光响应性微凝胶的分子设计和智能材料构筑

微凝胶能够在外界刺激下改变自身尺寸,是一类重要的智能材料构筑基元。光刺激具有可远程控制、能快速切换等特点,在刺激响应性材料的设计中受到了广泛关注。将光刺激响应性基元引入到微凝胶体系,可以得到一系列具有重要应用前景的智能材料。本文综述了近年来光响应微凝胶的研究进展,总结了赋予微凝胶光响应性的四种分子设计,包括光致异构化型、光致生热型、光致(解)交联型、光致生酸型;介绍了光响应微凝胶在调光材料、药物控释、信息显示和自修复凝胶等领域的应用;展望了该领域的研究方向、发展和应用前景。     

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.     

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.     

偶氮液晶嵌段共聚物自组装和光响应性研究进展

偶氮液晶嵌段共聚物是指分子中带有偶氮苯基团的液晶嵌段共聚物.偶氮液晶嵌段共聚物兼具偶氮聚合物的光响应性和液晶嵌段共聚物自组装形成多尺度有序结构的特性,是一类有重要应用前景的新材料.本文简要综述了近10年来偶氮液晶嵌段共聚物的研究进展,以几种典型的偶氮液晶嵌段共聚物为例,介绍嵌段共聚物在本体以及溶液状态下自组装,自组装形貌的光致变化,以及偶氮液晶嵌段共聚物在光全息存储领域等的研究进展.     

刺激响应型聚合物刷的研究进展

本文综述了刺激响应型聚合物刷的研究进展,阐述了刺激响应型聚合物刷的分类、与基体表面的连接方式以及常规制备方法,介绍了离子强度、温度、pH值、光、溶剂等刺激响应型聚合物刷及其研究现状,并对相应的刺激响应机理进行了探讨。此外,本文还综述了多重刺激响应型聚合物刷的制备设计思路及其刺激响应特性,概述了聚合物刷在响应外界刺激后对基体的弯曲作用以及利用该作用进行可控三维自组装,并对刺激响应型聚合物刷的应用前景进行了展望。     

偶氮型液晶高分子的研究及应用

偶氮液晶高分子由于其具有特殊的光致异构和光致变色等光学性质,在光信息贮存材料、光开关材料和非线性光学设备材料等领域具有巨大的应用潜力,近年来得到了国内外研究者的广泛关注。本文概述了偶氮型液晶高分子的结构特征,详细介绍了主链型偶氮液晶高分子、侧链型偶氮液晶高分子、树枝状偶氮液晶高分子以及星型偶氮液晶高分子的研究现状及在光储存、光开关及光调制偏振片等方面的应用进展,指出了存在的问题和研究方向。     

光和温度刺激响应型材料*

刺激响应型材料是一类在环境因素刺激下,自身的某些物理或化学性质发生相应变化的材料。刺激因素包括光、温度、pH、离子强度、电场和磁场等。本文综述了近年来光和温度刺激响应型材料的研究进展,主要从光响应型水凝胶和光致变色材料的结构类型及应用概述了光响应型材料的发展;同时从温度响应型水凝胶、热致形状记忆材料和热敏变色材料几方面介绍了温度响应型材料的研究进展及应用,并展望了光和温度刺激响应型材料在多学科领域的应用前景。     

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。     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.