Lyotropic liquid crystalline phases formed in ternary mixtures of 1-cetyl-3-methylimidazolium bromide/p-xylene/water: a SAXS, POM, and rheology study

The phase behavior of ternary mixtures of 1-cetyl-3-methylimidazolium bromide (C(16)mim-Br)/p-xylene/water is studied by small-angle X-ray scattering (SAXS), polarized optical microscopy (POM), and rheology measurements. Two types of lyotropic liquid crystalline phases are formed in the mixtures: hexagonal and lamellar. The structural parameters of the lyotropic liquid crystalline phases are calculated. Greater surfactant content in the sample leads to denser aggregation of the cylindrical units in the hexagonal liquid crystalline phase. The increase in lattice parameter and thickness of the water layer in lamellar phase are attributed to the increase of water content, and the area per surfactant molecule at the hydrophobic/hydrophilic interface for lamellar phase is found to be larger than that for hexagonal phase. The structural parameters of the liquid crystalline phases formed from the cetyltrimethylammonium bromide (CTAB) system are larger than those for the C(16)mim-Br system. The rheological properties of the samples are also found to be related to the structure of the liquid crystalline phases.     

Electrical conductivity of lyotropic phases of dodecylbenzenesulphonates with Li+, Na+, and K+ ions in water

The electrical conductivity of dodecylbenzenesulphonate (DoBS) ionic lyotropic liquid crystal of the systems: LiDoBS (dodecylbenzenesulphonic acid lithium salt)/water, NaDoBS (dodecylbenzenesulphonic acid sodium salt)/water, and KDoBS (dodecylbenzenesulphonic acid potassium salt)/water were investigated by impedance spectroscopy in the frequency range from 0.5 Hz to 0.5 MHz. The electrical conductivity of lyotropic LiDoBS was higher than that of isotropic phase. The electrical conductivity isotropic KDoBS and NaDoBS was higher than the conductivity of lyotropic ones. The temperature dependence of electrical conductivity was investigated in the systems LiDoBS/water and KDoBS/water for different phases. The activation energy of electrical conductivity is lowest for the normal hexagonal phase LiDoBS/water. Such systems based on anionic surfactants are of interest as the electrolyte for the supercapacitors.     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO₃ has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.     

Silica thin-layer chromatographic studies of surfactants with mixed aqueous-organic eluents containing thiourea: simultaneous separation of co-existing cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, and polyoxyethylene (20) sorbitan monolaurate

Silica thin-layer chromatography of three surfactants using various solvent systems is described. The mutual separation of coexisting cetyltrimethylammonium bromide (CTAB), dodecyltrimethyl-ammonium bromide (DTAB), and polyoxyethylene (20) sorbitan monolaurate (Tween 20) is achieved on silica layer using 5% aqueous thiourea-acetone-methanol (60:20:20,v/v/v) as the mobile phase. The effect of the carbon chain length of alcohols (methanol, ethanol, n-propanol, and n-butanol) on the mobility of these surfactants is examined on silica layers. The comparative study is performed with sulfur- (thiourea) and oxygen- (urea) containing compounds in the eluent on the mobility as well as on the separation of co-existing CTAB, DTAB, and Tween 20. The interference on the resolution of the mixture of CTAB, DTAB, and Tween 20, due to presence of metal cations as impurities, is also examined. The limits of detection of CTAB, DTAB, and Tween 20 are estimated.     

离子液体在多水相液液平衡体系中的作用

通过用短链离子液体(1-乙基-3-甲基咪唑溴盐[C2mim]Br、1-丁基-3-甲基咪唑溴盐[C4mim]Br)部分或全部取代SDS/DTAB/PEG/NaBr/H2O多水相体系中的无机盐NaBr,用长链离子液体十二烷基-3-甲基咪唑溴盐[C12mim]Br部分取代体系中阳离子表面活性剂DTAB,系统研究了离子液体在分相体系中的作用及其对分相体系性质的影响.研究表明,SDS/DTAB/PEG/NaBr/H2O混合体系形成的四水相体系可以看作"聚合物双水相"与"表面活性剂双水相"共存的结果.短链离子液体([C2mim]Br、[C4mim]Br)较强的亲水性能赋予其较强的盐析能力,在混合体系中表现出明显的盐效应,保证了四水相体系中"聚合物双水相"的存在.短链离子液体与聚合物之间的相互作用及其对表面活性剂之间相互作用的影响均不可忽略.对混合体系的相行为,共存多相的性质有重要的影响.而长链离子液体[C12mim]Br主要通过自身的疏水作用影响"表面活性剂双水相"的性质,充当表面活性剂的角色.然而,[C12mim]Br与DTAB分子结构上的差异,导致表面活性剂分子在"表面活性剂双水相"的两相重新分配,影响了对应两相的体积及萃取能力.可见,通过调节离子液体的烷基链长、混合体系中的含量等可获得具有特定性质的多水相体系.     

Morphological characteristics of the lyotropic and gel phases in the cellulose/NH3/NH4SCN system

Solutions of cellulose in the ammonia/ammonium thiocyanate (24.5/75.5 w/w) solvent form several stable phases. Of particular interest in this work are the temperature-dependent liquid crystalline and gel phases which are stable at cellulose concentrations above 6% w/v. While the temperature-composition conditions yielding these phases are reasonably well established, very little is currently known about the morphological characteristics of lyotropic and gelled cellulose. Polarized light microscopy is employed here to demonstrate that solutions at temperatures above the gel melting point are birefringent, composed of liquid crystals. Field-emission scanning electron microscopy has been used to (i) examine the three-dimensional network in cellulose gels, and (ii) correlate network morphology with cellulose molecular weight and solution concentration. Results obtained from two complementary sample preparation techniques (i.e., critical point drying and freeze drying) are compared to identify and minimize artifacts, and reveal that gel formation occurs as the solutions phase-separate into polymer-rich anisotropic and solvent-rich isotropic phases. The polymer-rich phase is highly interconnected and forms a fibrillar network, with fibrils measuring 20–70 nm in diameter. © 1996 John Wiley & Sons, Inc.     

Synthesis,thermal and lyotropic liquid crystalline properties of protic ionic salts

A series of protic ionic salts were synthesised by a simple acid–base reaction from various pyridine derivatives and dodecylbenzenesulfonic acid in a common organic solvent and characterised in terms of their thermal and lyotropic liquid crystalline properties using various experimental techniques. All of them exhibited lyotropic liquid crystalline phases in toluene, methanol, acetonitrile, dimethyl sulfoxide and water. Their critical concentrations for the formation of biphasic solutions and concentrations for the formation of lyotropic solutions were quite broad depending on the dielectric constants of the solvents. Their lyotropic phases were identified as lamellar phases, since their textures exhibited bâtonnets, oily streaks and mosaic textures. They can potentially be used for many organic transformations, which may have implications in green chemistry.     

Structural,thermal, dielectric and optical behaviour investigations of water-free ZnO/lyotropic liquid crystal nanocolloids

ABSTRACT

Zinc oxide (ZnO) nanoparticles of spherical symmetry (average size of ≈ 20 nm) have been synthesised via a non-aqueous lyotropic liquid crystalline (LLC) templating process. Lyotropic liquid crystalline nanocolloids are prepared via dispersing 0.05, 0.1 and 0.5 wt.% ZnO nanoparticles in non-aqueous lyotropic phase. No structural phase change has been seen with the doping of nanoparticles as stable lamellar phases are observed in all the cases. Stability of the lamellar structure and orientation of the ZnO nanoparticles in the liquid crystalline matrix may be attributed to the interfacial surface charge interactions. A significant increase and pronounced dispersion in dielectric permittivity of the ZnO/LLC nanocolloids could be the result of parallel coupling among guest/host, higher dipole- moment of the ZnO nanoparticles and Maxwell-Wagner polarisation. The variation of relaxation parameters has also been discussed and correlated with the dielectric and structural parameters. ZnO/lyotropic nanocolloids devices exhibit dc conductivity of the order of 10^?5S/m owing to the increase in the number of ions (of the order of 10¹⁹m^?3) in the doped systems. Nanocolloids exhibits, the refractive index of range 1.40 to 1.45 and the wide bandgap of the range 4.1–4.5 eV.     

溶致液晶的结构及应用研究进展

本文评述了溶致液晶的相态和结构以及其相态随浓度变化的特点，并着重介绍了溶致液晶在新型纳米材料全盛中的应用，在生物医学中的应用，在化学反应中的催化作用，以及在工业中的作用。     

表面活性剂溶致液晶的流变学性质

系统阐述了三种溶致液晶(六角状、立方状和层状液晶)的流变性质,概括了各自的流变性特点并给出了其理论模型,特别对立方相的流变学模型和层状相的剪切诱导转变作用进行了较详细的说明.讨论了因为这种转变而导致的囊泡的形成,并且在表面活性剂和嵌段共聚物中均可观察到剪切诱导的结构转变.     

Spontaneous vesicles, disks, threadlike and spherical micelles found in the solubilization of DMPC liposomes by the detergent DTAC

Iron oxide/MCM-41 nanocomposites, Fe(2)O(3)/MCM-41, containing 5%, 10%, and 20% (w/w) iron oxide, were prepared via a direct nonhydrothermal method at room temperature. The preparations were preformed by using iron(III) nitrate, tetra-ethoxysilane (TEOS), and cetyltrimethylammonium bromide (CTAB) mixed or unmixed with dodecyltrimethylammonium bromide (DTAB). The produced materials were dried and calcined at 550 °C for 3 h. Test materials were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), N(2) gas adsorption/desorption isotherms, small angle and wide angle X-ray diffraction (XRD). Results indicate that mixing of CTAB with DTAB does not harm the formation of blank MCM-41 structure. For the composite Fe(2)O(3)/MCM-41 materials, results showed formation of more stable MCM-41 structure with higher surface area and improved porosity in the presence of mixed (CTAB+DTAB) than in the presence of single (CTAB) surfactants for up to 10% Fe(2)O(3)/MCM-41 (w/w). This was explained in terms of the effect DTAB on contraction of the template micellar size to compensate for the expected size expansion upon the addition of ionic iron(III) nitrate precursor. Highly dispersed Fe(2)O(3) nanoparticles were formed in all cases even with the highest iron oxide percentage. Formation of the nanocomposites was postulated to be determined by fast nucleation and slow growth of iron oxide species, which facilitated formation of well dispersed iron oxide nanoparticles inside and on the wall of the MCM-41 material.     

Rheology of a lyotropic mesophase through a stress-relaxation experiment

We report on the first rheological study of the structural relaxations in a nematic liquid crystalline phase. Linear dynamic and transient shear experiments were applied to a polydomain nematic phase of the CTAB/water system: a liquid crystalline mixture composed of 28 wt% CTAB at 35 degrees C. The decay of the shear modulus, G(t), was analyzed using the CONTIN inverse Laplace transform to obtain a distribution of relaxation times which were compared with ones from the usual fitting procedure based on a generalized Maxwell model. The behavior of the nematic lyotropic structure of the CTAB/water system is characterized by the presence of both slow and fast relaxation times. These were interpreted as being due to a progressive loss of the lyotropic domain orientation and to the breaking/reforming process of the cylindrical aggregates, respectively.     

X-ray diffraction study of the structure of carboxymethylcellulose-cationic surfactant complexes.

We have investigated dilute aqueous solutions of an anionic polymer (carboxymethylcellulose) mixed with cationic surfactants of different chain lengths (dodecyl to octadecyl trimethylammonium bromides: DTAB, TTAB, CTAB and OTAB). The structures of the concentrated phases formed above the precipitation threshold were studied by X-ray diffraction. Different body-centred cubic structures with space groups Pm3n were observed in the presence of surfactant with a short aliphatic chain (DTAB), despite the fact that the polymer persistence length is comparable to the repeat distance of the structure (5 nm). For larger surfactant chain lengths (TTAB and CTAB), the structure of the precipitates can be either cubic (Pm3n) or 2D hexagonal depending on the initial surfactant and polymer concentrations. For still larger chain length (OTAB), the structure becomes lamellar. This structural evolution from micellar cubic towards 2D hexagonal and lamellar is attributed to the decrease of the local curvature of the surfactant aggregates, as observed for flexible synthetic polymers and short DNA fragments under similar conditions. Furthermore, the structure of the bulk complexes formed just below the precipitation threshold anticipates the structure seen in the precipitated phases.     

溶致液晶体系研究及其在三次采油中的应用

研究了石油磺酸盐/正戊醇/水的三元体系和石油磺酸盐/癸烷/正戊醇/水的拟三元体系相图中的液晶区域,揭示了不同组分对液晶区域大小的影响以及液晶的流变性和液晶的结构.在三次采油中,用六角状溶致液晶体系代替三元复合驱体系进行化学驱油,虽然驱油效率更高,但需要进一步降低液晶驱油体系的成本.     

溶致液晶及其在纳米结构材料合成中的应用*

有序纳米结构材料是一类具有广泛应用前景的新材料,在分离、催化、传感器等领域的应用潜力巨大。近年来,利用溶致液晶模板合成纳米结构颗粒和薄膜材料的研究取得了一系列重要进展,包括新纳米结构金属和半导体材料的合成、由过渡金属水合物与表面活性剂构建的新液晶体系、溶致液晶与其它模板结合制备具有多级孔结构的新材料、影响液晶体系及纳米结构材料有序性与稳定性的关键因素、以及纳米结构形成机理等方面的内容。本文就上述几个方面的近期研究成果进行了总结与综述,并展望了利用溶致液晶模板合成纳米结构材料需要进一步深入开展的内容,有助于化学、化学工程和材料科学等领域的相关研究工作。     

Cyclodextrin-surfactant coassembly depends on the cyclodextrin ability to crystallize

Full equilibrium phase diagrams are presented for two ternary systems composed of the cationic surfactant dodecyltrimethylammonium bromide (DTAB), water (D(2)O), and a cyclodextrin, either β-cyclodextrin (β-CD) or (2-hydroypropyl)-β-cyclodextrin (2HPβCD). (2)H NMR, SAXS, WAXS, and visual examination were used to determine the phase boundaries and characterize the nature of the phases formed. Additionally, diffusion (1)H NMR was used to investigate parts of the diagrams. The water solubility of 2HPβCD is 80% (w/w), whereas it is only 1.85% (w/w) for β-CD. Solubility increases for both species upon complexation with DTAB; while the increase is minute for 2HPβCD, it is dramatic for β-CD. Both systems displayed an isotropic liquid solution (L(1)) one-phase region, the extension of which differs extensively between the two systems. Additionally, the DTAB:2HPβCD:water system also comprised a normal hexagonal (H(1)) area, which was not found for the DTAB:β-CD:water system. In the DTAB:β-CD:water system, on the other hand, we found cocrystallization of DTAB and β-CD. From this work we conclude that DTAB and CD molecules form 1:1 inclusion complexes with high affinities. Moreover, we observed indications of an association of 2HPβCD to DTAB micelles in the isotropic solution phase, which was not the case for β-CD and DTAB micelles. This is, to our knowledge, the first complete phase diagrams of surfactant-CD mixtures; as a novel feature it includes the observation of cocrystallization at high concentrations.     

Structural behaviour of mixed cationic surfactant micelles: a small-angle neutron scattering study

Self-assembly in mixtures of two single-chain cationic surfactants, with different tail lengths (CTAB and DTAB) as well as of a single-chain (DTAB) and a double-chain (DDAB) cationic surfactant, with identical tail lengths, have been investigated with small-angle neutron scattering (SANS) and rationalised in terms of bending elasticity properties. The growth behaviour of micelles with respect to surfactant composition appears completely different in the two surfactant mixtures. DTAB form small oblate spheroidal micelles in presence of [NaBr] = 0.1 M that transform into prolate spheroidal mixed CTAB/DTAB micelles upon adding moderate amounts of CTAB, so as to give a mole fraction y = 0.20 in solution. Most unexpectedly, upon further addition of CTAB the mixed CTAB/DTAB micelles grow with an almost equal rate in both length and width directions to form tablets. In contrast to this behaviour, mixed DDAB/DTAB micelles grow virtually exclusively in the length direction, in presence of [NaBr] = 0.1 M, to form elongated ellipsoidal (tablet-shaped) and subsequently long wormlike micelles as the fraction of DDAB in the micelles increases. Mixed DDAB/DTAB micelles grow to become as long as 2000 Å before an abrupt transition to large bilayer structures occurs. This means that the micelles are much longer at the micelle-to-bilayer transition as compared to the same mixture in absence of added salt. It is found that the point of transition from micelles to bilayers is significantly shifted towards higher fractions of aggregated DTAB as an appreciable amount of salt is added to DDAB/DTAB mixtures, indicating a considerable reduction of the spontaneous curvature with an increasing [NaBr]. By means of deducing the various bending elasticity constants from our experimental results, according to a novel approach by ours, we are able to conclude that the different growth behaviours appear as a consequence of a considerably lower bending rigidity, as well as higher saddle-splay constant, for DDAB/DTAB surfactant mixtures in presence of [NaBr] = 0.1 M, as compared to mixtures of CTAB/DTAB in [NaBr] = 0.1 M and DDAB/DTAB in absence of added salt.     

The Diammoniates of dipotassiumtetraethinylozincate and -cadmate: K2M(C2H)4.2NH3 (M = Zn, Cd)

By reaction of KC(2)H and K(2)Zn(CN)(4) in liquid ammonia, the diammoniate K(2)Zn(C(2)H)(4).2NH(3) was obtained. K(2)Cd(C(2)H)(4).2NH(3) was synthesized by reacting KC(2)H, Cd(NH(2))(2), and acetylene in liquid ammonia. The crystal structures of the air and temperature sensitive compounds were determined by X-ray single crystal diffraction at low temperatures (T = 170 K). Both compounds crystallize in the monoclinic space group I2/a (No. 15) with Z = 4. K(2)Zn(C(2)H)(4).2NH(3): a = 7.289(1) A, b = 12.765(2) A, c = 14.066(2) A, beta = 98.11(2) degrees. K(2)Cd(C(2)H)(4).2NH(3): a = 7.444(1) A, b = 12.619(3) A, c = 14.304(2) A, beta = 98.94(1) degrees. Characteristic structural motifs are tetrahedral [M(C(2)H)(4)](2-) fragments (M = Zn, Cd) and zigzag chains of edge sharing distorted (C(2)H)(6) octahedra centered by potassium ions. These zigzag chains are connected by a second type of crystallographically distinct potassium ions that also bind to two ammonia molecules.     

Lyotropic liquid crystalline phase behaviour of a monomeric and a polymeric monosaccharide amphiphile in aqueous solution

Monomeric and polymeric amphiphiles were synthesized which exhibit lyotropic liquid crystalline phases in aqueous solution. The hydrophobic group of the monomeric surfactant is a dodecane-group esterified with acrylic acid. The hydrophilic unit is a monosaccharide derivative. By radical polymerization the monomer (N-D(-)-gluco-N-methyl-(12-acryloyloxy)-dodecane-l-amide) is converted into the corresponding polymeric surfactant. The monomer as well as the polymer exhibit a lyotropic 1.c. phase of lamellar structure. Owing to the polymerization the regime of the lamellar phase is greatly enlarged for the polymer, compared to the monomeric sufactant. These results confirm earlier investigations on non-ionic ethylene-glycol surfactants.     

Vanadium Pentoxide Sol and Gel Mesophases

Colloidal suspensions of V₂O₅ ribbon-like particles display optical textures typical of lyotropic nematic phases. Tactoids (small nematic droplets) and then isotropic phases are formed as these systems are diluted. Nematic suspensions can be oriented by applying a magnetic or an electric field. Such a liquid crystal behavior is mainly due to the highly anisotropic shape of vanadium oxide colloidal particles. Acid dissociation at the oxide/water interface gives rise to surface electrical charges and electrostatic repulsion should also be responsible for the stabilization of the nematic phases. Anisotropic xerogel layers are formed when these gels are deposited and dried onto flat substrates. X-ray diffraction patterns of such coatings exhibit a series of 00l harmonics due to the turbostratic stacking of the oxide particles. Dehydration is reversible and fluid mesophases are again obtained via a swelling process when water is added to the xerogel.