Solid State Structure and Lyotropic Mesomorphism of Rare-Earth Trisdode cylsulphates in the Water-Ethylene Glycol System

The phase behaviour of lanthanide(Ⅲ) dodecylsulphates, Ln(C 12 H 25 SO 4) 3, by thermo optical microscopy using Lawrence penetration technique was investigated. The lyotropic phase behaviour of lanthanide(Ⅲ) dodecylsulphates in ethylene glycol water in mixtures hereof, depends on the composition of the solvent. For pure ethylene glycol and mixtures of ethylene glycol and water three different mesophases are formed, i.e. a lamellar, a cubic and a hexagonal phase, whereas when water is used as solvent no cubic phase is formed. The size of the lanthanide ion has no influence on the mesomorphism of these metallomesogens, although the smaller the lanthanide ion the lower the solubility.

INFLUENCE OF MOLECULAR WEIGHT OF CHITIN AND ITS THREE DERIVATIVES ON CRITICAL CONCENTRATION OF LYOTROPIC LIQUID CRYSTALLINE PHASE TRANSITION

The critical concentration of lyotropic liquid crystalline phase transition for chitin derivatives was determined using a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution for chitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore it can be used as an indicator of the chain rigidity.

ODD-EVEN EFFECT OF LYOTROPIC LIQUID CRYSTALLINE PROPERTIES OF AROMATIC-ALIPHATIC COPOLYAMIDES

A series of aromatic-aliphatic copolyamides containing different aliphatic diamine units was synthesized by low temperature solution polycondensation. The liquid crystalline critical concentration (c*) and liquid crystalline critical temperature (T*) of these copolyamides exhibited an odd-even zigzag effect with the odd-even variation of carbon atom number in the aliphatic diamines used.

LYOTROPIC LIQUID CRYSTALLINE BEHAVIOR OF FIVE CHITOSAN DERIVATIVES

Five chitosan derivatives, i.e. O-butyryl chitosan, O-benzoyl chitosan, N-phthaloyl chitosan, N-maleoyl chitosan and O-cyanoethyl chitosan, were prepared from chitosan. All of them had better solubility than chitosan, and demonstrated lyotropic liquid crystalline behavior in various solvents. The critical liquid crystalline behavior of three O-substituted chitosan derivatives was evidently different from two N-substituted analogues. Typical fingerprint textures of cholesteric phase were only observed in three O-substituted derivatives. The critical concentration (v/v%) of three O-substituted derivatives does not depend on the acidity of acidic solvents.

KINETICS OF MESOPHASE FORMATION OF A LYOTROPIC AROMATIC POLYAMIDE

The kinetics of mesophase formation of a lyotropic aromatic polyamide from isotropic state has been studied by means of depolarized light intensity. Avrami type analysis of the data gives an exponent close to 1, which suggests the nucleation followed by one-dimensional growth. No influence of blending flexible chain from nylon 6 to the aromatic polyamide on the kinetics of mesophase formation was observed.

Studies on the Phase Behavior of Lyotropic Liquid Crystal in DAD/C_4OH/n-C_8H_(18)/D_2O System

The lytropic liquid crystals in dodecanic acid diethanolamine (DAD) /n-butanol (C4OH) /octane (n-C8H18) /deuteron (D2O) system were studied to determine the phase regions and were investigated by 2H-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods.The results indicate that the lamellar,hexagonal and cubic liquid crystals all exist in the above system.Keeping the weight ratio of DAD and C4OH constant,the microphase Structure,2H quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.

Lyotropic Liquid Crystal Electrochemical Polymerization of Thiophene-Based Monomers: Polymerization in Cholesteric Liquid Crystal and Columnar Phase

Synthesis of conductive polymer poly([thiophene]-[benzo[1,2,3]thiadiazole] [thiophene]) (abbreviated as P(T-Btdaz-T)) was achieved by electrochemical polymerization in hydroxypropyl cellulose (HPC)/N,N-dimethylformamide (DMF) in liquid crystal state. The polymer thus obtained shows fingerprint texture, which is derived from helical structure of the HPC in cholesteric liquid crystal state. Fourier transform infrared spectroscopy measurements revealed that the polymer film is P(T-Btdaz-T)/HPC composite. Circular dichroism optical absorption spectroscopy measurements show that the polymer has the optical activity. Next, electrochemical polymerization of 3,4-ethylene-dioxythiophene (EDOT) was carried out in columnar phase liquid crystal. The polymer transcribes the columnar structure and shows optical structure resembling columnar liquid crystal electrolyte solution.

LYOTROPIC AND THERMOTROPIC LIQUID CRYSTALL INE TRIALKYL CELLULOSES OBTAINED DIRECTLY FROM CELLULOSE ACETATE IN DIMETHYL SULFOXIDE

Highly substituted n-atkyl celluloses with sidechains 3 to 10 carbon atoms long have been prepared from cellulose acetate, sodium hydroxide and n-alkyl bromides with dimethyl sulfoxide as solvent. Synthetic conditions of n-alkyl celluloses were studied with respect to reaction temperature, time and yield. The molecular structure of the n-alkyl celluloses, which were obtained as white powders or as sticky, soft and birefringent solids at room temperature, was investigated by IR and NMR spectra and elemental analysis. The highly substituted n-alkyl celluloses all exhibited both therotropic and lyotropic liquid crystalline cholesteric phases in some non-polar solvents. The metting behavior and solubility of the n-alkyl celluloses were examined.

Lyotropic liquid crystals of tetradecyldimethylaminoxide in water and the in situ formation of gold nanomaterials

Lyotropic liquid crystals(LLCs)produced by the self-assembly of surfactant in water represent an important class of highly ordered soft materials that have a wide range of applications.This study investigates the LLCs formed by a zwitterionic surfactant(tetradecyldimethylaminoxide,C 14 DMAO)in water.The organization of C 14 DMAO within the LLCs was determined based on a detailed analysis of small-angle X-ray scattering measure-ments and polarized microscopy observations of a typical sample.Additional to the singe-phase region,which has a hexagonal organization,several two-phase regions were observed,exhibiting the coexistence of hexago-nal/cubic,cubic/lamellar,and hexagonal/lamellar phases.The phase behavior showed an obvious dependence on temperature,with more pronounced two-phase regions at lower temperatures.Using the LLCs as a matrix,Au nanospheres,nanoellipsoids,and nanorods were prepared without requiring additional reducing reagents.These three-and one-dimensional Au nanomaterials could be converted to two-dimensional plates via the introduc-tion of a small amount of cationic surfactant to the LLCs,such as cetyltrimethylammonium bromide(CTAB)and 1-hexadecyl-3-methylimidazolium bromide([C 16 MIm]B),which showed pronounced surface-enhanced Raman scattering activity towards solid rhodamine.The LLCs loaded with CTAB(or[C 16 MIm]B)and HAuCl 4 exhibited slightly different structures and mechanical strength from the original LLCs,thereby forming a new class of highly crowded colloidal materials.

Studies on the phase properties of lyotropic liquid crystals of Brij35/sodium oleate/oleic acid/water system: By means of polarizing microscope, SAXS, 2H-NMR and rheological methods

The pseudo-quaternary phase diagram of Brij35/sodium oleate/oleic acid/water systems has been investigated, and the liquid crystal area has been identified, which covers about two thirds of the whole phase diagram. The liquid crystal structure and behavior have been also studied by using polarizing texture, small angle X-ray scattering, 2H-NMR and rheometer etc. The result shows that when the composition of the system changes along the line of AA′ in this large liquid crystal region, the structural change is cubic→cubic/lamellar→lamellar→lamellar/hexagonal→hexagonal. Meanwhile, we made the first attempt of systematic study of the rheological properties of the above system. The lattice constants of cubic and hexagonal liquid crystals are 10.53 and 5.68 nm, respectively.

Doping silver nanoparticles in AOT lyotropic lamellar phases

The organic lyotropic liquid crystal with long-range structural order is used as template to assemble inorganic/organic hybrid by doping pre-fabricated Ag nanoparticles. The lamellar hybrid with both hydrophilic and hydrophobic particles doped simultaneously is realized for the first time. The change of template structure after doping and the stability origin of dual-doped system are characterized by small angle X-ray scattering and polarized optical microscopy. Results show that the interaction and space matching between surfactant bilayers and doped particles are key factors to obtain stable hybrid.

Syntheses and lyotropic liquid crystal properties of a series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30

A series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30, Na16[As4W30M4(H2O)2O112]·XH2O (M = Zn,Cu,Co,Ni,Mn and Cd), have been synthesized for the first time and structurally characterized by elemental analysis, IR and 183W NMR spectra. The crystal structure of Na16[As4W30Cu4(H2O)2O112]·63H2O was determined to be a triclinic system, of P1 symmetry, a = 1.2721(3) nm, b = 2.451 6(5) nm, c = 2.6450(5) nm,

Formulation of lyotropic liquid crystal emulsion based on natural sucrose ester and its tribological behavior as novel lubricant

The tribological behavior of oil-in-water emulsions formulated with natural lyotropic liquid crystal(LLC)emulsifiers based on natural sucrose ester was studied for the first time.Polarized optical microscopy,synchrotron radiation small-angle X-ray scattering,wide-angle X-ray scattering,and synchrotron radiation infrared microspectroscopy demonstrated that LLC emulsifiers were tightly ordered at the oil–water interface with a distinct nematic texture.The viscosity of emulsion was observed to change over time.Moreover,the zeta potential and laser particle size distribution verified the emulsion’s satisfactory stability.The frictional shearing test proved that the coefficient of friction of the emulsion versus pure oil decreased by 34.2%.The coefficient of friction of the emulsion with liquid crystal decreased 10.1%versus that without liquid crystal.Although liquid crystal emulsion did not exhibit outstanding anti-wear performance compared with pure oil,its wear volume was 29.4%less than the emulsion without liquid crystal.X-ray photoelectron spectroscopy and scanning electron microscope–energy dispersive X-ray spectroscopy(SEM–EDS)proved that the tribo-film of the emulsion with liquid crystal was formed synergistically by the liquid crystal phase with the base oil.The formulation affecting the lubricant quality was further studied by orthogonal experiments.The resulting Stribeck curve behavior suggested that proper composition with a slightly higher viscosity can better reduce friction in both boundary lubrication and mixed lubrication regimes.The lubrication mechanism indicated that the periodically ordered liquid crystal was transported to the sliding asperity in the form of emulsion droplets,which bored the pressure and released the oil to form a tribo-film.This LLC emulsion is environmentally friendly and potentially non-irritant to the skin.Thus,it has promising application prospects as novel water-based and biological lubricants.

Stable graphene oxide-based lyotropic liquid crystals for interfacial lubrication

Lyotropic liquid crystals have lubricating properties due to their ordered assembly and fluidity,whose mesogens are often characterized by amphiphilic properties.Despite the attention that graphene oxide(GO)has been studied as a novel amphiphilic lyotropic mesogen this decade,and GO applied as a lubrication additive has been demonstrated in both oil and water-based systems,little research reveals the interfacial lubrication of GO liquid crystals yet.This work reports that GO aqueous dispersion can form lyotropic liquid crystals above a specific critical concentration of 5.00 mg/mL,providing a form of stable water-based lubricant,which can keep stable for several months and can reduce friction by 37.3%and wear by 25.24%.The liquid crystal phase was verified by polarizing microscope and synchrotron radiation small-angle X-ray scattering,and its rheological properties and viscoelasticity were studied by interfacial rheometer.The formation of lyotropic liquid crystals can enhance the stability of GO aqueous dispersions at high density,simultaneously ensuring friction decrease and anti-wear effect.It is attributed to the stable nematic network by the ordered GO sheets.The ordered assembly structure bears vertical shear force,therefore,reducing the wear.It is also assumed that the wide lateral size of graphene oxide promotes the nematic phase thus smoothes the graphene oxide film composed spontaneously under the coincidence of lamellar liquid crystal and 2D layered material.Through this work,the interlayer lubrication of GO was optimized,and the problem of GO dispersion sedimentation was solved by self-assembly.The range of interfacial lubrication of GO aqueous dispersion has been expanded and the synergistic effect is conducive to the environmentally friendly lubricants.

Preparation of Nano-porous Materials(Ⅰ) by Polymerization of Amphiphile Self-assemblies

The polymerization of amphiphilic self assemblies is a promising method to synthesize nano structured materials with novel properties. These materials have many attractive features for their application in biomedical area and materials science, such as catalysis, separation, surface modification, and therapeutics areas. A general review on the polymerization of lipids and surfactant self assemblies to amphiphilic self assemblies is given in this paper with 49 references. The polymerization and the subsequently resulted structure of lipids in different morphologies are summarized. The polymerization of polymerizable surfactants(surfmers) in emulsion and liquid crystalline phases are also discussed. The potential application of new nano porous materials is briefly described.

Nanotechnology: Effective topical delivery systems

Nanotechnology has received much interest nowadays. It isdefined as techniques, methods or processes to fabricate nanoscalestructures with size less than 100 nm. The deliveryof a compound via skin offers many advantages including beingpain-free, ease of administration, avoidance of hepatic firstpassmetabolism and low cost. However, the major barrier ofthis route is the stratum corneum, which is the outermostlayer of the epidermis. Thus effective nanodelivery systemsare essential and no wonder why these systems reveal significantroles in delivery of cosmetics, drugs and biologicalproducts via topical routes these days. There are a variety ofnanodelivery systems for topical route. However, this presentationcovers polymeric nanoparticles and amphiphilicassociationstructures, which are the systems of the author’sparticular interest.

STUDIES ON CRITICAL CONCENTRATION OF LIQUID CRYSTALLINE ETHYLCELLULOSE

Critical concentrations of lyotropic liquid crystalline ethylcellulose in more than ten solvents were determined using both Abbe refractometer and polarized microscopy. Critical concentration C-crit of forming Liquid crystal phase decreased with increasing solubility parameter delta of solvent until approaching the delta of polymer. Although the alcohols used as solvents had the same variation rule, the critical concentration values of their solutions were much higher, due to their excessive large hydrogen bond component of delta. The experiments of using mixed solvents which showed good linear relation between C-crit and delta also proved this rule. A technique of Transmission Optical Analysis was first used to estimate the concentration dependence of critical phase transition temperature T-crit of EC, and a T-C phase diagram could be drawn.

INFRARED SPECTROSCOPIC CHARACTERIZATION OF CONFORMATIONAL DEFECTS OF POLYBENZAMIDE

Theoretical results of normal coordinate analysis of polybenzamide performed with two conformational isomerized models, the cis trans and the all-trans conformation, have been adopted to examine a number of infrared spectra of films of the polymer treated in a subsequent annealing process and a cooling process. It shows, in this investigation, that two sets of infrared spectral profiles around 1400 cm^(-1) and 900 cm^(-1) behave quite attractively. Their spectral behaviours have been correlated to the conformational defect variation in samples, and reasonably predicted by the normal coordinate calculation.

A Dual Effect of Au-Nanoparticles on Nucleic Acid Cholesteric Liquid-Crystalline Particles

Au-nanoparticles (size about 2 nm, but not 5 or 15 nm) are capable of effectively incorporating into quasinematic layers of particles of cholesteric liquid-crystalline dispersion formed by double-stranded nucleic acid molecules of various families (DNA and poly(I)xpoly(C)). This Au-size-dependent process is accompanied by a decrease in amplitudes of abnormal bands in the CD spectra specific to initial cholesteric liquid-crystalline dispersions and simultaneously by an appearance of plasmon resonance band in visible absorption spectrum. The study of properties of particles of cholesteric liquid-crystalline dispersion treated with Au-nanoparticles by means of various physico-chemical methods demonstrates that incorporation of Au-nanoparticles into quasinematic layers of these particles results in two effects: i) it facilitates reorganization of the spatial cholesteric structure of particles, and ii) it induces the formation of Au-clusters in the content of particles. It is not excluded that these effects represent a possible reason for genotoxicity of Au-nanopar- ticles.

Synthesis and self-assembly behavior of 2,5-diphenylethynyl thiophene based bolaamphiphiles

Novel T-shaped bolaamphiphiles consisting of a bent 2,5-diphenylethynyl thiophene rigid core with two terminal glycerol units and a lateral n-alkyl chain have been synthesized via Kumuda and Sonogashira coupling reactions as key steps. Their liquid crystalline behavior was investigated by polarizing optical microscopy （POM）, differential scanning calorimetry （DSC）, and X-ray diffraction （XRD）. All such bolaamphiphiles can self-organize into square honeycomb LC phases with p4rnm symmetries in the presence of water, UV and PL measurements indicate fluorescent properties making them potential candidates for application in fluorescence sensor devices.