液晶纤维素及其衍生物材料的结构与性能

基于国内外最新研究文献，系统论述了液晶纤维素及其衍生物薄膜、纤维、功能分离膜、交联凝胶等材料的成型、结构与性能。指出这类液晶聚合物具有胆甾相或向列相液晶态。与各向同性态的同种材料相比，各向异性态的液晶纤维素及其衍生物材料具有更优异性能。双轴取向液晶三乙酸纤维素薄膜的拉伸强度和弹性模量分别可310MPa和6．3GPa；由液晶态干湿法纺丝所获得的高分子量纤维素纤维的抗张强度和弹性模量分别可高达2．2GPa和65GPa。液晶纤维素及其衍生物分离膜也表现出高得多的气体选择透过性能。其液晶交联凝胶中，凝胶所占质量分数高达98％，以及具有显著不同于各向同性态凝胶的液胀行为。液晶纤维素及其衍生物可望作为生产高级包装膜、功能纤维、气体分离膜、各向异性功能凝胶等的重要材料。     

对硝基苯甲酸胆甾醇酯的合成及其分子自组装结构研究

 从对-硝基苯甲酸与胆甾醇出发,采用DCC、DMAP酯化法一步合成了对硝基苯甲酸胆甾醇酯,产物结构经核磁、X射线衍射单晶结构测试得到证实;化合物的液晶行为采用偏光显微镜(POM),差示扫描量热仪(DSC)等手段进行了研究.研究表明,该化合物为具有胆甾相的液晶分子,建立了化合物形成胆甾相的分子组装模型,并分析了化合物从晶体结构到液晶相结构转变过程中分子自组装结构的变化过程.通过对比,讨论了苯环上的取代基对苯甲酸胆甾醇酯衍生物液晶性质的影响.     

几种胆甾醇酯的合成与表征

 从相应的羧酸衍生物出发,采用DCC,DMAP酯化的方法合成了4种胆甾醇酯:多取代苯甲酸胆甾醇酯5,6,7及联苯丁酮酸胆甾醇酯9.偏光显微镜(POM)及示差扫描量热法(DSC)研究表明,多取代苯甲酸胆甾醇酯5,6,7为具有胆甾相的液晶分子.9为1种新型的胆甾醇酯化合物,其结构均未见文献报道.     

Optical isotropy and iridescence in a smectic 'blue phase'

When liquid crystal molecules are chiral, the twisted structure competes with spatially uniform liquid crystalline orders, resulting in a variety of modulated liquid crystal phases, such as the cholesteric blue phase, twist grain boundary and smectic blue phases. Here we report a liquid crystal smectic blue phase (SmBP(iso)), formed from a two-component mixture containing a chiral monomer and a 'twin' containing two repeat units of the first molecule connected by a linear hydrocarbon spacer. The phase exhibits the simultaneous presence of finite local-order parameters of helices and smectic layers, without any discontinuity on a mesoscopic length scale. The anomalous softening of elasticity due to a strong reduction in entropy caused by mixing the monomer and the twin permits the seamless coexistence of these two competing liquid crystal orders. The new phase spontaneously exhibits an optically isotropic but uniformly iridescent colour and automatically acquires spherical symmetry, so that the associated photonic band gap maintains the same symmetry despite the local liquid crystalline order. We expect a range of unusual optical transmission properties based on this three-dimensional isotropic structure, and complete tunability due to the intrinsic softness and responsiveness of the liquid crystalline order against external fields.     

含氨酯基的壳聚糖衍生物的胆甾液晶螺旋性质

用圆偏振光二向色性谱法研究了3种含氨酯基的壳聚糖衍生物的胆甾液晶螺旋性质.结果表明，3种衍生物的质量分数为65%的氯仿溶液都呈现胆甾液晶相.此外，CD谱观察结果显示侧基结构对其胆甾螺旋方向有明显的影响.     

含氟及手性交联剂的液晶弹性体的合成与性能

合成向列液晶单体:4-((4-烯丙氧基)苯甲酰氧基)苯基-4-氟苯甲酸)酯(M1)和非液晶手性交联剂:双(4-((4-烯丙氧基)苯甲酰氧基)异山梨醇酯)(MC).按不同比例将M1和MC接枝共聚到聚甲基含氢硅氧烷上,得到含氟手性液晶弹性体PI~PVIII.用红外光谱、核磁共振表征单体和聚合物结构,用差示扫描量热仪、热失重仪、偏光显微镜及X射线衍射等手段研究其液晶性能.结果表明,含氟类短而硬的液晶基元更易被手性诱导,出现性能优异的胆甾相.其中,PI为向列型液晶,PII~PVII为出现油丝和Grandjean织构的胆甾型液晶,PVIII没有液晶性.弹性体玻璃化转变温度随着手性交联剂含量的增加先增大后减小,熔点和清亮点均呈下降趋势.所合成的液晶弹性体热稳定性好,质量损失5%时的热失重温度均在300℃以上.     

十二烷基苯磺酸钠/正庚烷/水体系的溶致液晶相研究

在十二烷基苯酸钠（ＮａＤＢＳ）和正庚烷水溶液中分别加入脂肪醇和ＮａＣｌ时，研究了体系中的相态结构和相转变的规律。在较高浓度的 ＮａＤＢＳ体系中长链醇（从正戊醇到正辛醇）促使层状液晶相的形成，短链醇如正丁醇和正丙醇的加入则无液晶态结构出现．ＮａＣｌ的加入引起液晶相的形成．     

新型甲基丙烯酸酯类手性液晶单体及其聚合物的表征

制备了含薄荷基的三种甲基丙烯酯类单体(M1~M3)及聚合物(P1~P3),其化学结构通过了FT-IR和1H-NMR的表征;采用DSC,POM,XRD等研究了这些单体及聚合物的液晶性能,并利用紫外/可见/近红外光谱仪测试了手性单体的选择反射性质.研究表明:M1与P1均无液晶性,而M2与M3在升降温过程中都出现了液晶性和选择反射现象,其中M2呈现手性近晶相C相及胆甾相,M3仅呈现胆甾相;此外,随着液晶核刚性的增加或柔性间隔基长度的缩短,对应单体的熔点和清亮点均升高.除了P1,P2与P3均为互变热致液晶聚合物,呈现胆甾相的彩色织构,且其液晶相温度范围远大于对应单体的液晶相范围.     

甲亚胺液晶共聚醚的合成及研究（Ⅳ）

用个晶基和柔性更好的非个晶基共聚的方法合成高分子液晶，通过热台偏光显微镜、ＤＳＣ和Ｘ－光衍射仪对所合成的共聚物进行了结构和相态表征，讨论了共聚物组成对共聚物相变温度和相态的影响，确定了共聚物要呈现液晶态，允许非介晶组份在其组成中的最高含量。     

乙基纤维素溶致液晶条带织构生长和松弛的动态过程

用偏光显微镜和透射光强分析技术，观察乙基纤维素－间甲酚和乙基纤维素－苯酚两个溶致液晶体系条带织构的生长和松弛的动态过程。结果表明条带织构生成的临界浓度高于液晶态形成的临界浓度，但低于两相并存向安全各向异性转变的浓度。     

胆甾相液晶材料相变与分子构造相关性的机械旋转模型研究

首次报告利用液晶分子的机械旋转模型研究胆甾相液晶材料相变与分子构造相关性的研究结果.通过对不同质量的系列胆甾相液晶材料的研究,发现材料的相变温度随着分子的变长而降低.我们利用液晶分子的机械旋转模型给予了很好的解释.该研究拓宽了液晶分子机械旋转模型的应用范围.     

Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon.

Crystalline and amorphous forms of silicon are the principal materials used for solid-state electronics and photovoltaics technologies. Silicon is therefore a well-studied material, although new structures and properties are still being discovered. Compression of bulk silicon, which is tetrahedrally coordinated at atmospheric pressure, results in a transition to octahedrally coordinated metallic phases. In compressed nanocrystalline Si particles, the initial diamond structure persists to higher pressure than for bulk material, before transforming to high-density crystals. Here we report compression experiments on films of porous Si, which contains nanometre-sized domains of diamond-structured material. At pressures larger than 10 GPa we observed pressure-induced amorphization. Furthermore, we find from Raman spectroscopy measurements that the high-density amorphous form obtained by this process transforms to low-density amorphous silicon upon decompression. This amorphous-amorphous transition is remarkably similar to that reported previously for water, which suggests an underlying transition between a high-density and a low-density liquid phase in supercooled Si (refs 10, 14, 15). The Si melting temperature decreases with increasing pressure, and the crystalline semiconductor melts to a metallic liquid with average coordination approximately 5 (ref. 16).     

含两种介晶基元的侧链聚硅氧烷的液晶性能

用两种液晶单体 4 丙烯酰氧基 1 丁酸胆甾醇酯和 4 烯丙氧基苯甲酸对氰基苯酯通过接枝共聚 ,引入到聚甲基含氢硅氧烷中制得了一系列侧链液晶聚合物·通过采用傅立叶转换红外光谱 (FTIR)对其结构进行了表征·用差示扫描量热方法 (DSC)及偏光显微分析方法 (POM )等研究了该系列液晶聚合物和单体的液晶性能·随着聚合物结构中胆甾醇酯类单体组分质量分数的增加 ,系列液晶聚合物的玻璃化温度呈现上升趋势·所有聚合物都具有较宽的介晶相范围·     

Light-induced liquid crystallinity

Liquid crystals are traditionally classified as thermotropic, lyotropic or polymeric, based on the stimulus that governs the organization and order of the molecular system. The most widely known and applied class of liquid crystals are a subset of thermotropic liquid crystals known as calamitic, in which adding heat can result in phase transitions from or into the nematic, cholesteric and smectic mesophases. Photoresponsive liquid-crystal materials and mixtures can undergo isothermal phase transitions if light affects the order parameter of the system within a mesophase sufficiently. In nearly all previous examinations, light exposure of photoresponsive liquid-crystal materials and mixtures resulted in order-decreasing photo-induced isothermal phase transitions. Under specialized conditions, an increase in order with light exposure has been reported, despite the tendency of the photoresponsive liquid-crystal system to reduce order in the exposed state. A direct, photo-induced transition from the isotropic to the nematic phase has been observed in a mixture of spiropyran molecules and a nematic liquid crystal. Here we report a class of naphthopyran-based materials that exhibit photo-induced conformational changes in molecular structure capable of yielding order-increasing phase transitions. Appropriate functionalization of the naphthopyran molecules leads to an exceedingly large order parameter in the open form, which results in a clear to strongly absorbing dichroic state. The increase in order with light exposure has profound implications in optics, photonics, lasing and displays and will merit further consideration for applications in solar energy harvesting. The large, photo-induced dichroism exhibited by the material system has been long sought in ophthalmic applications such as photochromic and polarized variable transmission sunglasses.     

阳离子表面活性剂相图和微乳液结构的电导研究

考察了醇类（正丁醇、正己醇、正辛醇和正癸醇）和油（正辛烷）含量对十六烷基三甲基溴化铵（ＣＴＡＢ）／醇／正辛烷／水体系相图的影响，并用电导法确定了微乳液的结构（Ｗ／Ｏ、Ｂ．Ｃ．和Ｏ／Ｗ）；同时考察了ＮａＣｌ浓度和盐类（ＮａＣｌ、ＣａＣｌ２和ＡｌＣｌ３）对ＣＴＡＢ／正丁醇／水体系溶致液晶的影响．结果表明：正辛烷含量（１０％）恒定时，醇破链增长，微乳液区域减小；醇（正丁醇）固定时，体系中油含量增加，微乳液区域也减小．ＣＴＡＢ／正丁醇／水体系包合一个富水Ｌ１（Ｏ／Ｗ）区、富油Ｌ２（Ｗ／Ｏ）区和液晶Ｌ．Ｃ．区；盐的加入，液晶区域增大，且盐浓度越大，离子电荷数越高，液晶区域越大．     

Shear-induced molecular precession in a hexatic Langmuir monolayer

Liquid crystalline behaviour is generally limited to a select group of specially designed bulk substances. By contrast, it is a common feature of simple molecular monolayers and other quasi-two-dimensional systems, which often possess a type of in-plane ordering that results from unbinding of dislocations-a 'hexatic' liquid crystalline phase. The flow of monolayers is closely related to molecular transport in biological membranes, affects foam and emulsion stability and is relevant to microfluidics research. For liquid crystalline phases, it is important to understand the coupling of the molecular orientation to the flow. Orientationally ordered (nematic) phases in bulk liquid crystals exhibit 'shear aligning' or 'tumbling' behaviour under shear, and are described quantitatively by Leslie-Ericksen theory. For hexatic monolayers, the effects of flow have been inferred from textures of Langmuir-Blodgett films and directly observed at the macroscopic level. However, there is no accepted model of hexatic flow at the molecular level. Here we report observations of a hexatic Langmuir monolayer that reveal continuous, shear-induced molecular precession, interrupted by occasional jump discontinuities. Although superficially similar to tumbling in a bulk nematic phase, the kinematic details are quite different and provide a possible mechanism for domain coarsening and eventual molecular alignment in monolayers. We explain the precession and jumps within a quantitative framework that involves coupling of molecular orientation to the local molecular hexatic 'lattice', which is continuously deformed by shear.     

Biomimetic self-templating supramolecular structures

In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials. During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures. A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres, distinctively coloured skin tissues from cholesteric phase fibre bundles, and mineralized tissues from hierarchically organized fibres. Nature's self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods. However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.     

偶氮,亚胺,酯类液晶的合成及中心桥键对介晶性的影响研究

报道了偶氮化合物ｐ－Ｈ２１Ｃ１０Ｏ－Ｃ６Ｈ４－Ｎ→‖Ｎ－Ｃ６Ｈ４－ＣＯＯＣｈ，亚胺化合物ｐ－Ｈ２１Ｃ１０Ｏ－Ｃ６Ｈ４－ＣＨ→‖Ｎ－Ｃ６Ｈ４－ＣＯＯＣｈ，酯类化合物ｐ－Ｈ２１Ｃ１０Ｏ－Ｃ６Ｈ４－ＣＯＯＣｈ，（Ｃｈ ａｓ ｔｈｅ ａｂｂｒｅｖｉａｔｉｏｎ ｏｆ ｃｈｏｌｅｓｔｅｒｙｌ ｇｒｏｕｐ）的合成，结构鉴定，以及ＤＳＣ和偏光显微镜对其介晶性研究的结果，并对中心桥键对介晶性的影响进行了讨论。     

静电场中多畴结构胆甾相液晶的物理变化过程

反射型胆甾相液晶显示具有许多传统液晶显示（LCD）不可比拟的优点，称为第3代LCD，本文分析了构成这类显示的多畴胆甾相液晶在静电场下各状态的物理变化过程。文中以单畴为研究对象，根据胆甾相液晶的Frank弹性连续体理论，建立了静电场中单畴从平面积构态（P态）到焦锥织构态（FC态）以及FC态到场致向列相态（H态）各状态间转化的物理方程。为进一步研究多畴胆甾相液晶相变的动力学变化规律打下了基础。     

同步辐射X射线衍射原位研究等规聚丙烯取向中间相的相转变

利用同步辐射宽角X射线衍射原位研究了淬冷得到的中间相和由其被拉伸得到的取向中间相在升温和等温退火下向晶体的转变过程.实验结果表明,虽然两者开始相转变形成晶体的温度是相同的,但发生大量相转变所需的温度,取向的中间相要明显高于淬冷直接得到的中间相,这说明前者具有更高的稳定性.通过对比两种不同中间相的初始结构,发现取向后的中间相在沿拉伸方向31螺旋结构具有更大的长程有序,从而导致了其具有更高的熔点.