光致变色螺萘并噁嗪配合物的褪色过程动力学研究(英文)

报导了一种带5’－CO2Me取代基的螺嗪（A）的开环形式（B）与金属离子的配合作用，利用紫外可见吸收光谱研究了金属离子浓度的影响，并证明了有色体配合物（C）的主要消色过程是先解离出金属离子生成（B）．再褪色生成闭环无色体（A）．未观测到由（C）直接褪色生成（A）的过程·     

螺噁嗪类光致变色化合物的合成研究进展

光致变色螺噁嗪;双光致变色螺噁嗪;螺噁嗪聚合物;合成;微波合成     

螺噁嗪光致变色反应机理研究进展

20世纪80年代中期以来, 关于螺噁嗪在光致变色过程中的光化学和光物理现象的研究非常活跃. 综述了近20年来对溶液中的螺噁嗪、晶体螺噁嗪以及固体介质中的螺噁嗪的光致变色机理研究结果, 同时介绍了实验研究方法和理论研究方法在螺噁嗪光致变色过程研究中的应用, 分析了取代基对光致变色性质的影响. 阐述了机理研究对新型螺噁嗪设计合成的重要指导意义.     

螺噁嗪光致变色反应机理研究进展

20世纪80年代中期以来, 关于螺噁嗪在光致变色过程中的光化学和光物理现象的研究非常活跃. 综述了近20年来对溶液中的螺噁嗪、晶体螺噁嗪以及固体介质中的螺噁嗪的光致变色机理研究结果, 同时介绍了实验研究方法和理论研究方法在螺噁嗪光致变色过程研究中的应用, 分析了取代基对光致变色性质的影响. 阐述了机理研究对新型螺噁嗪设计合成的重要指导意义.     

几种取代螺吲哚啉萘并噁嗪的合成

螺吲哚啉-2,3'-[3H]萘并[2,1-b][1,4]噁嗪(简称螺噁嗪)是一类耐光疲劳性能优于螺吡喃的光致变色物^[1]。Fox以及Ono先期合成了这类化合物^[2],最近Pottier等考察了取代基对性能的影响^[3,4]。但所涉及的取代基(CH₃、CH₃O、Cl、NO₂)多在母体结构中吲哚环的5( 6)位,且N-烷基碳链较短,蔡环上有取代基的情形较少见^[5]。     

螺噁嗪化合物的合成及其光致变色性能的研究

合成了3种新型的螺噁嗪化合物,并通过IR,MS,1H NMR对其结构进行了表征。研究了1位和9’位上取代基对螺噁嗪光致变色性能的影响;不同溶剂对螺噁嗪最大吸收波长的影响;对螺噁嗪的热褪色速率进行了动力学的研究。结果表明,当螺噁嗪1位的取代基为柔性结构,9’位连接能形成更稳定共轭体系的取代基时有利于开环体热稳定性的提高。     

超声波辐射下光致变色螺噁嗪类化合物的快速合成

在超声波辐射条件下,以Fischer碱、1-亚硝基-2,7-二羟基萘为原料,无水乙醇为溶剂快速合成了三个螺嗪类光致变色化合物,通过1 H NMR、IR对目标产物的结构进行了表征,讨论了超声辐射时间对合成产率的影响,利用超声波法合成螺噁嗪类光致变色化合物反应速率快、产率有所提高.     

9'-(4-烯丙氧基苯甲酰氧基)吲哚啉螺萘并噁嗪的合成及其光谱性质

合成了７种９－羟基吲哚啉螺萘并恶嗪衍生物（ＨＳＰａ－ｇ）和７种９‘－（４－烯丙氧基苯甲酰氧基）吲哚啉螺萘并恶嗪衍生物（ＡＳＰａ－ｇ）,ＡＳＰａ－ｇ的＾１Ｈ ＮＭＲ结果表明,当１位是苄基或乙基时,与氮相连的亚甲基的２个氢的化学位移不等价,属ＡＢ自旋系统。     

Synthesis and photochromic properties of substituted naphthopyran compounds

A group of 3,3-diaryl-3H-naphtho[2,1-b]pyran compounds with functional substituents at the 5- and 6-positions of the naphthopyran skeleton and the para positions at the 3-aryl moieties were prepared through condensation reactions between 2-naphthol derivatives and 1,1-diarylprop-2-yn-1-ol derivatives. The chemical structures of the compounds were confirmed by NMR and MS. The crystal structure of 3,3-diphenyl-6-morpholino-3H-naphtho[2,1-b]pyran (4b) was determined and the relationship between the pyran substructure and photochromism was discussed. The photochromic properties were studied as well, and decoloration kinetics of colored forms was fitted to the biexponential model. Among these compounds, 4b was considered to be the best one due to the large ΔOD of colored form, which is one of the most important properties used in the photochromic material.     

尿素改性制备螯合剂的研究

以玉米淀粉为原料,分别制备交联淀粉、醚化淀粉、胺基淀粉和DTC改性淀粉,并对四种改性淀粉的最佳制备条件进行了研究。通过对各样品进行FTIR和SEM分析,并对DTC改性淀粉进行了CuSO4溶液螯合实验。FTIR和SEM分析均表明,淀粉改性成功,且通过螯合实验分析可知,在中性CuSO4溶液中,螯合性能随DTC改性淀粉硫含量的增加而增加;在不同pH的CuSO4溶液中对螯合性能进行比较,当pH=11,硫含量为1.54%(wt),DTC改性淀粉用量为0.10g时,螯合性能达到最高值500.9mg/g。     

Kinetic spectrophotometric determination of tetraphenylporphinecobalt(II) based on photochromism of immobilized norbornadiene

The cobalt(II) complex is detected spectrophotometrically by its catalysis of a photochromic isomerism of norbornadiene (NBD). NBD is immobilized on porous glass beads, and is isomerized to quadricyclane (QC) by UV irradiation. The beads are then immersed in a solution containing tetraphenylporphinecobalt(II) [TPPCo(II)], and the QC is converted back to NBD by a catalytic reaction with TPPCo(II). The rate constant, measured spectrophotometrically, is proportional to the concentration of TPPCo(II). The detection limit of TPPCo(II) is 60 μM for a reaction period of 1 h. This spectrophotometric detection can be applied repetitively without any supply of the chemical reagent, as NBD immobilized on the porous glass beads can be re-isomerized to QC by UV irradiation.     

Oxidation of Substituted Benzyl Alcohols by Quinoxalinium Dichromate. A Kinetic Study

Summary. Quinoxalinium dichromate (QxDC) oxidizes benzyl alcohol and substituted benzyl alcohols smoothly in dimethyl sulfoxide (DMSO) and in the presence of acid to the corresponding aldehydes. The reaction has unit dependence on each of the alcohol, QxDC, and acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electron-withdrawing groups retard the reaction, and the rate data obey Hammetts relationship. The reaction constant was –1.09±0.01 at 303K. Oxidation of ,-dideuteriobenzyl alcohol indicated the presence of a substantial primary kinetic isotope effect (k_H/k_D=6.78 at 303K). The reaction failed to induce the polymerization of acrylonitrile. The rates of oxidation were determined at different temperatures and the activation parameters were evaluated. The analysis of the dependence of the kinetic isotope effect on temperature indicated that the reaction involves a symmetrical cyclic transition state. A suitable mechanism is proposed.     

甲醛-乳酸-丙酮-Mn2+-BrO-3-H2SO4振荡反应动力学分析研究

甲醛对乳酸 丙酮 Mn2+ BrO-3 H2SO4化学振荡反应的诱导期tin有显著的影响,甲醛浓度的对数ln[HCHO]与诱导期倒数的对数ln(1/tin)有良好的线性关系,线性范围为5.0×10-8～1.0×10-3mol·L-1。在此浓度范围内,该体系是一重现性好,灵敏度高,操作简单的甲醛动力学分析测试体系。获得的诱导期、周期的表观活化参数Ein、Ep分别为64.7kJ·mol-1、65.0kJ·mol-1。     

光致变色化合物的研究——1，3，3—三甲基—6‘—（1—哌啶基）—螺[2H—吲哚—2，3’—[3H]吡啶[3,2—f][1,4]苯并恶嗪]的合成

螺嗪类化合物是在螺吡喃基础上发展起来的一类新的光致变色化合物 ,与螺吡喃相比 ,具有化学性质稳定 ,光响应快 ,抗疲劳性好等优点 ,在光信息记录、非银感成像、非线性光电器件、光过滤器、防伪以及装饰等领域具有很大的应用潜力[1] 。吲哚啉螺嗪的基本结构及光致色变过程可表示为 :　　其中Ｘ为 (杂 )芳环与苯环相并 ,可带有取代基。螺嗪ＳＰ(Ｓｐｉｒｏｏｘａｚｉｎｅ)经光λ1激发后 ,开环变成具有大共轭体系的开环体ＰＭＣ(Ｐｈｏｔｏｍｅｒｏｃｙａ ｎｉｅｓ) ,从而使其光吸收红移 ,停止激发后 ,ＰＭＣ可通过λ2 或以热作用方式回…     

Kinetic study on photochromism of WO3 aqueous sol and its enhancement accompanying spectral changes by the addition of TiO2 aqueous sol

Photochromism of a WO₃ aqueous sol has been investigated in a nitrogen atmosphere under controlled temperature. Effects of ageing of the WO₃ sols, concentrations of WO₃ sols or Cl⁻ ion and temperature on the coloring rate were examined. The coloring rate was the first-order with respect of the WO₃ concentration. The coloring process was accelerated by an addition of TiO₂ aqueous sols. Spectral changes were measured using the mixing sol with various molar ratios (γ) of WO₃ and TiO₂. The absorption spectra changed from those having the single peak at 775 nm to those with two peaks at 640 and 980 nm. Such spectral transformation was ascribed to the structural change of the WO₃ nanoclusters, depending on the γ value and the concentration of Cl⁻ ion.     

硫化亚铁阴极的电极过程机理

应用循环伏安法研究了硫化亚铁阴极的电极过程机理 ,电极反应过程伴随着难溶硫化亚铁的形成与溶解 ,该电极过程受欧姆电阻控制 .根据循环伏安曲线峰电流和峰电位与扫描速度平方根成线性关系 ,提出了电极过程的欧姆电阻控制模型 ,导出峰电位和峰电流与扫描速度之间的关系式 ,理论分析与实验结果一致 .     

Process development for the decoloration of Panax notoginseng extracts: A design space approach

A systematic, yet simple method for the decoloration of Panax notoginseng extracts has been developed by static adsorption tests and response surface methodology. Through static adsorption experiment screening, acidic alumina was selected because of its high decoloration ratio and saponin recovery ratios. Using response surface methodology, the correlation between the process parameters (i.e., sample volume and flow rate) and decoloration performance was modeled. A design space of the decoloration process was subsequently established through the proposed models. The verification experimental values were in good agreement with the predicted values. The design space was proven reliable, because all the verification experimental results attained the criteria for design space development. Moreover, most of the saponins adsorbed by the acidic alumina could be recovered through dynamic desorption using water and ethanol. The method developed in the current study is highly efficient, flexible, and easy to control, thus providing a promising approach for the decoloration of Panax notoginseng extracts with consistent decoloration performance.     

Synthesis and spectroscopic characterization of red-shifted spironaphthoxazine based optical switch probes

Spironaphthoxazine (NISO) is an efficient optical switch probe that has applications in high contrast detection of Förster resonance energy transfer (FRET) using optical lock-in detection (OLID). NISO exists in two distinct states, spiro (SP) and merocyanine (MC), that can be independently controlled by using alternate irradiation with near ultraviolet and visible light. Unfortunately, the SP-state of NISO has an absorption centered at 350 nm, which may lead to phototoxic effects when manipulating the probe within a living cell. To overcome this problem we introduce new, red-shifted amino-substituted NISO probes compared to NISO that undergo an efficient SP to MC transition in response to irradiation by using 405-nm light, which is less damaging to living cells. This study details the synthesis of amino-substituted NISO and their N-hydroxysuccinimide ester and maleimide derivatives and their use in generating covalent attached protein conjugates. This study also presents a characterization of the spectroscopic and optical switching properties of these red-shifted NISO probe in solution.