stage was not enough to stabilize the mesophases at this stage. Once the hydrophilic/ hydrophobic balance rebuilt where the effect of the hydroxyl group was not significant, the liquid crystalline behavior may more rely on the interaction of the hydrophobic part rather than the intermolecular H-bondings. of all the series. Examining these curves, we could find an increase of the clearing point relative to the increasing methylene groups. This kind of behavior is similar with other carbohydrate based liquid crystals, for example, the alkyl -D-glucosides with short aliphatic chains, [START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF] indicating that the van der Waals attractions also have effects on the formation of thermotropic liquid crystalline phases.

The effects of aliphatic chain and the substituted position on the liquid crystalline behavior of the series

The substitution position has a significant effect on the melting points. The O-3 and O-4 series had relative lower melting points compared to O-2 and O-6 families. This kind of behavior was also observed in other systems, for example the series of mono-O-dodecylpyranoses, where the two middle positions showed higher melting points than the other outer two positions. For the clearing points, the effect of substitution positions is not as significant as that on the melting points, but it conveys some interesting information. As shown in Fig. 3.32, for the longer chains (14, 16), these compounds behaved a consistent decreasing manner as the order of 97 > 99 > 101 > 105. But the equivalents bearing the chain length of 12 carbons behaved a strange manner. At this chain length, the 99c showed the highest clearing point, no mesophases were observed in the 101c compound, and 97c and 105c compounds had a similar isotropization temperature which was lower than the 99c. This unusual manner could be regarded as the boundary where the hydrophilic/hydrophobic balance met its limit. At this point, the inter-and intra-molecular H-bond played a central role in the formation of mesophases. And this difference of the interaction may eventually enhance the liquid crystalline behavior for O-3, or suppress the liquid crystalline behavior in the case of O-4.

Structure study by modeling

In order to understand the possible structure-properties relationships in these series, the energy minimized models of the molecules with C8 chain, 97a, 99a, 101a, 105a, were examined in the gas phase at absolute zero, as shown in Fig. 3.33, with two epimers respectively. The effect of intra-and inter-molecular H-bondings was investigated in terms of effective distance between the hydroxyl group on the aliphatic chain and the neighboring hydroxyl groups on the sugar head. The closest interaction distances are shown in the models. For 97a, the hydroxyl group in the alkyl chain has one possible interaction with the OH-3 with an effective H-bonding distance of 4.2 Å for one epimer and 5.0 Å for the other. A similar situation was detected in the case of compound 105a where the possible interaction is at 4.2 Å and 3.6 Å, respectively. Since the aliphatic chain of 99a is located inbetween the O-2 and O-4 position, the possibility of the additional hydroxyl group interacting with the OH-2 and OH-4 is largely increased, with the effective distance at 3.0 Å and 5.6 Å for one epimer, 5.3 Å and 3.9 Å for the other. In this case, a preference of forming the intramolecular Hbondings is much higher than the 97a and 105a. A similar conclusion could also be drawn for the compound 101a. As a consequence, these configurations may employ a more rigid structure, where the alkyl chain and glucoside unit are more likely to fixed together, compared to the 97a and 105a. with the S/R, where R is the constant value of 8.314 J K -1 mol -1 . The results are listed in Table 3.6. Observed in other systems, the enthalpy of transition increases as the chain length extends, which indicates that the mesophase is becoming more organized and less like the liquid, the rule could also be applied for these series as the methylene groups 97a 99a 101a 105a increased. When comparing with these values in regarding of substitution positions, the compound 101d possesses a lowest enthalpy value, along with the S/R, which could be interpreted as that the compound is more disorganized than the others. This may be the reason for why the Sm A* was not observed for the 101c. And it also suggests that the Hbondings in this system is intra-rather than inter-, that is to say, the additional hydroxyl group would have more chance to interact with the hydroxyl groups inside the molecule. Once this intramolecular H-bonding was formed, the compound may create a pseudo-six member ring, which reduces the hydrophilic /hydrophobic balance. As a result, the msophase stability was reduced. And for the longer chain, since the hydrocarbon chain began to dominate the transition behavior, the formation of pseudo-six ring would be interrupted by the flexibility of aliphatic chain.

In contrast, the 99 series exhibited relative high enthalpy values, which met their summit at chain length of C14. This array of values indicate that hydroxyl groups in this series are preferred the intermolecular H-bondings, suggesting that the mosophase is formed easily and stabilized well. The effective H-bondings could also be used to explain the melting behaviors of these compounds. An obvious explanation could be given as the additional hydroxyl group in the aliphatic chain substituted in the middle positions of the sugar has more chance to form intramolecular H-bonding than the outer couples. At lower temperature, the effective hydroxyl groups in these compounds to bridge with other molecules are less, thus the ratio of intermolecular H-bonding is low, leading to less stable crystal state. As a result, the melting points of compounds of 99 and 101 are lower than that of 97 and 105. A more insightful comment stands on the global structure of the molecule. In the 97 and 105 series, since the orientations of hydroxyl groups on the sugar head are the same, they could take part in building up the interactions with other molecules. This process might not be disturbed as the aliphatic chain could be packed aside. In other two systems, because of the location of substitution is inbetween those with hydroxyl groups, the opportunities of disturbing the intermolecular H-bonding by the alkyl chain is much higher, leading to the lower melting points.

Compound H / J mol -1 T / K S / J mol -1 K -1 DS/R 97c

Lyotropic study

The lyotropic liquid crystalline behaviors of these compounds were also investigated. The experiments were carried out by examining contact preparations, which is designed as a small amount of water is added into the space by the coverslip and glass plate where the sample is. As a result, from contact frontier to inside solid, the glucoside sample forms a gradient of concentration from high to low. The plate is then examined under the transmission light microscope. The results are listed in Table 3.7. As observed, according to different concentrations, the molecules formed hexagonal, cubic and lamellar mesophases, which are similar to some simple sugar head derivatives. [155,156] The Fig. 3.34 shows the defect images of lyotropic liquid crystalline mesophases as lamellar, cubic, and hexagonal of compound 101c. A general tendency for these compounds is that as the aliphatic chain length increased, the types of mesophases were limited. For example, for the compounds 101b with the shorter chain, the molecule showed hexagonal and cubic phases. When the chain extended for 14, 101d, the mesophases observed was just the cubic, Fig. 3.35. These phenomena indicate that as the alkyl chain extended, the relative cross-sectional area of the sugar head to the alkyl chain decreased, resulting that the curvature of the system was not sufficient to support the formation of mesophases. And since the aliphatic chain became to dominate the portion of molecule, the compound was turned to be hydrophobic which was not soluble in water.

Interestingly, compounds where the alkyl chain is attached in the O-2 position exhibited increased curvature compared to the other compounds. This indicates that the crosssectional area of the sugar is larger for these materials in comparison to the other homologous series. The 99 series showed a tendency for lower curvature than the other analogues, where the hexagonal phase was only observed for the shortest chain lengths, which disappeared the chain length reached C10.

Conclusions

A new family of methyl n-O-(2-hydroxylalkyl)--D-glucopyranosides have been synthesized

and characterized. The synthesis methods involved partially protecting the hydroxyl groups on the glucopyranoside head to make target position available, followed by being etherified with different chain lengths of 1,2-epoxyalkanes. The final products were obtained by removing the protecting groups. The structures of final products were identified by NMR and mass spectroscopy to be the desired compounds.

Their thermotropic liquid crystalline behaviors were investigated by means of transmission light microscopy and DSC experiment. As observed, the Sm A* phases are the dominant phases. Comparing with our previous investigation of similar systems based on sucrose, [113] these compounds show relatively low transition temperatures. The substitution position has little effect on the mesophase formation, yet a significant one on the melting points.

The clearing point increases as the aliphatic chain extends. When the chain length is 14 or 16, the transition temperature decreases as the substituted chain moved from O-2 to O-6.

For the C12 series, the effect of position is different, possibly due to a preference for intermolecular H-bonding, as indicated by significantly higher transition enthalpies for all O-3 compounds, while in the case of O-4 compounds, intramolecular H-bondings would be the dominant factor. Moreover, for these latter O-4 compounds, modeling shows that the hydroxyl group of the aliphatic chain and the sugar hydroxyl groups may have a very approaching distance.

Chapter 4

Synthesis and thermotropic liquid crystalline behavior of new glycosteroidic amphiphiles

Introduction

Cholesterol is abundant in the membranes of most mammalian cells. [157] For example, it covers 15% of total weight of skin surface lipids. [158] The role of cholesterol associating with sphingolipids in the concept of "lipid rafts" is well known. [START_REF] Lingwood | Lipid Rafts As a Membrane-Organizing Principle[END_REF]159,160] Cholesterol's unique structure, where two different facial geometrical graphs as the hydroxyl group on the C-3 and methyl substituents on the C-10, C-13, and C-17 are orientated in  face, is considered to be responsible for these properties. Molecular modeling is shown as A in Fig. 4.1. [161] Cholesterol is also an important mesogen in the liquid crystal domain. It is a topic of several reviews recently. [162,163] Over 3300 cholesterol-based LCs with a variety of structures have of cholesterol; [161] (B) Helical structure of cholesteric liquid crystal [162] Its conjugates with carbohydrates, in the big family namely steroidal glycosides, are ubiquitous compounds. The structures of two recently found compounds in this family are shown in Fig. 1.9. [START_REF] Ben-Menachem | A newly discovered cholesteryl galactoside from Borrelia burgdorferi[END_REF][START_REF] Kawakubo | Natural Antibiotic Function of a Human Gastric Mucin Against Helicobacter pylon Infection[END_REF]

Synthesis of C4 spacer

The key step towards the C4 linker compound is the olefin cross-metathesis between the allyamide obtained from CMGL, and the allyl cholesteryl ether. This metathesis reaction was discovered around the 1950s, and the main contributors to the discovery, Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock, received the Nobel Prize in 2005. The accepted mechanism of this reaction is shown in Fig. 4.4, as the olefin being firstly coordinated with a metal alkylidene to form a metallacyclobutane intermediate, which further exchanges with the other olefins to generate the more entropic stable product. [165] Fig. 4.4: Catalystic cycle of olefin metathesis [165] Nowadays, the ruthenium-based catalysts are the most widely used in olefin metathesis, since they show a good tolerance towards oxygen, water and functional groups and a good catalytic activity. In this synthesis, we employed the Grubbs-Hoveyda catalyst 2 nd generation.

The structure is shown in Fig. 4.5.

126

The NMR data fits with what was reported in literature. [166] Coupling of carbohydrate olefin 107 and cholesteryl olefin 108 was carried out in DCM in the presence of Grubbs-Hoveyda catalyst, and the desired glycosteroid was obtained in 72% yield, Scheme 4. The acetyl groups were then removed by NEt 3 in a mixture of MeOH and H 2 O, Scheme 4.4.

The reaction was monitored by TLC using the eluent of. Removal of acetyl groups could be seen in the 1 H NMR and [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR. In the proton NMR, the three single peaks around  2.03 ppm belonging to CH 3 of acetyl group in the spectrum of starting material disappeared in that of the final compound, while in carbon NMR, the disappearing of three peaks around 174.5 ppm belonging to C=O also indicated the cleavage of ester bond. All other H and C atoms were found in the spectra. The mass measured by mass spectrometry of the resulting compound at 678.2 (M+ H) confirmed the structure of the compound.

Synthesis of C6 and longer spacers

When applying the same method using olefin metathesis for synthesizing the longer linkers series, the attempts failed as the reaction outcome was in favor of the homocoupling process and not the desired cross-coupling one. This might be due to the loss of electronic effects on the carbohydrate olefin where the nitrogen of amide group could no longer improve the activity of double bonds since more carbon atoms were set between them. Thus, we developed an alternative synthetic strategy, which relied on the connection of aminoalkylethers of cholesterol with -CMGL.

This necessitated the prior synthesis of these -aminoalkylethers of cholesterol. Firstly we followed a method reported by Cha S.W et al. [167] to get the -hydroxyalkylethers of cholesterol. The tosylated cholesterol 112 was reacted with a large amount of 1, -akyldiol (30 eq.) in anhydrous 1,4-dioxane leading to the cholest-5-en-3-yl -hydroxyalkyl ether 113.

The diols were soluble in dioxane at the reaction temperature, thus the reaction was carried out in the homogeneous atmosphere. After the reaction, since the diols were not well soluble in cool dioxane, the excess diol would precipitate. As a result, a large amount of excess diols would be separated from the product by filtration. The desired compound was then purified The structure of these compounds were confirmed by NMR spectroscopy and by comparing the data with the ones reported in literature. [167] The product had only the  configuration at the C-3 of cholesterol, owing to the mechanism of the reaction. As indicating in Fig. 4.9, the bond between tosyl group and the steroid is easily broken by the presence of a proton, generating the carbocation at the C-3 of cholesterol. Then the nearby double bond is cleaved and an intermediate with the carbocation at the C-6 position is formed. This mechanism is called "mesomerical stabilization" in steroid chemistry. [168] Since the reaction is thermodynamically controlled, the nucleophiles will attack at the C-3; and for stereoelectronic reasons, the bond will be exclusively formed from the upper side () of the steroid molecule. Fig. 4.9: Mechanism explaining the retention of coupling [168] The next step is to convert the terminal OH group to an amino group. This was accomplished in three steps. First, the hydroxyl was treated with methanesulfonyl chloride (MsCl) to obtain the mesylate, which is a very good leaving group. The resulting compound was washed with saturated NaCl solution several times until the solution was neutral. Solvents were evaporated off and the residue was used directly with sodium azide (NaN With azido compounds in hands, the amino analogues were obtained by treatment with triphenylphosphine (PPh 3 ) and water in THF, the standard conditions for the Staudinger reaction, shown in Scheme 4.7. From the TLC plate, the R f of the resulting amino compounds were near 0.3 using the eluent of DCM/ MeOH (9/1 vol.), and the spot shape was not a dot but an ellipse, typical of amino compounds which have strong interaction with the silica gel. Thus a small amount of NEt 3 was added (0.5 % vol.) to improve the alkalinity of the eluent. The residue was then submitted to column chromatography using the same condition to get the pure compound, and the yields of amino compounds were up to 96%. In the proton NMR of the amino analogues, the H of the methylene group near the amino appeared around 2.71 ppm instead of  3.25 ppm in the spectrum of starting azido compounds. Also in carbon NMR, the signal of CH 2 NH 2 appeared at  39.9 ppm when compared to 51.6 ppm of CH 2 N 3 . Fig. 4.11 shows proton and carbon NMR spectra of cholest-5-en-3-yl 6-aminohexyl ether 115a. The mass data of 486.3 (M+H + ) for cholest-5-en-3-yl 6aminohexyl ether also confirms the formation of amino group, which fits with the data described in the literature. [169] [137,138] was added to a solution of cholesteryl aminoalkyl ethers in anhydrous DCM. The mixture was stirred under Ar at room temperature overnight. After the reaction, the solution was concentrated under vacuum and purified by the column chromatography using the eluent of DCM/ acetone (9/1). The procedure of using the amino products without purification to open the lactone ring was also tried. In this procedure, the cholest-5-en-3-yl 8-azidooctyl ether was employed. After reduction of the azido to an amino group, the solvent was evaporated under vacuum and the residue was dried over the pump. Then it was dissolved in DCM and reacted with the lactone (1.3 eq.) to get the final product in nearly 50% yield from the starting azido compound, similarly to the previous examples.

The same reaction conditions as the one used for the C4 linker compound was employed for the deacetylation of these longer linkers, as shown in scheme 4.9. The disappearance of 3 singlet peaks of CH 3 around 1.99 ppm in 1 H NMR and 3 peaks of C=O of acetyl group around 170 ppm in the [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR indicates the deprotection of hydroxyl groups on the sugar head, whereas all other C and H atoms were identified in the spectra.

Synthesis of disubstituted glycosteroids by O-2 carbamatation

The tri-O-acetyl protected glycosteroids, having their OH-2 as the only free OH, were submitted to reaction with alkyl isocyanates of different chain lengths. The final glucosteroidic bolaphiles were then obtained by deacetylation with NEt 3 in the condition previously described. Scheme 4.10 shows the procedure of this step. Table 4 In order to attach the alkyl isocyanates, two methods were employed. One was at room temperature in the presence of NEt 3 as the catalyst and the other one was at 45 o C with 1,8diazabicycloundec-7-ene (DBU). By applying these two methods on a same compound, it was found that the yields from these two methods were competitive. However, the first method using NEt 3 used 10 equivalents of isocyanate against 1.5 eq. in the one using DBU, and the urea formed by excess isocyanates is problematic for the purification of final products. This urea was formed by undesired hydrolysis of isocyanates which was difficult to prevent even though being careful to exclude water from the solvents and reagents. It was found that the urea was not well soluble in the organic solvents, such as DCM, EtOAc, toluene or pentane, or their binary mixtures. This allowed the removal of a large amount of urea by filtration. However, after the purification on silica gel column, some urea was still present as an impurity, detected by mass spectroscopy.

It has also been tried to get rid of urea by combining the attaching of alkyl isocyanates and deactetylation steps together, where large proportion of urea was filtered after the first step.

After the deacetylation, as the polarity of eluent using for purifying the final products was much higher than that used in the first step, it was thought that the urea might come before the product so that the separation could be done. But it did not allow to excluding all the urea impurity easily. Thus several successive chromatography columns were necessary to finally get the pure desired disubstituted compounds which were free of urea as demonstrated by absence of the typical urea peak in mass spectroscopy.

When we switched to the method using the DBU as the base for synthesizing the linker 6 and 8 series with longer side chains, from 14 to 18 carbon atoms, it was found that though the urea was still a problem in this method, less time was needed to get the pure final compounds.

When the final molecule was not well soluble in CDCl 3 , a mixture of CDCl The transition enthalpies of columnar to isotropic liquid are small as shown in Table 4.9.

They are weak which indicates that the hexagonal columnar phase is disordered. If the phase was more ordered (crystal like), a much higher lattice enthalpy would show. The polar interactions of the head groups are contributing to the centre of the column but the phase is being driven by steric factors which occur because the side-chain is filling space making the molecule appear wedge-like. For the L4 and L6 series, the transition enthalpies with side chain of 16 were the highest, while for the L8, an increasing manner of enthalpies as the side chain extends were found. These results may be due to the interactions of additional aliphatic chain and the cholesterol moiety.

L (n)

Effect of the length of linker and side chain on the liquid crystalline behaviors

Comparing the transition temperatures of non substitution homologues, they firstly decrease rapidly as the linker extends from L4 to L8, and then the decrease goes by a slower manner as the chain extends further. This kind of behavior could be seen in the many carbohydratebased liquid crystals of a long chain substitution like 18 to 26, where the aliphatic moiety dominates the transition behavior as hydrophilic/hydrophobic balance leans towards the hydrophobic part of the system. The increasing amount of carbon atoms also brought into the system more flexibility, which decoupled the effects of the sugar group from the cholesteryl moiety. Thus, the role of bulky cholesterol moiety in this system is more like a long aliphatic chain with a very rigid level, which is the reason of the high transition temperature.

Interestingly, when the side chain was attached, the resulting clearing point was shown to depend more on the length of the side chain rather than the linker. The transition temperature decreases as the side chain extends. With the same side chain, the transition temperatures of different linkers did not change with very rough increase or decrease manner, rather fluctuating within a small range. For the side chain S6 series, this range is even at 2 o C, however, a dramatic increase of transition enthalpies (>1 J mol -1 ) as a function of linker lengths could be seen from the DSC experiments, shown in Table 4.8.

Molecular modeling study

In order to well understand the structure/performance relation in the glucosteroid series, the molecular modeling study could offer some structural information to support the previous observations.

As shown above, for the C4, C6, C8 linker, the side chain with 14 carbons is the limit where the columnar phases are formed. This indicates that at this stage the molecular shape begins to change. The following study was based on the C4 linker. At no or short chain length (C4-C12) only a Sm A* phase is evident which indicates that the molecule is rod-like in shape and the alkyl chain must occupy space alongside the spacer and cholesterol unit, Fig. 4.24.

However, once the chain length is increased (C14-C18) the chain is now large enough that at higher temperatures where the chain has more dynamic freedom to move it prefers to orient away from the spacer and cholesterol unit and hence the molecular shape changes from rodlike to wedge-like and a phase transition from Sm A* to hexagonal columnar occurs. The energy minimised molecular model shown in Fig. 4.25 for compound 124e demonstrates how the spacer overlaps with terminal alkyl chain of the cholesteryl unit in a rod-like shape whereas when the chain is allowed greater freedom for motion the molecular shape becomes more wedge-like than rod-like. It is expected that the structure of the hexagonal columnar phase consists of several molecules orienting together to form discs and these discs form the column where the centres of the columns are occupied by the sugar units and the outer parts are filled with the cholesteryl and alkyl moieties. When this shape change occurs there is a stabilisation of the columnar liquid crystal mesophase and instead of a decrease in clearing point an increase with chain length is now observed. For C8 linker, as the aliphatic chain bearing the cholesteryl moiety was long enough to minimize the effect of the cholestryl part as the bulky rigid moiety which covered the side chain in shorter linker system, the Sm A* phase was not observed while the columnar phase was the unique liquid crystalline phase shown in this chain length.

Conclusion

In this chapter, we described the synthesis of a family of glucosteroids with a spacer which is of different length of 4, 6, 8, 10 and 12 carbon atoms between the carbohydrate ring and the cholesterol moiety. Also 2-O derivatives from these compounds of an aliphatic side chain length varying from 4 to 18 carbon atoms were synthesized taking advantage of CMGLs strategy. For the spacer C4, it was adapted by olefin cross-metathesis to couple the allyl glucoside and allyl cholesteryl blocks together. For other lengths of spacers, the aliphatic chains were first etherified with the cholesterol, followed by being converted the terminal group into amino group, which were further used to open the lactone ring. The combination of aliphatic side chains are conducted by the carbamation of alkyl isocyantes with OH-2. The structures of compounds of each step were characterized by NMR spectroscopy, mass spectroscopy and for some special compounds, for example the azido intermediates, the FTIR spectroscopy was used to identify the structure.

Their thermotropic liquid crystalline behaviors were investigated by the means of polarized optical microscopy, and DSC. The results of this studied could be summarized in two aspects, no or the short side chain species and long side chain species.

For the no side chain or short side chain species, where the length of side chain is within 12 carbons, the Sm A* phases were dominated, indicating these compounds owned a rod-like shape. The clearing points of these compounds were decreasing as the chain length extended. In comparison of the compounds with no side chains, the clearing points also showed a decrease tendency as the chain length extended. Both of these observations could be explained by the flexibility brought by the increasing carbon atoms or the randomization during the packing of aliphatic chains.

For long side chain species, where the lengths of side chain are from 14 to 18, the exhibition of Sm A* mesophases was observed in a more limited temperature range as the spacer extended, and finally at C8, no Sm A* mesophases were observed. These observations could be related to a less rod-like structure shown with longer spacer series. Also in these species, a second hexagonal columnar mesophases were shown, indicating the topology structures of these compounds are wedge-like. Structural modeling study showed an expanded structure was formed by the lipid and steroid parts. And the transition temperatures of columnar phases to isotropic liquid increased as the side chain length extended.

Chapter 5

Synthesis of neoglucosyl laurdans and their evaluation in fluorescence microscopy

Introduction

Fluorescent technology is widely used nowadays as an efficient approach to study the live routine of the organisms. [170][171][172][173] This technology has several advantages over the traditional way of studying the cell biology, for example, it could be used to observe the events in the cells in situ [174,175] and follow the molecular dynamics in the functional area, like "lipid raft", with a minimization of impact of the probe itself on the studied phenomena. [START_REF] Lingwood | Lipid Rafts As a Membrane-Organizing Principle[END_REF]176,177] Many probes have been developed for this purpose, which could be categorized into some types with respect to their brightness and emission wavelength, as shown in Fig. 5.1. Some microscopic technologies are developed, too, to reveal better image, like fluorescence resonance energy transfer (FRET), fluorescence lifetime microscopy, two-photon excitation fluorescence (TPEF) microscopy. [174,178] Several requirements are needed for the probe applied, like wavelength, brightness, stability, and pharmacokinetics. [170] Fig. 5.1: Standard fluorescent probes ranked according to brightness and maximum emission wavelength (color of the compounds) [179] Since some probes are hydrophobic, the introduction of hydrophilic moiety to make it soluble in water is necessary. Among the choices, the carbohydrate moiety is very ideal, since it enhances the solubility of the final compound.

Our initial idea of developing the new probe is to investigate the microdomain in the membranes, referring to "lipid raft". The structure of this new probe was adapted of the previous glucosteroid studied in this thesis. Since a cholesterol moiety was in the structure, we expected it would have some interactions towards this microdomain rich in the Laurdan, commercial name for 6-dodecanoyl-2-(dimethylamino) naphthalene, compound 129 in Fig. 5.3, was found to have very good quantum yield in TPEF microscopy. [178,180,181] However, its hydrophobic property made it less efficient for this study. A recent attempt by modifying the laurdan by introducing a hydrophilic carboxylic acid was performed, [182,183] compound 130 in Fig. 5.3, and received a good result in solubility and stronger two-photon excited fluorescence emission. A first series of probes was prepared in Professor Peter Goekjian`s lab with hydrophilic parts introduced such as sarcosine ethyl ester 131, Nmethylpiperazine 132, aminoacetaldehyde 133 N-methyl aminoacetaldehyde dimethylacetal 134, and N-methylallylamine 135,. In the light of previous studies on carbohydrate-based fluorescent probes in our lab, [143] we thought that combining a sugar moiety to the laurdan part, taking advantage of water solubility and fluorescent stability, would be an interesting modification of the system.

Synthesis procedure

To achieve this goal, two structures bearing the carbohydrate moieties were proposed firstly to be tested, one was based on glucose 136 and the other was based on cellobiose 137, Fig.

Synthesis of 6-dodecanoyl-2-bromonaphthalene

The synthesis of this compound was adapted the method explored by Kim, H. M et al. [183] .

The compound they reported was 6-hexanoyl-2-methoxynaphthalene, but we found that bromide has a same localized effect like methyoxyl group which resulted in a same substitution position of dodecanoyl group.

The synthesis was using the typical Friedel-Crafts reaction catalyst, AlCl 3 , and nitrobenzene as the solvent. After the reaction, the nitrobenzene was removed in vacuum, and the final product was purified by crystallization from the cold MeOH. The structure of the compound was confirmed by M. Mouhdine CHENIOUR in his thesis. [184]

Synthesis of the N 1 -Boc-N 2 -methyl-1,3diaminopropane

Inspired by the work of Rannard S. P. et al. [185] the Boc anhydride was firstly reacted with imidazole to obtain Boc-imidazole, followed by the selectively coupling with primary amine of Compared to the process described in the paper, the condition of present first step was mild.

After 2h, the reaction was finished as only one spot was shown by thin layer chromatography (TLC). The solution was then washed with the saturated NaCl solution. Then the obtained organic phase was dried and filtered, followed by the evaporation of the solvent to get the white solid. The yield of this step was high, up to 98%.

With this intermediate in hands, we went through the second step where the Boc group went to protect the primary amine of N-methyl-1,3-diaminopropane, following the literature procedure. Since the bond of the imidazole and the carboxyl group is fragile, water at high temperature might cleave this bond, which would result in imidazole, t-butanol and CO 2 . [185] Thus, anhydrous toluene was used and the compound 139 was carefully dried under the pump. With careful handling, the yield of final compound 140 was up to 95% according to 1 HNMR. The signals are agreed with the data reported in the literature. [186]

Amination of 6-dodecanoyl-2-bromonaphthalene and

N 1 -Boc-N 2 -methyl-1,

3-diaminopropane

The palladium-involved C-N cross coupling, or Buchwald-Hartwig amination, has become very popular as it offers a great efficiency towards the constitution of aromatic C-N bonds, which is widely used in the pharmaceutical field. [187] This system commonly consists of four components: ligands; palladium precursors; base; solvents. A possible mechanism of this reaction is shown in Fig. 5.5.

Pd (0) R X R Pd (II) X L n R Pd (II) L n R 1 NH R 2 N R 2 R 1 Base Salt R N R 2 R 1

Oxidative addition Reductive elimination

Transmetallation L n Fig. 5.5: Proposed mechanism of C-N coupling [188] In this experiment, the tris(dibenzylideneacetone)dipalladium( 0

S-Phos

For this reaction, a careful control was needed. Though some reports demonstrated that water might improve the reaction performance, [189] it was found to hinder the reaction in this experiment. Thus, the dried amino product was crucial to this reaction.

From the [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR spectrum, we could see a significant shift of C-3'' from  136.

Synthesis of CMG derived probes

The compound 141 was then N-deprotected in the presence of TFA for 16h. After removal of excess TFA under the vacuum, the amino compound was then reacted with glucose and cellobiose derived lactones, followed by the deacetylation in the mixture of MeOH/ H 2 O/ NEt 3 at the ratio of 8/1/1. The target compounds were obtained. The procedure is shown in Scheme 5.5. After deacetylation, the disappeared proton signals around  1.90 to 2.08 ppm of CH 3 of acetyl groups are very obvious in product 1 HNMR spectrum. Another proof could be seen as the carbon signals of C=O of acetyl groups around  174.5 ppm disappeared in the [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR.

H-9 H-8 C-3'' C 3'' -H 8 C 3'' -H 9

Fluorescence properties

The fluorescence properties of two compounds were studied first by measuring the fluorescence in various solvents of different polarities and then when included in liposomes in order to have a preliminary information of their behavior within a supramolecular system considered as a membrane model.

Characterization of fluorescence in various solvents.

Since the environments in which the probes should be used are complex in terms of polarity, a series of solvents having various polarities was chosen for mimicking this situation, namely from low to high polarity THF, DMF, DMSO, ethanol, and water. The excitation wavelength was set at 385 nm, while the emission wavelengths were detected in the range of 400 nm to 600 nm. The normalized emission curves of these two probes are shown in Fig. 5.10 and 5.11, respectively. As seen in the figures above, the spectra of these probes show gradual bathochromic shifts as the polarity of solvent increases. The  fl max of water is the highest while that of THF is the lowest, and the difference between the two is nearly 70 nm, showing that these two probes have a high sensitivity to the polarity of environment. The spectra of the probes in water contain a lot of noise, because of the very low fluorescence intensities detected by the equipment. The probes were found to be well soluble in water at this concentration, so this low intensity is not the result of a low concentration, but the classical consequence of the high polarity of the solvent. The un-normalised fluorescence intensities for probe 136 are shown in Fig. 5.12, where the curve in purple is the solution in water with the highest intensity at 549.574. In contrast, the fluorescence intensities shown in other solvents were within the same order of magnitude which is more than 40000 and relatively high compared to water. A similar result was also obtained for probe 137. These results indicate that since the probes would be applied to the membrane whose condition is hydrophobic, they should be useful because of providing a good contrast under the microscope.

Fluorescent tests of probes in model membrane

Liposomes constructed by bilayer association of dimyristoylphosphatidylcholine (DMPC), as shown in Fig. 5.13, were prepared by extrusion according to a standard procedure. [190] In this experiment, the liposome of LUV (large unilamellar vesicles) was selected, whose diameter is ranging from 80 to 800 nm. The probes were firstly dissolved in ethanol and mixed with the DMPC at the concentration of 1/400 molar ratio (probe/lipid). After the hydration and extrusion of lipids, the fluorescence performance of labeled liposomes was measured in terms of emission wavelengths recorded in the range of 420 to 550 nm under the condition of a scanning excitation wavelength from 300 and 420 nm. The data were obtained at every 5 degree in the range of temperature of 15 to 45 o C, based on which a 3D spectrum could be drawn. Two examples of probe 136 at different temperatures are shown Fig. 5.14, where a shift of the maximum emission wavelength from low to high temperature is seen. From these spectra, the maximum excitation and emission wavelengths were obtained. It was observed that by increasing the temperature, the excitation wavelength decreased on a small range (<10 nm) whereas the emission wavelength increased on a larger range (30 nm).

A similar behavior was observed for probe 137. The maximum emission wavelengths of these probes were investigated as a function of temperatures, as shown in Fig. 5.15 and 5.16. At low temperature, the liposomes were tightly packed, forming a hydrophobic environment, as a result the maximal emission wavelength was low; whereas at high temperature, the alkyl chain of DMPC had more freedom to fluid around, the space between the lipids expanded where more water had penetrated into the liposome. At this stage, the  em max was found red shifted. These results show that these probes are sensitive to their environment, in agreement with the observations in the solvents of different polarities.

Conclusion

In this chapter, we reported two new neogluco-laurdan probes for the purposes of detecting microdomains in the membrane. The synthesis involved Buchwald amination and CMGLs strategy, which were well performed. The products were characterized by NMR and mass spectroscopy to be the desired compounds.

The fluorescence properties of the probes were investigated in different solvents and when applied to liposomes, unveiling their sensitivity to the environment. In polar solvents, corresponding to the high temperature in liposomes experiments, the max emission wavelength was higher than that in unpolar solvents or liposomes at low temperatures.

Further investigations by preparing other liposomes system involving phospholipids will be conducted, and investigations on the fluorescent efficiency of the probes in real cells are also scheduled.

General conclusion

In this study, we have synthesized two families of new carbohydrate-based amphiphilic derivatives: a series of alkyl glucoside ethers varying in terms of chain length and position on the sugar, and a series of glucosteroids varying in terms of alkyl spacer and, for the disubstituted systems, in terms of alkyl side chain length. By the means of analytical methods, such as NMR spectroscopy, mass spectroscopy and elementary analysis, the structure of all the compounds was carefully established, as well as their purity. Their liquid crystalline behaviors were studied by the means of transmission light microscopy and differential scanning calorimetry.

The liquid crystalline studies of these two families showed that the formation of mesophases were strongly dependent on the structural factors, such as hydrophilic/hydrophobic balance, intra-and inter-molecular H-bondings and relative cross-sectional area of sugar head to aliphatic tails.

For the methyl glucoside ethers family, the Sm A* phases were the unique thermotropic mesophases observed by these compounds, indicating that the cross-sectional areas of hydrophobic part relative to that of sugar head approached to 1:1. The C12 chain length was found to be the limit where the molecules could form the mesophases. For chain length C14 and longer, the clearing points show a consistent decrease as the aliphatic chain moved from O-2 to O-6, sequentially. The C12 series, the behavior was more irregular: the clearing point for the O-3 ether was the highest, and no mesophases was observed for O-4. Structural modeling studies allowed to discuss these observations, notably with respect to possible inter-or intramolecular H-bonding interactions.

The lyotropic liquid crystalline behaviors of these compounds were also studied. Upon increasing the amount of water added to the compounds, a sequence of mesophases, from lamellar, cubic and hexagonal, was observed, which was expected for such monosubstituted systems.

For the thermotropic behaviors of the glucosteroids, as the spacer length extended, where more flexibility was introduced in the systems, the clearing points decreased. This tendency was enhanced as the additional side chain was attached. With a short side chain, the Sm A* phases were observed due to the similar relative cross-sectional areas of sugar head to hydrophobic moieties. For the C-4 spacer series, when the side chain extended to C14, a second type of mesophases appeared, which were identified as hexagonal columnar phases.

Modeling suggested that partition of the lipidic moieties, either showing cholesterol-alkyl chain interactions, or preferring cholesterolcholesterol and alkyl chainalkyl chain packing could be the main driving force for this behavior.

In the case of the C6 spacer series, same observations were made however with Sm A* phases showing more limited temperature range. For the C8 spacer series, only the columnar phase was observed. All these observations were discussed in terms of interactions between cholesterol and the aliphatic chain.

The two families of compounds which have been studied illustrate how much the behavior can be essentially related to polar interactions (H-bonding), therefore to the sugar moiety, for the ether series, or to hydrophobic interactions (lipid-lipid) in the glucosteroid series. In this latter series, preference for either steroid-steroid or steroid alkyl packing appears as an insight in understanding the behavior of complex lipids, showing potentially more than one conformational structure with important consequences on the supramolecular level, therefore to their potential biological role. This could be regarded as "lipid denaturation" by analogy to the protein denaturation. Also, when we see that compounds like the glycosteroids having an long chain ester -CAG, BbGL-I, are found to exist in Nature, and how much glycolipidcholesterol interactions were recently shown to be critical in some biological processes, it is hoped that our observations can provide a new vision angle for the study of complex lipids and glycolipids.

As a start to develop new probes targeting the "lipid raft" microdomain in membranes, we also explored a sequence towards carbohydrate laurdan hybrids. Further development of this strategy and evaluation of the biological properties is programmed within new collaborative projects.

Experimental section A. General aspect

The solvents used for reactions and chromatography were bought from SDS, Carolo Erba, and Sigma-Aldrich. Most of the solvents used in the syntheses were distilled before use, dichloromethane over the P 2 O 5 , THF over Na and benzophenone, and DMF over CaH 2 .

The reagents used in this thesis were bought from Aldrich and used directly without purification.

The TLC plates are from Merck 60F, coated with silica gel GF 254 (0.25 mm).

The purification using the chromatographies is by column of silica gel flash Merck (60, 40-63 m)

NMR spectroscopy: Bruker AC or DRX spectrometers at 75.47 MHz (100.61 MHz, or 125.77 MHz) for [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] C NMR and 300.13 MHz (or 400.13 MHz, or 500.13 MHz) for 1 H NMR.

Chemical shifts () are given in parts per million (ppm) and were measured relative to the signal of tetramethylsilane (= 0)

The peak of remaining chloroform is at 7.26 ppm, which was used as a calibration of spectra using CDCl 3 as the uniqud solvent. In case of mixture, the peak of TMS was used as calibration. The chemical shift was determined in ppm. The abreviations used in the list of NMR characterization are: s (singulet); ls (large singulet); d (doublet); t (triplet); dt (doublet and triplet); dd (doublet of doublet); q (quadruplet); m (multiplet).

Mass spectroscopy:

The spectra were recorded by Centre de Spectrométrie de Masse of the Université Claude Bernard (Villeurbanne) using electrospray (ESI) technique

C. Fluorescent properties of probes

Probes features in solvents: Absorption spectra were recorded on a Hewlett-Packard 8453 diode array spectrophotometer. Fluorescence measurements (excitation and emission spectra) were performed with a Hitachi F4500 fluorometer. The spectra were recorded at 25 o C using a 1 cm path length thermostated quartz micro-cuvette.

Probes features in LUV (Large Unilamellar Vesicles) at different temperatures:

Liposomes were prepared by pure DMPC according to a standard procedure. Fluorescence data were obtained using a Hitachi F4500 fluorometer. Emission spectra were recorded between 420 and 550 nm for each excitation wavelength between 300 and 400 nm and at several temperatures between 15 to 45 o C. The probes were initially dissolved in ethanol and were added to the liposomes to reach a 3 M final concentration, corresponding to a 1:400 (probe: phospholipids) molar ratio. Colorless soft matter To a solution of neoglucolipid 109 (420 mg, 0.52 mmol) in THF (5 mL), 10% Pd on charcoal (60 mg) was added. The suspension was stirred under H 2 and the reaction was carefully monitored by TLC. The reaction was stopped after 2 hours when only one spot remained on the TLC. The suspension was filtrated over a silica gel pad and the solvent was evaporated.

D. Synthetic procedures and characterizations of all

The obtained crude residue was chromatographied on silica gel using a toluene/acetone (7/3) mixture and gave compound 110 (0.345 mg, 83%) as a white solid.

D.2.2.2 Cholest-5-en-3-yl -aminoalkyl ether

The cholest-5-en-3-yl -azidoalkyl ether (0.1 mmol) was dissolved in THF/H 2 O (2.5 ml, 4:1)

and triphenylphosphine (1.1 eq.) was added. The mixture was stirred at 50℃ with addition of 0.1% of NEt 3 . After completion of the reaction, monitored by TLC (9:1, DCM: MeOH), the solvent was evaporated and the crude was purified by column chromatography on silica-gel (9:1, DCM: MeOH with 0.5% vol. of NEt 3 ). : 171.7, 170.7, 169.6, 169.5 (3xC=O in Ac, C8), 141.1 (C5"), 121.5 (C6"), 99.0 (C1), 79.0 (C3"), 73.7 (C3), 70.6 (C2), 68.2 (C5), 68.2 (C4), 68.0 (C16), 67.9 (C7), 61.9 (C6), 56.8 (C14"), 56.2 (C17"), 50.3 (C9"), 42.4 (C13"), 39.9 (C9), 39.6 (C16"), 39.3 (C24"), 39.3 (C4"), 37.4 (C1"), 37.0 (C10"), 36.3 (C22"), 35.9 (C20"), 32.0 (C7"), 32.0 (C8"), 30.2, 29.5, 29.5, 29.3 (C-octyl), 28.3 (C2"+12"), 28.1 (C25"), 26.9, 26.2 (C-octyl), 24.4 (C15"), 23.9 (C23"), : 171.7, 170.7, 169.6, 169.5 (3xC=O in Ac, C8), 141.1 (C5"), 121.5 (C6"), 99.0 (C1), 79.0 (C3"), 73.7 (C3), 70.6 (C2), 68.2 (C5), 68.2 (C4), 67.9 (C18, C7), 61.9 (C6), 56.8 (C14"), 56.2 (C17"), 50.3 (C9"), 42.4 (C13"), 39.9 (C9), 39.6 (C16"), 39.3 (C24"), 38.9 (C4"), 37.4 (C1"), 37.0 (C10"), 36.3 (C22"), 35.9 (C20"), 32.0 (C7"), 32.0 (C8"), 30.3, 29.8, 29.5, 29.6, 29.5, 29.5, 29.3 (C-decyl), 28.6 (C2"), 28.3 (C12"), 28.1 (C25"), 26.9, 26.2 (C-decyl), 24.4 (C15"), 23.9 (C23"), 22.9 (C26"), 22.6 (C27"), 21.1 (C11"), 21.0, 20.8, 20.7 (3CH 3 CO), 19.5 (C19"), 18.8 (C21"), 11.9 (C18") m/z (HRMS) : : 171.7, 170.7, 169.6, 168.7 (3xC=O in Ac, C8), 141.2 (C5"), 121.5 (C6"), 99.0 (C1), 79.0 (C3"), 73.8 (C3), 70.6 (C2), 68.2 (C5), 68.2 (C4), 67.9 (C20), 67.3 (C7), 61.9 (C6), 56.9 (C14"), 56.2 (C17"), 50.3 (C9"), 42.4 (C13"), 39.9 (C9), 39.6 (C16"), 39.3 (C24"), 38.9 (C4"), 37.4 (C1"), 37.0 (C10"), 36.3 (C22"), 35.9 (C20"), 32.0 (C7"), 32.0 (C8"), 30.3, 29.9, 29.9, 29.7, 29.7, 29.6, 29.6, 29.5, 29.5, 29.4 (C-dodecyl), 28.6 (C2"), 28.3 (C12"), 28.1 (C25"), 27.0, 201 26.3 (C-dodecyl), 24.4 (C15"), 23.9 (C23"), 22.9 (C26"), 22.6 (C27"), 21

Cholest-5-en-3

D.2.2.4 Synthesis for glucosteroid amphiphiles

The partially protected compound acetyl-Glu-L n -cholesterol (0.1mmol) was dissolved in a MeOH/Et 3 N/H 2 O (8/1/1, 10 mL) mixture and was further stirred at RT for 15 hours. The reaction was then coevaporated three times with water and the obtained white residue was subjected to silica gel chromatography using a CH 2 Cl 2 /MeOH (95/5) to give the corresponding neoglycolipid. 69.9 (C4), 68.1 (C16), 66.7 (C7), 61.4 (C6), 56.7 (C14"), 56.1 (C17"), 50.1 (C9"), 42.3 (C13"), 39.7 (C9), 39.5 (C16"), 39.1 (C24"), 39.0 (C4"), 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 30.0, 29.3, 29.2, 29.1 (C-octyl), 28.3 (C2"), 28.2 (C12"), 27.9 White solid

Glucosteroid L4 amphiphile (111)

D.2.2.5 Synthesis of glucosteroid bolaphiles

To a solution of acetyl-Glu-L n -cholesterol in CH 2 Cl 2 (0.1 mol L -1 ), the proper alkyl isocyanate (10 eq.) and catalytic amounts of triethylamine (50 L) were added under nitrogen. The mixture was stirred for 3 days at room temperature, the white solid formed during the reaction was filtrated and the solvent was evaporated. (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 30.0, 29.7, 29.6, 29.6, 29.6, 29.6, 29.5, 29.4, 29.4, 29.3, 29.2, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.8, 26. (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 30.0, 29.7, 29.7, 29.6, 29.6, 29.5, 29.5, 29.4, 29.4, 29.3, 29.2, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.8, 26. After the addition, the reaction mixture was added by 1.4 g of AlCl 3 . At this stage, the ice bath was removed and the reaction continued at room temperature for 2 h, which was quenched with 40 ml of distilled water. Extracted 3 times with ethyl acetate (30 mL), the organic phases were combined and washed with brine (30 mL) 3 times. Then the organic phases were dried over Na 2 SO 4 and concentrated under reduced pressure. The desired compound were then obtained by recrystalizing in cold ethanol as white solid (1.1 g, 30 % of yield)

White solid In a Schlenk tube was added 100 mg of compound 138, 69 mg of N 1 -Boc-N 2 -methyl-1,3aminopropane, 18.7 mg of Pd 2 (dba) 3 , 18.2 mg of S-Phos and 300 mg of Cs 2 CO 3 . The tube was then degassed by classic process, followed by enveloping the tube with Ar. After injection of 1 mL of anhydrous dioxine, the tube was heat up to 105 o C and stirred for 16h.

The product was purified by silica gel using the eluent of ethyl acetate/ petroleum ether (5/95).

Yellow solid The 141 was N-deprotected in DCM (1 mL) using TFA (1 mL). The mixture was stirred at room temperature for 16h, followed by evoparation of solvent in vacuum. A small amount of toluene (1 mL) was then added and the solution was evaporated in vacuum and this process was repeated 3 times to remove the trace of TFA. After that, the residue was dissolved in anhydrous DCM (3 mL), which was added the solid of CMGLs. The reaction was carried on for 16h at room temperature. Then the product was purified by silica gel chromatography using the eluent of DCM/acetone (8/2). Mol. Wt.: 742.9

Acetyl

Fig. 1 :Figure 2 :

 12 Fig. 1 : Structures des produits ciblés dans ce travail

Figure 3 :

 3 Figure 3 : Obtention des éthers en position 2 et 3

14 Figure 4 :

 144 Figure 4 : Obtention des éthers en position 4

Figure 5 :

 5 Figure 5 : Obtention des éthers en position 6

Figure 6 :Figure 9 :

 69 Figure 6 : Synthèse pour obtenir des glucostéroïdes

36 Figure 10 :Figure 11 :Chapter 4 4 . 3 4 . 4 4 . 4 . 3 .

 36101144344443 Figure 10 : Structures des glycosondes preparées.

Fig. 1 :

 1 Fig. 1: Chemical structures of desired compounds

  using the CMGLs strategy to prepare other carbohydrate-based amphiphiles, designed in the context of a project aimed at developing new fluorescent probes, 3 in Fig 1.

Fig. 1 . 4 :

 14 Fig. 1.4: Structures of alkyl nitrogen compounds (R is H or low-molecular -weight alkyl

Scheme 1 . 1 :

 11 Scheme 1.1: Industrial synthetic procedure for obtaining sorbitan esters

Scheme 1 . 2 :

 12 Scheme 1.2: Industrial manufacturing procedure for obtaining sucrose esters

3 :

 3 Scheme 1.3: Industrial manufacturing procedure for obtaining alkyl polyglucosides

Fig. 1 . 7 :

 17 Fig. 1.7: Chemical structure of GM1 ganglioside

Fig. 1 . 8 .Fig. 1 .

 181 Fig.1.8.[START_REF] Hamberg | Isolation and structure of a new galactolipid from oat seeds[END_REF]

Fig. 1 . 9 : 1 . 3 . 3 . 2

 191332 Fig. 1.9: Chemical structures of some steroid glycosides

Fig. 1 . 10 :

 110 Fig. 1.10: Chemical structures of glycolipd biosurfactants available in the market

Fig. 1 . 11 :

 111 Fig.1.11: Chemical structure of p-methyoxylbenze-2, 6-di-benzoyl--D-galactopyranoside

Fig 1 . 12 :

 112 Fig 1.12: Schematic representation of (I) specific binding of peanut agglutin (PNA) to the MWCNT-Tbf-PEG-Lac-8 surface, (II) inhibition of the specific binding by soluble lactose, (III)

3 OFig. 1 . 13 :

 3113 Fig. 1.13: Chemical structures of -D-glucoside lipids 6, 7 and 6, 6`-dimycolic ester of trehalose 8

Fig. 1 . 14 :

 114 Fig. 1.14: The structure formed by self-organizing and self-assembling liquid crystals

Fig. 1 .

 1 Fig. 1.15: A: Illustration of molecular structure and the packing type for lamellar (Sm A*)

  be packed into columns, which will be further aggregated paralleling into 2D mesophases, like hexagonal (Col h ), rectangular (Col r ), oblique (Col o ) or square (Col s ), as shown in Fig.1.18. As the packing forces between and within the columns are from the interactions of the hydrophobic fraction of molecules, these disc-groups are easy to diffuse, leading to the low viscosity. In the case of carbohydrate-based amphiphiles, the hexagonal mesophases are normally observed compared to other columnar phases, the schematic representation is shown in Fig.1.18.

Fig. 1 . 19 :

 119 Fig. 1.19: Illustration of molecular structure (up) and the packing type for cubic mesophases

Fig 1 . 20 :

 120 Fig 1.20: Phase diagram of alkyl -D-glucopyranoside in water solution[107]

IsoFig. 1 . 21 :

 121 Fig. 1.21: The relation of curvature and mesophase types in thermotropic and lyotropic liquidcrystalline behaviors[108]

Fig. 1 . 22 :

 122 Fig.1.22: The transition temperatures of alkyl -D-glucopyranosides[START_REF] Jeffrey | Carbohydrate liquid crystals[END_REF]

Fig. 1 . 23 :

 123 with short chain length, there are no mesophases; once the chain in long enough (thus bringing equilibrium to the hydrophilic hydrophobic balance of the molecule, the mesophases are observed, and as the chain extends, the transition temperature increases, as indicated in A; And this tendency will meet a critical proportion B, from which the transition temperature begins to decrease, as C, due to the randomization of increasing aliphatic chain length.

Fig. 1 . 23 :

 123 Fig. 1.23: Transition temperature (T) dependency on the aliphatic chain length (n) ofhomologous series[109]

Fig. 1 .

 1 Fig.1.25: The chemical structures and liquid-crystalline properties of psychosine and its

  decyl derivative show a passage from crystal-columnar-cubic-isotropic liquid phases across the phase diagram as the temperature increases. The transition temperatures of the O--Dgalactopyranosyl-tri-O-alkyl pentaerythritols derivatives with different alkyl chain lengths are

Fig 1 . 26 :

 126 Fig 1.26: Thermotropic liquid crystalline behaviors of dedecyl glucopyranoside and x-O-dodecyl-D-glucopyranoses

  .6. From the study of molecule modeling, Fig. 1.27, the compounds substituted at the position of a and f were more wedge-like, thus they could show the cubic and the columnar phases, thus the observations were confirmed.

Fig. 1 . 27 :

 127 Fig. 1.27: Molecular modelings on the effect of substitutions of n-O-(2-hydroxyldodecyl)-sucroses[113]

Fig. 1 . 28 :

 128 Fig. 1.28: Thermotropic behaviors of acyclic polyols lipids

Fig. 1 . 29 :

 129 Fig. 1.29: Proposed schematic representations of arrangements in the mesophases of 4-(4'-N, N-didodecylaminophenylazo) phenyl -D-galactopyranoside and 4-(4'-N, Ndidodecylaminophenylazo) phenyl -D-glucopyranoside[114]

Fig 1 . 30 :

 130 Fig 1.30: Thermotropic behaviors of octyl D-glucofuranoside and octyl D-glucopyranoside[115]

Fig. 1 .Fig. 1 . 32 :

 1132 Fig.1.31: The transition temperature of mono-substituted xylitol system with linkage of ether, thioether ester and amide as the function of aliphatic chain length[116]

  1.33-1.35, below show some conventional mesophases exhibited by carbohydrate-based amphiphiles. Recent equipments include rather precise heating plates which allow estimating the transition temperatures with 0.1 to 1°C accuracy.

Fig. 1 .

 1 Fig. 1.33: Defect texture of lamellar mesophases with hyperbolic and elliptical lines (black arrows) and oily streaks and fringes around air bubbles (here a Sm A* lamellar phase is

15

 15 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

Fig. 1 .Fig. 1 .

 11 Fig. 1.36 shows a DSC curve for the first heating cycle of 6-O-tetradecyl--Dgalactopyranose, where the melting point is 114 o C and clearing point is 169 o C.[110]

Fig. 2 . 1 :

 21 Fig. 2.1: Formation of D-glucono-1,4-lactone and 1,5-lactone

Scheme 2 . 2 :

 22 Scheme 2.2: Synthetic path for 1,4-D-gluconolatone[126]

Scheme 2 . 3 :

 23 Scheme 2.3: Synthetic paths for 1,5-and 1,4-L-galctonolactones 20 and 21[127, 128]

Scheme 2 . 4 :

 24 Scheme 2.4: Oxidation of D-glucose by Aspergillus niger

Fig. 2 . 2 : 2 . 2 .

 2222 Fig. 2.2: Chemical structures of representations of several bicyclic carbohydrate lactones

  Further reaction with acetic anhydride led to the 3, 4, 6-tri-O-acetyl--D-glucopyranoside 2-O-lactone (-CMGL) by a ring-closure reaction. Trehalulose, (1--D-glucopyranosyl-D-fructopyranose), a less available other disaccharide also obtained from sucrose by bioconversion, could also be used in this reaction.

Scheme 2 . 6 :

 26 Scheme 2.6 O O O N

Fig. 2 . 3 :

 23 Fig. 2.3: Chemical structures of obtained -CMGLs by different protecting group

Scheme 2 . 8 :Scheme 2 . 9 :

 2829 Scheme 2.8: Synthesis of -and -glucopyranoside lactones 33 and 35, and -and -galactopyranoside lactones 34 and 36[139]

OBn Scheme 2 . 10 :Scheme 2 . 11 :

 210211 Scheme 2.10: Synthetic process for benzylated -D-glucopyranoside lactone 45, and -Dgalatopyranoside lactone 46

Scheme 2 .

 2 Scheme 2.12 Synthetic process of -and -D-glucopyronside lactones by using the tert-butyl bromoacetate[140]

Fig. 2 . 4 :

 24 Fig. 2.4: Chemical structures of pseudodisaccharides of glucose-glucose 56, glucosegalactose 57, glucose-uridine 58 by amide linkage

Fig. 2 . 5 :

 25 Fig. 2.5: The resulting compounds bearing the functional groups and possibilities of functionnalizations on OH-2

25 Fig. 2 . 7 :

 2527 Fig. 2.7: Chemical structures of-unsaturated carbonyl compounds derived from

  .), THF, r.t.

Scheme 2 . 20 :

 220 Scheme 2.19.

Fig. 2 . 8 :

 28 Fig. 2.8: Sm A* defect textures of dodecyl amide methylcarboxyl glucopyranoside at 91.1 o C

Fig. 2 . 9 :

 29 Fig.2.9: Chemical structure of glucosteroid analogs and their transition temperatures[147]

  In previous investigations of our group on sucrose hydroxyalkylethers, it was observed that different topological shapes, as the 2-hydroxyldodecyl chain switched sequentially around the sucrose moiety, led to different types of mesophases. (see page 52 in the first section) This phenomenon was found to have a relation with the modification of the intramolecular hydrogen bonding between the two monosaccharide moieties of the sucrose. The focus was made on changes in the sucrose conformation, precisely on the way the two monosaccharidic moieties of sucrose arrange spatially, but neither the role of the additional hydroxyl group in the hydroxyalkyl ether linkage, nor the effect of the length of the alkyl chain on the hydrophilic hydrophobic balance were studied. Thus, a systematical study with respect to the aliphatic chain length and substitution position on a simple glucidic head was undertaken for this purpose.

1 :

 1 Scheme 3.1: General synthetic procedure leading to the monosbstituted hydroxyalkylethers

Scheme 3 . 2 :

 32 Scheme 3.2: The synthetic procedure for obtaining the methyl 3-O-benzyl-4,6-Obenzylidene--D-glucopyranoside 96

Fig. 3 . 96 Fig. 3 . 96 C 2 Fig. 3

 39639623 Fig. 3.1: 1 H-1 H COSY spectrum of methyl 3-O-benzyl-4,6-O-benzylidene--Dglucopyranoside 96

Scheme 3 . 3 :

 33 Scheme 3.3: The synthetic path for the synthesis of methyl 2-O-(2-hydroxyalkyl)--Dglucopyranosides 97

Fig. 3 .Scheme 3 . 4 : 1 C 91

 334191 Fig. 3.4: 13 C NMR spectrum of methyl 2-O-(2-hydroxydodecyl)--D-glucopyranoside 97c

Fig. 3 .

 3 Fig. 3.5: 1 H-1 H COSY spectrum of methyl 2-O-(2-hydroxydodecyl)--D-glucopyranoside 97c

Fig. 3

 3 Fig. 3.6: 1 H-13 C HSQC spectrum of methyl 2-O-(2-hydroxydodecyl)--D-glucopyranoside 97c

Scheme 3 . 5 :

 35 Scheme 3.5: Synthesis of methyl 2-O-benzyl-4,6-O-benzylidene--D-glucopyranoside 98 The structure of methyl 2-O-benzyl-4,6-O-benzylidene--D-glucopyranoside 98 was also studied by COSY, Fig. 3.8, HSQC, Fig. 3.9, and HMBC, Fig. 3.10. For this compound, the anomeric proton appears at  4.51 ppm in the 1 HNMR. The nearby proton in C-2 could be found at  3.36 ppm from the connection of C-1, as a shape of dd, followed by C-3 at  4.06 ppm, triplet shape. Their carbon signals could be identified as  80.2 ppm for C-2 and  70.7 ppm for C-3 by HSQC. The protons of the methylene unit on the Bn group are found at  4.70 and 4.60 ppm, respectively, which is because of AB system. From the HMBC, these protons are found to have interaction with the signal at  80.2 ppm, which proves that the OH-2 was protected.

Fig. 3 . 98 H 3

 3983 Fig. 3.8: 1 H-1 H COSY spectrum of methyl 2-O-benzyl-4,6-O-benzylidene--Dglucopyranoside 98

Fig. 3 98 C8Scheme 3 . 6 :H 3 Fig. 3 .Fig. 3 .

 39836333 Fig. 3.9: 1 H-13 C HSQC spectrum of methyl 2-O-benzyl-4,6-O-benzylidene--Dglucopyranoside 98

Scheme 3 . 7 : 98 Fig. 3 .

 37983 Scheme 3.7: Synthetic procedure for methyl 2,3,6-tri-O-benzyl--D-glucopyranoside 100

Fig. 3 .Scheme 3 . 8 :

 338 Fig. 3.16: 1 H-13 C HMBC spectrum of methyl 2,3,6-tri-O-benzyl--D-glucopyranoside 100

Fig. 3 .Fig. 3 .

 33 Fig. 3.17: 1 H-1 H COSY spectrum of methyl 4-O-(2-hydroxydodecyl)--D-glucopyranoside 101c

Scheme 3 . 9 :Fig. 3 .HFig. 3 . 14 Scheme 3 . 10 :

 393314310 Scheme 3.9: Synthetic procedure for methyl 2,3,4-tri-O-benzyl--D-glucopyranoside 104

Fig. 3 .Fig. 3 . 3 . 2 . 5 10 Scheme 3 . 11 :

 3332510311 Fig. 3.23: DEPT spectrum of methyl 6-O-(2-hydroxydodecyl)--D-glucopyranoside 105c

Fig. 3 .Fig. 3 .

 33 Fig. 3.26: DSC curves of methyl 3-O-(2-hydroxyalkyl)--D-glucopyranosides 98

Fig. 3 .

 3 Fig. 3.27 shows the defect image of compound 97e at 90 o C of the identical focal-conic defects of elliptical and hyperbolic lines (which are inside the white circle). The formation of

Fig. 3 .

 3 Fig. 3.27: Defect texture of compound 97e at 90 o C showing A) focal-conic domains and the elliptical and hyperbolic lines (in the white circle); B) oily streaks and fringes around air bubbles (arrow)

3 : 4 : 5 :

 345 Transition temperatures ( o C) and enthalpies (J g -1 ) of transition shown in square bracket for the O-Transition temperatures ( o C) and enthalpies (J g -1 ) of transition shown in square bracket for the O-Transition temperatures ( o C) and enthalpies (J g -1 ) of transition shown in square bracket for the regular chains For these 6-alkyl ethers (106), the Sm A* phase showed up when the aliphatic chains consisted of 8 carbon atoms, where the equivalent of 105a was not observed. And with longer chain, the two counterparts acted in a similar manner, the transition temperatures were all at around 35 o C along with a very close enthalpy values.

Fig. 3 .

 3 Fig. 3.28-3.31 illustrate the melting point and the clearing point as the function of chain length

Fig. 3 . 28 :Fig. 3 . 29 :Fig. 3 . 30 :Fig. 3 . 31 :

 328329330331 Fig. 3.28: The melting points and the clearing points as a function of chain length (n) of 2-O-(2-hydroxyalkyl)--D-glucopyranosides 97

Fig. 3 . 32 :

 332 Fig. 3.32: The clearing points as a function of substitution positions

Fig. 3 . 33 :

 333 Fig. 3.33: Energy minimized models of 97a, 99a, 101a and 105a

Fig. 3 . 34 :

 334 Fig. 3.34: Defect textures of mesophases shown by compound 101c: A) view from the microscope; B) view from microscope with a waveplate (X100 magnification)

Fig. 3 . 35 :

 335 Fig. 3.35: Lamellar and cubic phases of compound 101d (X100 magnification)

  been tested and studied. Due to its chirality with 8 chiral centers on the moiety and rigid structure, the cholesterol-based LCs could form cholesteric mesophases, showing unique optical properties in the forms of helical supra-structure, shown as B in Fig. 4.1.

Fig. 4 .

 4 Fig. 4.1: (A) The molecular structure (upper), molecular modeling (middle), and space-filling

Fig. 4 . 3 :Scheme 4 . 1 : 4 . 2

 434142 Fig.4.2: A) Chemical structure of GlcNAc-E 4 -cholesterol and B) its performance in water solution according to the concentration (lines are guides for the eyes, but the error of their positions in terms of glycolipids percentage is ±5%)[164]

Fig. 4 . 5 :

 45 Fig. 4.5: Chemical structure of olefin metathesis catalyst

Scheme 4 . 2 :

 42 Scheme 4.2: Synthetic procedure for spacer 4 with double bonds

Fig. 4 . 7 :Scheme 4 . 3 :

 4743 Fig. 4.7: Identification of Z configuration by NMR spectroscopy: A) selective excitation of peak at 5.54 ppm; B) tocsy 1D spectrum to find the nearby =CH; C) homodecoupling of CH 2 to identify the coupling constant

Fig. 4

 4 Fig. 4.8: 1 HNMR spectrum of compound 110

Scheme 4 . 4 :

 44 Scheme 4.4: Removing acetyl groups on the sugar head

Scheme 4 . 5 :

 45 Scheme 4.5: Synthetic procedure giving cholest-5-en-3-yl -hydroxyalkyl ethers 113

Scheme 4 . 6 :Fig. 4 .

 464 Scheme 4.6: Synthetic procedure giving cholest-5-en-3-yl -azidoalkyl ethers 114

Scheme 4 . 7 :

 47 Scheme 4.7: Synthetic procedure giving cholest-5-en-3-yl -aminoalkyl ethers 115

Fig. 4 .

 4 Fig. 4.11: NMR spectra of cholest-5-en-3-yl 6-aminohexyl ether 115a. A) 1 HNMR; B) 13 CNMR

Scheme 4 . 8 :Fig. 4 .

 484 Scheme 4.8: Ring opening reaction of CMGL by cholesteryl -aminoalkyl ethers

Scheme 4 . 9 :

 49 Scheme 4.9: Deacetylation of compounds with C6, C8, C10, and C12 spacers

  .1 lists the yields of final compounds with different n and m values. Compounds will be referred to as LnSm in the following sections.

138 Fig. 4 . 1

 13841 Fig. 4.13: 1 HNMR spectrum of compound 125e (L6S16)

Fig. 4 . 15 :

 415 Fig. 4.15: Defect textures (×100 magnification) of Sm A* phases showing by A) 111 at 200 o C and B) 124b at 170 o C

Fig 4 . 16 :

 416 Fig 4.16: Defect textures (×100 magnification) of 124e A) Col h phase at 158 o C; B) phase transition Col h to Sm A*; C) Sm A* phase at 140 o C. D) Col h phases of 124f at 164 o C

Fig. 4 .

 4 Fig. 4.18: Thermotropic behaviors for L6 series as function of side chain lengths

Fig. 4 . 20 :

 420 Fig. 4.20: Thermotropic behaviors for L10 series as function of side chain lengths

Fig. 4 . 21 :

 421 Fig. 4.21: Thermotropic behaviors for L12 series as function of side chain lengths

Fig. 4 . 22 :

 422 Fig. 4.22: The clearing points of different side chains as function of the length (n) of linkers

Fig. 4 . 23 :

 423 Fig. 4.23: The transition temperatures of columnar phases to isotropic liquid with different side chains as function of the length (n) of linkers

Fig. 4 . 24 :Fig. 4 . 25 :

 424425 Fig. 4.24: Minimum energy molecular model showing the rod-like appearance for compound 124d

Fig. 5 . 2 :

 52 Fig. 5.2: Chemical structure of designed compound

Fig. 5 . 3 :

 53 Fig. 5.3: Chemical structures of laurdan and modified laurdan derivatives

Fig. 5 . 4 :

 54 Fig. 5.4: Chemical structures of desired probes based on glucose and cellobiose scaffolds 136 and 137

Scheme 5 . 1 :

 51 Scheme 5.1: General procedure for obtaining carbohydrate-based laurdans

Scheme 5 . 2 :

 52 Scheme 5.2: Synthetic procedure of 6-dodecanyol-2-bromoanphthalene

N-methyl 1 , 3 -Scheme 5 . 3 :

 1353 Scheme 5.3: Synthetic procedure for N 1 -Boc-N 2 -methyl-1,3-diaminopropane 140

Scheme 5 . 4 :

 54 Scheme 5.4: Synthetic procedure of amination and the chemical structure of Pd 2 (dba) 3 and

  Fig. 5.6: 1 H-13 C HMBC spectrum of compound 141

1 =C 7

 17 Scheme 5.5: Synthesis of glucosyl and cellobiosyl laurdan derivatives 136 and 137

Fig. 5 . 10 :Fig. 5 . 11 :

 510511 Fig. 5.10: Normalized emission spectra of 136 in different solvents

Fig. 5 . 12 :

 512 Fig. 5.12: The fluorescent intensities of probe 136 of same concentration in different solvents

Fig. 5 .

 5 Fig. 5.13: Schematic presentation of LUV bilayer and the structure of DMPC

Fig. 5 . 15 :Fig. 5 . 16 :

 515516 Fig. 5.15: Performance of probe 136 in DMPC liposomes (purple for first trial; dark blue for second trial)

Optical rotation:

  Perkin Elmer 241 polarimeter at 589 nm (sodium D line). The measurements were carried out at 20 o C and the concentrations are reported in g/100 mL Elementary analysis: The measurements were performed by the Service Central d'Analyse of CNRS (Vernaison) B. Characterizations of liquid crystalline behaviors Polarized optical microscopy: Phase identification and determination of melting point and transition temperatures were carried out by thermal polarized light microscopy using a Zeiss Axioskop 40 polarizing transmitted light microscope equipped with a Mettler FP82HT microfurnace in conjunction with a FP90 Central Processor. Differential scanning calorimetry: Differential scanning thermograms (scan rate 10° min-1) were obtained using a Mettler DSC822 e operating on the Star e software. The results obtained were standardized to indium (measured onset 156.68 °C, H 28.47 Jg -1 , lit. value 156.60 °C, H 28.45 Jg -1 ).

7 ( 3 (Methyl 2 2 ( 4 (Methyl 3 Methyl 3 : 4 . 13 CNMR ( 75 Methyl 3 : 4 .Methyl 3 D. 1 . 2 : 4 . 13 CNMR ( 75 Methyl 4 5 (Methyl 4 Methyl 4 5 ( 5 (D. 1 . 3

 732243341375343124137545445513 Monobenzylated methyl 4, 6-O-benzylidene--D-glucopyranoside can be obtained by two methods, either via the stannylene by reaction with dibutyltin oxide or in the presence of tetrabutylammonium iodide and aqueous NaOH in DCM at room temperature.Both methods give mixtures of the two possible monobenzylated products at O-2 (major compound for the first method) or at O-3 (major compound for the second method). Reaction of 1,2epoxyalkanes with methyl 2-or 3-O-benzyl-4,6-O-benzylidene--D-glucopyranosides, in the presence of DABCO/DMAP/DMSO yielded methyl 3-O-benzyl-2-O-(2-hydroxyalkyl)-4,6-Obenzylidene--D-glucopyranosides or 2-O-benzyl-3-O-(2-hydroxyalkyl)-4,6-O-benzylidene--D-glucopyranosides in 55-70% yield. Deprotection by acidic treatment (cat. ptoluenesulphonic acid in methanol) followed by Pd-catalyzed hydrogenation in MeOH-EtOAc afforded methyl 2-O-(2-hydroxyalkyl)--D-glucopyranosides and 3-O-(2-hydroxyalkyl)--MHz, CDCl 3 ) : : 4.82 (d, 1H, J = 3.6 Hz, H-1), 3.88-3.68 (m, 4H, H-3, H-9, H-6), 3.60-3.10 (m, 6H, H-2, H-4, H-5, H-8a, H-8b, H-8a', H-8b' ), 3.43 (s, 3H, OCH 3 ), 1.41-1.26 (m, 10 H, H-octyl ether), 0.87 (t, 3H, J = 7.2 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 97.9 (C1+C1'), 81.3 (C2+C2'), 76.3 (C8), 73.2 (C3), 71.5 (C5), 71.2 (C9), 70.1 (C4), 61.C6+C6'), 55.3 (OCH 3 ), 33.0, 31.9, 29.5, 25.6, 22.8, 14.2 m/z (HRMS) : calcd for C 15 H 30 O 7 Na: 345.1884; found: 345.1878 Methyl 2-O-(2-hydroxydecyl)--D-glucopyranoside (97b) MHz, CDCl 3 ) : : 4.82 (s, 1H, H-1), 4.24 (s, 4H, OH), 3.88-3.65 (m, 4.5H, H-3, H-9, H-6, H-8a), 3.58-3.40 (m, 3H, H-4, H-5, H-8a', H-8b'), 3.40 (s, 3H, OCH 3 ), 3.30 (m, 1.5H, H-2, H-8b), 1.42-1.25 (m, 14H, H-decyl ether), 0.87 (t, 3H, J = 7.2 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 97.8 (C1), 97.7 (C1'), 81.1 (C2), 79.6 (C2'), 76.2 (C8), 74.2 (C8'), 73.1 (C3), 72.6 (C3'), 71.4 (C5), 71.3 (C5'+C9), 70.2 (C9'), 70.0 (C4), 69.8 (C4'), 61.5 (C6), 61.4 (C6'), 55.OCH 3 ), 33.0, 32.0, 29.9, 29.8, 29.7, 29.5, 25.9, 25.7, 22.8, 14.2 m/z (HRMS) : calcd for C 17 H 34 O 7 Na: 373.2197; found: 373.2193 MHz, CDCl 3 ) : : 5.59 (s, 1H, OH), 5.11 (s, 1H, OH), 4.77 (m, 1H, H-1), 4.35 (m, 1H, OH), 3.88-3.65 (m, 4.5H, H-3, H-9, H-6, H-8a), 3.60-3.45 (m, 3H, H-4, H-5, H-8a', H-8b'), 3.35 (s, 3H, OCH 3 ), 3.26 (m, 1.5H, H-2, H-8b), 1.37-1.21 (m, 18H, H-dodecyl ether), 0.83 (t, 3H, J = 6.9 Hz, CH 3 ) 13 CNMR (75 MHz, CDCl 3 ) : : 97.7 (C1), 97.6 (C1'), 81.0 (C2), 79.5 (C2'), 76.1 (C8), 74.2 (C8'), 73.0 (C3), 72.5 (C3'), 71.4 (C5), 71.2(C5'), 70.1 (C9), 69.9 (C9'), 69.8 (C4), 69.7 (C4'), 61.4 (C6), 61.3 (C6'), 55.OCH 3 ), 32.9, 32.0, 29.9, 29.8, 29.7, 25.8, 25.6, 22.7, 14.1 m/z (HRMS) : calcd for C 19 H 38 O 7 Na: 401.2510; found: 401.2506Methyl 2-O-(2-hydroxytetradecyl)--D-glucopyranoside (97d) MHz, CDCl 3 ) : : 4.82 (s, 1H), 3.88-3.70 (m, 4.5H, H-3, H-9, H-6, H-8a), 3.61-3.43 (m, 3H, H-4, H-5, H-8a', H-8b'), 3.68-3.31(m, 5.5H, H-2, H-8b, 4OH), 3.40 (s, 3H, OCH 3 ), 1.40-1.25 (m, 22H, Htetradecyl ether), 0.86 (t, 3H, J = 6.8 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 97.8 (C1), 97.6 (C1'), 81.3 (C2), 79.6 (C2'), 76.3 (C8), 74.3 (C8'), 73.1 (C3), 72.6 (C3'), 71.4 (C5), 71.2 (C5'+C9), 70.2 (C9'), 70.1 (C4), 69.9 (C4'), 61.7 (C6+C6'), 55.3 (OCH 3 ), 32.9, 32.1, 29.9, 29.8, 29.8, 29.7, 29.5, 25.9, 25.7, 22.8, 14.3 m/z (HRMS) : calcd for C 21 H 42 O 7 Na: 429.2823; found: 429.2815 Methyl 2-O-(2-hydroxyhexadecyl)--D-glucopyranoside (97e) MHz, CDCl 3 ) : : 4.82 (m, 1H, H-1), 3.90-3.73 (m, 4.5H, H-3, H-9, H-6, H-8a),3.61-3.43 (m, 7H, H-4, H-5, H-8a', H-8b', 4OH), 3.40 (s, 3H, OCH 3 ), 3,31 (m, 1.5H, H-2, H-8b), 1.40-1.25 (m, 26H, Hhexadecyl ether), 0.88 (t, 3H, J = 7.2 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 97.8 (C1), 97.6 (C1'), 81.3 (C2), 79.6 (C2'), 76.3 (C8), 74.3 (C8'), 73.1 (C3), 72.6 (C3'), 71.4 (C5), 71.2 (C5'+C9), 70.2 (C9'), 70.1 (C4), 69.9 (C4'), 61.7 (C6+C6'), 55.3 (OCH 3 ), 32.9, 32.1, 29.9, 29.8, 29.8, 29.7, 29.5, 25.9, 25.7, 22.8, 14.3 m/z (HRMS) : calcd for C 23 H 46 O 7 Na: 457.3136; found: 457.3130. MHz, CDCl 3 ) : : 4.75 (d, 1H, J = 3.6 Hz, H-1), 3.88 (m, 0.5H, H-8a), 3.79 -3.69(m, 3.5H, H-6, H-9, H-8a'), 3.68-3.38 (m, 5H, H-2, H-3, H-4, H-5, H-8b, H8b'), 3.42 (s, 3H, OCH 3 ), 1.40-1.27 (m, 10H, Hoctyl ether), 0.87 (t, 3H, J = 7.2 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 99.8 (C1+C1'), 84.4(C3), 83.8 (C3), 78.1 (C8), 72.6 (C2), 72.4 (C2'), 71.7 (C5+C5'), 71.C9), 71.1 (C9'), 70.4 (C4), 70.0 (C4'), 62.2 (C6), 62.1 (C6'), 55.5 (OCH 3 ), 33.1, 31.9, 29.5, 25.7, 25.6, 22.7, 14.2 m/z (HRMS) : calcd for C 15 H 30 O 7 Na: 345.1884; found: 345.1881 accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés White solid 1 HNMR (300 MHz, CDCl 3 ) : : 4.73 (d, 1H, J = 3.3 Hz, H-1), 3.90 (d, 0.5H, J = 9.1Hz, H-8a), 3.85-3.71 (m, 3.5H, H-6, H-9, H-8a'), 3.65-3.40 (m, 5H, H-2, H-3, H-4, H-5, H-8b, H8b'), 3.39 (s, 3H, OCH 3 ), 1.37-124 (m, 14H, H-decyl ether), 0.86 (t, 3H, J = 6.9 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 99.8 (C1+C1'), 84.1 (C3), 83.3 (C3'), 78.0 (C8), 72.4 (C2), 72.3 (C2'), 71.6 (C5), 71.5 (C5'), 71.4 (C9), 70.9 (C9'), 70.0 (C4), 69.6 (C4'), 61.7 (C6+C6'), 55.4 (OCH 3 ), 33.1, 32.0, 29.9, 29.8, 29.7, 29.4, 25.7, 25.6, 22.8, 14.2. m/z (HRMS) : calcd for C 17 H 34 O 7 Na: 373.2197; found: 373.2189 73 (d, 1H, J = 2.7 Hz, H-1), 3.93 (d, 0.5H, J = 10.8Hz, H-8a), 3.86-3.70 (m, 3.5H, H-6, H-9, H-8a'), 3.65-3.40 (m, 5H, H-2, H-3, H-4, H-5, H-8b, H8b'), 3.40 (m, 3H, OCH 3 ), 1.37-1.24 (m, 18H, H-dodecyl ether), 0.86 (t, 3H, J = 6.9 Hz, CH 3 ) MHz, CDCl 3 ) : : 99.8 (C1+C1'), 84.1 (C3), 83.4 (C3'), 78.0 (C8), 72.4 (C2), 72.3 (C2'), 71.6 (C5), 71.5 (C5'), 71.0 (C9+C9'), 70.0 (C4), 69.6 (C4'), 61.8 (C6), 61.7 (C6'), 55.4 (OCH 3 ), 33.1, 32.0, 29.9, 29.8, 29.5, 25.8, 25.7, 22.8, 14.2 m/z (HRMS) : calcd for C 19 H 38 O 7 Na: 401.2510; found: 401.2498 72 (d, 1H, J = 3.3 Hz, H-1), 3.93 (d, 0.5H, J = 9.3Hz, H-8a), 3.85-3.70 (m, 3.5H, H-6, H-9, H-8a'), 3.63-3.43 (m, 5H, H-2, H-3, H-4, H-5, H-8b, H8b'), 3.40 (m, 3H, OCH 3 ), 1.35-1.22 (m, 22H, H-tetradecyl ether), 0.86 (t, 3H, J = 6.9 Hz, CH 3 ) 13 CNMR (75 MHz, CDCl 3 ) : : 99.8 (C1+C1'), 83.9 (C3), 83.2 (C3'), 78.0 (C8), 72.3 (C2), 72.2 (C2'), 71.6 (C5), 71.4 (C5'), 71.0 (C9+C9'), 69.8(C4), 69.4 (C4'), 61.6 (C6), 61.5 (C6'), 55.3 (OCH 3 ), 33.0, 32.0, 29.9, 29.8, 29.7, 29.5, 25.8, 25.7, 22.8, 14.2 m/z (HRMS) : calcd for C 21 H 42 O 7 Na: 429.2823; found: 429.2811 MHz, CDCl 3 ) : : 4.75 (d, 1H, J = 3,4 Hz, H-1), 3.97 (d, 0.5H, J = 9.1Hz, H-8a), 3.88-3.70(m, 3.5H, H-6, H-9, H-8a'), 3.68-3.40 (m, 5H, H-2, H-3, H-4, H-5, H-8b, H8b') 3.35 (m, 3H, OCH 3 ), 3.21 (s, 4H, OH), 1.40-1.25 (m, 26H. H-hexadecyl ether), 0.87 (t, 3H, J = 6.8 Hz, CH 3 ) 13 CNMR (75 MHz, CDCl 3 ) : : 99.8 (C1+C1'), 84.3 (C3), 83.6 (C3'), 78.0 (C8), 72.5 (C2), 72.4 (C2'), 71.6 (C5), 71.4 (C5'), 71.1 (C9+C9'), 70.3 (C4), 69.9 (C4'), 62.1 (C6), 62.0 (C6'), 55.5 (OCH 3 ), 33.1, 32.1, 29.9, 29.7, 29.5, 25.7, 25.6, 22.8, 14.3 m/z (HRMS) : calcd for C 23 H 46 O 7 Na: 457.3136; found: 457.3128 Synthesis of 4-O-(2-hydroxyalkyl)--D-glucopyranosides Methyl 4,6-O-benzylidene-α-D-glucopyranoside was reacted with benzyl bromide in the presence of NaH/DMF followed by selective reductive opening of the benzylidene ring with NaBH 3 CN/CH 3 SO 3 H/THF to give methyl 2,3,6-tri-O-benzyl--D-glucopyranoside. It was reacted with 1, 2-epoxyalkanes in the presence of DABCO/DMAP/DMSO to yield benzylated 4-O-(2-hydroxyalkyl)-ethers of methyl glucoside, which were deprotected by Pd-catalysed hydrogenation in MeOH-EtOAc to afford methyl 4-O-(2-hydroxyalkyl)--D-glucopyranosides 72 (d, 1H, J = 3.6Hz, H-1), 4.08 (s, 4H, OH), 3.86-3.64 (m, 5H, H-3, H-6, H-8a, H-8a', H-9), 3.60-3.45 (m, 3H, H-2, H-5, H-8b, H-8b'), 3.42-3.39 (m, 1H, H-4), 3.36 (m, 3H, OCH 3 ), 1.39-1.24 (m, 10H, H-octyl ether), 0.85 (t, 3H, J = 6.9 Hz, CH 3 ) MHz, CDCl 3 ) : : 99.7 (C1+C1'), 79.5 (C4), 78.0 (C4'), 77.9 (C8), 76.2 (C8'), 74.0 (C3), 73.8 (C3'), 72.4 (C2), 72.3 (C2'), 72.1 (C9), 71.2 (C5), 71.1 (C5'), 70.9 (C9'), 61.5 (C6+C6'), 55.3 (OCH 3 ), 33.1, 32.9, 31.9, 29.5, 25.8, 25.6, 22.8, 14.1 m/z (HRMS) : calcd for C 15 H 30 O 7 Na: 345.1884; found: 345.1881 MHz, CDCl 3 ) : : 4.76 (d, 1H, J = 3.6 Hz, H-1), 3.90 (s, 4H, OH), 3.88-3.65 (m, 5H, H-3, H-6, H-8a, H-8a', H-9), 3.61-3.45 (m, 3H, H-2, H-5, H-8b, H-8b'), 3.46-3.38 (m, 1H, H-4), 3.39 (s, 3H, OCH 3 ), 1.41-1.25 (m, 14H, H-decyl ether), 0.86 (t, 3H, J = 6.8 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 99.4 (C1), 99.3 (C1'), 79.6 (C4), 78.1 (C4'), 77.4 (C8), 76.4 (C8'), 74.5 (C3), 72.8 (C3'), 72.7 (C2), 72.6 (C2'), 72.3 (C9), 71.2 (C5), 71.1 (C5'), 70.9 (C9'), 61.7 (C6), 61.6 (C6'), 55.OCH 3 ), 33.1, 32.9, 32.0, 29.8, 29.7, 29.4, 25.8, 25.6, 22.8, 14.2 m/z (HRMS) : calcd for C 17 H 34 O 7 Na: 373.2197; found: 373.2188 MHz, CDCl 3 ) : : 4.72 (d, 1H, J = 3.6 Hz, H-1), 3.85-3.67 (m, 5H, H-3, H-6, H-8a, H-8a', H-9), 3.63-3.45 (m, 3H, H-2, H-5, H-8b, H-8b'), 3.46-3.28 (m, 1H, H-4), 3.39 (s, 3H, OCH 3 ), 1.40-1.23 (m, 18H, H-dodecyl ether), 0.86 (t, 3H, J = 6.9 Hz, CH 3 ) 13 CNMR (75 MHz, CDCl 3 ) : : 99.6 (C1), 79.7 (C4), 78.0 (C4'), 76.2 (C8'), 74.2 (C3), 73.9 (C3'), 72.5 (C2), 72.4 (C2'), 72.2 (C9), 71.2 (C5), 71.1(C5'), 70.9 (C9'), 61.6 (C6+C6'), 55.4 (OCH 3 ), 33.1, 32.9, 32.0, 29.9, 29.8, 29.5, 25.9, 25.7, 22.8, 14.2 m/z (HRMS) : calcd for C 19 H 38 O 7 Na: 401.2510; found: 401.2525 MHz, CDCl 3 ) : : 4.75 (d, 1H, J = 3.1Hz, H-1), 3.88-3.67 (m, 5H, H-3, H-6, H-8a, H-8a', H-9), 3.62-3.50 (m, 3H, H-2, H-5, H-8b, H-8b'), 3.45 (m, 1H, H-4), 3.40 (s, 3H, OCH 3 ), 3.35 (s, 4H, OH), 1.42-1.25 (m, 22H, H-tetradecyl ether), 0.87 (t, 3H, J = 6.9 Hz, CH 3 ) 13 CNMR (100 MHz, CDCl 3 ) : : 99.6 (C1), 99.5 (C1'), 79.7 (C4), 78.8 (C4'), 77.9 (C8), 76.3 (C8'), 74.5 (C3), 74.2 (C3'), 72.7 (C2), 72.6 (C2'), 72.3 (C9), 71.2 (C5), 71.1 (C5'), 70.9 (C9'), 61.8 (C6), 61.7 (C6'), 55.OCH 3 ), 33.1, 32.9, 29.9, 29.8, 29.5, 25.8, 25.7, 22.8, 14.3 m/z (HRMS) : calcd for C 21 H 42 O 7 Na: 429.2823; found: 429.2823 Methyl 4-O-(2-hydroxyhexadecyl)--D-glucopyranoside (101e) MHz, CDCl 3 ) : : 4.75 (d, 1H, J = 3.6 Hz, H-1), 3.88-3.68 (m, 5H, H-3, H-6, H-8a, H-8a', H-9), 3.63-3.45(m, 3H, H-2, H-5, H-8b, H-8b'), 3.45-3.38 (m, 1H, H-4), 3.40 (s, 3H, OCH 3 ), 3.22 (s, 4H, OH), 1.42-1.25 (m, 26H, H-hexadecyl ether), 0.87 (t, 3H, J = 6.8 Hz, CH 3 ) 13 CNMR (75 MHz, CDCl 3 ) : : 99.5 (C1), 99.4 (C1'), 79.7 (C4), 78.2 (C4'), 77.9 (C8), 76.3 (C8'), 74.6 (C3), 74.3 (C3'), 72.7 (C2), 72.6 (C2'), 72.3 (C9), 71.2 (C5), 71.1 (C5'), 70.9 (C9'), 61.8 (C6), 61.7 (C6'), 55.OCH 3 ), 33.1, 32.9, 32.1, 29.9, 29.8, 29.7, 29.5, 25.9, 25.7, 22.8, 14.3 m/z (HRMS) : calcd for C 23 H 46 O 7 Na: 457.3136; found: 457.3128 Synthesis of 6-O-(2-hydroxyalkyl)--D-glucopyranosides Tritylation and subsequent benzylation of methyl -D-glucopyranoside afforded methyl 2,3,4tri-O-benzyl-6-trityl--D-glucopyranoside which was deprotected under acidic conditions to give compound (only OH-6 is available). The structure of this compound was confirmed by comparison to an identical compound obtained from an alternative reductive opening of the benzylidene. It was reacted with 1,2-epoxyalkanes in presence of DABCO and DMAP in DMSO at 110 o C for 16 h followed by catalytic hydrogenation to give the desired methyl 6

[

  MHz, CDCl 3 ) : : 7.14 (t, 1H, NH), 5.28 (m, 1H, H-6"), 5.21 (t, 1H, J = 9.7 Hz, H-3), 4.95 (t, 1H, J = 9.8 Hz, H-4), 4.84 (d, 1H, J = 3.5 Hz, H-1),4.26-3.92 (m, 5H, H-5, H-6a, H-6b, H-7a, H-7b), 3.75 (dd, 1H, J = 3.7 and 9.9 Hz, H-2),3.37 (t, 2H, J = 6.7 Hz, H-18), 3.20 (m, 2H, H-9), 3.06 (m, 1H, H-3"), 2.34-0.74 (m, 66H, H-Cholesterol, 3xAc, CH 2 -10 to CH 2 -17), 0.61 (s, 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 ) :

22. 9 (

 9 C26"), 22.6 (C27"), 21.1 (C11"), 21.0, 20.8, 20.7 (3CH 3 CO), 19.5 (C19"), 18.8 (C21"), 11.9 (C18") m/z (HRMS) : 860.5852 (M + H + , C 49 H 82 NO 11 requires 860.5882) MHz, CDCl 3 ) : : 7.14 (t, 1H, NH), 5.28 (m, 1H, H-6"), 5.21 (t, 1H, J = 9.7 Hz, H-3), 4.95 (t, 1H, J = 9.8 Hz, H-4), 4.84 (d, 1H, J = 3.5 Hz, H-1),4.26-3.92 (m, 5H, H-5, H-6a, H-6b, H-7a, H-7b), 3.75 (dd, 1H, J = 9.9 Hz, 3.7, H-2),3.37 (t, 2H, J = 6.7 Hz, H-18), 3.20 (m, 2H, H-9), 3.06 (m, 1H, H-3"), 2.34-0.74 (m, 66H, H-Cholesterol, 3xAc, CH 2 -10 to CH 2 -17), 0.61 (s, 3H, s, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 ) :

  888.6162 (M + H + , C 51 H 86 NO 11 requires 888.6195) MHz, CDCl 3 ) : : 7.16 (t, 1H, NH), 5.34 (m, 1H, H-6"), 5.25 (t, 1H, J = 9.7 Hz, H-3 ), 5.02 (t, 1H, J = 9.9 Hz, H-4), 4.89 (d, 1H, J = 3.7 Hz, H-1),4.32-3.97 (m, 5H, H-5, H-6a, H-6b, H-7a, H-7b), 3.80 (dd, 1H, J = 3.8 and 9.8 Hz, H-2),3.43 (t, 2H, J = 6.8 Hz, H-20), 3.25 (m, 2H, H-9), 3.11 (m, 1H, H-3"), 2.38-0.74 (m, 70H, H-Cholesterol, 3xAc, CH 2 -2 to CH 2 -19), 0.66 (s, 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 ) :

  MHz, CDCl 3 /MeOD) : : 5.28 (m, 1H, H-6"), 4.72 (d, 1H, J = 3.7 Hz, H-1), 4.08 (d, 1H, J = 15.9 Hz, H-7a), 3.91 (d, 1H, J = 15.9 Hz, H-7b), 3.74-3.60 (m, 3H, H-6a, H-6b, H-3), 3.57-3.32 (m, 5H, H-2, H-4, H-5, CH 2 -14), 3.22-3.01 (m, 3H, CH 2 -9, H-3"), 2.32-2.03 (m, 2H, H4"), 1.96-0.77 (m, 54H, H-Cholesterol, CH 2 -10 to CH 2 -13), 0.60 (s, 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 /MeOD) : : 170.1 (C8), 140.8 (C5"), 121.5 (C6"), 99.4 (C1), 79.1 (C3"), 73.6 (C3), 72.3 (C5), 71.6 (C2),

(

  C25"), 26.8, 26.0 (C-octyl), 24.2 (C15"), 23.8 (C23"), 22.7 (C26"), 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 11.8 (C18") m/z (HRMS) : 734.5552 (M + H + , C 43 H 76 O 8 N requires 734.5565)

3 (

 3 MHz, CDCl 3 / MeOD) : : 5.21 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.5 Hz, H-1), 4.40 (dd, 1 H, J = 3.4 and 10.1 Hz, H-2), 4.00 (d, 1 H, J = 15.6 Hz, H-7a), 3.83 (d, 1 H, J = 15.6 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-6b, H-3), 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -16), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.06-2.93 (m, 3 H, CH 2 -18, H-3"), 2.26-2.00 (m, 2 H, H4"), 1.96-0.77 (m, 77 H, H-Cholesterol, CH 2 -10 to CH 2 -15, CH 2 -19 to CH 3 -31), 0.54 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 / MeOD) : : 169.5 (C8), 156.2 (C17), 140.8 (C5"), 121.5 (C6"), 97.1 (C1), 79.1 (C3"), 73.4 (C2), 72.C5), 71.2 (C3), 70.1 (C4), 68.1 (C16), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.1

0, 24 . 2 ( 83 Glucosteroid 3 (

 242833 C15"), 23.7 (C23"), 22.7 (C26"), 22.6 , 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C31), 11.8 (C18") m/z (ESI) : 973.8 (M+H + ), 995.8 (M+Na + ) [] D 20 +30 (c 0.9 in CH 2 Cl 2 /MeOH (9/1)) Elemental analysis: Found: C 70.66, H 10.71, N 2.71. C 58 H 104 N 2 O 9 +H 2 O requires C 70.30, H 10.71, N 2.MHz, CDCl 3 / MeOD) : : 5.23 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.5 Hz, H-1), 4.40 (dd, 1 H, J = 3.4 and 10.1 Hz, H-2), 3.98 (d, 1 H, J = 15.6 Hz, H-7a), 3.83 (d, 1 H, J = 15.6 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-6b, H-3), 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -16), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.05-2.93 (m, 3 H, CH 2 -18, H-3"), 2.25-2.00 (m, 2 H, H-4"), 1.96-0.67 (m, 81 H, H-Cholesterol, CH 2 -10 to CH 2 -15, CH 2 -19 to CH 3 -33), 0.54 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 / MeOD) : : 169.5 (C8), 156.2 (C17), 140.8 (C5"), 121.6 (C6"), 97.1 (C1), 79.1 (C3"), 73.4 (C2), 72.C5), 71.2 (C3), 70.1 (C4), 68.1 (C16), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.2

0, 24 . 2 ( 6 ( 75 Glucosteroid 3 ( 2 ( 8 ( 70 Glucosteroid: 5 .

 242675328705 C15"), 23.7 (C23"), 22.7 (C26"),22.6, 22.4, 22.3 (C27"), 21.0 (C11"),19.3 (C19"), 18.C21"), 14.0, 13.9 (C33),11.8 (C18") m/z (ESI) : 1001.8(M+H + ), 1023.8 (M + Na + ) [] D 20 +26 (c 1 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: Found: C 70.42, H 10.70, N 2.68. C 60 H 108 N 2 O 9 +H 2 O requires C 70.72, H 10.80, N 2.MHz, CDCl 3 / MeOD) : : 5.23 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.6 Hz, H-1), 4.40 (dd, 1 H, J = 3.6, 10.1 Hz, H-2), 4.00 (d, 1 H, J = 15.6 Hz, H-7a), 3.83 (d, 1 H, J = 15.3 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-6b, H-3) 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -16), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.05-2.90 (m, 3 H, CH 2 -18, H-3"), 2.30-2.00 (m, 2 H, H-4"), 1.96-0.67 (m, 85 H, H-Cholesterol, CH 2 -10 to CH 2 -15, CH 2 -19 to CH 3 -35), 0.53 (s, 3 H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 / MeOD) :: 169.5 (C8), 156.2 (C17), 140.8 (C5"), 121.5 (C6"), 97.1 (C1), 79.1 (C3"), 73.5 (C2), 72.C5), 71.2 (C3), 70.1 (C4), 68.1 (C16), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"), 36.C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 30.0,29.7, 29.6, 29.6, 29.4, 29.4, 29.3, 29.2, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"),26.8, 26.8, 26.1, 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), 22.6, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C35), 11.8 (C18") m/z (ESI) : 1029.8 (M+H + ), 1051.8 (M + Na + ) [] D 20 +29 (c 0.9 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: Found: C 71.72, H 10.87, N 2.61. C 62 H 112 N 2 O 9 +0.5H 2 O requires C 71.68, H, 10.98, N 2.35 (m, 1H, H-6"), 5.02 (d, 1H, J = 3.6 Hz, H-1), 4.55 (dd, 1H, J = 3.5 and 10.1 Hz, H-2), 4.15 (d, 1H, J = 15.6 Hz, H-7a), 3.98 (d, 1H, J = 15.6 Hz, H-7b), 3.89-3.75 (m, 3H, H-6a, H-6b, H-3), 3.61-3.52 (m, 4H, H-5, H-4, CH 2 -18 ), 3.25 (t, 2H, J = 7.2 Hz, CH 2 -9), 3.19-3.04 (m, 3H, CH 2 -20, H-3"), 2.40-2.10 (m, 2H, H-4"), 2.08-0.

D. 3 . 3

 33 13 CNMR (100MHz, CDCl 3 ) : 200.3 (C-11''), 156.2 (C-5), 148.8 (C-3''), 137.6 (C-5''), 131.1 (C-1''), 130.9 (C-8''), 129.8 (C-9''), 126.4 (C-6''), 125.5 (C-10''), 125.0 (C-7''), 116.3 (C-2''), 105.3 (C-4''), 79.6 (C-4), 50.4 (C-8), 38.8 (C-6), 38.6 (C-9), 38.5 (C-12''), 32.0 , 29.8, 29.8, 29.8, 29.7, 29.6, 29.5 (C-lauroyl), 28.5 (C-CH 3 Boc), 27.2 (C-21''), 25.0 (C-7), 22.8 (C-13''), 14.2 (C-22'') m/z (HRMS) : 497.3721 (M + H + , C 31 H 49 N 2 O 3 requires 497.3738) Synthesis of partially protected glucosyl and cellobiosyl laurdan probes (142, 143)

  [START_REF] Hill | Sugar-Based Surfactants for Consumer Products and Technical Applications[END_REF] CNMR (125MHz, CDCl 3 ) : 200.5 (C-11''), 171.9, 170.8, 169.5 (C-C=OCH 3 ), 169.2 (C-8), 152.9 (C-3''), 137.7 (C-5''), 130.9 (C-1''), 130.5 (C-8''), 129.8 (C-9''), 126.2 (C-6''), 125.1 (C-10''), 124.9 (C-7''), 116.2 (C-2''), 105.1 (C-4''), 99.2 (C-1), 73.7 (C-3), 69.9 (C-2), 68.2 (C-4), 67.9 (C-5), 67.4 (C-7), 61.7 (C-6), 50.5 (C-11), 39.0 (C-12), 38.6 (C-12''), 37.1 (C-9), 32.0 (C-20''), 29.8, 29.8, 29.8, 29.7, 29.6, 29.5 (C-lauroyl), 25.0 (C-10), 24.9 (C-13''), 22.8 (C-21''), 21.1, 20.9, 20.8, (C-C=OCH 3

4. 32 (D. 3 . 4

 3234 dd, 1H, J = 1.9, 12.0 Hz, H-6a), 4.13 (dd, 1H, J = 4.1, 12.4 Hz, H-6'a), 4.13 (d, 1H, J = 15.9 Hz, H-7a), 4.13 (dd, 1H, J = 5.0, 12.0 Hz, H-6b), 4.01-3.92 (m, 2H, H-7b, H-6'b), 3.81 (m, 1H, H-5), 3.65-3.56 (m, 3H, H-2, H-4, H-5'), 3.43 (m, 2H, H-11), 3.40-3.16 (m, 2H, H-9), 2.99 (s, 3H, H-12), 2.94 (t, 2H, J = 7.4 Hz, H-12''), 2.05-1.92 (m, 18H, H-Ac), 1.80 (m, 2H, H-10), 1.69 (m, 2H, H-13''), 1.37-1.13 (m, 16H, H-14''-21''), 0.81 (t, 3H, J = 6.9 Hz, H-22'') 13 CNMR (125MHz, CDCl 3 ) : 200.5 (C-11''), 172.0, 170.6, 170.4, 170.3, 169.5, 169.3 (C-C=OCH 3 ), 169.0 (C-8), 152.9 (C-3''), 137.7 (C-5''), 131.0 (C-1''), 130.7 (C-8''), 129.9 (C-9''), 126.2 (C-6''), 125.2 (C-10''), 124.8 (C-7''), 116.2 (C-2''), 105.4 (C-4''), 101.0 (C-1'), 98.9 (C-1), 76.1 (C-2), 73.6 (C-3), 73.0 (C-3'), 72.0 (C-5'), 71.7 (C-2'), 71.0 (C-4), 69.1 (C-5), 67.9 (C-4'), 67.4 (C-7), 61.9 (C-6), 61.8 (C-6'), 50.4 (C-11), 38.5 (C-12), 38.5 (C-12''), 37.1 (C-9), 32.0 (C-30''), 29.8, 29.8, 29.8, 29.7, 29.6, 29.5 (C-lauroyl), 27.2 (C-10), 25.0 (C-13''), 22.8 (C-21''), 21.0, 20.9, 20.8, 20.7, 20.7 (C-C=OCH 3 ), 14.2 (C-22'') m/z (HRMS) : 1031.4937 (M + H + , C 52 H 75 N 2 O 19 requires 1031.4959), 1053.4753 (M + Na + , C 52 H 75 N 2 NaO 19 requires 1053.4778) [] D 20 +31 (c 0.8 in CH 2 Cl 2 ) Synthesis of glucosyl and cellobiosyl laurdan probes (144,145)The deactylation of compounds 142 and 143 was carried out in MeOH/H 2 O/NEt 3 (8/1/1) for 16h. The reaction was then coevaporated three times with water (10 mL) and the obtained residue was subjected to silica gel chromatography using a CH 2 Cl 2 /MeOH (95/5) to give the corresponding products.

13 C: 8 . 3 (A. 10 :A. 12 : 14 : 2 : 2 : 4 : 6 : 8 :

 138310121422468 NMR (101 MHz, CDCl 3 +MeOD) : 203.9 (C-11''), 172.7 (C-8), 151.1 (C-3''), 139.8 (C-5''), 132.6 (C-1''), 132.0 (C-8''), 131.8 (C-9''), 127.9 (C-6''), 126.8 (C-10''), 126.0 (C-7''), 118.0 (C-2''), 106.8 (C-4''), 101.4 (C-1), 75.3 (C-3), 74.5 (C-4), 73.5 (C-2), 71.7 (C-5), 68.4 (C-7), 62.8 (C-6), 51.6 (C-9), 40.0 (C-12), 39.8 (C-12''), 38.6 (C-11), 33.6, 31.2, 31.1, 31.1, 31.0, 31.0 (lauroyl), 28.4 (C-10), 26.8 (C-13''), 24.3 (C-21''), 15.4 (C-22''). m/z (HRMS) : 617.3778 (M + H + , C 34 H 53 N 2 O 8 requires 617.3796) 24 (s, 1H, H-9''), 7.81 (d, 1H, J = 1.6, 8.7 Hz, H-7''), 7.73 (d, 1H, J = 9.2 Hz, H-1''), 7.55 (d, 1H, J = 8.7 Hz, H-6''), 7.10 (dd, 1H, J = 2.2, 9.1 Hz, H-2''), 6.80 (s, 1H, H-4''), 4.73 (d, 1H, J = 3.7 Hz, H-1), 4.34 (d, 1H, J = 7.9 Hz, H-1'), 4.08 (d, 1H, J = 15.9 Hz, H-7a), 3.93 (d, 1H, J = 16.0 Hz, H-7b), 3.85-3.78 (m, 2H, H-6a, H-6'a), 3.82 (t, 1H, J = 9.2 Hz, H-3), 3.70 (dd, 1H, J = 2.6, 12.2 Hz, H-6b), 3.65-3.58 (m, 2H, H-5, H-6'b), 3.54-3.45 (m, 4H, H-2, H-4, H-11), 3.36-3.20 (m, 6H, H-9, H-2', H-3', H-4', H-5'), 3.02 (s, 3H, H-12), 2.97 (t, 2H, J = 7.5 Hz, H-12''), 1.83 (m, 2H, H-10), 1.68 (m, 2H, H-13''), 1.37-1.13 (m, 16H, H-14''-21''), 0.80 (t, 3H, J = 6.9 Hz, H-22'') 13 CNMR (125MHz, CDCl3 /MeOD= 9/1) : 203.0 (C-11''), 171.8 (C-8), 150.6 (C-3''), 139.2 (C-5''), 132.3 (C-1''), 131.9 (C-8''), 131.5 (C-9''), 127.6 (C-6''), 126.7 (C-10''), 125.9 (C-7''), 117.5 (C-2''), 106.8 (C-4''), 104.5 (C-1'), 100.8 (C-1), 80.9 (C-4), 77.9 (C-3'), 77.8 (C-4'), 73.5 (C-2'), 73.0 (C-3), 72.9 (C-2), 72.5 (C-5), 71.2 (C-5'), 68.3 (C-7), 62.6 (C-6'), 62.0 (C-6), 51.5 (C-9), 39.8 (C-12), 39.8 (C-12''), 38.2 (C-11), 33.2, 31.0, 30.9, 30.8, 30.8, 30.7 (lauroyl), 28.1 (C-10), 26.4 (C-13''), 24.0 (C-21''), 15.DSC curve of methyl 4-O-(2-hydroxyoctyl)--D-glucopyranosides (101a) A.11: DSC curve of methyl 4-O-(2-hydroxydecyl)--D-glucopyranosides (101b) DSC curve of methyl 4-O-(2-hydroxydodecyl)--D-glucopyranosides (101c) A.13: DSC curve of methyl 4-O-(2-hydroxytetradecyl)--D-glucopyranosides (101d) DSC curve of methyl 4-O-(2-hydroxyhexadecyl)--D-glucopyranosides (101e) A.15: DSC curve of methyl 6-O-(2-hydroxyoctyl)--D-glucopyranosides (105a) DSC curve of amphiphile L6 (120) B.1.2: DSC curve of amphiphile L8 (121) accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés B.1.3: DSC curve of amphiphile L10 (122) B.1.4: DSC curve of amphiphile L12 (123) accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés B. 2 Glucosteroidic bolaphiles B.2.1: DSC curve of bolaphile L4S4 (124a) DSC curve of bolaphile L4S8 (124b) B.2.3: DSC curve of bolaphile L4S10 (124c) DSC curve of bolaphile L4S12 (124d) B.2.5: DSC curve of bolaphile L4S16 (124f) DSC curve of bolaphile L4S18 (124g) B.2.7: DSC curve of bolaphile L6S6 (125a) DSC curve of bolaphile L6S8 (125b) B.2.9: DSC curve of bolaphile L6S12 (125c) 10: DSC curve of bolaphile L6S14 (125d) B.2.11: DSC curve of bolaphile L6S16 (125e) 12: DSC curve of bolaphile L6S18 (125f) B.2.13: DSC curve of bolaphile L8S6 (126a) 14: DSC curve of bolaphile L8S8 (126b) B.2.14: DSC curve of bolaphile L8S12 (126c) 15: DSC curve of bolaphile L8S14 (126d) B.2.16: DSC curve of bolaphile L8S16 (126e) 17: DSC curve of bolaphile L8S18 (126f) B.2.18: DSC curve of bolaphile L10S6 (127a) 19: DSC curve of bolaphile L10S8 (127b) B.2.20: DSC curve of bolaphile L10S12 (127c) 22: DSC curve of bolaphile L12S8 (128b) B.2.23: DSC curve of bolaphile L12S12 (128c)

  5.1. Introduction ........................................................................................................................ 5.2. Synthesis procedure ......................................................................................................... 5.2.1. Synthesis of 6-dodecanoyl-2-bromonaphthalene ............................................. 5.2.2. Synthesis of the N 1 -Boc-N 2 -methyl-1,3-diaminopropane ................................ 5.2.3. Amination of 6-dodecanoyl-2-bromonaphthalene and N 1 -Boc-N 2 -methyl-1,3diaminopropane ................................................................................................................ 5.2.4. Synthesis of CMG derived probes ...................................................................... 5.3 Fluorescence properties ................................................................................................... 5.3.1 Characterization of fluorescence in various solvents. .......................................

5.3.2 Fluorescent tests of probes in model membrane ............................................... 5.4 Conclusion .......................................................................................................................... General conclusion ........................................................................................................................... Experimental section ........................................................................................................................ A. General aspect ..................................................................................................................... B. Characterizations of liquid crystalline behaviors ............................................................. C. Fluorescent properties of probes ...................................................................................... D. Synthetic procedures and characterizations of all the products studied ..................... D. 1 Methyl n-O-(2-hydroxyalkyl)--D-glucopyranosides ........................................... D. 2 Glucosteroids ............................................................................................................ D.3 Synthesis of glucosyl and cellobiosyl probes ........................................................ Appendix ............................................................................................................................................ A. DSC curves of n-O-(2-hydroxyalkyl)--D-glucopyranosides ......................................... B. DSC curves of glucosteroids .............................................................................................. B. 1 Glucosteroidic amphiphiles ..................................................................................... B. 2 Glucosteroidic bolaphiles ........................................................................................ References ........................................................................................................................................

Table 1 .

 1 2.

	Type name	Formula	Representative	Characteristic
				Good water solubility
		ROSO 3 -M +	Sodium	and surface activity,
	Sulfate esters	(R is aliphatic	dodecylsulfate	reasonable chemical
		chain)	(SDS)	stability; easy-made,
				low-cost, easy acess
			alkylbenzene	Good pH stability,
	Sulfonic acid salts	R-SO 3 -M +	sulfonates (ABS), linear alkylbenzene	excellent water solubility, good wetting
			sulfonates (LABS)	properties, low cost
	Carboxylate soaps	R-COO -M + (R is tallow, fatty acid condensed with amino derivatives)	Classical soaps	Less sensible to hard water and low pH, low skin irritability, low toxicity
	Phosphoric acid esters	RO-PO 3 -M + (R is long-chain alcohol or phenol)	Lecithin, glyceryl esters containing one phosphate ester	Low foaming, good water solubility, resistant to high pH

Table 1 .

 1

2: Major types of anionic surfactants (M could be alkali metal or ammonium ion)

Production Volume[t/a] Average Price[euro/kg]

	Sucrose	150,000,000	0.25
	Glucose	30,000,000	0.30
	Sorbitol	650,000	1,80

54 O HO OH OH O HO OC n H 2n +1 OC n H 2n +1 H 2n +1 C n O

	n	Cryst	Col	Cub	Iso Liq
	6			62.3
	7	44.0		72.1	82.3
	9	36.0		59.4	76.2
	10	37.0		53.3	63.8
	11	30.0		38.3	43.4
	12	37.5	(	32.0)
	14	52.7
	16	58.2
	Table 1.4: Transition temperatures ( o C) and phase classifications for O--D-galactopyranosyl-
		tri-O-alkyl pentaerythritols [108]

Cryst Sm A* Iso Liq OH OH HO OH OC 12 H 25

		OH
		OH
	C 12 H 25 O		101.3	138.0
		OH
		OH
	OH
	OC	12 H	25
	HO		67.8	123.8
	OH
	OH
	Table 1.5: Transition temperatures ( o C) and phase classifications for x-O-dodecyl-(D or L)-
			xylitols [112]
	A similar study was carried out on the cyclic glucosyl derivatives, the dodecyl
	glucopyranoside and x-O-dodecyl -D-glucopyranoses family, see Fig. 1.26. They showed
	Sm A* phases, with a wide range of transition temperature, which was influenced by the
	location of substitution.
			49.5	114.7
	OH
	OH
	HO		69.1	123.1
	OC	12 H	25
	OH
			55

O

HO OH OH HO OC 12 H 25 O HO OH OH HO OC 12 H 25 O HO OC 12 H 25 OH HO O HO OH OC 12 H 25 HO O C 12 H 25 O OH OH HO O HO OH OH C 12 H 25 O Cryst 80.4 Sm A* 143.4 o C Iso Liq Cryst 92.5 Sm A* 167.2 o C Iso Liq Cryst 127.5 Sm A* 141.8 o C Iso Liq Cryst 77 Sm A* 151 o C Iso Liq Cryst 94 Sm A* 163 o C Iso Liq Cryst 109 Sm A* 140 o C Iso Liq OH OH OH OH

OH HO HO HO OH Cyclohexanone, DMF Ph Ph Ph O Ph Ru O Ph Ru Ph Ph Ph CO OC CO OC O OH HO HO HO O [(C 4 Ph 4 CO)(CO) 2 Ru] 2 [18] [(C 4 Ph 4 CO)(CO) 2 Ru] 2 [17]

  Scheme 2.1: Synthesis of -D-galactonolactone 17 catalyzed by dimeric ruthenium complex [(C 4 Ph 4 CO)(CO) 2 Ru] 2 18 in DMF[125]

	Galactose	87	21	92	54	93 :7
	Glucose Mannose	Time 16 87	T 45 21	Conversion Isolated yield / 98 86 91 41	99.9 :0.1 94 :6

.1 show the results.

O

Table 2 .

 2 1: Yields in lactones resulting from different sugars[125]

Table 2 .

 2 4.

	OH				OH
				tert-butyl bromoacetate
	HO HO	O	OH	NaH, DMF	HO HO	O	O	O	O
	HO			HO
							[54]

Scheme 2.13: Synthetic process of glucose with tert-butyl bromoacetate

[140]

Table 2 .

 2 4: Yields and :  conformation ratios obtained by different sugars[140]

DCM GLY, R = H, R' = Et L-ASP R = -CH 2 CO 2 Me, R' = Me GLU, R = -CH 2 CH 2 CO 2 Me, R' = Me PHE, R = -CH 2 C 6 H 5 , R' = Me TYR, R = -CH 2 C 6 H 4 OtBu, R' = tBu ASN, R = -H 2 CONH 2 , R' = tBu LYS, R = -(CH 2 ) 4 NHCbz, R' = Me

  The conditions and types of amine used are shown in Scheme 2.14. Starting from amino acid, an extended reaction time was needed and the yields were fair, Scheme 2.15.

										OH
					OAc
			AcO AcO		O O	O		1. R'NH 2 , DCM, DMAP, r.t. 2. NEt 3 /H 2 O/MeOH = 8/ 1/ 1, r.t.	HO HO	O OH O	O	H N	R'
					O	1. H 2 NR " NH 2 , DCM, DMAP, r.t.	R' = -C 12 H 25 , -C 14 H 29 , -C 16 H 33 , -CH 2 C≡CH, -(CH 2 ) 2 OC(O)C(Me)=CH 2
			OH
	HO HO		O OH O	O		O	HO	O	OH	OH OH	R " = -C 4 H 8 , -C 6 H 12
						R "
										OAc
	OAc
										O
										AcO
										AcO
										O	H	CO 2 R'
	O
	AcO									OH
				amino acid, DMAP, DCM
	AcO									O
										N	R
	O									H
	O
	O
						LYS, DMAP, DCM
										OAc
										O
										AcO
										AcO
										O	H	CO 2 Me
										OH
										O
										N
										H
	OAc
	O									AcO	O
	AcO	MeO	2 C	H
	AcO									O	NH
	O
	OH
										OH O
	O
		N								AcO
		H								AcO
				CO 2 Me

2. NEt

3 /H 2 O/MeOH = 8/ 1/ 1, r.t.

Scheme 2.15: Reactions of -CMGL with amine and diamines

[137]

D-ASP, DMAP,

1. TFA (16 eq.), DCM

  Further study on the post-modification on the resulting glycopolymer 89 gained some exciting results. With the azido group on the carbohydrate group, the possibility of bridging other functional group bearing the triple bond became available. This work is the first time showing that the preformed glycopolymer could afford a post modification (Scheme 2.19).

	2. CH	2 =CHC(O)Cl (1.25 eq.),
	Et (iPr) 2 N (4 eq.), THF, -5 o	C
				3. NEt	3 / H 2 O/MeOH = 1/ 1/ 8	[88]
				1. Tf	2 O, DCM, -5 o
				2. NaN 3 , DMF, 90 o	C
				3. CH 2 =CHC(O)Cl (1.25 eq.),
				Et (iPr) 2 N (4 eq.), THF, -5 o	C
	5. NEt	3 / H	2 O/MeOH = 1/ 1/ 8
				[89]

Scheme 2.18: Synthesis for glycomonomers 88 and 89

[145]

Table 2

 2

		OH
		O
	HO
	HO
		HO
		O	O
			C n H	2n+1
			N
			H
	Chain length (n)	Melting point ( o C)	Clearing point ( o C)
	6	63		/
	8	74		/
	10	81		94
	12	89		122
	14	92		178
	16	100		192

.5 shows the results observed by aliphatic series, Fig. 2.7 is the defect texture of Sm A* phases shown by dodecyl amide methylcarboxyl glucopyranoside under polarized light microscope.

Table 2 .

 2

6: Transition temperatures of alkyl amide methylcarboxyl glucopyranoside

[147]

  3.1. It relies on the preparation of partially protected methyl glucoside

derivatives which have only one define hydroxyl group available for etherification. Indeed, attempts for making directly the mono-substituted ether products from methyl glucoside proved unsuccessful. After etherification by reaction with 1,2-epoxyalkane, deprotection led to final monosubstituted ethers.

Table 3 .

 3

	Cpd No n K	Sm A*		Iso Tg
	99a	6 --	-	-	•	-5.4
	99b	8	[3.48] • 8.1	-	-	•	-9.8
	99c	10	--	•	[3.35] 48.7 §	•	-6.6
	99d	12	[34.37] • 32.7	•	[5.35] 66.2	•	-
	99e	14	[72.09] • 43.9	•	[2.35] 85.0	•	-

1: Transition temperatures ( o C) and enthalpies (J g -1 ) of transition shown in square bracket for the O-2 series

Table 3 .

 3

	Cpd No n K	Sm A*		Iso Tg
	101a	6	[2.46/6.75] • 25.2/31.3	-	-	• -14.7
	101b	8	[26.21] • 64.2	-	-	• -1.3
	101c	10	[55.77] • 33.7	-	-	• -4.2
	101d	12	[53.02] • 34.5	•	[0.27] 62.6	• -
	101e	14	[57.81] • 39.7	•	[1.68] 81.3	• -

2: Transition temperatures ( o C) and enthalpies (J g -1 ) of transition shown in square bracket for the O-3 series ( § there is a second peak at 42.0 o C)

Table 3 .

 3

Table 3 .

 3

7: Lyotropic behaviors of compounds 97, 99, 101, 105

Table 4 .

 4

	Scheme 4.10: Synthetic procedure of glucosteroidic bolaphiles
	(n = 4, 6, 8, 10, 12 and m = 4, 6, 8, 10, 12, 14, 16, 18)
	Linker (n)
		6	8	10	12
	Side (m)
	6	50%	61%	75%	69%
	8	61%	61%	66%	70%
	12	87%	67%	80%	67%
	14	52%	52%
	16	53%	41%
	18	50%	52%

1: The yields of glucosteroidic bolaphiles with different spacers and side chains after two steps

Table 4

 4

	.2 shows the

Table 4 .

 4 2: Yields of L6S8 and L12S8 obtained by two methods

Table 4 .

 4

	Cpd	m	K			Sm A*	Col h	Iso. Liq.
	121			60 [48.84]			244 [3.43]			
	126a	6		154 [37.22]			192 [3.81]		
	126b	8		126 [33.02]			188 [3.28]		
	126c	12		131 [16.92]			156 [0.86]		
	126d	14		123 [23.05]					144 [0.47]	
	126e	16		125 [18.41]					150 [0.89]	
	126f	18		131 [23.15]					170 [1.22]	
	Table 4.5: Phase transitions temperature (C) and enthalpies (J g -1 ) of transition shown in
				square bracket for L8 linker series
			240
								Iso
		C)	200
		o
		temperature (	120 160			Sm A*		Col
			80					Cryst
			0	2	4	6	8	10 12 14 16 18
						alkyl chain length (m)

Fig. 4.19: Thermotropic behaviors for L8 series as function of side chain lengths 6: Phase transitions temperature (C) and enthalpies (J g -1 ) of transition shown in square bracket for L10 linker series

Table 4 .

 4

	Cpd	m	K		Sm A*		Iso. Liq.
	123			100 [13.50]		239 [6.33]	
	128a	6		136 [35.49]		192 [6.45]	
	128b	8		118 [23.29]		177 [5.82]	
	128c	12		118 [30.96]		159 [4.23]	

7: Phase transitions temperature (C) and enthalpies (J g -1 ) of transition shown in square bracket for L12 linker series

Table 4 .

 4 ). The high enthalpies may be due to the residual H-bondings in the system. 8: Transition enthalpies (J mol -1 ) of Sm A* to liquid or columnar phases of all the series

	S (m)	L (n)	4	6	8	10	12
	0		14.116	7.847	4.673	7.742	8.011
	6		0.37 (S4)	3.193	4.424	5.746	7.031
	8		1.428	2.357	3.688	5.134	6.156
	12		0.787	0.436	0.91	2.424	4.224
	14		0.61	0.465
	16		1.597	0.318
	18		2.537	3.475

O-(2-hydroxytetradecyl)--D-glucopyranoside (105d)

	13 CNMR (100 MHz, CDCl 3 ) : : 4.74 (m, 1H, H-1), 3.90-3.63 (m, 2.5H, H-6, H-9), 3.63-3.55(m, 2H, H-3, H-5), 3.55-3.47 D. 2 Glucosteroids Elemental analysis:
	: 99.9 (C1), 99.8 (C1'), 76.5 (C8), 76.2 (C8'), 74.8 (C3), 74.3 (C3'), 72.1 (C2+C2'), 70.9 (C5), 70.8 (C5'), 70.8 (C9), 70,3 (C9), 70,3 (C6), 70.2 (C4), 70.2 (C6'), 69.7 (C4'), 55.4 (OCH 3 ), OMe HO 33.2, 31.9, 29.5, 25.7, 25.6, 22.8, 14.2 O O HO HO HO 8 9 1 (m, 1.5H, H-8a, H-4), 3.47-3.30 (m, 2.5H, H-2, H-8a', H-8b', H9' ), 3.36 (s, 3H, OCH 3 ), 3.25 Found: C, 67.24; H, 9.22; N, 2.03. C 45 H 71 O 11 N requires C, 67.39; H, 8.92; N, 1.75 (t, 0.5H, J = 9.3 Hz, H-8b), 1.42-1.20 (m, 22H, H-tetradecyl ether), 0.87 (t, 3H, J = 6.9 Hz, CH 3 ) D. 2. 1 Synthesis for the C4 linker compound m/z (ESI) :
	7 To a solution of (N-Allylcarbamoyl) methyl 3,4,6-tri-O-acetyl--D-glucopyranoside (100 mg, 13 824.4 (M + Na + ) CNMR (75 MHz, CDCl 3 ) : m/z (HRMS) : : 100.0 (C1), 99.9 (C1'), 76.5 (C8), 76.3 (C8'), 74.2 (C3), 74.1 (C3'), 72.0 (C2+C2'), 71.0 0.24 mmol) and allyl cholesteryl ether (530 mg, 1.24 mmol) in dichloromethane (1.5 mL), Grubbs-Hoveyda 2 nd generation catalyst (5%, 0.0078 g, 0.0124 mmol) was added. The 20 [α] D calcd for C 15 H 30 O 7 Na: 345.1884; found: 345.1886 Colorless soft matter 1 HNMR (300 MHz, CDCl 3 ) : (C5), 70.9 (C5'), 70.7(C9), 70.3 (C9'+C6), 70.2 (C6'), 69.6 (C4+C4'), 55.4 (OCH 3 ), 33.3, 32.1, gel using a toluene/acetone (7:3) eluting mixture and gave compound 109 (0.143 g, 72%, 30.0, 29.9, 29.8, 29.5, 25.8, 25.7, 22.8, 14.2 reaction was stirred under nitrogen at RT for 24h to be directly chromatographied on silica +52 (c 0.9 in CHCl 3 )
	Methyl 6-O-(2-hydroxydecyl)--D-glucopyranoside (105b) m/z (HRMS) : E:Z = 23:2) as a yellow foam
	: 4.74 (m, 1H, H-1), 3.85-3.63 (m, 2.5H, H-6, H-9,), 3.63-3.55 (m, 2H, H-3, H-5), 3.55-3.47
	(m, 1.5H, H-8a, H-4), 3.47-3.32 (m, 2.5H, H-2, H-8a', H-8b', H9' ), 3.36 (s, 3H, OCH 3 ), 3.23 calcd for C 21 H 42 O 7 Na: 429.2823; found: 429.2804
	HO (t, 0.5H, J = 9.3 Hz, H-8b), 1.40-1.20 (m, 18H, H-dodecyl ether), 0.84 (t, 3H, J = 6.9 Hz, 8 18"
	O Methyl 6-O-(2-hydroxyhexadecyl)--D-glucopyranoside (105e) O HO 9 CH 3 ) AcO O OAc 1" 6 19"
	13 CNMR (75 MHz, CDCl 3 ) : AcO	HO	O	7 1	O	HN	9	O	HO 3"	HO 6"	OMe 1 7		26" (27")
							12
	: 99.9 (C1), 99.8 (C1'), 76.4 (C8), 76.2 (C8'), 74.1 (C3), 74.0 (C3'), 71.9 (C2+C2'), 70.9 (C5), HO 8
	70.8 (C5'), 70.6 (C9), 70.2 (C9'+C6+C6'), 69.5 (C4+C4'), 55.3 (OCH 3 ), 33.2, 32.0, 29.9, 29.7, O 9
	White solid 29.4, 25.8, 25.7, 22.7, 14.2 Yellow foam									HO HO	O HO	1 OMe
													7
	1 HNMR (300 MHz, CDCl 3 ) : m/z (HRMS) : 1 HNMR (500 MHz, CDCl 3 ) :
	calcd for C 19 H 38 O 7 Na: 401.2510; found: 401.2504 : 4.75 (m, 1H, H-1), 3.80-3.63 (m, 2.5H, H-6, H-9,), 3.63-3.55 (m, 2H, H-3, H-5), 3.55-3.47 : 7.36 (t, 1 H, J = 5.4 Hz, N-H), 5.74 (m, 2H, H-10, H-11), 5.33 (m, 1H, H-6"), 5.26 (t, 1H, J = Colorless soft matter (m, 1.5H, H-8a, H-4), 3.47-3.32 (m, 2.5H, H-2, H-8a', H-8b', H9' ), 3.33 (s, 3H, OCH 3 ), 3.27 9.6 Hz, H-3), 5.00 (t, 1H, J = 9.6 Hz, H-4), 4.89 (t, 1H, J = 9.4 Hz, H-3), 4.89 (d, 1H, J = 3.0 (t, 0.5H, J =9.3Hz, H-8b), 1.40-1.20 (m, 14H, H-dectyl ether), 0.85 (t, 3H, J = 6.3 Hz, CH 3 ) 1 HNMR (300 MHz, CDCl 3 ) : Hz, H-1), 4.28 (dd, 1H, J = 4.6 and 12.3 Hz, H-6a), 4.22 (d, 1H, J = 15.9 Hz, H-7a), 4.09-3.96
	13 CNMR (75 MHz, CDCl 3 ) : : 99.9 (C1), 99.8 (C1'), 76.4 (C8), 76.2 (C8'), 74.1 (C3), 74.0 (C3'), 71.9 (C2), 70.9 (C5), 70.8 (C5'), 70.6 (C9), 70.1 (C9'+C6+C6'+C4), 69.5 (C4'), 55.3 (OCH 3 ), 33.2, 32.0, 29.8, 29.7, 29.4, 25.8, 25.7, 22.7, 14.2 HO 8 : 4.75 (s, 1H, H-1), 3.85-3.63 (m, 2.5H, H-6, H-9), 3.63-3.55 (m, 2H, H-3, H-5), 3.55-3.47 (m, 1.5H, H-8a, H-4), 3.47-3.32 (m, 2.5H, H-2, H-8a', H-8b', H9' ), 3.40 (s, 3H, OCH 3 ), 3.26 (t, 0.5H, J = 9.3 Hz, H-8b), 1.41-1.20 (m, 26H, H-hexadecyl ether), 0.87 (t, 3H, J = 6.9 Hz, CH 3 ) (m, 6H, H-6b, H-7b, H-5, CH 2 -12, H-9a), 3.80-3.77 (m, 3H, H-9b, H-2, OH), 3.10 (m, 1H, H-3"), 2.34 (m, 1H, H-4"a), 2.19 (m, 1H, H-4"b), 2.08, 2.06, 2.02 (3s, 9 H, 3 x CH 3 -Ac), 2.01-0.84 (m, 38 H, H-Cholesterol), 0.66 (s, 1H, CH 3 -18") Methyl 6-O O HO HO 1 9 CNMR (75 MHz, CDCl 3 ) : 13 13 CNMR (125 MHz, CDCl 3 ) :
	1 HNMR (400 MHz, CDCl 3 ) : m/z (HRMS) : : 171.4, 170.7, 169.7, 168.7 (3xC=O in Ac, C8), 140.7 (C5"), 128.8, 129.9 (C10, C11), 122.0 OMe HO 7 : 100.0 (C1), 99.9 (C1'), 76.5 (C8), 76.3 (C8'), 74.2 (C3), 74.1 (C3'), 72.1 (C2+C2'), 70.9 (C6"), 99.2 (C1), 79.1 (C3"), 73.4 (C3), 70.3 (C2), 68.2 (C5), 68.0 (C4), 67.9 (C12), 67.4 (C7), : 4.76 (d, 1H, J = 2.4 Hz, H-1), 3.80-3.63 (m, 2.5H, H-6, H-9,), 3.63-3.55 (m, 2H, H-3,H-5), calcd for C 17 H 34 O 7 Na: 373.2197; found: 373.2199 (C5+C5'), 70.7 (C9), 70.3 (C9'+C6), 70.2 (C6'), 69.7 (C4+C4'), 55.4 (OCH 3 ), 33.3, 32.1, 29.9, 61.9 (C6), 56.8 (C14"), 56.2 (C17"), 50.2 (C19"), 42.4 (C13"), 40.3 (C9), 39.8 (C16"), 39.6 3.55-3.47 (m, 1.5H, H-8a, H-4), 3.47-3.32 (m, 2.5H, H-2, H-8a', H-8b', H9' ), 3.40 (s, 3H, White solid 29.8, 29.5, 25.8, 25.7, 22.8, 14.3 (C24"), 39.1 (C4"), 37.2 (C1"), 36.9 (C10"), 36.3 (C22"), 35.9 (C20"), 32.1 (C7"), 32.0 (C8"), OCH 3 ), 3.27 (t, 0.5H, J = 9.3Hz, H-8b), 1.41 -1.22 (m, 10H, H-octyl ether), 0.87 (t, 3H, J = 7.2 m/z (HRMS) : 28.5 (C2"), 28.3 (C12"), 28.1 (C25"), 24.4 (C15"), 23.9 (C23"), 22.9 (C26"), 22.6 (C27"), 21.2 Hz, CH 3 ) Methyl 6-O-(2-hydroxydodecyl)--D-glucopyranoside (105c) 1 HNMR (300 MHz, CDCl 3 ) : (C11"), 21.0, 20.8, 20.7 (3CH 3 CO), 19.4 (C19"), 18.8 (C21"), 11.9 (C18")
	calcd for C 23 H 46 O 7 Na: 457.3136; found: 457.3121

Cholest-5-en-3-yl 10-azidodecyl ether (114c)

	: 170.6, 170.5, 169.5, 169.2 (3xC=O in Ac, C8), 140.3 (C5"), 121.8 (C6"), 99.4 (C1), 79.2 18" 1 HNMR (300 MHz, CDCl 3 ) : : 5.27 (m, 1H, H-6"), 3.37 (t, 2H, J = 6.8 Hz, H-10), 3.27 (t, 2H, J = 7.0 Hz, H-1), 3.05 (m, 1H,
	(C3"), 72.7 (C3), 69.3 (C2), 68.1 (C5), 67.9 (C4), 67.4 (C12, C7), 61.6 (C6), 56.6 (C14"), 56.0 (C17"), 50.0 (C9"), 42.2 (C13"), 39.6 (C9), 39.4 (C16"), 38.8 (C24"), 38.5 (C4"), 37.1 (C1"), 36.7 (C10"), 36.1 (C22"), 35.7 (C20"), 31.8 (C7"), 31.7 (C8"), 28.3 (C2"), 28.1 (C12"), 27.9 (C25"), 27.1 (C11), 25.7 (C10), 24.1 (C15"), 23.7 (C23"), 22.7 (C26"), 22.5 (C27"), 20.9 O 1 1" 3" 19" 26"(27") H-3"), 2.34-2.06 (m, 2H, H-4"), 2.42-0.75 (m, 55H, H-Cholesterol, CH 2 -2 to CH 2 -9), 0.61 (s, : 5.34 (m, 1H, H-6"), 3.45 (t, 2H, J = 6.8 Hz, H-8), 3.25 (t, 2H, J = 6.9 Hz, H-1), 3.12 (m, 1H, 3H, CH 3 -18") H-3"), 2.35-2.05 (m, 2H, H-4"), 2.00-0.75 (m, 51H, H-Cholesterol, CH 2 -2 to CH 2 -7), 0.61 (s, N 3 6 6" 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 ) :
	(C11"), 20.7, 20.6, 20.5 (3CH 3 CO), 19.3 (C18"), 18.6 (C21"), 11.7 (C19") 13 CNMR (75 MHz, CDCl 3 ) : : 141.3 (C5"), 121.5 (C6"), 79.1 (C3"), 68.2 (C10), 56.9 (C14"), 56.3 (C17"), 51.6 (C1), 50.4
	m/z : 826.0 (M + Na + ) [α] D 20 80%, White solid 1 HNMR (300 MHz, CDCl 3 ) : : 5.30 (m,1H, H-6"), 3.45 (t, 2H, J = 6.7 Hz, H-6), 3.26 (t, 2H, J = 6.9 Hz, H-1), 3.14 (m, 1H, (C9"), 42.5 (C13"), 40.0 (C16"), 39.7 (C24"), 39.4 (C4"), 37.4 (C1"), 37.1 (C10"), 36.3 (C22"), : 141.3 (C5"), 121.6 (C6"), 79.2 (C3"), 68.2 (C8), 56.9 (C14"), 56.3 (C17"), 51.6 (C1), 50.4 35.9 (C20"), 32.1 (C7"), 32.0 (C8"), 30.3, 29.6, 29.6, 29.5, 29.3, 29.0 (C-decyl), 28.6 (C12"), (C9"), 42.5 (C13"), 40.0 (C16"), 39.7 (C24"), 39.4 (C4"), 37.4 (C1"), 37.1 (C10"), 36.3 (C22"), 28.1 (C 12+25"), 26.7, 26.3 (C-decyl), 24.4 (C15"), 24.0 (C23"), 23.0 (C26"), 22.7 (C26"), 35.9 (C20"), 32.1 (C7"), 32.1 (C8"), 30.3, 29.5, 29.2, 29.0 (C-octyl), 28.6 (C2"), 28.4 (C12"), 28.2 (C25"), 26.7 , 26.3 (C-octyl), 24.4 (C15"), 24.0 (C23"), 22.7 (C26"+27"), 21.2 (C11"), 21.2 (C11"), 19.5 (C19"), 18.9 (C21"), 12.0 (C18")
	3H, CH 3 -18"); +55 (c 0.5 in CH 3 Cl) H-3"), 2.38-2.10 (m, 2H, H-4"), 2.00-0.80 (m, 47H, H-Cholesterol, CH 2 -2 to CH 2 -5), 0.64 (s, 19.5 (C19"), 18.9 (C21"), 12.0 (C18") m/z (HRMS) :
	13 CNMR (75 MHz, CDCl 3 ) : Elemental analysis: m/z (HRMS) : 590.5018 (M + Na + , C 37 H 65 ON 3 Na requires 590.5020)
	: 141.3 (C5"), 121.6 (C6"), 79.2 (C3"), 68.0 (C6), 56.9 (C14"), 56.3 (C17"), 51.6 (C1), 50.4 Found: C, 67.21; H, 9.20; N, 2.01. C 45 H 73 O 11 N requires C, 67.22; H, 9.15; N, 1.74 562.4704 (M + Na + , C 35 H 61 ON 3 Na requires 562.4707) [] D 20
	(C9"), 42.5 (C13"), 40.0 (C16"), 39.7 (C24"), 39.4 (C4"), 37.4 (C1"), 37.1(C10"), 36.3 (C22"), [α] D 20 -25 (c 1.2 in CH 2 Cl 2 )
	35.9 (C20"), 32.1 (C7"), 32.0 (C8"), 30.2, 29.0 (C-hexyl), 28.6 (C2"), 28.4 (C12"), 28.2 (25"), -24 (c 0.6 in CH 2 Cl 2 ) FTIR :
	D. 2. 2 Synthese of C6, C8, C10, C12 linker 26.7, 26.0 (C-hexyl), 24.4 (C15"), 24.0 (C23"), 23.0 (C26"), 22.7 (C27"), 21.2 (C11"), 19.5
	(C19"), 18.9 (C21"), 12.0 (C18") FTIR : 2095 cm -1 (N 3 )	18"
	O D.2.2.1 Synthesis for cholest-5-en-3-yl -azidoalkyl ether AcO OAc 6 1" 19" m/z (HRMS): 2095 cm -1 (N 3 )
	O To a solution of cholest-5-en-3-yl -hydroxyalkyl ether and Et 3 N (1.2 eq.) in CH 2 Cl 2 (20 mL) HN O O AcO HO 1 7 26" (27") 9 12 3" 6" 534.4398 (M + Na + , C 33 H 57 ON 3 Na requires 534.4394). Cholest-5
	0°C, MsCl (1.2 eq.) was added. The mixture was maintained at 0°C for 10 min and was then stirred at RT for 15h. Water (20 mL) was added and the mixture was extracted with CH 2 Cl 2 [α] D 20
	-23 (c 0.9 in CH 2 Cl 2 ) (3x15 mL). The organic layers were combined, washed with H 2 O (2x20 mL) and dried over 18" 19" White solid Na 2 SO 4 . After evaporation, the obtained crude residue was dissolved in DMF (20 mL) and 26"(27") 1"
	1 NaN 3 (1.3 eq.) was added and the solution was stirred at 60°C for 15h. Water (10 mL) was 1 HNMR (300 MHz, CDCl 3 ) : added and the mixture was extracted with CH 2 Cl 2 (3x10 mL). The organic layers were Cholest-5-en-3-yl 8-azidooctyl ether (114b) O N 3 10 3" 6"
	: 7.66 (t,1H, J = 5.4 Hz, N-H), 5.29-5.23 (m, 2H, H-6", H-3), 4.95 (t, 1H, J = 9.6 Hz, H-4), combined, washed with H 2 O (2x20mL) and dried over Na 2 SO 4 . After evaporation, the
	4.83 (d, 1H, J = 3.5 Hz, H-1), 4.28-3.99 (m, 5H, H-5, H-6a, H-6b, H-7a, H-7b), 3.76 (dd, 1H, J obtained crude residue was chromatographied on silica gel using a pentane/CH 2 Cl 2 (3/2) 18"
	19" = 3.5 and 9.8 Hz, H-2), 3.51-3.38 (m, 3H, H-9a, CH 2 -12), 3.14-3.06 (m, 2H, H-9b, H-3"), 2.31 (m, 1H, H-4"a), 2.10 (m, 1H, H-4"b), 2.03, 1.99, 1.98 (3s, 9H, 3 x CH 3 -Ac), 1.89-0.80 (m, 43H, 26"(27") 1" mixture and gave corresponding cholest-5-en-3-yl -azidoalkyl ether White solid
	1
	H-Cholesterol, CH 2 -10, CH 2 -11), 0.63 (s, 1H, CH 3 -18") O N 3 3" 6" 1 HNMR (300 MHz, CDCl 3 ) :
	8
	13 CNMR (75 MHz, CDCl 3 ) : Cholest-5-en-3-yl 6-azidohexyl ether (114a)
	White solid

-en-3-yl 12-azidododecyl ether (114d) O N 3 1 12 26"(27") 18" 19"

	13 CNMR (75 MHz, CDCl 3 ) :
	 141.3 (C5"), 121.5 (C6"), 79.0 (C3"), 68.2 (C12), 56.9 (C14"), 56.3 (C17"), 51.6 (C1), 50.3
	(C9"), 42.4 (C13"), 39.9 (C16"), 39.6 (C24"), 39.3 (C4"), 37.4 (C1"), 37.0 (C10"), 36.3 (C22"),
	35.9 (C20"), 32.1 (C7"), 32.0 (C8"), 30.3, 29.7, 29.6, 29.6, 29.6, 29.6, 29.2, 28.9 (C-dodecyl),
	28.6 (C2"), 28.3 (C12"), 28.1 (25"), 26.8, 26.3 (C-dodecyl), 24.4 (C15"), 23.9 (C23"), 22.9
	(C26"), 22.7 (C27"), 21.2 (C11"), 19.5 (C19"), 18.8 (C21"), 12.0 (C18")
	m/z (ESI)
	596.4 (M+H + )
	[] D 20
	-27 (c 0.5 in CH 2 Cl 2 )
	FTIR :
	2094 cm -1 (N 3 )
	1"
	3"	6"
	White solid
	1 HNMR (300 MHz, CDCl 3 ) :
	: 5.27 (m, 1H, H-6"), 3.37 (t, 2H, J = 6.8 Hz, H-12), 3.18 (t, 2H, J = 7.0 Hz, H-1), 3.05 (m,
	1H, H-3"), 2.33-2.05 (m, 2H, H-4"), 1.99-0.76 (m, 59H, H-Cholesterol, CH 2 -2 to CH 2 -11), 0.61
	(s, 3H, CH 3 -18")

-en-3-yl 8-aminooctyl ether (115b) O H 2 N 1 8 26"(27") 18" 19" 1" 3" 6"

	1 HNMR (300 MHz, CDCl 3 ) : : 141.3 (C5"), 121.5 (C6"), 79.1 (C3"), 68.3 (C8), 56.9 (C14"), 56.3 (C17"), 50.4 (C9"), 42.5 1 HNMR (300 MHz, CDCl 3 ) : : 7.44 (t, 1H, NH), 5.27 (m, 1H, H-6"), 5.21 (t, 1H, J = 9.8 Hz, H-3), 4.95 (t, 1H, J = 9.9 Hz,
	: 5.34-5.33 (m, 1H, H-6"), 3.45 (t, 2H, J = 6.6 Hz, H-6), 3.11 (m, 1H, H-3"), 2.71 (t, 2H, J = 6.9 Hz, H-1), 2.45-2.00 (m, 4H, H-4", NH 2 ), 2.00-0.80 (m, 47H, H-Cholesterol, CH 2 -2 to CH 2 -5), 0.64 (s, 3H, CH 3 -18"); (C13"), 39.9 (C1+C16"), 39.7 (C24"), 39.4 (C4"), 37.4 (C1"), 37.0 (C10"), 36.3 (C22"), 35.9 H-4), 4.83 (d, 1H, J = 3.7 Hz, H-1),4.26-3.92 (m, 5H, H-5, H-6a, H-6b, H-7a, H-7b), 3.75 (dd, : 8.23 (s, 2H, NH 2 ), 5.35-5.30 (m, 1H, H-6"), 3.44 (t, 2H, J = 6.8 Hz, H-1), 3.11 (m, 1H, H-3"), (C20"), 32.1(C7"), 32.0 (C8"), 30.3, 29.6, 29.5 (C-octyl), 28.6 (C2"), 28.4 (C12"), 28.1(C25"), 1H, J = 3.8 and 9.5 Hz, H-1),3.38 (t, 2H, J = 6.6 Hz, H-16), 3.20 (m, 2H, H-9), 3.06 (m, 1H, 2.74 (s, 2H, H-12), 2.40-2.10 (m, 2H, H-4"), 2.10-0.75 (m, 59H, H-Cholesterol, CH 2 -2 to CH 2 -26.9, 26.3 (C-octyl), 24.4 (C15"), 24.0 (C23"), 23.0 (C26"), 22.7 (C27"), 21.2 (C11"), 19.3 (C19"), 18.9 (C21"), 12.0 (C18") 11), 0.67 (s, 3H, CH 3 -18") H-3"), 2.45-0.70 (m, 62H, H-Cholesterol, 3xAc, CH 2 -10 to CH 2 -15), 0.61 (s, 3H, CH 3 -18")
	13 CNMR (75 MHz, CDCl 3 ) : m/z (ESI): 13 CNMR (75 MHz, CDCl 3 ) : 13 CNMR (75 MHz, CDCl 3 ) :
	: 141.3 (C5"), 121.6 (C6"), 79.1 (C3"), 68.1 (C6), 56.9 (C14"), 56.3 (C17"), 50.4 (C9"), 42.5 (C13"), 39.9 (C1), 39.9 (C16"), 39.7 (C24"), 39.4 (C4"), 37.4 (C1"), 37.0 (C10"), 36.3 (C22"), : 170.7, 169.7, 168.8 (3xC=O in Ac, C8), 141.1 (C5"), 121.6 (C6"), 99.2 (C1), 79.1 (C3"), : 141.6 (C5"), 121.7 (C6"), 79.3 (C3"), 68.5 (C12), 57.2 (C14"), 56.6 (C17"), 50.6 (C9"), 42.7 514.3 (M+H + ) (C13"), 42.0 (C1), 40.1 (C16"), 39.9 (C24"), 39.6 (C4"), 37.7 (C1"), 37.3 (C10"), 36.6 (C22"), 73.6 (C3), 70.4 (C2), 68.2 (C5), 67.9 (C4), 67.4 (C14, C7), 61.9 (C6), 56.8 (C14"), 56.2(C17"),
	35.9 (C20"), 32.1 (C7"), 32.0 (C8"), 30.3, 29.6 (C-hexyl), 28.6 (C2"), 28.4 (C12"), 28.2 (C25"), 36.2 (C20"), 32.5 (C7"), 32.3, 32.3, 30.6, 30.0, 29.8, 28.9, 28.9 (C-dodecyl), 28.6 (C2"), 28.6 50.3 (C9"), 42.4 (C13"), 39.9 (C9), 39.6 (C16"), 39.2 (C24"), 39.2 (C4"), 37.3 (C1"), 37.0
	26.8, 26.2 (C-hexyl), 24.4 (C15"), 24.0 (C23"), 23.0 (C26"), 22.7 (C27"), 21.2 (C11"), 19.5 (C19"), 18.9 (C21"), 12.0 (C18") (C10"), 36.3 (C22"), 35.9 (C20"), 32.0 (C7"), 32.0 (C8"), 30.1, 29.4 (C-hexyl), 28.5 (C2"), 28.3 (C12"), 28.4 (C25"), 27.2, 26.6 (C-dodecyl), 24.7 (C15"), 24.2 (C23"), 23.2 (C26"), 23.0 Cholest-5-en-3-yl-10-aminodecyl ether (115c) (C27"), 21.4 (C11"), 19.5 (C19"), 18.9 (C21"), 12.0 (C18") (C12"), 28.1 (C25"), 26.8, 26.1 (C-hexyl), 24.4 (C15"), 23.9 (C23"), 22.9 (C26"), 22.6 (C27"),
	18" 21.1 (C11"), 21.0, 20.8, 20.7 (3CH 3 CO), 19.5 (C19"), 18.8 (C21"), 11.9 (C18")
	m/z (ESI) : 486.3 (M+H + ) 584.4 (M+Na + ), 570.4 (M+H + ) m/z (ESI): m/z (HRMS):	1"	19"	26"(2 7")
	[α] D 20 832.5540 (M + H + , C 47 H 78 NO 11 requires 832.5569) O H 2 N 10 1 3"	6"
	-29 (c 0.8 in CH 2 Cl 2 ) D.2.2.3 Ring opening of CMGL by cholest-5-en-3-yl -aminoalkyl
	Yellow soft matter ether
	-yl 6-aminohexyl ether (115a) H 2 N 6 3" 6" H-1), 2.40-2.00 (m, 4H, H-4", NH 2 ), 2.00-0.75 (m, 51H, H-Cholesterol, CH 2 -2 to CH 2 -7), 0.61 O 12 1 1" 18" 19" 26"(27") 1 HNMR (300 MHz, CDCl 3 ) : : 8.30-7.62 (s, 2H, NH 2 ), 5.34-5.32 (m, 1H, H-6"), 3.43 (t, 2H, J = 6.8 Hz, H-10), 3.11 (m, 1H, H-3"), 3.02 (t, 2H, J = 7.7 Hz, H-1), 2.40-2.08 (m, 2H, H-4"), 2.08-0.75 (m, 55H, H-H-Cholesterol, CH 2 -2 to CH 2 -9), 0.67 (s, 3H, CH 3 -18") Cholest-5-en-3-yl-12-aminododecyl ether (115d) 18" To the cholest-5-en-3-yl -aminoalkyl ether dissolved in anhydrous CH 2 Cl 2 (c 2 M), the CMGl solid (1.3 eq.) was then added. After overnight of reaction (16h), the residue was purified by CCM using eluent of DCM/acetone (4/1) to obtain the pure compound. Acetyl-Glu-L6-cholesterol (116) OAc 18" 19" Cholest-5Yellow soft matter 1 HNMR (300 MHz, CDCl 3 ) : : 5.34-5.33 (m, 1H, H-6"), 3.45 (t, 2H, J = 6.8 Hz, H-8), 3.12 (m, 1H, H-3"), 2.80-2.60 (m, 2H, H 2 N 6" 3" O 7 14 1 26"(27") 6 1" O AcO 19" 1" O HN 6" 3" O O AcO HO 9 1 26"(27")
	(s, 3H, CH 3 -18")
	White solid
	Yellow soft matter 13 CNMR (75 MHz, CDCl 3 ) : Yellow soft matter 1 HNMR (300 MHz, CDCl 3 ) :
		196

  The obtained residue was dissolved in a MeOH/Et 3 N/H 2 O (8/1/1, 10 mL) mixture and was further stirred at 40°C for 3 hours. The reaction was then coevaporated three times with water and the obtained white residue was subjected to silica gel chromatography using a CH 2 Cl 2 /MeOH/Acetone/H 2 O (78/5/15/2) to Found: C 70.86; H 10.73; N 2.66. C 60 H 108 N 2 O 9 +H 2 O requires C 70.72; H, 10.80; N, 2.75 Found: C 68.27, H 10.47, N 3.03. C 50 H 88 N 2 O 9 +H 2 O requires C 68.30, H 10.32, N 3.19

	: 169.7 (C8), 156.3 (C13), 140.1 (C5"), 121.4 (C6"), 96.9 (C1), 79.0 (C3"), 73.1 (C2), 72.4 : 176.4 (C8), 169.8 (C13), 140.5 (C5"), 121.4 (C6"), 97.3 (C1), 79.3 (C3"), 73.4 (C2), 72.5 : 169.8 (C8), 156.3 (C13), 140.4 (C5"), 121.7 (C6"), 97.2 (C1), 79.2 (C3"), 73.3 (C2), 72.3 36.8 (C10''); 36.2 (C22"), 35.7 (C20''), 31.9 (C7''), 31.8 (C8''), 29.7, 29.7, 29.7, 29.7, 29.6, (C9"), 42.4 (C13"), 41.2 (C9), 39.8 (C16"), 39.6 (C24"), 39.1 (C4"), 38.8, 37.3 (C1"), 36.9 28.3 (C12"), 28.1 (C25"), 27.4, 27.0, 26.4, 24.4 (C15"), 23.9 (C23"), 22.9 (C26"), 22.8, 22.6 28.3 (C12"), 28.0 (C25"), 27.3, 27.3, 26.3, 24.3 (C15"), 23.9 (C23"), 22.8 (C26"), 22.7, 22.5 833.6 (M+H + ), 885.6 (M+Na + ) 861.7 (M+H + ), 883.7 (M+Na + ) 917.7 (M+H + ), 939.6 (M+Na + ) m/z (ESI) : 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.7, 25.8, 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), 29.5, 29.3, 29.3, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.7, 25.8, 24.2 (C15"), 23.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 29.9, 29.7, 29.7, 29.6, 29.6, 29.3, (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 31.7, 30.0, 29.7, 29.5, 29.4, 29.2, (C9"), 42.3 (C13"), 41.0 (C9), 39.7 (C16"), 39.4 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"), 36.8
	give the corresponding desired urethanes Or: (C5), 70.8 (C3), 69.8 (C4), 67.1 (C12), 66.1 (C7), 60.8 (C6), 56.4 (C14"), 55.8 (C17"), 49.8 (C9"), 41.9 (C13"), 40.2 (C14"), 39.4 (C24"), 39.1 (C16"), 38.6 (C9), 38.4 (C4"), 36.8 (C1"), 36.4 (C10"), 35.7 (C22"), 35.4 (C20"), 31.5 (C7"), 31.4 (C8"), 31.3, 27.9, 27.7, 27.5, 26.8, 25.8, 23.8 (C23"), 23.3 (C26"), 22.0, 21.8 (C27"), 20.6 (C11"), 19.4 (C19"), 18.7 (C21"), 18.0 (C16), 12.9 (C17), 11.2 (C18") m/z (HRMS) : (C5), 71.2 (C3), 70.1 (C4), 67.5 (C12), 66.5 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.2 (C9"), 42.3 (C13"), 41.0 (C14), 39.7 (C24"), 39.5 (C16"), 39.0 (C9), 38.8 (C4"), 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 29.7 , 29.7, 29.6, 29.3, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 27.2, 26.8, 26.2 , 24.2 (C15"), 23.8 (C23"), 22.6 (C26"), 22.6 , 22.4 (C27"), 21.0 (C11"), 19.1 (C19"), 18.0 (C21"), 13.4 (C21), 11.2 (C18) m/z (ESI) : (C5), 71.1 (C3), 70.5 (C4), 67.4 (C12), 66.4 (C7), 61.1 (C6), 56.6 (C14"), 56.0 (C17"), 50.1 (C9"), 42.2 (C13"), 40.9 (C9), 39.6 (C16"), 39.3 (C24"), 38.9 (C4"), 38.8, 38.7, 37.0 (C1"), 36.7 (C10"), 36.0 (C22"), 35.6 (C20"), 31.7 (C7"), 29.6 (C8"), 29.5, 29.4, 29.2, 29.2, 28.2 (C2"), 28.0 (C12"), 27.8 (C25"), 27.1, 26.7, 26.1, 24.1 (C15"), 23.6 (C23"), 22.5 (C26"), 22.2 (C27"), 20.9 (C11"), 19.1 (C19"), 18.4 (C21"), 13.8 (C23), 11.6 (C18") m/z (HRMS) : 29.6, 29.3, 29.3, 28.3 (C2''), 28.2 (C12"), 27.9 (C25"), 27.2 (C11), 26.8 (C23), 26.2 (C10), 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), 22.6 (C24), 22.4 (C27"), 21.0 (C11"), 19.2 (C19"), 18.6 (C21"), 13.9 (C25), 11.7 (C18") m/z (ESI) : 912.7 (M + Na + ) (C10"), 36.2 (C22"), 35.8 (C20"), 32.0 (C7"), 31.9 (C8"), 29.8-29.2, 28.4 (C2"), 28.3 (C12"), 28.0 (C25"), 27.3, 26.9, 26.3, 24.3 (C15"), 23.9 (C23"), 22.8 (C26"), 22.7, 22.5 (C27"), 21.1 (C11"), 19.4 (C19"), 18.7 (C21"), 14.1 (C27), 11.9 (C18") m/z (HRMS) : 939.7013 (M + Na + , C 54 H 96 N 2 O 9 requires 939.7014) (C27"), 21.2 (11"), 19.4 (C19"), 18.8 (C21"), 14.2 (C29), 11.9 (C18") m/z (HRMS) : 967.7329 (M + Na + , C 56 H 100 O 9 N 2 requires 967.7327) [] D 20 (C27"), 21.1 (C11"), 19.4 (C19"), 18.7 (C21"), 14.1 (C31), 11.9 (C18") m/z (HRMS) : 995.7641 (M + Na + , C 56 H 100 O 9 N 2 requires 995.7640) [] D 20 [] D 20 +36 (c 0.7 in CH 2 Cl 2 /MeOH (9/1)) Elemental analysis: Found: C 68.60, H 10.45, N 3.25. C 48 H 84 N 2 O 9 +H 2 O requires C 68.45, H 10.17, N 3.33 [] D 20 +33 (c 0.7 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: Found: C 69.01, H 10.31, N 3.22. C 50 H 88 N 2 O 9 +0.5H 2 O requires C 69.12, H 10.56, N 3.07 [] D 20 +34 (c 0.7 in CH 2 Cl 2 /MeOH, 9/1)) Elemental analysis: Found: C 70.49, H 10.76, N 2.96. C 54 H 96 N 2 O 9 requires C 70.70, H 10.55, N 3.05 22.6, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C31), 11.8 (C18") (C23"), 22.7 (C26"), 22.6, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C33), 11.8 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.7, 25.8, 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), 29.2, 28.4 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.8, 26.1, 24.2 (C15"), 23.8 (C23"), 22.7 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 31.4, 30.0, 29.6, 29.4, 29.4, 29.2, 946.5 (M+H + ), 968.5 (M+Na + ) [] D 20 +29 (c 0.9 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: (C18") 22.6, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C23), 11.8 (C18") (C26"), 22.6, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C25), 11.8 (C18") 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.4, 26.0, 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), m/z (ESI) : m/z (HRMS) : m/z (ESI) : 22.5, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 13.9 (C29), 11.8 (C18") m/z (ESI) : 973.8 (M+H + ), 995.8 (M+Na + ) 1001.8(M+H + ), 1023.8 (M + Na + ) 973.8 (M+H + ), 995.8 (M+Na + ) m/z (ESI) : 889.7 (M+H + ), 911.7 (M+Na + ) 20 [] D [] D 20 [] D 20 945.7 (M+H + ), 967.7 (M+Na + ) 20 [] D To a solution of starting material in THF (0.1 mol L -1 ), DBU (1.5 eq.) and alkyl isocyanate (1.5 eq.) were added. The mixture was stirred overnight at 45 o C under N 2 . Then the THF was removed under vacuum, the obtained solid was purified by SiO 2 gel column chromatography (DCM/Acetone, 95:5). The obtained compound was dissolved in a mixture of MeOH/NEt/H 2 O (8:1:1), stirring overnight. After evaporation, the residue was purified by SiO 2 gel column chromatography (DCM/MeOH, 95:5) Glucosteroid L4S4 bolaphile (124a) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 13 17 White solid 1 HNMR (400 MHz, CDCl 3 /MeOD) : : 7.17 (t, 1H, J = 5.6 Hz, NH), 6.57 (t, 1H, J = 5.3 Hz, NH), 5.26 (m, 1H, H-6"), 4.91 (d, 1H, J = 3.5 Hz, H-1), 4.45 (dd, 1H, J = 3.5 and 10.1 Hz, H-2), 4.07 (d, 1H, J = 15.4 Hz, H-7a), 3.90 (d, 1H, J = 15.4 Hz, H-7b), 3.80-3.71 (m, 2H, H-3, H-6a), 3.64 (dd, 1H, J = 5.5 and 12.3 Hz, H-6b), 3.50 (m, 1H, H-5), 3.46-3.40 (m, 2H, CH 2 -12), 3.37 (t, 1H, J = 9.6 Hz, H-4), 3.24-3.17 (m, 2H, CH 2 -9), 3.13-2.97 (m, 3H, H-3", CH 2 -14), 2.27 (ddd, 1H, J = 13.1 4.5 and 2.0 Hz,H-4"a), 2.09 (m, 1H, H-4"b), 1.99-0.70 (m, 49H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 to CH 2 -17), 0.61 (s, 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 /MeOD) : 799.5446 (M + Na + , C 44 H 76 N 2 O 9 requires 799.5449) [] D 20 +11 (c 0.4 in CHCl 3 /MeOH, 1/1) Glucosteroid L4S8 bolaphile (124b) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 13 21 White solid 1 HNMR (300 MHz, CDCl 3 /MeOD) : : 7.16 (t, 1H, J = 5.6 Hz, NH), 6.57 (t, 1H, J = 5.3 Hz, NH), 5.26 (m, 1H, H-6"), 4.91 (d, 1H, J = 3.6 Hz, H-1), 4.91 (dd, 1H, J = 3.6 and 10.1 Hz, H-2), 4.06 (d, 1H, J = 15.6 Hz, H-7a), 3.90 (d, 1H, J = 15.6 Hz, H-7b), 3.79-3.71 (m, 2H, H-3, H-6a), 3.64 (dd, 1H, J = 4.9 and 12.0 Hz, H-6b), 3.50 (ddd, 1H, J = 2.3, 4.9, and 12.0 Hz, H-5), 3.42-3.34 (m, 3H, CH 2 -12, H-4), 3.21-3.19 (m, 2H, CH 2 -9), 3.12-2.98 (m, 3H, H-3", CH 2 -12), 2.27 (m, 1H, H-4"a), 2.09 (m, 1H, H-4"b), 1.96-0.76 (m, 57 H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 to CH 2 -20, CH 3 -21), 0.60 (s, 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 /MeOD) : 856.7 (M + Na + ) [] D 20 +52 (c 0.5 in CHCl 3 /MeOH, 1/1) Elemental analysis: Found: C 68.45; H 10.17; N 3.33. C 45 H 73 O 11 N + 0.5 H 2 O requires C 68.72; H 10.15; N 3.23 Glucosteroid L4S10 bolaphile (124c) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 13 23 White solid 1 HNMR (400 MHz, CDCl 3 /MeOD) : : 7.03 (t, 1H, NH), 6.26 (t, 1H, NH), 5.25 (m, 1H, H-6"), 4.92 (d, 1H, J = 3.7 Hz, H-1), 4.46 (dd, 1H, J = 3.7 and 10.1 Hz, H-2), 4.06 (d, 1H, J = 15.5 Hz, H-7a), 3.89 (d, 1H, J = 15.6 Hz, H-7b), 3.80-3.70 (m, 2H, H-3, H-6a), 3.67 (m, 1H, H-6b), 3.50 (m, 1H, H-5), 3.46-3.36 (m, 3H, CH 2 -12, H-4), 3.24-3.17 (m, 2H, CH 2 -9), 3.13-2.97 (m, 3H, H-3", CH 2 -12), 2.27 (m, 1H, H-4"a), 2.10 (m, 1H, H-4"b), 2.00-0.73 (m, 61 H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 to CH 2 -20, CH 3 -21), 0.61 (s, 3H, CH 3 -18") 13 883.6390 (M + Na + , C 50 H 88 N 2 O 9 requires 883.6388) [] D 20 +25 (c 0.5 in CHCl 3 /MeOH, 1/1) Glucosteroid L4S12 bolaphile (124d) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 13 25 White solid 1 HNMR (300 MHz, CDCl 3 /MeOD) : : 5.28 (m, 1H, H6"), 4.91 (d, 1H, J = 3.6 Hz; H-1), 4.45 (dd, 1H, J = 10.1 Hz, H-2), 4,06 (d, 1H, J = 15.6 Hz, H-7a ), 3.88 (d; 1H, J = 15.6 Hz, H-7b), 3.76-3.68 (m, 3H, H-3, H-6a, H-6b), 3.52-3.37 (m, 4 H, H-5, H-4, CH 2 12), 3.20 (m, 2 H, CH 2 -9), 3.08-2.98(m, 3 H, H-3", CH 2 14), 2.26 (m, 1 H, H-4"a), 2.09 (m, 1 H, H4"b), 1.96-0.77 (m, 65 H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 à CH 2 -24, CH 3 -25), 0.60 (s; 3 H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 /MeOD) : [] D 20 +41 (c 0.4 in CHCl 3 /MeOH, 1/1) Elemental analysis: Found: C 69.57; H 10.44; N 3.12. C 52 H 92 O 9 N 2 +0.5 H 2 O requires C 69.66; H 10.44; N 3.16 Glucosteroid L4S14 bolaphile (124e) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 27 White solid 1 HNMR (300 MHz, CDCl 3 /MeOD) : : 7.03 (t, 1H, NH), 6.17 (t, 1H, NH), 5.35 (m, 1H, H-6"), 4.98 (d, 1H, J = 3.5 Hz, H-1), 4.54 (dd, 1H, J = 3.5 and 10.1 Hz, H-2), 4.14 (d, 1H, J = 15.6 Hz, H-7a), 3.96 (d, 1H, J = 15.6 Hz, H-7b), 3.87-3.77 (m, 3H, H-3, H-6a, H-6b), 3.60-3.47 (m, 4H, CH 2 -12, H-4, H-5), 3.28 (m, 2H, CH 2 -9), 3.21-3.04 (m, 3H, H-3", CH 2 -14), 2.34 (m, 1H, H-4"a), 2.17 (m, 1H, H-4"b), 2.03-0.80 (m, 69 H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 to CH 2 -26, CH 3 -27), 0.68 (s, 3 H, CH 3 -18") 13 CNMR (125 MHz, CDCl 3 /MeOD) : : 169.6 (C8), 156.4 (C13), 140.7 (C5"), 121.9 (C6"), 97.4 (C1), 79.4 (C3"), 73.5 (C2), 72.3 (C5), 71.4 (C3), 70.3 (C4), 67.6 (C12), 66.7 (C7), 61.4 (C6), 56.8 (C14"), 56.2 (C17"), 50.2 White solid 1 HNMR (500 MHz, CDCl 3 /MeOD) : : 5.35 (m, 1 H, H-6"), 4.92 (d, 1H, J = 3.0 Hz, H-1), 4.54 (dd, 1H, J = 3.0 and 9.9 Hz, H-2), 4.15 (d, 1H, J = 15.8 Hz, H-7a), 3.95 (d, 1H, J = 15.8 Hz, H-7b), 3.80-3.74 (m, 3H, H-3, H-6a, H-6b), 3.58-3.49 (m, 4H, CH 2 -12, H-4, H-5), 3.28 (m, 2H, CH 2 -9), 3.16-3.09 (m, 3H, H-3", CH 2 -14), 2.36 (m, 1H, H-4"a), 2.18 (m, 1H, H-4"b), 2.05-0.80 (m, 63H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 to CH 2 -28, CH 3 -29), 0.68 (s, 3H, CH 3 -18") 13 CNMR (75 MHz, CDCl 3 /MeOD) : : 169.9 (C8), 156.5 (C13), 140. 7 (C5"), 122.9 (C6"), 97.4 (C1), 79.5 (C3"), 73.5 (C2), 72.5 (C5), 71.4 (C3), 70.2 (C4), 67.7 (C12), 66.7 (C7), 61.3 (C6), 56.9 (C14"), 56.3 (C17"), 50.3 m/z (ESI) : m/z (ESI) : m/z (ESI) : (C9"), 42.2 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.0 (C4"), 39.0, 37.2 (C1"), 36.8 (C5), 71.2 (C3), 70.0 (C4), 68.1 (C16), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.1 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 29.9, 29.7, 29.7, 29.6, 29.6, 29.5, (C10"), 36.3 (C22"), 35.8 (C20"), 32.0 (C7"), 32.0 (C8"), 29.9-29.5 (12 x CH 2 ), 28.5 (C2"), 21.1 (C11"), 19.4 (C19"), 18.7 (C21"), 14.0 (C21), 11.9 (C18") (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C29), 11.7 (C18") (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 29.9, 29.7, 29.7, 29.6, 29.6, 29.3, (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.0 (C4"), 39.0, 37.2 (C1"), 36.8 (C5), 71.2 (C3), 70.0 (C4), 67.9 (C16), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.1 : 169.5 (C8), 156.3 (C17), 140.8 (C5"), 121.6 (C6"), 97.1 (C1), 79.1 (C3"), 73.4 (C2), 72.3 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C27), 11.8 (C18") (C9"), 42.4 (C13"), 41.2 (C9), 39.9 (C16"), 39.6 (C24"), 39.2 (C4"), 38.9, 37.3 (C1"), 36.9 White solid 1 HNMR (300 MHz, CDCl 3 /MeOD) : : 7.16 (t, 1H, NH), 6.46 (t, 1H, NH), 5.35 (m, 1H, H-6"), 5.01 (d, 1H, J = 3.6 Hz, H-1), 4.54 (dd, 1H, J = 3.6 and 10.1 Hz, H-2), 4.15 (d, 1H, J = 15.6 Hz, H-7a), 3.97 (d, 1H, J = 15.6 Hz, H-7b), 3.88-3.77 (m, 3H, H-3, H-6a, H-6b), 3.61-3.45 (m, 4H, CH 2 -12, H-4, H-5), 3.29 (m, 2H, CH 2 -9), 3.13 (m, 3H, H-3", CH 2 -14), 2.36 (m, 1H, H-4"a), 2.20 (m, 1H, H-4"b), 2.05-0.85 (m, 77 H, H-Cholesterol, CH 2 -10, CH 2 -11, CH 2 -15 to CH 2 -30, CH 3 -31), 0.68 (s, 3H, CH 3 -18") 13 CNMR (125 MHz, CDCl 3 /MeOD) : 1 HNMR (400 MHz, CDCl 3 /MeOD) : : 5.35 (m, 1H, H-6"), 5.01 (d, 1H, J = 3.7 Hz, H-1), 4.55 (dd, 1H, J = 3.6, 10.2 Hz, H-2), 4.14 (d, 1H, J = 15.6 Hz, H-7a), 4.00 (d, 1H, J = 15.6 Hz, H-7b), 3.90-3.75 (m, 3H, H-6a, H-6b, H-3), 3.61-3.52 (m, 4H, H-5, H-4, CH 2 -14 ), 3.25 (t, 2H, J = 7.3 Hz, CH 2 -9), 3.19-3.04 (m, 3H, CH 2 -16, H-3"), 2.40-2.10 (m, 2H, H-4"), 2.08-0.80 (m, 57 H, H-Cholesterol, CH 2 -10 to CH 2 -13, CH 2 -17 to CH 3 -21), 0.68 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 /MeOD) : : 169.5 (C8), 156.4 (C15), 140.9 (C5"), 121.7 (C6"), 97.3 (C1), 79.2 (C3"), 73.5 (C2), 72.3 (C5), 71.3 (C3), 70.3 (C4), 68.0(C14), 66.6 (C7), 61.4 (C6), 56.8 (C14"), 56.2 (C17"), 50.3 (C9"), 42.4 (C13"), 41.2 (C9), 39.8 (C16"), 39.6 (C24"), 39.1 (C4"), 39.1, 37.3 (C1"), 36.9 (C10"), 36.2 (C22"), 35.8 (20"), 32.0 (C7"), 31.9 (C8"), 31.5, 30.0, 29.7, 29.5, 28.5 (C2"), 28.3 (C12"), 28.1 (C25"), 26.8, 26.5, 25.9, 24.3 (C15"), 23.9 (C23"), 22.8 (C26"), 22.6, 22.6 (C27"), 1 4.14 (d, 1 H, J = 15.6 Hz, H-7a), 3.98 (d, 1H, J = 15.6 Hz, H-7b), 3.88-3.74 (m, 3H, H-6a, H-6b, H-3), 3.61-3.52 (m, 4H, H-5, H-4, CH 2 -14), 3.25 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.19-3.04 (m, 3 H, CH 2 -16, H-3"), 2.40-2.10 (m, 2 H, H-4"), 2.08-0.80 (m, 61 H, H-Cholesterol, CH 2 -10 to CH 2 -13, CH 2 -17 to CH 3 -23), 0.68 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 /MeOD) : : 169.5 (C8), 156.3 (C15), 140.8 (C5"), 121.6 (C6"), 97.2 (C1), 79.1 (C3"), 73.5 (C2), 72.3 (C5), 71.2 (C3), 70.1 (C4), 67.9 (C14), 66.5 (C7), 61.3 (C6), 56.7 (C14"), 56.1 (C17"), 50.2 (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.5 (C24"), 39.0 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 31.7 , 29.9, 29.7, 29.3, 29.2, 29.2, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.8, 26.7, 25.8, 24.2 (C15"), 23.8 (C23"), 22.7 (C26"), 22.6 (C), 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 14.0 (C23), 11.8 (C18") : 5.35 (m, 1 H, H-6"), 5.01 (d, 1H, J = 3.6 Hz, H-1), 4.55 (dd, 1 H, J = 3.6 and 10.0 Hz, H-2), H-6b, H-3), 3.61-3.44 (m, 4 H, H-5, H-4, CH 2 -14), 3.25 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.19-3.04 (m, 3 H, CH 2 -16, H-3"), 2.40-2.10 (m, 2 H, H-4"), 2.08-0.80 (m, 69 H, H-Cholesterol, CH 2 -10 13 CNMR (100 MHz, CDCl 3 /MeOD) : : 169.5 (C8), 156.3, 140.8 (C5"), 121.6 (C6"), 97.2 (C1), 79.1 (C3"), 73.5 (C2), 72.3 (C5), 71.2 (C3), 70.2 (C4), 67.9, 66.5 (C7), 61.3 (C6), 56.7 (C14"), 56.1 (C17"), 50.2 (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.5 (C24"), 39.0 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 29.9, 29.7, 29.7, 29.6, 29.6, 29.6, 29.4, 29.3, 28.4 28.2 (C12"), 27.9 (C25"), 26.8, 26.7, 25.8, 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), 22.6, 22.4 (C9"), 42.2 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.0 (C4"), 39.0, 37.2 (C1"), 36.8 (C5), 71.2 (C3), 70.1 (C4), 67.9 (C14), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.1 : 169.5 (C8), 156.3 (C17), 140.7 (C5"), 121.6 (C6"), 97.1 (C1), 79.1 (C3"), 73.4 (C2), 72.3 (C2"), 28.2 (C12"), 28.0 (C25"), 26.8, 26.7, 25.8, 24.2 (C15"), 23.8 (C23"), 22.7 (C26"), 22.6, CH 2 -13, CH 2 -17 to CH 3 -29), 0.54 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 /MeOD) :  : 169.5 (C8), 156.3, 140.7 (C5"), 121.6 (C6"), 97.2 (C1), 79.1 (C3"), 73.4 (C2), 72.3 (C5), 71.2 (C3), 70.1 (C4), 67.9, 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.1 (C9"), 42.3 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 29.9, 29.7, 29.6, 29.6, 29.6, 29.3, 28.3 (C2"), (C5), 71.2 (C3), 70.0 (C4), 67.9 (C14), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.1 : 169.5 (C8), 156.3 (C15), 140.7 (C5"), 121.6 (C6"), 97.2 (C1), 79.1 (C3"), 73.4 (C2), 72.3 13 13 CNMR (100 MHz, CDCl 3 / MeOD) : CNMR (75 MHz, CDCl 3 / MeOD) : 13 CNMR (100 MHz, CDCl 3 / MeOD) : (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.0 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 6b, H-3), 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -14), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.04-2.92 (m, 3 H, CH 2 -16, H-3"), 2.30-2.00 (m, 2 H, H-4"), 1.96-0.77 (m, 77 H, H-Cholesterol, CH 2 -10 to CH 2 -13, CH 2 -17 to CH 3 -31), 0.54 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 /MeOD) : : 169.5 (C8), 156.3 (C15), 140.7 (C5"), 121.6 (C6"), 97.1 (C1), 79.1 (C3"), 73.4 (C2), 72.3 3.98 (d, 1 H, J = 15.6 Hz, H-7a), 3.82 (d, 1 H, J = 15.6 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-6b, H-3), 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -14), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.05-2.90 (m, 3 H, CH 2 -16, H-3"), 2.30-2.00 (m, 2 H, H-4"), 1.96-0.77 (m, 81H, H-Cholesterol, CH 2 -10 to CH 2 -13, CH 2 -17 to CH 3 -33), 0.53 (s, 3 H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 / MeOD) : CH 2 -15, CH 2 -19 to CH 3 -27), 0.68 (s, 3 H, CH 3 -18") CH 2 -15, CH 2 -19 to CH 3 -23), 0.68 (s, 3 H, CH 3 -18") CH 2 -13, CH 2 -17 to CH 3 -31), 0.54 (s, 3 H, CH 3 -18") 3 H, CH 2 -18, H-3"), 2.39-2.13 (m, 2 H, H-4"), 2.08-0.80 (m, 73 H, H-Cholesterol, CH 2 -10 to 3 H, CH 2 -18, H-3"), 2.39-2.13 (m, 2 H, H-4"), 2.08-0.80 (m, 65 H, H-Cholesterol, CH 2 -10 to H, CH 2 -16, H-3"), 2.30-2.00 (m, 2 H, H-4"), 1.96-0.77 (m, 77 H, H-Cholesterol, CH 2 -10 to 6b, H-3), 3.61-3.52 (m, 4 H, H-5, H-4, CH 2 -16), 3.25 (t, 2 H, J = 7.4 Hz, CH 2 -9), 3.19-3.04 (m, 6b, H-3), 3.61-3.44 (m, 4 H, H-5, H-4, CH 2 -16), 3.25 (t, 2 H, J = 7.2 Hz, CH 2 -9), 3.19-3.04 (m, H-3), 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -14), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.04-2.92 (m, 3 4.13 (d, 1 H, J = 15.6 Hz, H-7a), 3.96 (d, 1 H, J = 15.6 Hz, H-7b), 3.87-3.74 (m, 3 H, H-6a, H-4.13 (d, 1 H, J = 15.6 Hz, H-7a), 3.91(d, 1 H, J = 15.6 Hz, H-7b), 3.88-3.73 (m, 3 H, H-6a, H-4.04 (d, 1 H, J = 15.6, H-7a), 3.88 (d, 1 H, J = 15.6 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-6b, : 5.35 (m, 1 H, H-6"), 5.01 (d, 1 H, J = 3.6 Hz, H-1), 4.55 (dd, 1 H, J = 3.6 and 10.1 Hz, H-2), : 5.35 (m, 1 H, H-6"), 5.01 (d, 1 H, J = 3.6 Hz, H-1), 4.53 (dd, 1 H, J = 3.4 and 10.0 Hz, H-2), : 5.21 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.5 Hz, H-1), 4.39 (dd, 1 H, J = 3.4 and 10.0 Hz, H-2), to CH 2 -13, CH 2 -17 to CH 3 -27), 0.68 (s, 3 H, CH 3 18") 4.00 (d, 1 H, J = 15.5 Hz, H-7a), 3.83 (d, 1 H, J = 15.6 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-3 H, CH 2 -16, H-3"), 2.30-2.00 (m, 2 H, H4"), 1.96-0.77(m, 73 H, H-Cholesterol, CH 2 -10 to 4.04 (d, 1 H, J = 15.6 Hz, H-7a), 3.88 (d, 1 H, J = 15.6 Hz, H-7b), 3.74-3.60 (m, 3 H, H-6a, H-: 5.23 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.5 Hz, H-1), 4.40 (dd, 1 H, J = 3.4 and 10.1 Hz, H-2), 1 1 HNMR (400 MHz, CDCl 3 / MeOD) : HNMR (400 MHz, CDCl 3 / MeOD) : 1 HNMR (400 MHz, CDCl 3 / MeOD) : 6b, H-3), 3.50-3.30 (m, 4 H, H-5, H-4, CH 2 -14 ), 3.11 (t, 2 H, J = 7.3 Hz, CH 2 -9), 3.08-2.92 (m, : 5.21 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.5 Hz, H-1), 4.39 (dd, 1 H,, J = 3.4 and 10.0 Hz, H-2), 1 HNMR (400 MHz, CDCl 3 / MeOD) : White solid White solid White solid 4.13 (d, 1 H, J = 15.6 Hz , H-7a), 3.98 (d, 1 H, J = 15.6 Hz, H-7b), 3.88-3.74 (m, 3 H, H-6a,  : 5.21 (m, 1 H, H-6"), 4.86 (d, 1 H, J = 3.5 Hz, H-1), 4.39 (dd, 1 H, J = 3.4 and 10.0 Hz, H-2), 1 HNMR (400 MHz, CDCl 3 / MeOD) : White solid : 5.35 (m, 1 H, H-6"), 5.01 (d, 1 H, J = 3.7 Hz, H-1), 4.55 (dd, 1H, J = 3.6 and 10.1 Hz, H-2), 1 HNMR (400 MHz, CDCl 3 / MeOD) : 1 White solid 29 HNMR (400 MHz, CDCl 3 / MeOD) : 25 23 HNMR (400 MHz, CDCl 3 /MeOD) : 31 13 [] D 20 +29 (c 0.4 in CHCl 3 /MeOH 5/1) Glucosteroid L4S16 bolaphile (124f) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 13 29 +38 (c 0.4 in CHCl 3 /MeOH, 5/1) Elemental analysis: Found: C 71.42; H 10.66; N 3.13. C 56 H 100 O 9 N 2 requires C 71.14; H 10.66; N 2.96 Glucosteroid L4S18 bolaphile (124g) O HN O O O HO HO OH O NH O 1 7 6 9 12 1" 3" 6" 18" 19" 26" (27") 13 +28 (c 1.0 in CHCl 3 /MeOH, 8/1) Glucosteroid L6S6 bolaphile (125a) O HN O O O HO HO OH O NH O 19" 18" 1" 3" 6" 26" (27") 1 7 6 9 14 15 21 White solid Glucosteroid L6S8 bolaphile (125b) O HN O O O HO HO OH O NH O 19" 18" 1" 3" 6" 26" (27") 1 7 6 9 14 15 23 White solid Glucosteroid L6S12 bolaphile (125c) O HN O O O HO HO OH O NH O 19" 18" 1" 3" 6" 26" (27") 1 7 6 9 14 15 27 White solid Glucosteroid L6S14 bolaphile (125d) O HN O O OH 18" +27 (c 1 in CHCl 3 /MeOH, 9/1) [] D 20 Found: C 70.41; H 10.59; N 2.91. C 56 H 100 N 2 O 9 +0.5H 2 O requires C 70.41; H 10.59; N 2.94 Glucosteroid L6S16 bolaphile (125e) +30 (c 0.5 in CH 2 Cl 2 /MeOH, 9/1) +34 (c 0.6 in CH 2 Cl 2 /MeOH, 9/1) +36 (c 0.7 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: Elemental analysis: Elemental analysis: +35 (c 0.7 in CH 2 Cl 2 /MeOH (9/1)) Elemental analysis: Found: C 69.05; H 10.51; N 2.65. C 58 H 104 N 2 O 9 +2H 2 O requires C 69.05; H 10.70; N 2.78 Elemental analysis: Found: C 68.93, H 10.46, N 3.06. C 52 H 92 N 2 O 9 +H 2 O requires C 68.84, H 10.44, N 3.09 19" 1" 6 O HO HO O NH 29 White solid O HN O O HO O NH 31 O HN O O HO HO O NH O 1 9 14 3" 6" 26"(27") 7 15 33 O HN O O O HO HO OH O NH O 19" 1" 3" 6" 26" (27") 1 7 6 9 16 17 O HN O O O HO O NH O 3" 6" 26" (27") 1 7 9 16 17 O HN O O HO NH 16 O 3" 6" 17 7 O 9 1 26" (27") HO OH 19" 1" 6 HO O 1" 6 19" OH O 6 1" 18" 18" 18" O 3" 14 OH 19" 6" 1 15 7 9 18" Glucosteroid L8S6 bolaphile (126a) Glucosteroid L8S8 bolaphile (126b) Glucosteroid L8S12 bolaphile (126c) O 3" 6" 1 7 9 14 15 O HO 1" 26" (27") 6 Glucosteroid L6S18 bolaphile (125f) 19" OH 26" (27") 18" Found: C 71.14, H 10.66, N 2.96. C 56 H 100 N 2 O 9 requires C 71.14, H 10.66, N 2.96

: 169.8 (C8), 156.5 (C13), 140.6 (C5"), 121.8 (C6"), 97.3 (C1), 79.4 (C3"), 73.4 (C2), 72.4 (C5), 71.2 (C3), 70.1 (C4), 67.5 (C12), 66.5 (C7), 61.2 (C6), 56.7 (C14''), 56.1 (C17''), 50.2 (C9''), 42.3 (C13''), 41.0 (C14), 39.7 (C24''), 39.5 (C16''), 39.0 (C9), 38.8 (C4''), 37.2 (C1''), : 169.6 (C8), 156.3 (C13), 140. 7 (C5"), 121.9 (C6"), 97.4 (C1), 79.4 (C3"), 73.4 (C2), 72.3 (C5), 71.4 (C3), 70.2 (C4), 67.6 (C12), 66.7 (C7), 61.4 (C6), 56.8 (C14"), 56.2 (C17"), 50.2

(C9"), 42.4 (C13"), 41.2 (C9), 39.8 (C16"), 39.5 (C24"), 39.1 (C4"), 38.8, 37.2 (C1"), 36.9 (C10"), 36.2 (C22"), 35.8 (C20"), 32.0 (C7"), 32.0 (C8"), 29.8-29.4 (14 x CH 2 ), 28.4 (C2"), : 169.4 (C8), 156.3 (C17), 140.9 (C5"), 121.6 (C6"), 97.2 (C1), 79.1 (C3"), 73.5 (C2), 72.3 (C5), 71.2 (C3), 70.1 (C4), 68.1 (C16), 66.4 (C7), 61.3 (C6), 56.7 (C14"), 56.1 (C17"), 50.2 (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.5 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"),

36.8

Glucosteroid L10S8 bolaphile (127b) O HN O O O HO HO OH O NH O 6 1 7 9 18 1" 3" 6" 26" (27") 18" 19" 19 27

  80 (m, 67H, H-Cholesterol, CH 2 -10 to CH 2 -17, CH 2 -21 to CH 3 -23), 0.69 (s, 3H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 / MeOD) :: 169.5 (C8), 156.3 (C19), 140.9 (C5"), 121.5 (C6"), 97.1 (C1), 79.0 (C3"), 73.4 (C2), 72.3 (C5), 71.2 (C3), 70.0 (C4), 68.1 (C18), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.2 (C19"), 42.3 (C13"),41.0 (C9), 39.7 (C16"), 39.4 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"),31.4, 30.0, 29.6, 29.5, 29.5, 29.5, 29.4, 29.3, 29.3, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.9, 26.4, 26.1, 24.2 (C15"), 23.7 Found: C 70.22, H 10.78, N 3.00. C 52 H 92 N 2 O 9 requires C 70.23, H 10.43, N 3.15 Hz, CH 2 -9), 3.19-3.04 (m, 3H, CH 2 -20, H-3"), 2.40-2.10 (m, 2H, H-4"), 2.08-0.80 (m, 71H, H-Cholesterol, CH 2 -10 to CH 2 -17, CH 2 -21 to CH 3 -25), 0.68 (s, 3H, CH 3 -18") C22"), 35.9 (C20"), 32.0 (C7"), 32.0 (C8"), 31.9, 30.1, 29.8, 29.6, 29.6, 29.6, 29.4, 29.3, 29.3, 28.5 (C2"), 28.3 (C12"), 28.1 (C25"), 27.0, 26.9, 26.2, 24.4 (C15"), 23.9 (C23"), 22.8 (C26"), 22.7, 22.6 (C27"), 21.1 (C11"), 19.4 (C19"), 18.8 (C21"), 14.1 (C27), 11.9 (C18") Found: C 69.48, H 10.65, N 2.95. C 54 H 96 N 2 O 9 +H 2 O requires C 69.34, H 10.56, N 2.99 , H-3), 3.61-3.52 (m, 4H, H-4, H-5, CH 2 -18 ), 3.25 (t, 2H, J = 7.4 Hz, CH 2 -9), 3.19-3.04 (m, 3H, CH 2 -20, H-3"), 2.40-2.10 (m, 2H, H-4"), 2.08-0.80 (m, 79H, H-Cholesterol, CH 2 -10 to CH 2 -17, CH 2 -21 to CH 3 -29), 0.68 (s, 3H, CH 3 -18") C22"), 35.9 (C20"), 32.0, 32.0, 30.2, 29.8, 29.7, 29.7, 29.7, 29.6, 29.6, 29.6, 29.4, 28.5 (C2"), 28.3 (C12"), 28.1 (C25"), 27.0, 26.9, 26.2, 24.4 (C15"), 23.9 (C23"), 22.8 (C26"), 22.7, 22.6 (C27"), 21.1 (C11"), 19.4 (C19"), 18.8 (C21"), 14.1 (C31), 11.9 (C18") Found: C 71.37, H 10.96, N 2.71. C 58 H 104 N 2 O 9 requires C 71.56, H 10.77, N 2.88 , H-3), 3.61-3.52 (m, 4H, H-5, H-4, CH 2 -20), 3.25 (t, 2H, J = 7.5 Hz, CH 2 -9), 3.19-3.08 (m, 3H, CH 2 -22, H-3"), 2.39-2.14 (m, 2H, H-4"), 2.08-0.80 (m, 71H, H-Cholesterol, CH 2 -10 to CH 2 -19, CH 2 -23 to CH 3 -27), 0.68 (s, 3H, CH 3 -18") C22"), 35.9 (C20"), 32.0 (C7"), 32.0 (C8"), 31.9, 31.5, 30.1, 29.8, 29.8, 29.7, 29.6, 29.6, 29.4, 29.3, 29.3, 28.5 (C2"), 28.3 (C12"), 28.1 (C25"), 27.0, 26.9, 26.5, 26.2, 24.4 (C15"), 23.9 (C23"), 22.8 (C26"), 22.7, 22.6, 22.6 (C27"), 21.1 (C11"), 19.4 (C19"), 18.8 Found: C 70.67, H 10.73, N 2.88. C 54 H 96 N 2 O 9 requires C 70.70, H 10.55, N 3.05 : 5.34 (m, 1H, H-6"), 5.00 (d, 1H, J = 3.6 Hz, H-1), 4.52 (dd, 1H, J = 3.6 and 10.1 Hz, H-2), 4.12 (d, 1H, J =15.6 Hz, H-7a), 3.96 (d, 1H, J = 15.6 Hz, H-7b), 3.87-3.73 (m, 3H, H-6a, H-6b, H-3), 3.59-3.50 (m, 4H, H-5, H-4, CH 2 -20), 3.23 (m, 2H, CH 2 -9), 3.17-3.06 (m, 3H, CH 2 -22, H-3"), 2.37-2.12 (m, 2H, H-4"), 2.06-0.78 (m, 75H, H-Cholesterol, CH 2 -10 to CH 2 -19, CH 2 -23 to CH 3 -29), 0.66 (s, 3H, CH 3 -18") C3), 70.1 (C4), 68.2 (C20), 66.4 (C7), 61.2 (C6), 56.7 (C14"), 56.1 (C17"), 50.2 (C9"), 42.3 (C13"), 41.1 (C9), 39.7 (C16"), 39.4 (C24"), 39.1 (C4"), 39.0, 37.2 (C1"), 36.8 (C10"), 36.1 (C22"), 35.7 (C20"), 31.9 (C7"), 31.8 (C8"), 31.7, 30.0, 29.7, 29.6, 29.6, 29.5, 29.5, 29.4, 29.3, 29.2, 29.2, 28.3 (C2"), 28.2 (C12"), 27.9 (C25"), 26.9, 26.8, 26.1, 24.2 (C15"), 23.7 (C23"), 22.7 (C26"), 22.5, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), Found: C 69.84, H 10.85, N 2.83. C 56 H 100 N 2 O 9 +H 2 O requires C 69.81, H 10.67, N 2.91 : 5.36 (m, 1H, H-6"), 5.02 (d, 1H, J = 3.6 Hz, H-1), 4.55 (dd, 1H, J = 3.5 Hz, 10.1, H-2), 4.13 (d, 1H, J = 15.6 Hz, H-7a), 3.98 (d, 1H, J = 15.6 Hz, H-7b), 3.88-3.74 (m, 3H, H-6a, H-6b, H-3), 3.61-3.52 (m, 4H, H-5, H-4, CH 2 -20), 3.25 (t, 2H, J = 7.5 Hz, CH 2 -9), 3.19-3.08 (m, 3H, CH 2 -22, H-3"), 2.39-2.14 (m, 2H, H-4"), 2.08-0.80 (m, 83H, H-Cholesterol, CH 2 -10 to CH 2 -19, CH 2 -23 to CH 3 -33), 0.68 (s, 3H, CH 3 -18") 13 CNMR (100 MHz, CDCl 3 / MeOD) : : 169.4 (C8), 156.2 (C21), 141.0 (C5"), 121.5 (C6"), 97.2 (C1), 79.1 (C3"), 73.5 (C2), 72.2 (C5), 71.3 (C3), 70.2 (C4), 68.2 (C20), 66.5 (C7), 61.3 (C6), 56.8 (C14"), 56.2 (C17"), 50.2 (C9"), 42.3 (C13"), 41.1 (C9), 39.8 (C16"), 39.5 (C24"), 39.1 (C4"+), 37.3 (C1"), 36.9 (C10"), 36.2 (C22"), 35.8 (C20"), 31.9 (C7"), 31.9 (C8"), 30.1, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1, 28.4 (C2"), 28.2 (C12"), 28.0 (C25"), 26.9, 26.8, 26.1, 24.3 (C15"), 23.8 (C23"), 22.7 (C26"), 22.6, 22.5 (C27"), 21.0 (C11"), 19.3 (C19"), 18.7 (C21"), 14.0 (C33), 11.8 (C18") Found: C 71.15, H 11.12, N 2.64. C 60 H 108 N 2 O 9 +0.5H 2 O requires C 71.31, H 10.87, N 2.77

	1 HNMR (400 MHz, CDCl 3 / MeOD) :
	13 CNMR (100 MHz, CDCl 3 / MeOD) :
	13 CNMR (100 MHz, CDCl 3 / MeOD) : 13 CNMR (100 MHz, CDCl 3 / MeOD) :
	: 169.6 (C8), 156.4 (C19), 141.0 (C5"), 121.6, 97.3 (C1), 79.2 (C3"), 73.6 (C2), 72.4 (C5),
	71.3 (C3), 70.3 (C4), 68.3 (C18), 66.6 (C7), 61.4 (C6), 56.9 (C14"), 56.2 (C17"), 50.3 (C9"), 42.4 (C13"), 41.2 (C9), 39.9 (C16"), 39.6 (C24"), 39.2 (C4"), 39.2, 37.3 (C1"), 37.0 (C10"), : 169.6 (C8), 156.4 (C19), 141.0 (C5"), 121.7 (C6"), 97.3 (C1), 79.2 (C3"), 73.6 (C2), 72.4 (C5), 71.4 (C3), 70.3 (C4), 68.3 (C18), 66.6 (C7), 61.4 (C6), 56.9 (C14"), 56.2 (C17"), 50.3 : 169.6 (C8), 156.4 (C21), 141.0 (C5"), 121.6 (C6"), 97.3 (C1), 79.2 (C3"), 73.6 (C2), 72.4 13 CNMR (100 MHz, CDCl 3 / MeOD) : (C5), 71.4 (C3), 70.2 (C4), 68.3 (C20), 66.6 (C7), 61.4 (C6), 56.9 (C14"), 56.2 (C17"), 50.3 (C23"), 22.7 (C26"), 22.5, 22.4 (C27"), 21.0 (C11"), 19.3 (C19"), 18.6 (C21"), 13.9 (C25), 11.8 (C18") m/z (HRMS) : 889.6868 (M + H + , C 52 H 93 N 2 O 9 requires 889.6876) [] D 20 +34 (c 0.7 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: (C9"), 42.4 (C13"), 41.2 (C9), 39.9 (C16"), 39.6 (C24"), 39.2 (C4"), 39.2, 37.3 (C1"), 37.0 (C9"), 42.4 (C13"), 41.2 (C9), 39.9 (C16"), 39.6 (C24"), 39.2 (C4"), 39.2, 37.3 (C1"), 37.0 : 169.6 (C8), 156.3 (C21), 140.9 (C5"), 121.5 (C6"), 97.1 (C1), 79.0 (C3"), 73.4 (C2), 72.3 36.3 (m/z (ESI) : 917.7 (M+H + ), 939.7 (M+Na + ) (C10"), 36.3 (m/z (HRMS) : 973.8 (M+H + ), 995.8 (M+Na + ) (C10"), 36.3 ((C21"), 14.1, 14.0 (C27), 11.9 (C18") m/z (HRMS) : (C5), 71.2 (13.9 (C29), 11.8 (C18") 20 [] D +30 (c 0.8 in CH 2 Cl 2 /MeOH, 9/1) [] D 917.7 (M+H + ), 939.7 (M+Na + ) 20 +31 (c 0.8 in CH 2 Cl 2 /MeOH, 9/1) 20 m/z (HRMS) : m/z (ESI) : [] D 967.7290 (M + Na + , C 56 H 100 N 2 O 9 requires 967.7321) 1001.8 (M+H + ) Elemental analysis: Elemental analysis: +31 (c 0.7 in CH 2 Cl 2 /MeOH, 9/1) Elemental analysis: 20 [] D [] D 20
	+31 (c 0.7 in CH 2 Cl 2 /MeOH, 9/1) +25 (c 0.4 in CH 2 Cl 2 /MeOH, 9/1)
	Glucosteroid L10S12 bolaphile (127c) Elemental analysis: Elemental analysis:
	Glucosteroid L12S6 bolaphile (128a)								18"
	HN Glucosteroid L12S8 bolaphile (128b) O O OH 6 O HO HO O NH O 1 7 9 19 HN O O OH 6 O HO HO O NH O 1 7 9 21 27 HN O O OH Glucosteroid L12S12 bolaphile (128c) 6 O HO HO 1 9 O NH O 7 21 HO O OH 6	31	18	O 20 20	3" O O	1" 3" 3"	19" 19" 6" 1" 19" 1" 1" 19"	6" 6"	18" 18" 18"	26" (27") 26" (27") 26" (27")
	White solid 1 HNMR (400 MHz, CDCl 3 / MeOD) : HN O O HO O NH O 1 7 9 21	29			20	O	3"		6"		26" (27")
	White solid White solid
	HNMR (400 MHz, CDCl 3 / MeOD) : 1 HNMR (400 MHz, CDCl 3 / MeOD) : White solid 1 : 5.35 (m, 1H, H-6"), 5.01 (d, 1H, J = 3.5 Hz, H-1), 4.55 (dd, 1H, J = 3.3 and 10.1 Hz, H-2), 33
	White solid

4.13 (d, 1H, J = 15.7 Hz, H-7a), 3.97 (d, 1H, J = 15.6 Hz, H-7b), 3.89-3.71 (m, 3H, H-6a, H-6b, H-3), 3.61-3.52 (m, 4H, H-4, H-5, CH 2 -18 ), 3.25 (t, 2H, J = 7.3 : 5.35 (m, 1H, H-6"), 5.01 (d, 1H, J = 3.6 Hz, H-1), 4.55 (dd, 1H, J = 3.4 and 10.0 Hz, H-2), 4.13 (d, 1H, J = 15.6 Hz, H-7a), 3.97 (d, 1H, J = 15.6 Hz, H-7b), 3.88-3.74 (m, 3H, H-6a, H-6b: 5.35 (m, 1H, H-6"), 5.01 (d, 1H, J = 3.7 Hz, H-1), 4.54 (dd, 1H, J = 3.5 and 10.1 Hz, H-2), 4.13 (d, 1H, J = 15.6 Hz, H-7a), 3.98 (d, 1H, J = 15.6 Hz, H-7b), 3.88-3.74 (m, 3H, H-6a, H-6b1 HNMR (400 MHz, CDCl 3 / MeOD) : D.

3 Synthesis of glucosyl and cellobiosyl probes D.3.1 Synthesis for 6-dodecanoyl-2-bromonaphthalene (138) (CH 2 ) 10 O Br C

  22 H 29 BrO Exact Mass: 388.14 Mol. Wt.: 389.37 2-bromonaphthalene (2.0 g, 1mmol) was dissolved in 9.6 ml of nitrobenzene under Ar, which was placed in an ice bath. Lauroylchloride (2.8 mol, 11.64 mL) was then added dropwised.

2 Synthesis for N 1 -Boc-N 2 -laurdan-N 2 -methyl-diaminopropane (141)

  1 HNMR (300MHz, CDCl 3 ) : 8.42 (s, 1H, H-9''), 8.05 (m, 2H, H-7'', H-1''), 7.81 (m, 2H, H-6'', H-2''), 7.62 (s, 1H, H-4''), 3.07 (t, 2H, J = 7.5 Hz, H-12''), 1.79 (m, 2H, H-13''), 1.37-1.26 (m, 16H, H-14''-21''), 0.88 (t, 3H, J = 6.6 Hz, H-22'') 38.8, 32.0 , 29.7, 29.8, 29.8, 29.7, 29.6, 29.5, 27.2, 22.8, 14.2 (C-lauroyl)

	m/z (HRMS) :
	389.1471 (M + H + , C 22 H 30 BrO requires 389.1475)
	H D.3.N Boc	6	8	N	O	(CH 2 ) 10
				9
			C 31 H 48 N 2 O 3
		Exact Mass: 496.37
			Mol. Wt.: 496.72

13 CNMR (75MHz, CDCl 3 ) : 200.3 (C-11''), 136.5 (C-3''), 134.9 (C-5''), 131.2 (C-1''), 131.2 (C-8''), 130.4(C-9''), 130.1 (C-6''), 129.5 (C-10''), 127.6 (C-7''), 125.3 (C-2''), 122.8 (C-4''),

  1 HNMR (400MHz, CDCl 3 ) : 8.22 (s, 1H, H-9''), 7.92 (d, 1H, J = 7.9 Hz, H-7''), 7.80 (d, 1H, J = 9.1 Hz, H-1''), 7.62 (d, 1H, J = 8.3 Hz, H-6''), 7.17 (s, 1H, H-2''), 6.89 (s, 1H, H-4''), 4.65 (s, 1H, H-NH), 3.52 (t, 2H, J = 7.2 Hz, H-8), 3.32-3.15 (m, 2H, H-6), 3.08 (s, 3H, H-9), 3.03 (t, 2H, J = 7.4, H-12''), 1.84 (m, 2H, H-7), 1.77 (m, 2H, H-13''), 1.45 (s, 9H, H-CH 3 X3), 1.49-1.13 (m, 16H, H-14''-21''), 0.88 (t, 3H, J = 7.4 Hz, H-22'')

  : 8.22 (s, 1H, H-9''), 7.83 (d, 1H, J = 8.5 Hz, H-7''), 7.70 (d, 1H, J = 8.8 Hz, H-1''), 7.55 (d, 1H, J = 8.4 Hz, H-6''), 7.30-7.25 (s, 1H, H-NH), 7.05 (d, 1H, J = 8.2 Hz, H-2''), 6.76 (s, 1H, H-4''), 5.14 (t, 1H, J = 9.5 Hz, H-3), 5.08 (t, 1H, J = 9.4 Hz, H-3'), 5.02 (t, 1H, J = 9.6 Hz, H-4'), 4.87 (t, 1H, J = 8.1 Hz, H-2'), 4.75 (d, 1H, J = 3.8 Hz, H-1), 4.45 (d, 1H, J = 7.9 Hz, H-1'),

	10''	23''
	11''
	C 52 H 74 N 2 O 19
	Exact Mass: 1030.49
	Mol. Wt.: 1031.15
	1 HNMR (500MHz, CDCl 3 )

  : 8.32 (s, 1H, H-9''), 7.87-7.78 (m, 2H, H-1'', H-7''), 7.62 (d, 1H, J = 8.8 Hz, H-6''), 7.30-7.66 (m, 1H, H-NH), 7.20 (dd, 1H, J = 2.4, 9.2 Hz, H-2''), 6.76 (s, 1H, H-4''), 4.84 (m, 1H, H-1), 4.20 (d, 1H, J = 15.8 Hz, H-7a), 4.02 (d, 1H, J = 15.8 Hz, H-b), 3.82 (dd, 1H, J = 2.2, 12.0 Hz, 6a), 3.76-3.68 (m, 2H, H-3, H-6b), 3.63-3.49 (m, 4H, H-2, H-5, H-11), 3.40-3.31 (m, 3H, H-4, H-9), 3.09 (s, 3H, H-12), 3.04 (t, 2H, J = 7.4 Hz, H-12''), 1.90 (m, 2H, H-10), 1.73 (m, 2H, H-13''), 1.46-1.18 (m, 16H, H-14''-21''), 0.86 (t, 3H, J = 6.8 Hz, H-22'')

1 HNMR (400MHz, CDCl 3 +MeOD)

Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

H 1 -H 2 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

HO H 1 -H 2 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2013ISAL0001/these.pdf © [R. Xu], [2013], INSA de Lyon, tous droits réservés

Abbreviations

ABS