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 determinedusing a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution forchitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore itcan 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 (7*) of these copolyamides exhibited an odd-even zigzag effect with the odd-even variation of carbon atom number in the aliphatic dimes used.

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.

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 solubilitythan chitosan, and demonstrated lyotropic liquid crystalline behavior in various solvents. The critical liquidcrystalline 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 dependon the acidity of acidic solvents.

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.

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.

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.

STUDIES ON CRITICAL CONCENTRATION OF LIQUID CRYSTALLINE ETHYLCELLULOSE

Critical concentrations of lyotropic liquid crystalline ethylcellulose in more than tensolvents were determined using both Abbe refractometer and polarized microscopy. Criti-cal concentration Ccrit of forming liquid crystal phase decreased with increasing solubilityparameter δ of solvent until approaching the δ of polymer. Although the alcohols usedas solvents had the same variation rule, the critical concentration values of their solutionswere much higher, due to their excessive large hydrogen bond component of δ. The experi-ments of using mixed solvents which showed good linear relation between Ccrit and δ alsoproved this rule. A technique of Transmission Optical Analysis was first used to estimatethe concentration dependence of critical phase transition temperature Tcrit of EC, and aT-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.

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.

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.

生物和人工自组装体系中的双连续立方结构

在数十亿年的进化过程中,大自然创造了多种复杂的多级结构,这些多级结构针对不同的生命活动具有组装体所不具有的优异性能.其中双连续立方结构通常能够用三周期极小曲面(TPMS)和它们的常平均曲率曲面(CMC)/平行曲面共同来描述.它们具有复杂的结构和独特的物理性质,得到了各个研究领域的广泛关注,同时也对它们的形成机理、晶体结构和性能表现的研究提出了新的挑战.本文对生物和人工自组装系统中相关曲面结构的形成机理及相互关系进行了总结和讨论.在生物体中具有几百纳米大尺度的多种生物立方膜及相关结构,而人工合成体系中往往只能形成与分子大小及曲率相对应的结构.值得注意的是,嵌段共聚物体系具有灵活的可设计性和丰富的相行为,为研究生物体系提供了一个理想的模型.对这两个体系中发现的一些现象进行比较和讨论,可以为全面理解分子形状和由此产生的界面曲率之间的关系,进而理解生物体的自组装过程提供新的思路.