光敏变色纤维材料

简单介绍了光敏变色纤维材料的发展情况，集中介绍了目前应用于纤维材料领域的光致变色有机化合物的光致变色机理、化合物类型，以及应用于纤维材料中的方法及这方面的发展趋势。     

二芳基乙烯类光致变色化合物的合成及其光电性质研究

在氮气及-78℃条件下,合成了两种二芳基乙烯类光致变色化合物1,2-双(2-甲基-5-(4-N,N-二甲氨基苯基)噻吩-3-基)全氟环戊烯(Ⅰa)和1,2-双(2-甲基-5-萘基噻吩-3-基)全氟环戊烯(Ⅱa),通过紫外-可见吸收光谱、荧光光谱、循环伏安法对其光谱特性和电化学性质进行了初步研究。在254nm紫外光照射下,Ⅰa和Ⅱa的氯仿溶液均由无色变为蓝色,最大吸收峰分别为620和570nm,在适当波长可见光照射下,均从有色态返回到无色态。通过UV-Vis光谱考察了这两种二芳基乙烯类化合物在溶液中的光致变色反应的动力学特征,实验结果表明,二芳基乙烯类光致变色化合物的闭环反应属于零级反应,开环反应为一级。电化学研究表明,在溶液中,Ⅰa和Ⅱa可发生不可逆的阳极氧化反应。     

Photobreeding Heterojunction on Semiconductor Materials for Enhanced Photocatalysis

Construction of heterojunctions to photocatalysts is one of the most promising approaches to improve charge separation efficiency; however, the established constructing processes usually require high-temperature conditions and/or the adding of highly concentrated or expensive exotic species, and the improvement of effective contact and charge exchange between heterojunction components remains a problem. This work proposes an unprecedented “photobreeding” method and realizes the direct growth of Zn nanowires and Mott–Schottky heterojunctions from ZnS or viologen-coated ZnS microspheres through a photochemical reaction at room temperature without external species, while demonstrating the hypothesis proposed 140 years ago on the formation of Zn in the photochromic process of ZnS. After photobreeding of the heterojunctions, the hydrogen production efficiency of the photocatalysts increases by 2 orders of magnitude. This inexpensive, facile and efficient synthetic method will find applications in H₂ production, organic synthesis, CO₂ reduction, nitrogen fixation, and so on.     

Sol—Gel法制备有机—无机复合光致变色膜

本文讨论了用ｓｏｌ－ｇｅｌ法在有机改性ＳｉＯ２基体中于室温下俘陷有机染料如螺吡喃或螺恶嗪，制备出具有光致变色功能的有机－无机复合膜。该膜层在可见光区的最大吸收峰位于６２０ｍｎ处。     

(DMA)3PMo12O40/聚乙烯醇复合薄膜的制备与性能

以有机-无机电荷转移杂化分子(DMA)3PMo12O40与聚乙烯醇(PVA)掺杂得到(DMA)3PMo12O40／PVA复合材料薄膜；对复合膜的结构、热性能、光色性和电化学性能进行了研究。该复合材料经紫外光照射后，吸光强度增加，价层吸收带(IVCT)展宽，表明具有良好的光色性：(DMA)3PMo12O40／PVA薄膜修饰电极的电化学行为显示该材料对KIO3有明显的催化作用。     

Light-Wavelength-Based Quantitative Control of Dihydrofolate Reductase Activity by Using a Photochromic Isostere of an Inhibitor

Photopharmacology has attracted research attention as a new tool for achieving optical control of biomolecules, following the methods of caged compounds and optogenetics. We have developed an efficient photopharmacological inhibitor—azoMTX—for Escherichia coli dihydrofolate reductase (eDHFR) by replacing some atoms of the original ligand, methotrexate, to achieve photoisomerization properties. This fine molecular design enabled quick structural conversion between the active “bent” Z isomer of azoMTX and the inactive “extended” E isomer, and this property afforded quantitative control over the enzyme activity, depending on the wavelength of irradiating light applied. Real-time photoreversible control over enzyme activity was also achieved.     

Efficient Photomodulation of Visible Eu(III) and Invisible Yb(III) Luminescences using DTE Photochromic Ligands for Optical Encryption

This work describes a class of complex combining three dithienylethene units and a lanthanide ion used as an optical system displaying a double encryption method: i) a colorful code, drawn and erased under UV and visible irradiations respectively, due to coloration and discoloration of the photochromic entities, and ii) a concomitant gradual disappearance and progressive restoration of the associated lanthanide ion luminescence triggered with the same stimuli. The innovation of the system stems from the emission color tunability, i.e., with either a lanthanide ion emitting only in the visible range (Eu³⁺) or with another lanthanide ion emitting only in the near infrared (NIR) range (Yb³⁺), therefore observable, or not, to the naked eye. This system is the very first one to achieve efficient repeatable modulation of pure NIR luminescence on photochemical command. Furthermore, it is proven to be highly efficient when embedded in a PDMS polymer opening real opportunities for practical applications as anti‐counterfeiting.     

Nucleoside‐Based Diarylethene Photoswitches: Synthesis and Photochromic Properties

Diarylethene photoswitches based on the natural nucleoside deoxyadenosine were designed and synthesized. In aqueous solution, some of them exhibited good photochromic properties, including clear changes in color upon irradiation at 365 nm, red‐shifts of the absorption wavelength, with good fatigue resistance, thermal stability, conversion efficiency, and base‐pairing properties.     

光响应型分子的合成及应用研究进展

光响应型分子作为一种刺激性响应分子,因其具有信号稳定、远程控制、瞬时性和环保性等优势,而广泛应用于智能材料、光控器件等领域,其中最典型、研究最广泛的当属光致异构分子。光致异构分子在特定波长光照下会发生结构变化,在宏观上有时会表现出颜色的改变,在另一波长光照下结构会重新变为原来的结构,颜色也会随之褪去。综述了螺吡喃、偶氮苯、二芳基乙烯等几种主流的光致异构分子的合成与制备、光响应机理以及在盐湖资源提取、药物检测、储能材料制备等实际生产生活中的应用,并对光响应分子在低成本环境友好合成、复合功能材料化、智能分子器件等方面的发展趋势进行了展望。     

螺吡喃6-nitroBIPS掺杂聚苯乙烯膜的全光调制特性研究

测量了螺吡喃 1',3',3' trimethylindolino 6 nitrospirobenzopyran(6 nitroBIPS)掺杂聚苯乙烯薄膜在紫外光抽运前后的吸收光谱 ,利用其吸收光谱的显著改变 ,对 5 90nm探测光的全光调制特性进行了研究。对调制随染料掺杂浓度和紫外光激发能量的依赖性进行了测量 ,理论模拟得出其光化学反应量子效率为 0 2 4和螺吡喃光化学产物光半花菁在 5 90nm处的摩尔吸收系数为 2 0× 10 4Lmol- 1 cm- 1 。被调制信号的前沿和后沿时间常数分别约为 131ns和 18μs。