掺杂聚合物对溶致液晶结构的影响

利用聚合物大分子作构建组分,将其掺杂到不同类型表面活性剂构成的溶致液晶中,考察对液晶相结构的影响．利用小角X射线散射及偏光显微镜对聚合物掺杂前后液晶的结构进行表征,并讨论了聚合物与液晶模板间的相互作用．对阴离子型表面活性剂琥珀酸二异辛酯磺酸钠(AOT)／水液晶体系,聚合物的嵌入使层间距d增大;而对非离子表面活性剂十二烷基聚氧乙烯醚(C12EO4)／水体系,除小分子量的聚乙二醇PEG400外,其它聚合物嵌入使d减小,表明聚合物分子类型、大小及浓度对溶致液晶的结构参数甚至组装方式有不同的影响机制．     

Lamellar Liquid Crystals Formed in Ternary DEP/Oil/Water Systems

Lamellar liquid crystals of the nonionic surfactant dodecyl polyoxyethylene (4) polyoxypropylene (5) ether (DEP) were investigated by means of phase diagram and rheological technique at 25°C in the presence of different solvents. The aqueous medium includes pure water, physiological saline and 20% sucrose solution, and the oil phase includes isopropyl myristate (IPM), oleic acid, and geraniol, which are all pharmaceutically accepted chemicals. The steady and dynamic rheological property analyses of the lamellar liquid crystals formed in DEP/H₂O/IPM system indicate that the lamellar samples constructed by this special surfactant behave as pseudo-plastic fluid with relatively high elasticity and possess defects in their assembled structure. Also in this system, the elastic character gets decreased with increase in the water content. Furthermore, the comparison investigations show that the relatively high polar oil component increases the network strength of the lamellar phase, while increase in the polarity of water phase enhances the structure defects.     

层状溶致液晶中磁性纳米粒子掺杂的研究

选择非离子表面活性剂十二烷基(4)聚氧乙烯醚(C₁₂E₄)与H₂O构成的溶致液晶(LLC)层状模板, 掺杂油酸铵包覆的Fe₃O₄亲水性磁性纳米粒子, 构建稳定的有机/无机杂合体. 用透射电镜(TEM), X射线粉末衍射(XRD), 偏光显微镜(POM), 小角X射线散射(SAXS)和振动探针式磁强计(VSM)等对粒子及掺杂前后的层状液晶相结构变化进行表征. 结果表明, 粒子掺入使LLC模板的层间距产生了改变, 同时增强了体系有序性．通过对杂合体表征结果的分析, 阐述了模板与粒子间相互作用的机理.     

Inorganic Polymerization in a Non-Ionic Lyotropic Lamellar Phase

Silicon tetramethoxide was polymerized within a nonionic lyotropic lamellar phase. After gelation, the birefringence of the sample is preserved and polarized light optical microscope observations reveal no segregation. High Resolution Small Angle X-ray Scattering patterns of the gel shows Bragg peaks characteristic of a layered structure. Freeze fracture experiments on the lamellar gel show stacks of parallel bilayers. The experimental observations indicate that the silica is located in the lamellar structure.     

溶致液晶中金属纳米粒子的掺杂及其作用机制研究

在用琥珀酸二异辛酯磺酸钠(AOT)构建的具有长程有序结构的层状溶致液晶内, 用不同方式导入预制的亲油或亲水贵金属纳米粒子, 可得到纳米粒子分布在不同介观空间内的无机/有机杂合体. 依据小角X射线散射和偏光显微镜结果, 通过分析掺杂纳米粒子与液晶模板的相互作用, 对掺杂前后体系结构的变化及制得杂合体的稳定性进行了表征. 结果表明, 除考虑掺杂粒子与层状模板空间的匹配外, 体系中静电斥力、范德华引力和Helfrich涨落力之间的平衡是维持液晶结构稳定的基本条件.     

层状溶致液晶中电沉积铂纳米线

以非离子表面活性剂四氧乙烯基正十二烷基醚与氯铂酸水溶液构建层状溶致液晶, 通过电沉积技术制备了金属铂纳米线. 分别采用偏光显微镜、小角X射线散射对液晶进行结构分析, 通过透射电镜和能量弥散X射线谱分析观测产物形貌并确定其组成. 结果表明, 相对于饱和甘汞电极, 沉积电势在0.05～0.20 V范围内, 金属铂沿表面活性剂双分子层膜生长, 反应前后液晶相的长程周期性结构无明显变化; 在0.10 V沉积电势下, 随反应时间从960 s延长至3840 s, 去除表面活性剂后沉积产物分别为层状纳米粒子、层状纳米线以及长度达十几微米且致密的纳米线. 讨论了层状液晶对沉积产物的结构导向作用.     

Dopant-Mediated Interactions in a Lecithin Lamellar Phase

Interactions induced by dopants in a lamellar phase constructed from the lecithin and water are analyzed by the small angle x-ray scattering (SAXS) technique. From SAXS patterns, scattering peak or curve shape changes disclose information on phase structure as well as the interactions between dopant and host matrices. At a certain concentration, two amphiphilic tri-block copolymers (Pluronic P123 and F127) as dopants squeeze themselves into the lecithin bilayers with PPO hydrophobic blocks and produce various effects on the lamellar phase depending on the length of PEO hydrophilic groups. Coexistence of two different lamellar phases is observed in P123-doped systems.     

掺杂聚苯胺溶致液晶相的产生和表征

聚苯胺（PAN）具有共轭结构,从理论上满足形成液晶相的基本条件［1,2］．但由于聚苯胺难溶、难熔,长期以来对于聚苯胺溶液（尤其是浓溶液）或熔体的研究甚少．近年来,人们采用具有“增塑作用”的大分子功能质子酸对聚苯胺进行掺杂,获得可溶于多种有机溶剂中的掺杂态聚苯胺［3～5］．然而,聚苯胺溶液的结构与性能的特点及能否产生溶致液晶相等问题目前尚未见报道．为此,我们研究了十二烷基苯磺酸（DBSA）掺杂聚苯胺在有机溶剂中形成液晶相的条件,探讨了不同掺杂方法对PAN－DBSA的溶解性及形成液晶棺的影响;采用差式扫描量热分…     

Utilising Saturated Hydrocarbon Isosteres of para Benzene in the Design of Twist-Bend Nematic Liquid Crystals

The nematic twist-bend (N_TB) liquid crystal phase possesses a local helical structure with a pitch length of a few nanometres and is the first example of spontaneous symmetry breaking in a fluid system. All known examples of the N_TB phase occur in materials whose constituent mesogenic units are aromatic hydrocarbons. It is not clear if this is due to synthetic convenience or a bona fide structural requirement for a material to exhibit this phase of matter. In this work we demonstrate that materials consisting largely of saturated hydrocarbons can also give rise to this mesophase.     

碳氢／碳氟表面活性剂复配体系溶致液晶的研究

以全氟辛酸钠－十六烷基三甲基溴化铵／正丁醇／水体系为研究对象，通过其相图的测定确立了液晶区．其液晶区域面积大于十六烷基三甲基溴化铵／正丁醇／水体系的液晶区．摄制了该体系液晶区系列样品的纹理照片，用小角Ｘ光衍射法测定了液晶各种组分变化时的层间距，并结合２ＨＮＭＲ谱图和纹理照片的对照和分析，从分子水平上研究了液晶的微观结构．     

正、负离子表面活性剂混合体系溶致液晶生成的相行为

研究了烷基(C8,C12,C14)三甲基溴化铵、烷基(C12,C14)溴化吡啶与烷基(C8,C12)硫酸钠混合体系溶致液晶形成的条件与结构的变化.在高浓度的水溶液中,随着正、负离子表面活性剂摩尔比接近于1,液晶结构由六角相过渡为层状相.表面活性剂非极性链长改变,对相行为影响显著,短碳链的正、负离子表面活性剂混合体系,在等摩尔比时,体系为层状液晶或立方液晶为主,夹杂少许沉淀.随碳链增长,两类表面活性剂间的静电吸引效果表现为生成沉淀的摩尔比例范围变宽,沉淀量增多,共存的液晶相减少,甚至消失.若只改变正离子的极性头基,季胺盐比吡啶盐与烷基硫酸盐的作用要强,形成不溶物的混合摩尔比例范围更宽.     

Igepal CO系列表面活性剂溶致液晶的结构特性

对壬基酚聚氧乙烯醚（IgepalCO）系列表面活性剂,生成何种溶致液晶与其EO基团数n有关,而在何浓度范围内生成溶致液晶则与生成溶致液晶的最低水含量及最大水增溶量有关．EO基团数n小于10时,生成层状液晶,n大于10时则生成六角状液晶,层状液晶两亲双层内,水与表面活性剂的最低摩尔比rmin和最高摩尔比rmax随EO基团数n增加分别是非线型增加与线型增加,在IgepalCO520（n＝5）中加入IgepalCO710（n＝10．5）,对层状液晶的生成无显著影响,在IgepalCO710中加入IgepalCO520,则对六角状液晶的生成产生显著影响,出现了六角状液晶向层状液晶的转变。     

油酸/三乙醇胺/液体石蜡水体系层状润滑性能

采用^2HNMRT和IR,表征了油酸／三乙醇胺／液体石蜡／水体系层状液晶的结构,并以该体系为润滑剂,测定了其在铝合金表面的磨痕宽度和摩擦系数,同时与液体石蜡和商用润滑剂12－羟基硬脂酸锂进行了比较。结果表明,OLA／TEA／LP／H2O体系丑状液晶具有较好的极压性能,对于铝合金材料是一种较好的润滑剂。     

十二烷基苯磺酸钠在SiO2表面聚集的分子动力学模拟

采用分子动力学方法研究了阴离子表面活性剂十二烷基苯磺酸钠(SDBS)在无定形SiO2固体表面的吸附. 设置不同的水层厚度, 观察固液界面和气液界面吸附的差异. 模拟发现表面活性剂分子能够在短时间内吸附到SiO2表面, 受碳链和固体表面之间相互作用的影响形成表面活性剂分子层, 并依据吸附量的大小形成不同的聚集结构; 在水层足够厚的情况下, 由于有较多的表面活性剂分子吸附在固体表面,从而形成带有疏水核心的半胶束结构; 计算得到的成对势表明极性头与钠离子或水分子之间的结合或解离与二者之间的能垒有关, 解离能垒远大于结合能垒, 引起更多Na+聚集在极性头周围而只有少数Na+存在于溶液中; 无论气液还是固液界面, 极性头均伸向水相, 与水分子形成不同类型的氢键. 模拟表明, 分子动力学方法可以作为实验的一种补充, 为实验提供必要的微观结构信息.     

用共轭亚油酸构筑层状液晶的药物传递系统

在水相中用共轭亚油酸(CLA)及其钠盐(SCL)构筑层状液晶相,并考察了其药物缓释行为.借助偏光显微镜并辅以目测确定CLA/SCL/H2O三元相图中的层状液晶相区,然后用偏光显微镜、小角X射线散射仪和旋转流变仪获得层状液晶的偏光织构、相参数和流变参数等,证实其适用于药物传递系统(DDS).采用透析法研究了负载亲水性药物5-氟尿嘧啶或亲油性药物姜黄素的层状液晶的释药曲线,结果表明,该类层状液晶对2种药物均有良好的缓释能力.     

由杂多酸衍生物制备溶致液晶

液晶是介于液态和晶态之间的一个独立的物质状态,溶致液晶是因溶质在一定浓度范围内分散在溶剂中而呈液晶相．自从１８８８年奥地利植物学家Ｒｅｉｎｉｔｉｚｅｒ和德国物理学家Ｌｅｈｍａｎｎ合作首次发现液晶态以来［１］,迄今为止己发现了五万种以上的液晶性物质．它...     

溶致液晶模板电化学沉积束状铂纳米材料

以非离子型三嵌段共聚物EO106PO70EO106 (F127)/正丁醇/氯铂酸水溶液构建的溶致液晶层状相为模板, 电化学沉积制备铂纳米材料. 透射电镜和扫描电镜显示, 产物为具有高长径比的纳米线形成的束状结构, 能量弥散谱与电极电势分析证实产物为铂单质, 而循环伏安测量表明产物的比表面积约为53 m2•g−1. 对影响产物形貌的因素和产物生成的可能机理进行了分析.     

Phase behavior of sucrose monoalkanoate in a water-long-chain alcohol system

Phase diagram of a water/sucrose monododecanoate (SE)/hexanol system was determined at 30°C. Aqueous micellar, reverse micellar, normal hexagonal liquid crystalline, and lamellar liquid crystalline phases appear in the phase diagram. The change in interlayer spacing and interfacial section area of surfactant in the liquid crystalline phases was investigated by small-angle x-ray scattering. Upon addition of water, the section area and the radius of cylindrical aggregates are almost constant in a hexagonal liquid crystal, whereas the distance between each cylinder is separated on the water-SE axis. The interlayer spacing slightly decreases or is almost unchanged on the surfactant-hexanol axis, because alcohol molecules penetrate into the palisade of bilayers. Although the average section area decreases with increasing alcohol content, each section area of SE and alcohol molecules are kept constant. Since the interfacial section area of alcohol is less than the section area of hydrocarbon chain, the phase transition from lamellar liquid crystal to reverse micelle occurs in an alcohol-rich region.     

A small-angle x-ray scattering study of starch gelatinization in excess and limiting water

The architecture of the starch granule, and its subsequent disruption due to the application of heat and water, known as gelatinization, is of wide interest. Small-angle x-ray scattering (SAXS) techniques have been used to study gelatinization in limiting and excess water. SAXS allows the absorption of water into the differing regions of the starch granule to be monitored. In excess water, a process of cooperative melting can be seen. In limiting water, the crystalline order melts at a higher temperature. These features have been studied, and observed features of the gelatinization related to those known from other techniques. © 1993 John Wiley & Sons, Inc.     

星型液晶的合成、相行为与应用研究

通过SiCl4的Si-Cl键与偶氮苯类液晶基元末端OH的有效联接，合成了三种新的 星型液晶，利用红外光谱（IR）、核磁共振（^1H NMR)对其分子结构进行了鉴定， 利用偏光显微镜（POM）和示差扫描量热法（DSC）对 其液晶相行为进行了表征， 并对其在毛细管气相色谱分析中的应用进行了初步探讨。