Liquid-crystalline comb copolymers with lipoamino acid side chains Synthesis and structure study

In order to obtain liquid-crystalline polymers without using classical mesogenic groups, comb copolymers consisting of a polyacrylamide main chain and lipoamino acid side chains have been synthesized. These copolymers were obtained by the polymerization of lipoamino acid macromonomers. These macromonomers were obtained from, α,ω-aliphatic amino acids by linking a polymerizable group at the amino end and an α-amino acid at the carboxyl end. The macromonomers were then transformed into comb copolymers by free-radical polymerization. These comb copolymers exhibit mesophases both in aqueous solution and in the anhydrous state. The range of stability and the structures of the mesophases were determined by X-ray diffraction. Two types of structures were found, corresponding to the lyotropic lamellar and hexagonal mesophases. The influences of the nature of the amino acid and the water concentration on the domain of stability and the geometrical parameters of the mesomorphic structures were investigated.     

Synthesis and mesomorphic structures of comb liquid-crystalline polymers with lipopeptidic side chains

Lipopeptidic macromonomers were synthesized from bi-functional lipids by two methods and transformed into comb copolymers with lipopeptidic side chains by radical polymerization of their acrylate, methacrylate, acrylamide or methacrylamide terminal group. X-ray diffraction and differential scanning calorimetry studies showed that comb copolymers exhibit both a thermotropic and a lyotropic behaviour and present smectic and nematic mesophases. The influence of the solvent concentration, the degree of polymerization of the peptidic chains and the nature of the main chains on the structural parameters of the smectic mesophases were established in the case of copolymers with liposarcosine side chains.     

Synthesis and phase behaviour of liquid-crystalline side group polyesters

Several series of liquid-crystalline side group polymers with a polyester backbone structure have been synthesized using mesogenic diethylmalonate and 1,3-propanediol derivatives. The structures of the polymer backbone and the mesogenic units have been varied systematically. As shown by differential scanning calorimetry, polarizing microscopy and X-ray diffraction, the side group polyesters exhibit nematic and/or smectic mesophases. Polyesters synthesized from mesogenic diethylmalonate derivatives can tolerate long non-mesogenic segments in the polymer main chain without losing their liquid crystal properties. X-ray studies suggest that some of the smectic polymers exhibit interdigitated bilayer S_A phases.     

Synthesis and mesomorphic behaviour of comb-like polymers based on lipopeptides with two hydrophobic chains

Abstract

Polymerizable lipopeptides with two hydrophobic chains were synthesized and transformed into comb-like polymers by radical polymerization. The structure of dry polymerizable lipopeptides and comb-like polymers and of their aqueous solutions was determined by X-ray diffraction. Comb-like polymers exhibit both thermotropic and lyotropic properties. Three types of mesomorphic structure were resolved: smectic B, smectic A and cylindrical hexagonal. The domains of stability of the mesophases and the values of their structural parameters were established.     

Thermotropic liquid-crystalline comb-like polymers with polyacrylamide main chain—I. Synthesis and mesomorphic structures of polymers with lipobiphenyl side chains

The synthesis of polymerizable lipobiphenyls, the study of the kinetics of their radical polymerization giving comb-like polymers, and the study of the thermotropic behaviour of the polymers are reported. Utilization of all the information provided by X-ray diffraction diagrams showed that polymers with polyacrylamide main chains and lipobiphenyl side chains exhibit successively, between room temperature and isotropization temperature, two mesophases: an ordered tilted double layer smectic phase SI2, and a disordered tilted double layer smectic phase SC2.     

Synthesis and mesomorphic behaviour of comb-like polymers based on lipopeptides with two hydrophobic chains

Polymerizable lipopeptides with two hydrophobic chains were synthesized and transformed into comb-like polymers by radical polymerization. The structure of dry polymerizable lipopeptides and comb-like polymers and of their aqueous solutions was determined by X-ray diffraction. Comb-like polymers exhibit both thermotropic and lyotropic properties. Three types of mesomorphic structure were resolved: smectic B, smectic A and cylindrical hexagonal. The domains of stability of the mesophases and the values of their structural parameters were established.     

Hydrogen bonding and the self-assembly of supramolecular liquid-crystalline materials

Novel supramolecular liquid-crystalline materials have been obtained by the hydrogen bond formation between different and independent molecules. The self-assembly of carboxylic acid and pyridine moieties that function as H-bond donors and acceptors, respectively, results in the formation of mesogenic complex structures. A wide variety of liquid-crystalline low molecular weight complexes have been prepared using this approach. This concept has been extended to the polymeric systems. Hydrogen-bonded liquid-crystalline polymers that exhibit mesophases over wide temperature ranges, ferroelectricity or photo-responsibility have been prepared by the molecular association. Moreover, liquid-crystalline polymer networks that show reversible smectic-isotropic phase transitions have been formed by the hydrogen bonds. The dynamics of the hydrogen bonding may contribute to the induction of the mesomorphism of the networks.     

Functional liquid-crystalline polyesters based on twin nonamethylene spaced p-oxybenzoate dyads and dithiols

A new series of thermotropic liquid-crystalline poly-(ester-β-sulphide)s 9Sn was prepared by reacting the mesogenic nona-methylene bis[4-(4-acryloyloxybenzoyloxy)benzoate] 1 with α,ω-alka-nedithiols of varying length. The polymers exhibit nematic and smectic mesophases, which are enantiotropic or monotropic in character, depending on the number n of methylene units in the dithiol precursor (n = 2–10). The phase transition parameters were determined and compared with those of closely related poly(ester-β-sulphide)s 6Sn. It is suggested that these systems may be suitable model polymers to test current theory of the existence of highly anisotropic or weakly anisotropic mesophases in polymers.     

Effect of sulfonic acid containing mesogens on liquid-crystalline behavior of polysiloxane-based polymers

A series of liquid-crystalline polysiloxanes synthesized by cholest-5-en-3-ol (3beta)-10-undecenoate and 4'-octanoyloxy-biphenyl-4-yl 4-allyloxy-3-sulfo-benzoate were prepared in a one-step reaction with sulfonic acid group contents ranging between 0 and 2.73 wt %. All the polymers displayed smectic mesophases with a large temperature range for the mesophases. With an increase of sulfonic acid containing mesogens in the polymers, the temperature of the glass transition did not change greatly, while the temperature of the clear point decreased. The hydrogen-bonding mesogen aggregates in the domains disturb the liquid-crystalline molecular mobility and orientation, leading to a decrease in temperature from the mesophase to the isotropic transition. Unlike the polymers containing lower sulfonic acid mesogens, some polymers showed a dendritic texture of the SmB* phase, indicating that the sulfonic mesogens enhanced the rigid moieties of the supermolecular structure of the liquid-crystalline phases. All the polymers displayed sharp and strong peaks at low angles around 2theta approximately 2.6 degrees and broad peaks at wide angles around 2theta approximately 17 degrees in X-ray measurements. The intensity of the strong peak at low angles in the X-ray profiles decreased with an increase of sulfonic acid mesogens in the polymer systems.     

Attempts Towards Novel Cycloalkane Liquid Crystals

Abstract

This paper is concerned with the relationship between molecular structure and liquid-crystalline properties of two types of functionalized cycloalkanes, i.e. cyclopentanes and cyclohexanes, in the latter case myo- and scyllo-inositol. The occurence of columnar or lamellar mesophases is discussed for a variety of new compounds in relation to: 1) the role of heteroatoms in side chains, 2) the core size and stereochemical arrangement of heteroalkyl side chains, and 3) the replacement of such side chains by hydroxyl groups. Both in the cyclopentane and inositol series various interesting examples of new multihydroxy liquid crystals have been synthesized and studied. Their mesophases are of supramolecular architecture based on hydrogen bonding networks.     

Synthesis and liquid crystalline structures of poly(L-lysine) containing undecanamidobiphenyl units in the side chains

In order to obtain liquid crystalline comb-like poly(L-lysine) bearing biphenylyl mesogenic groups in their side chains, we synthesized the 11-(biphenyl-4-carboxamido)undecanamidoL-lysine (KC10φφ) from L-lysine by a five step procedure and transformed the KC10 φφ into its polymerizable cyclic derivative (the N-carboxyanhydride or NCA derivative) by the action of diphosgene. We homopolymerized the NCA of KC10 φφ to obtain the polymer pKC10 φφ and copolymerized it with the NCA of trifluoroacetyl-L-lysine (Kt) to obtain block copolymers pKt-pKC10 φφ of various compositions. X-ray diffraction studies demonstrated the existence of mesophases for our homopolymers and copolymers, resolved the structure of the mesophases and established the influence of temperature and the composition of the copolymers on the structure of the mesophases. Homopolymers pKC10 φφ exhibit, as a function of temperature, three phases (CrE_d, SmB_d and SmA_d) deriving from the β -pleated sheet structure of polypeptides and proteins. The presence of a pKt block in copolymers pKt-pKC10 φφ transforms the smectic CrE_d structure into a SmA_d structure and, when the content of pKt block increases, into a bidimensional hexagonal structure similar to that of the homopolymers pKt.     

Thermal and dynamic mechanical behavior of polyurethanes based on diisocyanates and diethanolamine derivatives with mesogenic groups in side chain

Thermotropic polyurethanes were prepared from three commercial diisocyanates of various flexibility and eight diols (based on diethanolamine derivatives) with mesogenic groups in side chain with stoichiometric ratio of reactive isocyanate and hydroxy groups. Polymers were studied by dynamic mechanical spectroscopy, X-ray scattering, differential scanning calorimetry and polarizing microscopy. The effect of structure changes in the diisocyanates and diols, in particular changes in the end substituents bound to the mesogen, were investigated. Introduction of mesogenic diols into the polymers suppresses the occurrence of mesophases in comparison with neat diols; in the case of simple end substituents (such as hydrogen, nitro and nitrile), the mesophases disappear completely regardless of the structure of diisocyanate. Stiff end substituents (phenyl and alkoxy groups) stabilize the mesophases to such an extent that the negative influence of long polymer chains is compensated and the liquid-crystalline (LC) properties are recovered. Generally, the polymers prepared from the stiffest 2(4)-methyl-1,3-phenylene diisocyanate exhibit a most pronounced LC behavior.     

Liquid crystal polymers from swallow-tailed mesogens

Swallow-tailed compounds containing an acetylenic unit have been synthesized. Only those compounds with a three ring structure exhibited liquid-crystalline phases. The platinum catalysed addition of these monomers to compounds containing Si-H groups was used to synthesize polymeric materials. Only those polymers with the tetramethyldisiloxane unit showed mesophases. The synthesis, characterization, and phase behaviour are described.     

Helical pitch of ferroelectric liquid-crystalline polymers and copolymers

Ferroelectric liquid-crystalline polymers and copolymers were synthesized from acrylate polymers with side chains consisting of a flexible spacer unit, a mesogenic unit and an optically active substituent. In the chiral smectic C (S*_c) phases typical fan-shaped textures with equidistant lines (caused by the helical structures) were observed. It was found that the helical pitch increased with increasing polymer molecular weight. The helical pitch also increased in copolymers containing mixtures of right- and left-handed chiral side chains.     

Adsorption of comb copolymers on weakly attractive solid surfaces

In this work continuum and lattice Monte Carlo simulation methods are used to study the adsorption of linear and comb polymers on flat surfaces. Selected polymer segments, located at the tips of the side chains in comb polymers or equally spaced along the linear polymers, are attracted to each other and to the surface via square-well potentials. The rest of the polymer segments are modeled as tangent hard spheres in the continuum model and as self-avoiding random walks in the lattice model. Results are presented in terms of segment-density profiles, distribution functions, and radii of gyration of the adsorbed polymers. At infinite dilution the presence of short side chains promotes the adsorption of polymers favoring both a decrease in the depletion-layer thickness and a spreading of the polymer molecule on the surface. The presence of long side chains favors the adsorption of polymers on the surface, but does not permit the spreading of the polymers. At finite concentration linear polymers and comb polymers with long side chains readily adsorb on the solid surface, while comb polymers with short side chains are unlikely to adsorb. The simple models of comb copolymers with short side chains used here show properties similar to those of associating polymers and of globular proteins in aqueous solutions, and can be used as a first approximation to investigate the mechanism of adsorption of proteins onto hydrophobic surfaces.     

Synthesis and liquid crystalline structures of poly(L-lysine) containing undecanamidobiphenyl units in the side chains

In order to obtain liquid crystalline comb-like poly(L-lysine) bearing biphenylyl mesogenic groups in their side chains, we synthesized the 11-(biphenyl-4-carboxamido)undecanamidoL-lysine (KC10 ϕϕ) from L-lysine by a five step procedure and transformed the KC10 ϕϕinto its polymerizable cyclic derivative (the N-carboxyanhydride or NCA derivative) by the action of diphosgene. We homopolymerized the NCA of KC10 ϕϕto obtain the polymer pKC10 ϕϕand copolymerized it with the NCA of trifluoroacetyl-L-lysine (Kt) to obtain block copolymers pKt-pKC10 ϕϕof various compositions. X-ray diffraction studies demonstrated the existence of mesophases for our homopolymers and copolymers, resolved the structure of the mesophases and established the influence of temperature and the composition of the copolymers on the structure of the mesophases. Homopolymers pKC10 ϕϕexhibit, as a function of temperature, three phases (CrE_d, SmB_d and SmA_d) deriving from the β-pleated sheet structure of polypeptides and proteins. The presence of a pKt block in copolymers pKt-pKC10 ϕϕtransforms the smectic CrE_d structure into a SmA_d structure and, when the content of pKt block increases, into a bidimensional hexagonal structure similar to that of the homopolymers pKt.     

Thermotropic liquid crystalline comb-like polymers with polyacrylamide main chain. (2) Influence of the nature of the substituents of the biphenyl mesogenic core

Comb-like polymers with polyacrylamide main chains and three types of lipophilic biphenyl side chains have been synthesized and their thermotropic behaviour has been determined. All the polymers exhibit two smectic mesophases as a function of temperature, but the nature of the smectic mesophases is governed by the nature of the substituent R of the biphenyl core. For R = H, the polymers exhibit a double layer, ordered, tilted smectic S_i2 and a double layer, disordered, tilted smectic S_c2. For R = CN, the polymers exhibit a double layer, disordered, tilted smectic S_c2 and a double layer, disordered, perpendicular smectic S_A2. For R = O-CH₂-CH(CH₃)-C₂H₅, the polymers exhibit a double layer, ordered, tilted smectic S_f2 and a double layer, disordered, tilted smectic S_c2, these two structures being chiral when the substituent R is chiral. Comparison of the thermotropic behaviour of the polyacrylamide polymers with that of polymers with the same mesogenic cores but different main chains shows the high smectogenic power of the polyacrylamide skeleton.     

Syntheses of Peptidoglycolipid Analogs with Distinct Immunomodulating Activities

ABSTRACT

Amphiphilic 2-amino-2-deoxy-β-D-glucopyranosylamides were synthesized from N-protected glucosamine derivatives via N-glycosidation with fatty amines, subsequent N-acylation with fatty acid derivatives and deprotection. They could further be modified with amino acids to give peptido-glycopyranosyl amides, some of which exhibited strong immunostimulatory (BAY Q8939, 8) or immunoadjuvant (BAY R1005, 9) activities.     

A facile transformation of amino acids to functionalized coumarins

The synthesis of novel chiral coumarins functionalized with proteinogenic amino acid side chains via N-protected γ-amino-β-keto esters and their incorporation into the cell permeable HIV-1 TAT peptide through the modified solid phase peptide synthesis are described.     

Laterally attached liquid-crystalline polymers as stationary phases in reversed-phase high-performance liquid chromatography. III. Effect of the local anisotropic order on the separation of polycyclic aromatic hydrocarbons

Specific stationary phases based upon non-liquid-crystalline polymers, liquid-crystalline molecules and side-on fixed liquid-crystalline polymers (SO-LCP) have been synthesized for use as silica modified stationary phases in high-performance liquid chromatography (HPLC). The mesogenic side group of the SO-LCP was composed of three phenyl ring benzoate type with terminal alkoxy chains and was laterally linked to a polysiloxane backbone via an alkyl ester spacer arm. This study demonstrated that the shape recognition of stationary phases based upon SO-LCP towards the length-to-breath ratio (L/B) was strongly connected to the existence of a local liquid-crystalline order into the pores of silica gel, warranting the interest of the collective organization of mesomorphic materials in liquid chromatography. Furthermore, the chromatographic performances depended on the kind of anisotropic order and it was more advantageous to use smectic side-on liquid-crystalline polymer than nematic and obviously non-liquid-crystalline ones. Finally, for a series of polymers having the same mesomorphism, the larger the temperature stability range of the mesophase, the more pronounced the local order effect and the higher the shape recognition.