First carbazole-based lamellar liquid crystal system

The synthesis and characterization of seven polysubstituted 9-arylcarbazole derivatives is described. The influence of the number of chains peripherally bonded to the core, as well as the length of the chains, on the mesophase behaviour of the synthesized systems has been studied. The nature of the linking group between the core and the peripheral chains has also been considered. One of these compounds displays liquid crystalline behaviour, as confirmed by optical polarizing microscopy, differential scanning calorimetry and X-ray diffraction, being the first carbazole-based lamellar liquid crystal system reported in the literature.     

油酸钠/水/十六烷/三丙烯酸季戊四醇酯体系层状 液晶的聚合

将十六烷增溶于油酸钠(NaOL)/水体系层状液晶的油层,共聚单体三丙烯酸季戊四醇酯(PETA)增溶于油酸钠/水体系层状液晶的两亲双层。72℃下,以增容于油层中的十六烷作为阻隔。在层状液晶同一两新双层内的两新分子油酸钠与共聚单体PETA之间进行共聚,得到了具有层状结构、并具有较好表面活性的共聚物。     

Phase behavior and self-organized structures of diglycerol monolaurate in different nonpolar organic solvents

Nonaqueous phase behavior and reverse micellar structures of diglycerol monolaurate (DGL) in different nonpolar organic solvents, such as n-decane, n-tetradecane, and n-hexadecane, have been studied over a wide range of compositions and temperatures. The equilibrium phases are identified by means of visual observation and small-angle X-ray scattering (SAXS). A solid phase present at lower temperature swells small amount of oils and transforms into a lamellar liquid crystalline structure at higher temperature. The melting temperature of the solid phase is virtually constant at all mixing ratios of the surfactant and oil. With the further increase of temperature, the liquid crystal transforms into an isotropic single-liquid phase near the surfactant axis, whereas there is a coexistence region of two isotropic phases near the solvent axis. The area of the two-liquid (II) phase region depends largely on the hydrocarbon chain length of the oils, the longer chain leading to the wider II area. Accordingly, the DGL surfactant is most miscible with decane, exhibiting a reduced miscibility with increasing solvent hydrocarbon chain length. Increasing temperature enhances the dissolution tendency of the surfactant in oil, where the two-liquid phase transforms into an isotropic single phase. SAXS analysis based on the GIFT technique is used to characterize the structure of the reverse micellar aggregates in the isotropic single-phase liquids. We have demonstrated that instead of changing polarity or a functional group of the solvent molecules, if we optimize the hydrophilic nature of the surfactant head group, the alkyl chain length of the solvent oils can serve as a tunable parameter of the micellar geometry. The hydrophilic surfactant DGL interestingly forms cylindrical micelles in nonpolar oils, decane, and tetradecane in the dilute region above the II phase region. The micellar size shows temperature dependence behavior, and the micellar length goes on increasing with decreasing temperature; eventually we found a signature of the onset of critical fluctuations in the deduced pair-distance distribution function near the phase separation line. The signature of the attractive interaction between the cylindrical reverse aggregates when a phase separation line is approached is likely to be a precursor of critical phenomenon. Doping with a trace of water results in a similar but more pronounced structural enhancement. The transfer free energy of diglycerol moiety from a hydrophilic environment to different hydrocarbon oils may account for these phenomena.     

三组份非水体系的溶致液晶的研究

在非水三元体系(卵磷脂,乙二醇,甲醇)中能得到溶致液晶,其中溶剂必须经过严格的脱水处理,本文使用偏振光显微镜确定溶致液晶的相图,获得一些典型照片,用低角度X射线衍射仪测定其几何参数,结果表明所得液晶为层状液晶,并对在该体系中,由于甲醇浓度的改变而引起了卵磷脂分子的平均截面积、液晶层间距和其渗透率变化规律作了理论探讨和分析。     

Molecular location in a nonaqueous lyotropic liquid crystal polymer

A surfactant bis[2-(10-undecenoyloxycarbonyl)ethyl] (p-vinylbenzoyl) methylammonium chloride formed a lamellar liquid crystal in native form and retained the structure after polymerization. Addition of heptadiene, of glycerylmonomethacrylate, and of both to the surfactant monomer gave an isotropic solution, which was transformed to a lamellar liquid crystal after polymerization. Low angle X-ray diffractometry was used to determine the interlayer spacing and to estimate the location of the added molecules. 1.6-Heptadiene was located between methyl group layers of the surfactant chains with 46 vol % of the molecules penetrating between the hydrocarbon chains of the surfactant. Addition of both the polar and the nonpolar monomer followed by polymerization caused the latter to be expelled from the space in between the chains.     

Extreme swelling of a lyotropic lamellar liquid crystal

The evolution of the OBS/water/decane/pentanol lyotropic lamellar crystal is followed from 0% to more than 90% decane content. The lamellar spacing (d) varies then from 35 Å to 11000 Å. The swelling is followed with small angle x-ray scattering and the Bragg divergence in the intensity is found to disappear in moderately swollen lamellar crystal (d from 200 Å up to 800 Å) while the central scattering increases. More striking is the reappearance of the Bragg divergences observed by SAXS (d from 800 Å to 1100 Å) and for extremely swollen lamellar crystals in the angular distribution of scattered light (d from 2 000 Å to 10 000 Å). We discuss these observations along the lines of the recent models of swollen lamellar liquid crystals and in particular the apparent evolution of the dilute lamellae.     

Triton X-100/C10H21OH/H2O体系层状液晶中超微粒子材料PbS的合成

将Pb(NO3)2和Ns2S分别溶于Triton X-100/C10H21OH/H2O体系层状液晶溶剂层中, 混和即可在溶剂层中生成PbS粒子, 并以层状液晶中溶剂层厚度的大小, 限定所合成PbS粒子的尺寸小于10nm, 改变有关组分含量对PbS超微粒子大小无显著影响, 所合成PbS超微粒子的平均粒径均小于10nm.     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Alkyl chain order in a lamellar lyotropic liquid crystal with varying surface charge density

Abstract

The alkyl chain order in the lamellar liquid-crystalline phase formed in the octylamine/octylammonium chloride/water system has been investigated by ²H N.M.R. at constant mole ratio water/amphiphile and varying charge of the lamellae. The results are correlated to the dimensions of the aggregate obtained from X-ray low angle diffraction measurements.     

Alkyl chain order in a lamellar lyotropic liquid crystal with varying surface charge density

The alkyl chain order in the lamellar liquid-crystalline phase formed in the octylamine/octylammonium chloride/water system has been investigated by ²H N.M.R. at constant mole ratio water/amphiphile and varying charge of the lamellae. The results are correlated to the dimensions of the aggregate obtained from X-ray low angle diffraction measurements.     

Orientational anisotropy in the polydomain lamellar phase of a lyotropic liquid crystal

Diffusion-diffusion correlation measurements by NMR are used to investigate the degree of orientational order in the lamellar phase of Aerosol OT (bis(2-ethylhexyl) sodium sulfosuccinate) and water at a range of surfactant concentrations (25, 33, and 50 wt %). We show that true isotropy of the domains is found at the lowest concentration but that at higher concentrations deviations from isotropy can be found, as evidenced by asymmetry on the 2D correlation distributions. We further discuss the significance of asymmetry in diffusion-diffusion exchange experiments, 2D distributions that should always be symmetric in steady state.     

Shear-induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50°C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at “Plateau borders” with three or more sides. Where walls meet three at a time, they do so at approximately 120° angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.     

Trition X-100/C_(10)H_(21)OH/H_2O体系层状液晶中纳米羟基磷灰石粉体的合成

本文以Triton X-100/C10H21OH/H2O体系层状溶致液晶为模板,Ca(NO3)2和(NH4)2HPO4为反应物,在一定的pH条件下,通过三元相图确定了层状液晶单相区域,并合成了羟基磷灰石(HA)纳米颗粒。用傅立叶红外光谱(FTIR),X射线衍射(XRD)和透射电子显微镜(TEM)对产物进行了表征。并考察了不同助表面活性剂浓度和不同表面活性剂浓度对产物的形貌和尺寸的影响。结果表明所制备的HA纳米颗粒平均直径为8~10nm、长度在100nm左右,呈针状。助表面活性剂浓度对HA形貌及尺寸影响不大,但是在一定范围内改变表面活性剂浓度可以起到调控HA纳米颗粒形貌和尺寸的作用。     

Determination of aflatoxins in olive oil by liquid chromatography-tandem mass spectrometry

A liquid chromatography-tandem mass spectrometric with electrospray ionization (LC/ESI-MS/MS) method for determining the four naturally occurring aflatoxins (AFs) B1, B2, G1, and G2 in olive oil is proposed. AFs were extracted from oil sample by means of matrix solid phase dispersion (MSPDE), utilizing C18 as dispersing material. No further purification step, such as lipid removal, was performed. Aflatoxin M1, the hepatic metabolite of AFB1, was employed as internal standard. Olive oil extract was analyzed by LC/ESI-MS/MS in positive ionization mode, with multireaction monitoring acquisition. Due to a signal suppression ranging between 4 and 23%, quantitation was performed by matrix-matched calibration curves. The regression line coefficients of determination were above 0.9991. Sample recoveries ranged from 92 to 107%, with relative standard deviations below 13% for spiking levels between 0.5 and 5 ng g⁻¹; method quantification limits ranged between 0.04 and 0.12 ng g⁻¹. The developed LC/ESI-MS/MS method, although not as sensitive as LC coupled to fluorescence detection, is rapid, selective, accurate and precise, thus it can be used as confirmatory assay. The MSPDE appears suitable for application to other oleaginous matrices and for multiresidue investigation.     

层状液晶中氧化铜纳米片的制备及电容性能研究

以十二烷基硫酸钠、苯甲醇和硫酸铜溶液形成的层状液晶为模板,通过恒电位电沉积法制备得到层状氧化铜纳米片。运用扫描电镜、能谱和X-射线衍射等手段对其形貌和结构进行表征,并对产物的电化学性能进行研究。结果表明:所制备的层状氧化铜纳米片具有较高的比电容、较好的循环稳定性和较小的电极电阻,可作为电容器的电极材料。     

Synthesis of the rare earth compound nanosheets induced by lamellar liquid crystal

Synthesis of rare earth compound nanosheets with uniform thickness is of potential interest to the luminescent materials. Herein, whole series of rare earth hydrates and oxides nanosheets have been synthesized by using lamellar liquid crystal as a template, except Ce and Pm. Polarizing microscope images and transmission electron microscopy images show that the lamellar liquid crystal can prevent the rare earth hydrate nanosheets from curving to nanotubes in the processes of synthesis. The synthesized nanosheets have a uniform thickness of 10–15 nm and can retain morphology after being calcined at 650 °C. After facile chemical treatment, the functionalized rare earth compounds were obtained, which have unique luminescent property.     

Evolution of a lamellar domain structure for an equilibrating lyotropic liquid crystal

Aerosol OT/water exhibits a lamellar phase over a wide range of concentrations. We show, by magnetic resonance (NMR) and scanning electron microscopy (SEM), that the morphology of the lamellar phase varies significantly across that range and that the rate of equilibration depends strongly on concentration (25, 33, and 50 wt %) with, paradoxically, the faster equilibration at higher surfactant concentrations. We find that the 25 wt % sample exhibits a defect-rich local structure, characteristic of a superposed L(3) character. Further into the lamellar region, at 33 wt %, this defect-rich structure persists heterogeneously, while, at 50 wt %, the lamellar phase domains are highly ordered. The NMR methods used here included (2)H spectroscopy and the two-dimensional NMR method, diffusion-diffusion exchange spectroscopy (DEXSY). The latter was used to obtain quantitative information on the domain sizes and defects within the polydomain lamellar mesophase. Comparison of the NMR with the SEM results suggests that, at 25 wt % AOT, bilayer defects play an important role in influencing the (2)H NMR and DEXSY NMR results.     

Solubilization of oil in a mixed cationic liquid crystal

The mixing fraction of didodecyldimethylammonium bromide (DDAB) in dodecyltrimethylammonium bromide + DDAB to produce a lamellar liquid crystal (L _α) abruptly decreases upon addition of a small amount of m-xylene, whereas the mixing fraction becomes constant at high m-xylene content. Similar results were obtained in saturated hydrocarbon systems. It is considered that oil molecules in the surfactant palisade layer increases the effective cross-sectional area per surfactant head group, a_s, whereas a_s is constant if the oil molecules are solubilized in the core of the liquid crystal. The volume fraction of penetrating oil in the total solubilized oil is defined as a penetration parameter, Pe, which is calculated from small-angle X-ray scattering data. Pe is high in the m-xylene system, whereas it is low in the n-decane system. Even in the same oil system, Pe decreases dramatically with increasing solubilization. Hence, most of the oil added penetrates into a palisade layer at an early stage of oil addition. This causes a change in the mixing fraction of surfactant in the L _α phase. Thereafter the oil is solubilized in the core of the bilayer with further addition of oil. Received: 20 April 1998 Accepted: 16 July 1998     

Stabilization of O/W emulsion with hydrophilic/hydrophobic clay particles

In this study, a stabilizing behavior of clay in a 40/60 w/w oil-in-water (O/W) emulsion is investigated by macro- and microscopic morphological observations, rheology, and X-ray diffraction measurements. Hydrophilic and hydrophobic clays (Montmorillonites) are tested for stabilization of emulsion. When hydrophilic clay showing interfacial localization is added to the emulsion, emulsion is not stable to phase separation (creaming). With hydrophobic clay, the emulsion shows phase inversion to water-in-oil (W/O) emulsion due to the increase in oil viscosity which results in phase separation of sedimentation. On the other hand, with the mixture of hydrophilic and hydrophobic clays, the emulsion shows a synergistic macroscopic and microscopic stabilization due to the formation of composite structure at the interface by hydrophilic and hydrophobic clays.