液晶弹性体刺激形变研究

开发可以通过外部刺激产生机械形变的人工致动材料是一个近年来的研究热点。其中,液晶弹性体因结合了聚合物网络的橡胶弹性和液晶的有序性而具有独特的性质,在热、光、电等的外界刺激下可以产生可逆的形状记忆效应。本文综述了液晶弹性体响应多种外界刺激产生各种形变的行为,主要介绍了有关热致形变液晶弹性体、电致形变液晶弹性体、化学刺激导致形变的液晶弹性体及光致形变液晶弹性体的研究进展,阐述了各类液晶弹性体产生形变的机理包括热致、电致和光致相转变,讨论了影响其响应性能的主要因素,并展望了这一领域的发展前景。     

近红外光响应液晶弹性体

刺激-响应液晶弹性体是一类新兴的智能聚合物材料,其在外界刺激(热、光、电、磁场等)下会产生大尺寸的可逆形变,因此具有广阔的应用前景。由于单轴取向的液晶基元的微观顺序或分子结构的变化,整个液晶弹性体材料在液晶相向各向同性相转变过程中可以发生非常大的可逆宏观形变。其中,由于近红外光的强穿透力和对生物组织的低毒性,近红外光响应液晶弹性体受到了科学家们的广泛关注。近红外光响应液晶弹性的变形机制主要分为两大类。一种是通过掺杂无机或有机上转换材料将近红外光转化为低波长的光,激发偶氮苯发生顺反异构化。另一种近红外光响应液晶弹性体利用导热填料的光热效应将光转化为热,从而进一步诱导液晶相向各向同性相转变,从而使液晶弹性体材料发生形变。这些优点使近红外光响应液晶弹性体具有潜在的应用价值,如驱动器、人造器官、智能表面和微型机器人等。本文综述了近红外激光响应材料的研究进展,详细介绍了近红外光响应材料的主要变形机理及其应用,并对近红外光响应液晶弹性体和软驱动器的发展前景进行了展望。     

腰接型侧链液晶弹性体研究进展

液晶弹性体是交联型液晶大分子,兼具液晶取向有序性和交联聚合物熵弹性等特性,在传感器、触发器、微流体装置和仿生器件等方面具有很好的应用前景.制备液晶弹性体的微结构,探索其独特的刺激响应性,是目前液晶弹性体研究的重要方向.侧链液晶弹性体的液晶相态类型取决于其液晶基元和主链的连接方式.腰接型侧链液晶弹性体倾向于形成向列型液晶相,具有较快的响应速度和形变程度,是一类独特的液晶弹性体.本文重点介绍腰接型液晶弹性体微结构(如微米柱、微米线等)的制备;利用金纳米粒子的光热转换效应,实现液晶弹性体光响应性的新途径;以及腰接型侧链液晶弹性体仿生微结构的功能性等.同时还对该领域的发展前景进行了展望.     

光响应超分子聚合物

超分子聚合物是超分子化学、高分子化学和材料化学领域的研究热点.将光响应的功能基团以非共价作用构筑到超分子聚合物体系中,得到光响应型超分子聚合物,从而能够将超分子聚合物的独特性质与光化学反应的优势有效地结合起来,从而构筑新型的光功能材料.本文总结了近年来本课题组有关光响应超分子聚合物方面的研究工作:介绍了主链型的光响应超分子聚合物的光调控组装和解离,超分子聚合物和共价聚合物的光控可逆切换和光调控组装形貌;另外还举例介绍了具有自修复和室温磷光发射等功能的侧链型光响应超分子聚合物,并对刺激-响应的超分子聚合物领域的发展做了展望.     

光致形变液晶高分子

交联液晶高分子兼具液晶的各向异性和高分子网络的弹性,并且具有优异的分子协同作用.在交联液晶高分子中引入光响应基团,例如偶氮苯后,即可赋予其光致形变性能,利用分子协同作用可以将光化学反应引起的分子结构变化放大为宏观形变,从而将光能直接转化成机械能.通过合理的分子结构和取向设计可以使液晶高分子产生诸如伸缩、弯曲、扭曲、振动等多种形式的光致形变,并用于各类光控柔性执行器件的构筑,在人工肌肉、微型机器人、微量液体操控等领域呈现出独特的优势和广阔的应用前景.本文总结和评述了光致形变液晶高分子的研究,包括材料结构对光致形变性能的影响、新型可加工光致形变材料的研究、利用可见光和近红外光触发形变的策略,以及光致形变液晶高分子微执行器在微量液体操控中的应用,最后展望了该领域的发展方向.     

木质素接枝偶氮苯液晶聚合物的合成与表征及光响应性能研究

以天然高分子木质素为原料,通过亲核取代反应将木质素改性成为大分子引发剂,引发偶氮苯单体的原子转移自由基聚合(ATRP),得到一系列木质素基光响应聚合物.接枝后的木质素的热稳定性明显改善,且平均接枝率达到72.8%时才能表现出液晶行为.小角X射线散射和偏光显微镜的结果表明所形成的液晶相为近晶C型,层间距为3.21nm.在此基础上,用紫外-可见吸收光谱(UV-Vis)对木质素基液晶聚合物的光响应性进行研究,发现溶液中的光响应性比膜状态的光响应速率快.在紫外光的辐照下,木质素基液晶聚合物表现出快速的光致液晶-各向同性相变行为.     

胆甾相液晶结构色的光调控

胆甾相液晶是一类具有周期性螺旋超结构的软光子晶体,能够选择性地反射不同波长的光产生结构色.在向列相液晶中掺杂光响应手性分子是制备光响应胆甾相液晶的普遍方法.在外界光源的刺激下,光响应手性分子的空间结构改变,诱导螺旋超结构的螺距发生变化,从而调控胆甾相液晶的结构色,因此光响应胆甾相液晶在滤光器、传感器、可调光学激光器和动态显示等领域具有广阔的应用前景.总结了不同光响应手性分子构筑的胆甾相液晶体系,分析了手性分子结构设计对胆甾相液晶结构色调控的影响,最终讨论了光响应胆甾相液晶目前面临的挑战以及未来的发展方向.     

刺激响应降解型聚合物水凝胶

作为一类重要的高分子材料,聚合物水凝胶由于其优良的理化性能和生物学特性而被广泛应用于生物医药领域,降解特性是其作为生物医用材料的重要性能指标。刺激响应降解型水凝胶是指在环境因素刺激下凝胶网络发生响应性断裂,进而产生凝胶-溶胶或溶胀-降解转变的一类智能高分子材料。这一响应降解特性可通过将环境敏感性断裂基团引入到聚合物凝胶网络中来实现。与水凝胶常规的水解、酶解相比,刺激响应降解因具有空间或时间上的可控特性而引起人们的广泛关注。本文重点介绍了pH响应、光响应以及氧化还原响应降解型聚合物水凝胶的设计方法、降解机理及其最新研究进展,并对刺激响应降解型水凝胶未来的研究方向进行了展望。     

刺激响应聚合物在生物医药中的应用

刺激响应聚合物是一类能够根据外界环境变化,如p H、离子、温度、光等刺激而改变自身物理化学性质的功能性聚合物。近年来,刺激响应聚合物由于其独特的刺激-响应功能性,在疾病诊断、药物递送、传感器等领域具有广泛的应用。根据不同刺激类型,刺激响应聚合物有不同分类。本文根据化学刺激、物理刺激及生物刺激三方面,综述了刺激响应聚合物的合成方法及其响应机理,并对这类功能材料的应用前景进行了展望。     

智能响应蓝相液晶光子晶体

具有刺激响应性的智能驱动材料已成为材料科学领域的研究热点之一。液晶的超分子自组装结构与其刺激响应特性使其在新型智能功能材料的开发应用上具有天然优势。蓝相液晶由于其独特的三维超分子自组装结构、软物质特性以及可见光波段的选择性光反射,被认为是最具潜力的智能光子晶体材料之一。在温度、光照、电场、湿度等外场刺激作用下,蓝相超分子自组装结构的晶体学参数或相态非常容易发生变化,造成光子带隙的改变进而呈现出反射颜色的变化。因此,蓝相的外场响应性能及在智能材料上的应用引起了研究者的广泛关注。本文综述了智能响应蓝相液晶光子晶体外场响应性能方面的前沿动态,对蓝相液晶光子晶体的光、磁、电、力、湿度响应等方面取得的系列重要的研究成果进行了总结,并对该领域目前存在的挑战以及未来发展趋势做出展望。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.