光致变形型高分子材料

光致变形型高分子材料以光为激发源,在没有机械接触的情况下,能够快速改变尺寸和形状。本文介绍了光致变形的高分子凝胶、无定形高分子、液晶弹性体和光致形状记忆高分子材料,并对各种材料的光致变形机理进行解释。无定形高分子的光致变形较小,目前研究重点是具有各向异性的液晶弹性体。文中着重介绍了具有偶氮苯介晶基元的液晶弹性体的光致变形研究,在光照下这类材料只要有1%的偶氮苯介晶基元发生顺反异构,就会发生光致变形。     

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.     

金表面偶氮苯自组装膜的光电化学响应

金表面偶氮苯自组装膜的光电化学响应王永强，王健，于化忠，蔡生民，刘忠范（北京大学化学与分子工程学院智能材料研究中心，北京，１００８７１）关键词偶氮苯，自组装膜，光致异构化，电化学偶氮苯基团特征的光致异构化及电化学响应在分子开关器件和超高密度信息存储等...     

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。     

偶氮苯顺反异构化机理研究进展

偶氮苯的光致顺反异构化是许多偶氮类功能材料光响应的基础.近年来,偶氮苯的顺反异构化机理受到了广泛关注.本文综述了这方面的一些最新研究进展,针对偶氮苯光致异构化过程中有争议的旋转和反转机理问题,从争论的起源到目前的研究结论进行了系统总结,同时也提出了一些尚需深入研究的问题.     

模拟跨膜信号的偶氮苯化合物的合成及表征

在一种仿G蛋白耦合型信号转导的人工超分子系统中引入一类偶氮苯结构的化合物,用来模拟跨膜受体。选用偶氮苯类化合物为受体是因为该化合物具有光致异构化的特性,能够引入光信号。实验合成了苯丙氨酸甲酯偶氮苯、缬氨酸甲酯偶氮苯、谷氨酸甲酯偶氮苯,并用红外光谱、紫外可见光谱以及核磁共振方法进行表征,结果显示,所合成的产物是预期产物。     

新型弯曲形双偶氮苯类液晶合成及光致异构性能研究

弯曲形偶氮苯液晶由于其偶氮键独特的光致可逆异构化性能,已成为光电子信息材料研究的热门课题,但光响应速度慢已成为制约其发展的关键因素.目前报道的弯曲型偶氮类液晶化合物的偶氮键都距离中心核较远的位置,光致异构的响应时间较长,大都在分钟以上,不利于光敏器件应用研究.本工作试图以2-甲基-1,3-间苯二胺为中心核,将偶氮键紧挨中心核两边,末端为直链烷基,设计合成了一系列新型弯曲形双偶氮苯类液晶化合物,以期缩短光响应时间.通过IR, 1H NMR, 13C NMR和ICP-MS光谱鉴定这些化合物的分子结构,经差示扫描量热仪(DSC)和偏光显微镜(POM)测定其液晶相变温度和相态织构;并通过测定2-甲基-1,3-双(4-((4-庚基苯基)酯基)-1-(E)-偶氮苯基)苯(2c)的紫外-可见光的吸收光谱研究其光致异构化性能,通过UV-Vis光谱仪和偏光显微镜(POM)测定其液晶化合物以及掺杂向列相液晶材料的光致异构现象和响应时间.实验结果表明,所有设计合成的弯曲形双偶氮苯类液晶化合物均具有近晶相相态,且相态温度范围较宽,当近晶相态化合物2c掺杂到向列相混合液晶中时,其光致异构响应时间为2~3 s,在日光下液晶态恢复时间为3~4s,在乙酸乙酯稀溶液中时10s可达到光稳态.说明这类弯曲形双偶氮液晶化合物具有较快的光致异构响应速度.     

光响应细胞粘附界面

光响应分子的响应过程可以通过简单调控光源波长、光强度以及曝光时间进行调节,近年来基于光响应分子构建的智能界面被越来越多地应用于调控细胞粘附行为。目前,用于构筑调控细胞粘附行为的光响应智能界面的功能分子主要有偶氮苯、螺吡喃以及它们的衍生物。基于这些光响应功能分子的光致异构化,光响应智能界面会发生物理化学性质转变,进而实现可控的细胞粘附和去粘附。设计光控细胞粘附界面为研究细胞粘附、迁移以及细胞诊断提供了一种新型便捷的策略。     

顺,反式偶氮苯的热化学和光化学转化

顺、反式偶氮苯的热化学和光化学转化孔令仁（南京大学环境科学与工程系，２ｌ００３）孔京（南京大学化学化工学院，２ｌ００３）偶氮苯的光致和热致异构化已有很多研究［１，２］，在我国尚未列入实验教学。我们建立了“顺、反式偶氮苯的热化学和光化学转化”实验［３］...     

石墨烯/偶氮杂化材料研究进展

石墨烯作为一种新型二维平面纳米材料,表现出许多优异的物理性质.含偶氮苯的化合物和聚合物作为功能材料具有独特的光响应性质.将石墨烯的特性与偶氮材料的光响应性相结合,有望发展一类具有卓越性能的新型光电功能材料.本文总结了石墨烯/偶氮杂化材料这一研究方向的最新进展,重点介绍了杂化材料的制备、表征和光电功能性质等,并简要展望了这类材料的发展前景.     

Effects of Spacers on Photoinduced Reversible Solid-to-Liquid Transitions of Azobenzene-Containing Polymers

Photoisomerization in some azobenzene-containing polymers (azopolymers) results in reversible solid-to-liquid transitions because trans- and cis-azopolymers have different glass transition temperatures. This property enables photoinduced healing and processing of azopolymers with high spatiotemporal resolution. However, a general lack of knowledge about the influence of the polymer structure on photoinduced reversible solid-to-liquid transitions hinders the design of such novel polymers. Herein, the synthesis and photoresponsive behavior of new azopolymers with different lengths of spacers between the polymer backbone and the azobenzene group on the side chain are reported. Azopolymers with no and 20 methylene spacers did not show photoinduced solid-to-liquid transitions. Azopolymers with 6 or 12 methylene spacers showed photoinduced solid-to-liquid transitions. This study demonstrates that spacers are essential for azopolymers with photoinduced reversible solid-to-liquid transitions, and thus, gives an insight into how to design azopolymers for photoinduced healing and processing.     

Photoinduced Reversible Solid-to-Liquid Transitions and Directional Photofluidization of Azobenzene-containing Polymers

Photoinduced reversible liquefaction and solidification of polymers enable processing and healing of polymers with light. Some azobenzene-containing polymers(azopolymers) exhibit two types of photoinduced liquefaction properties: photoinduced reversible solid-toliquid transition and directional photofluidization. For the first type, light switches the glass transition temperature(Tg) values of azopolymers and induces reversible solid-to-liquid transitions. For the second type, polarized light guides solid azopolymers to flow along the polarization direction. Here, we compare the two types of photoliquefaction and discuss their mechanisms. Recent progresses and applications based on photoliquefaction of azopolymers are also highlighted.     

Azopolyesters with Intrinsic Crystallinity and Photoswitchable Reversible Solid-to-Liquid Transitions

Herein, we introduce a variety of azopolyesters (azobenzene-based polyesters) with remarkable intrinsic crystallinity and photoinduced reversible solid-to-liquid transition abilities from copolymerization of azobenzene-based epoxides with cyclic anhydrides. The length of the soft alkyl side-chain inlaid with azobenzenes and stereoregularity of main-chain of azopolymers have tremendous effects on crystallization properties of the resulting polyesters with melting temperature (T_m) in the range of 51–251 °C. Moreover, some of azopolyesters possess excellently photoinduced reversible solid-to-liquid transition performance thanks to trans-cis photoisomerization of azobenzenes. Trans-azopolyesters are yellow solids with T_ms or glass transition temperatures (T_gs) above room temperature, whereas cis-polymers are red liquids with T_gs below −20 °C. These azopolyesters could be applied as novel light-switchable adhesives for quartz/quartz, wood/wood and quartz/wood adhesion, with the strength in the range of 0.73–0.89 MPa for trans-polymers. Conversely, the adhesion strength of liquefied cis-azopolyesters generated from the irradiation of trans-polymers by UV light was about 0.1 MPa, which shows light enable to control the adhesion process with high spatiotemporal resolution.     

Control of the Orientation and Photoinduced Phase Transitions of Macrocyclic Azobenzene

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups ( 1 ) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be ?0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.     

Host–Guest [2+2] Cycloaddition Reaction: Postsynthetic Modulation of CO2 Selectivity and Magnetic Properties in a Bimodal Metal–Organic Framework

Simultaneous tuning of permanent porosity and modulation of magnetic properties by postsynthetic modification (PSM) with light in a metal–organic framework is unprecedented. With the aim of achieving such a photoresponsive porous magnetic material, a 3D photoresponsive biporous framework, MOF1, which has 2D channels occupied by the guest 1,2‐bis(4‐pyridyl)ethylene (bpee), H₂O, and EtOH molecules, has been synthesized. The guest bpee in 1 is aligned parallel to pillared bpee with a distance of 3.9 Å between the ethylenic groups; this allows photoinduced PSM of the pore surface through a [2+2] cycloaddition reaction to yield MOF2. Such photoinduced PSM of the framework structure introduces enhanced CO₂ selectivity over that of N₂. The higher selectivity in MOF2 than that of MOF1 is studied through theoretical calculations. Moreover, MOF2 unveils reversible changes in T_c with response to dehydration–rehydration. This result demonstrates that photoinduced PSM is a powerful tool for fabricating novel functional materials.     

Light‐Driven Reversible Intermolecular Proton Transfer at Single‐Molecule Junctions

Photoresponsive molecular systems are essential for molecular optoelectronic devices, but most molecular building blocks are non‐photoresponsive. Employed here is a photoinduced proton transfer (PIPT) strategy to control charge transport through single‐molecule azulene junctions with visible light under ambient conditions, which leads to a reversible and controllable photoresponsive molecular device based on non‐photoresponsive molecules and a photoacid. Also demonstrated is the application of PIPT in two single‐molecule AND gate and OR gate devices with electrical signal as outputs.     

Polar Order,Mirror Symmetry Breaking,and Photoswitching of Chirality and Polarity in Functional Bent-Core Mesogens

In recent years, liquid crystals (LCs) responding to light or electrical fields have gained significant importance as multifunctional materials. Herein, two new series of photoswitchable bent-core liquid crystals (BCLCs) derived from 4-cyanoresorcinol as the central core connected to an azobenzene based wing and a phenyl benzoate wing are reported. The self-assembly of these molecules was characterized by differential scanning calorimetry (DSC), polarizing light microscopy (POM), electro-optical, dielectric, second harmonic generation (SHG) studies, and XRD. Depending on the direction of the COO group in the phenyl benzoate wing, core-fluorination, temperature, and the terminal alkyl chain length, cybotactic nematic and lamellar (smectic) LC phases were observed. The coherence length of the ferroelectric fluctuations increases continuously with decreasing temperature and adopts antipolar correlation upon the condensation into superparaelectric states of the paraelectric smectic phases. Finally, long-range polar order develops at distinct phase transitions; first leading to polarization modulated and then to nonmodulated antiferroelectric smectic phases. Conglomerates of chiral domains were observed in the high permittivity ranges of the synclinic tilted paraelectric smectic phases of these achiral molecules, indicating mirror symmetry breaking. Fine-tuning of the molecular structure leads to photoresponsive bent-core (BC)LCs exhibiting a fast and reversible photoinduced change of the mode of the switching between ferroelectric- and antiferroelectric-like as well as a light-induced switching between an achiral and a spontaneous mirror-symmetry-broken LC phase.     

Low-molecular-weight photoresponsive supramulecular hydrogel based on a dicationic azobenzene-bridged pyridinium hydrogelator

Photoresponsive supramolecular hydrogel was fabricated from a small azobenzene-bridged dicationic pyridinium salt in the aqueous solution. The UV-vis light triggered reversible gel-sol transformation of such low-molecular-weight supramolecular hydrogel was systematically investigated through various analytical techniques.     

Light‐Driven Reversible Alignment Switching of Liquid Crystals Enabled by Azo Thiol Grafted Gold Nanoparticles

Stimuli‐directed alignment control of liquid crystals (LCs) with desired molecular orientation is currently in the limelight for the development of smart functional materials and devices. Here, photoresponsive azo thiol (AzoSH) was grafted onto gold nanoparticles (GNPs). The resulting hybrid GNPs were able to homogeneously mix with a commercially available nematic LC host, as evidenced by Cryo‐TEM. Interestingly, the LC nanocomposites were found to undergo reversible alignment transition upon light irradiation as a consequence of the trans–cis photoisomerization of the azo groups on the GNP surface. LC molecules in either planar or bare glass cells were able to change their alignment to vertical upon UV irradiation, while the vertically aligned LC molecules returned to the planar or random orientation under visible irradiation. Neither the azo thiol molecules nor the unfunctionalized GNPs alone promoted the alignment of the LC molecules in the system upon light irradiation. The photoinduced vertical alignment without applied electric or magnetic field was very stable over time and with respect to temperature. Furthermore, an optically switchable device based on the photostimulated reversible alignment control of LCs was demonstrated.     

Metal-Organic Frameworks with Novel Catenane-like Interlocking: Metal-Determined Photoresponse and Uranyl Sensing

The assembly of two tripyridinium-tricarboxylate ligands and different metal ions leads to seven isostructural MOFs, which show novel 2D→2D supramolecular entanglement featuring catenane-like interlocking of tricyclic cages. The MOFs show tripyridinium-afforded and metal-modulated photoresponsive properties. The MOFs with d¹⁰ metal centers ( 1-Cd , 1-Zn , 2-Cd , 2-Zn ) show fast and reversible photochromism and concomitant fluorescence quenching, 1-Ni displays slower photochromism but does not fluoresce, and 1-Co and 2-Co are neither photochromic nor fluorescent. It is shown here that the network entanglement dictates donor-acceptor close contacts, which enable fluorescence originated from interligand charge transfer. The contacts also allow photoinduced electron transfer, which underlies photochromism and concomitant fluorescence response. The metal dependence in fluorescence and photochromism can be related to energy transfer through metal-centered d-d transitions. In addition, 1-Cd is demonstrated to be a potential fluorescence sensor for sensitive and selective detection of UO₂²⁺ in water.