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.     

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.     

新型棒状苯基咪唑苯酯类化合物的合成及其液晶性能研究

以Ullmann偶合反应为关键步骤, 合成了带端氧基链的苯基咪唑苯酯系列化合物, 采用偏光显微镜(POM)、差示扫描量热仪(DSC)及X衍射等手段研究了其液晶行为. 研究表明, 通过改变末端烷氧基链的长度及数目, 这类分子可组装形成向列相(N)和层列相(SmA)等液晶相态, 但随着烷氧基链数目的增多, 这类分子的液晶相消失, 初步找出了这类化合物结构与液晶性能间的关系, 通过对相关化合物的单晶X衍射结构及其液晶相的2D-X衍射测试结果的分析得出, 这类化合物通过分子自组装形成的层列相具有双分子层状结构(SmA₂).     

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.     

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.     

含蒽刚柔三嵌段低聚物的合成及自组装

通过Sonogashira偶联等反应,合成了2种含蒽的三嵌段十字型化合物1和2;通过1H NMR和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF MS)对其结构进行了表征.利用差示扫描量热法(DSC)、偏光显微镜(POM)及小角X射线散射实验(SAXS)对2种化合物的本体自组装行为进行了研究.结果表明,在本体状态下,连接聚环氧乙烷(PEO)作为柔性链的化合物在液晶中间相自组装成倾斜柱状相和向列相,以烷基链为柔性链的化合物未形成液晶相,在固态相是层状结构.     

基于电场调控的胆固醇基液晶薄膜对成纤维细胞生长分化的影响

通过外加电场对胆固醇-g-聚乳酸低聚物(Cholesteryl-oligo(L-lactic acid),CLA)薄膜的液晶有序性进行调节，并评价其对成纤维细胞黏附、增殖和分化的影响。采用差示扫描量热仪检测CLA聚合物液晶性；以外加直流电场调控薄膜液晶有序性，X射线衍射仪和偏光显微镜检测电场调控下CLA薄膜液晶有序性的改变；Cell Counting Kit-8试剂盒检测成纤维细胞在CLA薄膜上的黏附与增殖行为，免疫荧光染色法和蛋白免疫印迹法检测成纤维细胞表型转化特征蛋白α-平滑肌肌动蛋白(α-Smooth muscle actin, α-SMA)表达水平。结果表明，CLA聚合物具有液晶性，外加电场可通过诱导CLA液晶分子的有序排列调控CLA薄膜液晶性，CLA薄膜液晶性增强有利于成纤维细胞的增殖与α-SMA蛋白表达。说明电场调控可在不改变CLA聚合物薄膜基质材料组成的前提下，通过增加薄膜的液晶有序性，促进成纤维细胞向肌成纤维细胞表型转化。     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

 用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

单一非离子表面活性剂制备胶质气体泡沫的稳定性

用单一的十二烷基醇聚氧乙烯醚(C12EOn)非离子表面活性剂制备了稳定的胶质气体泡沫(CGA). 采用偏光显微镜和流变仪对其表面活性剂溶液相态和泡沫体系的微观结构及流变行为进行研究, 以探索CGA的稳定化机理. 实验结果表明, 分别由C12EO3和C12EO5制备的CGA分散体系中均存在层状液晶相, 层状液晶吸附在气泡的界面上. CGA稳定性可达20 h以上, 没有明显的相分离发生. 而分别由C12EO7和C12EO9制备的CGA呈现由胶束组成的连续相, 不存在液晶相结构, 因而其稳定性较差, 仅能维持数分钟. 实验结果表明, 层状液晶相结构可以显著提高CGA的稳定性. 其稳定作用的机理是通过影响泡沫排液过程, 增强Gibbs-Marangoni效应, 从而提高气泡液膜强度和减缓气相扩散速率.     

含有十二烷基酚聚氧乙烯(10)醚的溶致液晶体系的研究

本文以非离子表面活性剂十二烷基酚聚氧乙烯(10)醚(TX-10)/苯乙烯/水组成的三元体系为研究对象, 绘制了三元相图, 选取液晶区域作为研究对象, 配制系列样品, 摄制了纹理照片, 用小角X光衍射法测定了液晶中各种组分变化时间的层间距, 并结合^2H NMR谱图和纹理照片的对照以及互为补充的分析, 为精确区分液晶结构提供了新的途径。这不仅对于基础理论研究, 同时对于日用化工和帮次采油都具有一定指导意义。     

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.     

非离子表面活性剂层状液晶的结构与增溶作用

相行为研究表明，与ＴｒｉｔｏｎＸ－１００／Ｃ＿６Ｈ＿６／Ｈ＿２Ｏ体系相比，ＴｒｉｔｏｎＸ－１００／Ｃ＿（１０）Ｈ＿（２１）ＯＨ／Ｈ＿２Ｏ体系更易于生成层状液晶，并更为稳定，小角Ｘ－射线衍射表明；ＴｒｉｔｏｎＸ－１００／Ｃ＿（１０）Ｈ＿（２１）ＯＨ／Ｈ＿２Ｏ体系层状液晶中，Ｃ＿（１０）Ｈ＿（２１）ＯＨ与ＴｒｉｔｏｎＸ－１００交替排列于两亲双层中，Ｃ＿（１０）Ｈ＿（２１）ＯＨ／ＴｒｉｔｏｎＸ－１００重量比增加，两亲双层厚度ｄ＿０值不变。以Ｃ＿６Ｈ＿６代替Ｃ＿（１０）Ｈ＿（２１）ＯＨ后，Ｃ＿６Ｈ＿６存在于两亲双层的油层和渗入ＴｒｉｔｏｎＸ－１００分子链尾周围，使得溶剂渗透率减少，并且Ｃ＿６Ｈ＿６／ＴｒｉｔｏｎＸ－１００增加，ｄ＿０值增加。     

Improved identification of conjugated linoleic acid isomers using silver-ion HPLC separations

Silver-ion high-performance liquid chromatography (Ag+-HPLC) has been shown to be effective in the resolution of most of the isomers of conjugated octadecadienoic acids (18:2), also known as conjugated linoleic acid (CLA). The CLA isomers identified in natural fats from ruminants are a mixture of numerous positional and geometric isomers from 7,9- to 12,14-18:2. Ag+-HPLC separates both geometric (trans,trans < cis/trans < cis,cis) and positional CLA isomers using the mobile phase hexane/acetonitrile (99.9:0.1). The elution volumes for the CLA isomers were not only affected by the concentration of acetonitrile (in the prepared mobile phase) but also with successive runs during the day using a prepared mobile phase batch, due to the partial solubility of acetonitrile in hexane. However, this drift does not affect the relative resolution of the CLA isomers. The addition of diethyl ether to the mobile phase partly stabilizes the solvent mixture. In order to facilitate the interpretation of Ag-+HPLC chromatograms, the relative retention volumes (RRV) were calculated for each CLA isomer. Toluene was added to all the test portions and served as an estimator of dead volume, whereas the elution of the ubiquitous 9c,11t-CLA isomer was chosen as unity (1.00). Expressing the elution of all the CLA isomers as their RRV greatly helped to standardize each CLA isomer, resulting in relatively small coefficients of variation (% CV) for the trans,trans (<1.5%) and cis/trans (<0.5%) CLA isomers. The identification of the CLA isomers was further facilitated by synthesis of authentic CLA isomers. All the geometric CLA fatty acid methyl esters (FAME) from positions 6,8- to 13,15-CLA were commercially available or synthesized by a combination of partial hydrazine reduction of known polyunsaturated fatty acids followed by alkali isomerization, isolation of products, and further iodine-catalyzed geometric isomerization. Based on expressing the elution volume as RRV and the availability of the synthetic CLA isomers, a unique reversal of the elution order of the c/t CLA isomers was found. It is also proposed that the retention times of CLA isomers by gas chromatography (GC) should be expressed as their relative retention times (RRT) relative to methyl gamma-linoleneate. The availability of CLA reference materials and the application of RRV and RRT to Ag+-HPLC and GC separations, respectively, will greatly improve in the identifications of CLA isomers.     

液晶模板法制备Au纳米线

利用非离子表面活性剂C₁₂E₄的层状液晶作为模板,以氯金酸(HAuCl₄)水溶液作为体系的水相和反应物,并利用C₁₂E₄中EO基团的还原性制备了Au的纳米线.研究表明,反应物的浓度、液晶体系的组成和反应时间都将影响产物的形貌.在适当条件下,可以得到直径约为20nm,长度达到几微米的均匀金纳米线,并探讨了纳米线形成过程中层状液晶的模板作用.     

Synthesis of inorganic gels in a lyotropic liquid crystal medium. I. Synthesis of silica gels in lamellar phases obtained from non-ionic surfactants

Some lamellar phases made with aqueous lyotropic liquid crystals were used as templates for the gelation of a silica inorganic network from tetramethylorthosilicate (TMOS). The aim was to synthesize materials with an anisotropic texture.Lamellar phases were obtained by using non-ionic surfacants. At first, structural, textural and rheological properties of the lamellar phases were studied. Then, the evolution of the system after introduction of the alkoxide, i.e., during the sol-gel transition, was followed by low angle X ray diffraction and rheological measurements. Finally, a textural study of dried gels was carried out.The formation of gels with a lamellar structure was analysed by compressing the total phase diagram (quaternary system) to a ternary system. The hydrolysis and condensation reactions of the TMOS are strongly influenced by the presence of the structured lamellar phase. Gelation seems to happen around the liquid crystal microdomains. A schematic model of gelation is proposed based on experimental observations.     

STUDIES ON THE PHASE DIAGRAM OF THE SURFACTANT/1-PENTANOL / WATER TERNARY SYSTEM II: THE LIQUID CRYSTALLINE PHASE

The phase behavior of liquid crystalline in the ternary system of dodecyl dimethyl ammonium hydroxyl propyl sulfonate(DDAHPS)/1pentanol(C5HnOH) / water deuteron(D₂O) has been investigated by polarizing optical microscopy, ²H NMR spectroscopy methods. The results indicate that two kinds of liquid crystals (the lamellar, and the hexagonal) exist in the liquid crystalline phase region. In this paper, we also use the polarized Raman spectroscopy method to measure the values of the order/ disorder parameters and the values of the environment polarity parameters for the samples selected from the liquid crystalline phase region, and compare these two parameters of the samples with those of solid state DDAHPS and liquid state pentan-l-ol.     

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.     

Lamellar Liquid Crystals of Brij 97 Aqueous Solutions Containing Different Additives

Lamellar liquid crystals of Brij 97 aqueous solutions were investigated by means of rheological techniques and SAXS at 25 °C, in the presence of various additives including isopropyl myristate, oleic acid, ionic liquid bmim-PF₆ and bmim-BF₄. The lamellar phases show high elasticity as indicated by their mechanical and discrete relaxation spectra, which is expected to be an advantage when they are used as drug delivery vehicles. It is noted that in comparison with other systems, the lamellar phase formed in the Brij 97/water/IPM system has the lowest storage and loss moduli, implying that it has a weak network strength and less stable internal structure. The Brij 97/water/oleic acid system is the most shear resistance, whereas the Brij 97/water/bmim-PF₆ system exhibits fluid-like viscoelastic properties to some extent. These differences are analyzed through SAXS data for the different location of the additive in the lamellar phase.     

Effect of sodium diclofenac loads on mesophase components and structure

We studied the effect of a model electrolytic drug on intermolecular interactions, conformational changes, and phase transitions in structured discontinuous cubic QL lyotropic liquid crystals. These changes were due to competition with hydration of the lipid headgroups. Structural changes of the phase induced by solubilization loads of sodium diclofenac (Na-DFC) were investigated by directly observing the water, ethanol, and Na-DFC components of the resulting phases using 2H and 23Na NMR. Na-DFC interacted with the surfactant glycerol monoolein (GMO) at the interface while interfering with the mesophase curvature and also competed with hydration of the surfactant headgroups. Increasing quantities of solubilized Na-DFC promoted phase transitions from cubic phase (discontinuous (QL) and bicontinuous (Q)) into lamellar structures and subsequently into a disordered lamellar phase. Quadrupolar coupling of deuterated ethanol by 2H NMR showed that it is located near the headgroups of the lipid and apparently is hydrogen bonded to the GMO headgroups. A phase transition between two lamellar phases (L alpha to L alpha*) was seen by 23Na NMR of Na-DFC at a concentration where the characteristics of the drug change from kosmotropic to chaotropic. These findings show that loads of solubilized drug may affect the structure of its vehicle and, as a result, its transport across skin-blood barriers. The structural changes of the mesophase may also aid controlled drug delivery.