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.     

光致变色全氟环戊烯类二芳烯化合物的合成及其性质研究

合成了两种新的二芳基乙烯类光致变色化合物1，2-双(2-甲基-5-(4-乙氧基苯基)噻吩-3-基)全氟环戊烯(1a)和1，2-双(2-甲基-5-(对氟苯基)噻吩-3-基)全氟环戊烯(2a)，并且研究了其在不同溶剂和浓度中的UV-Vis光谱、荧光性质和光致变色反应动力学特征．实验结果表明，化合物1a和2a具有良好的光致变色性质和较强的荧光；光致变色闭环反应为零级反应，开环反应为一级反应．     

光致变色二芳烯掩膜及在近场光存储中的应用

合成了在超分辨率近场结构（Super-RENS）存储方式中适合做掩膜层和记录层材料的两种全氟二芳烯，旋涂法制备了实验存储盘片，并进行了近场存储实验．初步的实验表明，光致变色二芳烯掩膜层可以缩小聚焦激光的直径，得到小尺寸记录信息．掩膜层中二芳烯的浓度，对近场存储结果影响很大，存在一个最佳浓度使记录光斑的尺寸减少到最小．     

变色树脂镜片及光致变色染料的筛选

介绍了变色树脂镜片的历史、发展、树脂类型、镜片制作工艺,从化学键变化角度分析了光致变色染料的类型及性能筛选,并深入探讨了螺吡喃和螺嗪类光致变色染料的性能影响因素和结构改性方法。     

基于分子内能量传递的双二芳烯光控荧光开关

具有良好光致变色性质的双二芳烯DDTE-1、DDTE-2和DDTE-3分子在紫外光下的光异构化会引起有效的分子内能量传递,使它们的荧光被淬灭从而构成高效的光控荧光开关。荧光开关的工作效率和响应水平取决于其闭环态二芳烯(DTE)单元和发荧光的桥基之间能量的匹配程度,而激发态桥基的能量被其上的取代基所调制。基于双二芳烯C—O异构体的特殊性质,讨论了分子内能量传递的过程。     

光致变色化合物螺萘并吡喃的合成及光谱性能

以2-萘酚、苯肼和3-甲基-2-丁酮为原料,设计并合成了一种含萘环螺吡喃类光致变色化合物:1,3,3-三甲基吲哚啉螺萘并吡喃,通过1HNMR、IR和元素分析表征了它的分子结构,利用紫外光谱和荧光光谱对目标化合物的吸收光谱和光致发光光谱进行了研究,初步探索了目标产物的光致变色性能。吸收光谱结果表明,目标分子(闭环体)的二氯甲烷溶液(1×10-4mol/L)在可见光区基本无吸收而呈现无色,但经254 nm的紫外光照射后其开环体在480 nm处有较强的吸收而呈现红色(A=1.1),停止紫外光照射溶液恢复为无色,显示了良好的光致变色性能;发光光谱结果显示,目标分子经紫外光激发后其开环体在433 nm处有较强的蓝光发射。     

Preparation and photochromic properties of waterborne polyurethane containing spirooxazine groups

Two novel photochromic spirooxazines, SO 1 and SO 3, were successfully prepared and characterized by Fourier transform infrared spectroscopy (FTIR), ¹H-NMR, and mass spectrometry with electrospray ionization (ESI-MS). SO 1 was doped and grafted with waterborne polyurethane (WPU) to afford D₁-WPU and G₁-WPU. D₃-WPU was prepared by doping SO 3 with waterborne polyurethane. FTIR spectra indicated that SO 1 was grafted onto waterborne polyurethane successfully. Scanning electron microscopy proved that spirooxazines of D-WPU can be effectively dispersed in a waterborne polyurethane matrix, and spirooxazines of G-WPU are evenly distributed in the copolymer. The results showed that the light transmittance of modified waterborne polyurethane films decreased compared with pure waterborne polyurethane films, but the water resistance and tensile strength were better. Ultraviolet–visible spectra demonstrated that the thermal stability of spirooxazine derivatives improved significantly after being modified. The fading rate constant of the D₃-WPU film (k = 0.0079 s^-1) during the discoloration process decreased 9.77 times in contrast to SO 3 in ethanol, which showed that the thermal stability of spirooxazine in WPU film was obviously enhanced. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47067.     

吲哚啉螺吡喃光致变色化合物研究的最新进展

综述了近年来吲哚啉螺吡喃研究现状与动向，介绍了它们的结构，合成方法以及在光信息存储材料中的光致变色性能.有45篇参考文献.     

掺杂萘并吡喃的涂料光致变色性能研究

制备了一种能用太阳光（或紫外光）控制色彩变换的涂料。研究表明，通过光调控开关，将有机光功能材料的信息存储与显示功能在高分子载体（涂料）中得到充分展示。光调控的、智能化的新材料，使色彩变化多样，能丰富人们的生活。     

Fluorescence Activation with Photochromic Auxochromes

The inherent reversibility of photochromic transformations can be exploited to switch on and off the fluorescence of appropriate organic chromophores under optical control. In turn, the photoactivation of fluorescence permits the monitoring of dynamic processes in real time as well as the reconstruction of images with spatial resolution at the nanometer level. Thus, the identification of viable structural designs to construct and operate photoactivatable fluorophores on the basis of photochromic processes can translate into the realization of valuable analytical tools for biomedical research. In this context, a strategy was designed to connect a simple photochromic oxazine to essentially any fluorescent chromophore with a pendant formyl group. In the resulting fluorophore photochrome dyads, the photoinduced interconversion of the photochromic component between its two states controls that ability of the fluorescent component to absorb exciting radiation and emit as a result. Under these conditions, the interplay of two illuminating beams, designed to operate the photochromic component and excite the fluorescent one, respectively, offers the opportunity to switch fluorescence reversibly for multiple cycles. Furthermore, the fluorophore photochrome dyads described herein can be entrapped within the hydrophobic core of polymer micelles and operated under these conditions in aqueous solutions and within the intracellular environment.     

苯氧基蒽醌的合成及光致变色机理探讨

介绍了3-甲基-1-苯氧基-9,10-蒽醌的光致变色机理,用紫外-可见光谱探讨了目标化合物在240—300 nm及300—550 nm两个波段范围内其由“trans”醌式转变为“ana”醌式的光致变色行为,并用紫外-可见光谱数据证实了苯氧基蒽醌光致变色行为中醌结构的变化.     

Fluorescence Intensity Modulation in Photochromic Conjugated Polymer Systems

The ability to modulate fluorescence intensity with a light signal enables a variety of applications based on fluorescence imaging. One approach to fluorescence photomodulation involves using a photochromic moiety that responds to a light signal in conjunction with a nearby fluorophore. We employ conjugated polymers based on poly(p-phenylene vinylene) (PPV) as the fluorophore in photochrome-fluorophore systems for fluorescence modulation. Advantages of using conjugated polymers for this purpose include their intrinsic energy migration processes that enable amplified fluorescence quenching as well as their processability. Here we present examples of PPV-based photomodulation systems that employ photochromic dyes from three common photochromic families: azobenzenes, spironaphthoxazines, and diarylethenes. In all cases we observe reversible fluorescence quenching due to fluorescence resonance energy transfer to the photogenerated form of the photochrome. Examples of the photomodulation of photochromic PPV systems in organic solution, polymer films, and conjugated polymer nanoparticles are presented.     

Rational Design of Double-Check Mercury Ion Chemosensors Based on Photochromic Compounds

A new photochromic compound, S1 , containing a trans-cis photoisomerizable unit and a mercury detecting chemosensor unit, has been designed and synthesized. S1 displayed dramatic selectivity for mercury ions over other ions, through fluorescence intensity measurement. In addition, in the photostationary state, a colorimetric response to mercury ions was also achieved. The fluorescence turn-off of S1 by mercury ions was defined as the first check, while mercury-induced colorimetric variation in the photostationary state was set as the second check. Thus, a double-check mercury chemosensor can be achieved.     

有机光致变色化合物光化学稳定性能研究

良好的光化学稳定性是光致变色化合物实现工业实际应用的前提和保证。研究比较了几种有机光致变色化合物的可逆光致变色性的热稳定性和耐疲劳性等光化学稳定性能,提出了提高光化学稳定性的几种可行方法。     

N-甲基螺噁嗪光致变色染料的合成及其光致变色性质研究

以1,3,3-三甲基-2-亚甲基吲哚啉和1-亚硝基-2-萘酚为原料合成了N-甲基-3,3-二甲基螺吲哚啉-2,3'[3H]萘并[2,1-b][1,4]噁嗪,对其进行了紫外和红外光谱以及元素分析,并对其光致变色性质以及主要影响因素温度、溶剂和pH进行了研究.结果表明,该化合物具有良好的光致变色性和一定的酸致变色性;温度、溶剂极性和pH对其光致变色性有不同程度的影响.     

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。     

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。     

6－（4－甲氧基苯氧基）－5，12－萘并萘醌的合成与光致变色性质

以6－氯－5,12－萘并萘醌为起始原料,合成了6－（4－甲氧基苯氧基）－5,12－萘并萘醌,通过元素分析、 IR、1 H NMR和EIMS对其结构进行了表征。研究表明：6－（4－甲氧基苯氧基）－5,12－萘并萘醌可以发生类似于苯氧基萘并萘醌的光异构化反应, trans－form的最大吸收峰出现在395 nm处,而ana－form在450 nm和481 nm处显示出特征双峰,并且只在408 nm处有一个等吸光点。     

基于光控二芳基乙烯的手性向列相液晶体系研究进展

光控手性分子开关结合到液晶材料体系中,可以有效利用其光诱导的手性变化,实现远程光刺激液晶材料的自组装螺旋超结构。二芳基乙烯（DAE）是一类新型的、有前景的光致变色分子,作为智能光响应开关,在手性向列相液晶材料体系中表现出优异的性能。本文重点围绕结构设计,总结了一系列具备不同螺旋扭曲力（HTP）的手性DAE分子及其在液晶自组装螺旋结构中所产生的特定性能,如光可逆宽范围调控和光控手性反转。该类光控DAE手性向列相液晶体系在手性调控、光学显示、可调谐激光等领域具有巨大的应用潜力。最后讨论了该领域面临的挑战和机遇,并指出了未来可能的发展方向。     

基于光控二芳基乙烯的手性向列相液晶体系研究进展

光控手性分子开关结合到液晶材料体系中,可以有效利用其光诱导的手性变化,实现远程光刺激液晶材料的自组装螺旋超结构。二芳基乙烯（DAE）是一类新型的、有前景的光致变色分子,作为智能光响应开关,在手性向列相液晶材料体系中表现出优异的性能。本文重点围绕结构设计,总结了一系列具备不同螺旋扭曲力（HTP）的手性DAE分子及其在液晶自组装螺旋结构中所产生的特定性能,如光可逆宽范围调控和光控手性反转。该类光控DAE手性向列相液晶体系在手性调控、光学显示、可调谐激光等领域具有巨大的应用潜力。最后讨论了该领域面临的挑战和机遇,并指出了未来可能的发展方向。