磺酸型双子表面活性剂的溶致液晶结构研究

合成了一种磺酸型双子表面活性剂6,6 -(丁基-1,4-二基双氧)双(3-壬基苯磺酸)(9BA-4-9BA), 利用偏光显微镜和X射线衍射分析仪研究了其在水溶液和乙酸乙酯溶液中的溶致液晶结构变化. 结果表明, 9BA-4-9BA在两种溶剂及其混合溶剂中均可出现溶致液晶态结构, 并且双子表面活性剂的溶致液晶相态与溶液浓度和溶剂种类密切相关. 随着浓度增加, 9BA-4-9BA水溶液溶致液晶结构由立方相经由片层立方相转变为层状液晶相, 乙酸乙酯溶液中主要以层状液晶相存在.     

泊洛沙姆F127和丹皮酚对GMO液晶相变的影响

对GMO/H₂O, GMO/F-127/H₂O和GMO/paeonol/H₂O三种体系的液晶特性进行了考察, 结合粘度及偏光纹理绘制相图, 运用“drying”方法的原理鉴别了反相胶束和立方相液晶, 并采用临界堆积参数p值理论探讨水溶性和脂溶性物质引起液晶相变的机理. 结果表明水溶性泊洛沙姆F127可使层状液晶区域变宽, 立方相液晶区域变窄|脂溶性丹皮酚可使层状液晶和立方相液晶区域变窄, 反相六角相液晶变宽. 本研究通过对单油酸甘油酯(GMO)液晶特征的研究, 为其作为载体的应用提供了理论基础.     

剪切场作用下环形二嵌段共聚物微相形态变化的耗散粒子动力学研究

采用耗散粒子动力学(Dissipative particle dynamics, DPD)方法研究了在剪切场作用下, 环形二嵌段共聚物微观相分离过程中的形态变化. 在层状(lamellae, LAM)体系中发生了微相的平行重取向和平行-垂直转变以及剪切导致的波动不稳定现象. 对于穿孔层状(Perforated lamellae, PL)体系, 强剪切导致了穿孔层状-柱状(Hexagonal cylinder, HEX)微相转变. 在剪切场作用下, 柱状体系中同样也有平行重取向发生. 可以用相区破坏-相区重生的两步机理描述微相的平行重取向、平行-垂直转变以及PL-HEX转变现象. 在球状相(Body centered cubic, BCC)体系中发现了剪切诱导相融合.     

CPDB／正丁醇／正辛烷／水体系溶致液晶的^2HNMR和DSC法研究

测定了溴化十六烷基吡啶／正丁醇／正辛烷／水体系的相平衡，在液晶区域选取样品点，用＾２ＨＮＭＲ和差示扫描量热法，并与液晶纹理相对照研究了该区域的相结构变化，结果表明，在一定温度下，随着含水量的增加，体系从单一的Ｗ／Ｏ型微乳液→微乳液和层状液晶共存→层状液晶与六角状液晶共存→层状、六角状与六角状向立方状过渡晶型的三相共存→立方状→Ｏ／Ｗ型微乳液过度，在组成固定情况下，研究了该体系液晶相结构随温度升高所     

Brij35／油酸钠／油酸／水体系的溶致液晶性质——应用偏光显微镜,SAXS,~2H-NMR和流变等方法

首先研究Brij35(十二烷基聚氧乙烯(23)醚)/油酸钠/油酸/水体系的拟三元相图, 发现该体系最大的特点是溶致液晶占相图总面积的2/3. 对O/W型微乳液进行流动曲线研究, 属于牛顿流体. 对溶致液晶体系开展了偏光显微镜, SAXS, ²H-NMR等方法的研究. 当体系组成沿着相图中AA¢线改变时, 其液晶结构变化的顺序是, 立方状液晶→立方状与层状液晶共存→层状液晶→层状液晶与六角状液晶共存→六角状液晶. 并且对上述体系系统地开展了流变性质的研究. 其结果再一次证实液晶结构随着体系中某组分的改变而发生变化. 同时还得到立方液晶和六角状液晶的晶格参数, 分别为10.53和5.68 nm.     

阴离子表面活性剂为模板合成双重介孔结构二氧化硅

本文报道以阴离子表面活性剂十二烷基肌氨酸钠为模板,合成具有层状结构和蠕虫状介观结构的双重介孔二氧化硅颗粒．这些颗粒的尺度在300～50011111,氮气吸附表明其比表面为536m^2/g,孔体积为0．83cm^3／g,具有3nm和12nm的双重介孔分布．层状结构形成可归因于表面活性剂形成的层状液晶相模板,而无序蠕虫相是由表面活性剂柱状液晶相模板诱导形成的．层状液晶相的产生可归因于部分质子化的羧酸表面活性剂诱导的柱状相到层状相的转化．     

蔗糖对MO/水立方液晶体系流变性质的影响

主要研究了蔗糖对甘油单油酸脂(monoolein, MO)/水立方液晶体系的流变学性质及其相行为的影响. 根据体系流变性质的变化和偏光显微镜照片, 得出随着蔗糖含量的增加, MO/水体系发生了由反相立方液晶到反相六角状液晶的相转变. 蔗糖与MO分子通过氢键相互作用, 减弱了两亲分子间的静电斥力. 当蔗糖含量增加到一临界值时, 体系的立方结构被破坏, 继续增加蔗糖的含量, 体系就会形成新的反相六角状液晶.     

小角X射线散射表征AOT/水层状溶致液晶的有序性

用小角X射线散射研究了AOT/水层状溶致液晶的有序性. 通过对散射曲线的解析, 讨论了表面活性剂浓度、温度和助表面活性剂等三个方面对溶致液晶层状相结构有序性的影响. 在一定的范围内, 提高温度, 改变表面活性剂浓度和加入少量助表面活性剂可使碳氢链排列由稀疏转变为密实, 层状相也相应地由“柔性双层”过渡到更加有序化的“平面双层”. 基于形状因子和体系内分子间作用力, 提出了层状相形成与有序化的机理, 同时采用分子模拟的方法展现了不同浓度下的液晶结构.     

液晶态磷脂酰乙醇胺脂质体和LB膜结构的研究

用原子力显微镜、小角X射线散射和³¹PNMR分别对液晶态磷脂酰乙醇胺脂质体和LB膜结构进行了研究.用原子力显微镜观察到了液晶态脂质体的立方相和双层膜共存的结构图像.研究结果表明,两相共存的状态与双亲性分子的结构、浓度以及介质的组分和pH等因素有关.用小角X射线散射和³¹PNMR研究发现,在DEPE液晶态中,钠盐诱导形成Q²²⁹(Im3m)立方相.DEPE液晶态分别在37.5℃出现L_β→L_α可逆相变,在63.5℃出现L_α→H_Ⅱ可逆相变.     

混合表面活性剂双水相性质的研究

本文利用电导法及冷冻蚀刻实验技术研究了正负离子表面活性双水相上相中的液晶结构状态及其相关性质。在双水相相体积比一组成关系曲线上及上相电导率—组成曲线上,均存在明显的转折。转折处组成是有偏光现象的双水相与无偏光现象的双水相的分水岭,立方液晶导电能力与容纳水的能力强于层状液晶或六方液晶。冷冻蚀刻实验证实了无偏光现象的立方液晶的存在。本文对一些机理进行了讨论。     

On structural transitions in a discontinuous micellar cubic phase loaded with sodium diclofenac

An intermediate mesophase of lyotropic liquid crystalline structure from the ternary mixtures of glycerol monooleate, water, and ethanol was recently characterized in our lab. This mesophase, termed Q(L), consists of discrete discontinuous micelles arranged in a cubic array. The Q(L) phase can solubilize very significant loads of water-insoluble anti-inflamatory drug sodium diclofenac (Na-DFC). Close examination of the internal structures of the lyotropic liquid structure upon increasing the solubilization loads reveals the existence of three structural transitions controlled by the Na-DFC levels. Up to 0.4 wt% Na-DFC, the Q(L) structure remains intact with some influence on the hydration of the headgroups and on the intermicellar forces. However, at 0.8 to 1.2 wt% Na-DFC, the discontinuous micellar cubic phase is transformed into a more condensed mesophase of a bicontinuous cubic phase. At > or =1.2 wt% Na-DFC, the cubic phase is converted into a lamellar phase (L(alpha)). Within 5.5 to 7.3 wt% Na-DFC the mesophase is progressively transformed into a less ordered lamellar structure. At 12 wt% Na-DFC crystals tend to precipitate out. At low Na-DFC concentrations the drug behaves like a lyotropic or kosmotropic salt and can salt-out the surfactant from its water layer, but at higher levels it behaves like a hydrotropic, chaotropic salt and can salt-in the surfactant. The Na-DFC location and position within the interface as well as its polarization and partial ionization are strongly affected by its solubilization contents and the structure that it is inducing. In the cubic phase the drug is located less close to the hydration layer while once transition occurs it is exposed more to the water layer and the surfactant headgroups.     

Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 °C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 ? following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms an L(2) phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L(α)) at room temperature and up to ～ 40 °C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q(II)(D)) and gyroid (Q(II)(G)) bicontinuous cubic phases in addition to an L(α) phase.     

Synthesis and lyotropic phase behavior of novel nonionic surfactants for the crystallization of integral membrane proteins

A series of new sugar-based nonionic surfactants have been synthesized and their lyotropic liquid crystalline properties characterized. When in contact with water, these surfactants formed a range of lyotropic liquid crystalline phases, including cubic, hexagonal, and lamellar, as well as a separate micellar phase. These are features that have promise for the crystallization of integral membrane proteins.     

Rheological properties of lyotropic liquid crystals encapsulating curcumin

This study constructed new curcumin-loaded lyotropic liquid crystals containing pharmaceutically accepted oil, and ethyl oleate (EtOL). Three liquid crystalline phases including lamellar, hexagonal, and cubic phases were identified by means of the polarized optical microscopy and rheology method. By analyzing the shear viscosity (η_0.1), the viscosity of curcumin-liquid crystals is smaller than those without curcumin. Dynamic rheological results show that: Dissolved curcumin in EtOL can make the elastic modulus of hexagonal and cubic phase increase compared with that without curcumin, while the elastic modulus of lamellar phase decreases. Dissolved curcumin in Brij 97 can lead to the decreasing of the elastic modulus for cubic and lamellar phases, whereas it has little influence on hexagonal phase. When the curcumin is solubilized in both EtOL and Brij 97, the elastic modus of hexagonal phase increase, the elastic modus of lamellar and cubic phases decrease compared with that without curcumin. Furthermore, three temperature turning points were identified by the change in the slope of tanδ (G″/G′) for curcumin-hexagonal liquid crystal. These studies might be a help to study the storage of drug carrier and in vitro release properties of lyotropic liquid crystals containing curcumin.     

Templating Polymerization of Dodecylammonium Surfactants with Polymerizable (Meth)acrylate Counter Ions

Both dodecylammonium acrylate (I) and dodecylammonium methacrylate (II) are reactive surfactants in which the polymerizable group is the organic counterion. Templating polymerization of I and II from the lyotropic liquid crystalline (LLC) lamellar phase was successfully performed with conservation of the supramolecular structure. A 20 wt% aqueous solution of II formed cubic bicontinuous phases, even upon addition of divinyl benzene (DVB). Polymerization from the cubic phases was attempted without and with DVB (3 wt%). Bicontinuous cubic phases always evolved toward lamellar structures upon polymerization.     

Ordered 2-D and 3-D nanostructured amphiphile self-assembly materials stable in excess solvent

Amphiphile lyotropic liquid crystalline self-assembly materials are being used for a diverse range of applications. Historically, the most studied lyotropic liquid crystalline phase is probably the one-dimensional (1-D) lamellar phase, which has been employed as a model system for biomembranes and for drug delivery applications. In recent years, the structurally more complex 2-D and 3-D ordered lyotropic liquid crystalline phases, of which reversed hexagonal (H(2)) and reversed cubic phases (v(2)) are two prominent examples, have received growing interest. As is the case for the lamellar phase, these phases are frequently stable in excess water, which facilitates the preparation of nanoparticle dispersions and makes them suitable candidates for the encapsulation and controlled release of drugs. Integral membrane protein crystallization media and templates for the synthesis of inorganic nanostructured materials are other applications for 2-D and 3-D amphiphile self-assembly materials. The number of amphiphiles identified as forming nanostructured reversed phases stable in excess solvent is rapidly growing. In this article, different classes of amphiphiles that form reversed phases in excess solvent are reviewed, with an emphasis on linking phase behavior to amphiphile structure. The different amphiphile classes include: ethylene oxide-, monoacylglycerol-, glycolipid-, phosphatidylethanolamine-, and urea-based amphiphiles.     

Polymerisation in lyotropic liquid-crystalline phases of dioctadecyldimethylammonium bromide

The polymerisation of styrene in lyotropic liquid-crystalline (LC) phases of dioctadecyldimethylammonium bromide (DODAB) in water is explored. Amphiphile concentrations between 20 and 50 wt % are employed. The study is set out as a model study for polymerisation reactions in nonstabilised, nonfunctional bilayer systems. X-ray characterisation was used to assess the phase behaviour of the lyotropic mesophases before, during and after polymerisation. The DODAB/water system forms the lamellar phase within the concentration range considered. Addition of styrene to the lamellar phase of DODAB at an equimolar ratio induces a phase shift to a bicontinuous cubic phase at elevated temperatures near the phase-transition temperature. Upon polymerisation within this cubic phase, the phase structure is maintained if the system is kept at constant temperature; however, if the polymer/amphiphile phase is cooled, the lamellar phase, being typical of the DODAB/water system, is restored. It is concluded that, as a result of phase separation between the polymer and the amphiphile phase, the polymerisation in lyotropic LC phases does not provide a stable copy of the templating amphiphile phase. This is in analogy to the observations for polymerisations in other lyotropic phases. Received: 16 March 2000 Accepted: 1 July 2000     

Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes

A series of chelating amphiphiles and their gadolinium (Gd(iii)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.     

Phenomenological theory of the nematic to lamellar phase transition in lyotropic liquid crystals

A phenomenological theory is presented to describe the nematic to lamellar phase transition in lyotropic liquid crystals. The problem of the first or second order transition is explored by means of the variation of the surfactant concentration. The possibility of the tricritical point at the nematic to lamellar phase transition is discussed in a phenomenological way. The influence of the electrolyte on this transition is also discussed by varying the coupling between the electrolyte concentration variables and the order parameters. The theoretical prediction is found to be in good qualitative agreement with experimental results.     

Hydrostatic pressure effects on a hydrated lipid inverse micellar Fd3m cubic phase

Over a range of hydration, unsaturated diacylglycerol/phosphatidylcholine mixtures adopt an inverse micellar cubic phase, of crystallographic space group Fd3m. In this study hydrated DOPC:DOG mixtures with a molar ratio close to 1 : 2 were examined as a function of hydrostatic pressure, using synchrotron X-ray diffraction. The small-angle diffraction pattern at atmospheric pressure was used to calculate 2-D sections through the electron density map. Pressure initially has very little effect on the structure of the Fd3m cubic phase, in contrast to its effect on hydrated inverse bicontinuous cubic phases. At close to 2 kbar, a sharp transition occurs from the Fd3m phase to a pair of coexisting phases, an inverse hexagonal H(II) phase plus an (ordered) lamellar phase. Upon increasing the pressure to 3 kbar, a further sharp transition occurs from the H(II) phase to a (fluid) lamellar phase, in coexistence with the ordered lamellar phase. These transitions are fully reversible, but show hysteresis. Remarkably, the lattice parameter of the Fd3m phase is practically independent of pressure. These results show that these two lipids are miscible at low pressure, adopting a single lyotropic phase (Fd3m); they then become immiscible above a critical pressure, phase separating into DOPC-rich and DOG-rich phases.