光敏剂N-丁基-2-乙氧基硫代吖啶酮的合成

以邻氯苯甲酸和对乙氧基苯胺为原料，经过胺的苯基化、二芳胺的环化、N－烷基化、硫代化反应合成了N－丁基－2－乙氧基硫代吖啶酮。各步中间产物和目标产物的结构均经红外光谱和质谱确认，通过正交设计实验，得出环化反应的最佳反应条件：温度为100℃，时间为30min，浓硫酸为2－羧基－4′－乙氧基二苯胺的配比为5：1（mL/g)，在此条件下反应收率达78．6％。N－丁基－2－乙氧基硫代吖啶酮的光吸收可延伸到540 nm，在可见光区的最大吸收峰为503nm.     

以吖啶染料荧光猝灭为基础的卤素阴离子检测研究

合成了两种吖啶及吖啶橙盐类小分子化合物和带有吖啶盐的三元共聚物，研究了它们在溶液中的荧光被卤素离子猝来的问题，发现它们能强烈地被碘离子所猝灭而不易被氯离子猝灭，表明这类化合物有可能用于在有氯离子存在条件下对碘、溴离子的检测，对荧光猝灭机理进行的研究发现，卤素离子的猝灭能力并不和它们对发光化合物的系间窜越和三重态的生成等有关，而是和阴离子对极化分子的作用减弱了分子内的电荷转移能力相关。     

7-氯-9-苯基-3,4-二氢吖啶-1（2H）-酮的合成及其与牛血清白蛋白的相互作用研究

以5-氯-2-氨基二苯甲酮与1,3-环己二酮在碘催化下缩舍得到7-氯-9-苯基-3,4-二氢吖啶-1（2H）-酮（Y）.通过IR、1HNMR、13CNMR、MS及元素分析对其结构进行了表征,运用荧光猝灭法研究了Y与牛血清白蛋白（BSA）的相互作用,确定了Y对BSA荧光的猝灭机理,测定了Y与BSA之间的结合常数、结合位点数及热力学参数.结果表明,Y对BSA具有良好的静态猝灭作用,其相互作用的结合常数为3.9044×104 L·mol-1,结合位点数约为1,主要作用力类型为疏水作用力.     

以聚醚链相连的9—氨基吖啶,苯甲酸酯二元体系的合成及分…

本文用聚四乙二醇柔性链将９－氨基吖啶和不同取代基的苯甲酸酯连接起来，合成了一类新型二元分子体系，对各种体系中９－氨基吖啶和电子转移荧光猝灭进行了研究，并根据稳态荧光猝灭计算了体系中的荧光猝灭效率和荧光猝灭速率常数。     

N,N′-二甲基喹吖啶酮的合成研究

采用N 烷基化反应,在喹吖啶酮上引入两个甲基,得到N,N′ 二甲基喹吖啶酮,该化合物具有良好的溶解性,能发出强烈的桔红色荧光。     

液—液相转移催化反应合成N—烃基取代吖啶酮

吖啶酮是合成吖啶类化合物的主要中间体。吖啶类化合物在医药（特别是抗癌药物）［1,2]、染料和感光材料方面都有广泛的用途[3]。1979年，Galy和Barbe[5]首先报道了用相转移催化法合成N-烃基取代吖啶酮，使用的催化剂为三乙基辛基氯化铵（TEBAC），反应要在甲苯中回流5天，且得到的是O-取代和N-取代吖啶酮的混合物，产率也只有41％～66％。1981年，NIshi[6]等人对上述方法进行了改进，以丁酮为溶剂，加入50％的NaOH水溶液，反应在较温和的条件下进行，反应产率提高到75％～83％。我们以前曾以液一液相转移催化法合成过N一烃基取代吩…     

3—碘—苯并吡喃—4—酮与2—硫代嘧啶类的Michael加成反应

报道了具有α，β－不饱和羰基的３－碘－苯并吡喃－４－酮（１）与２－硫代嘧啶发生Ｍｉｃｈａｅｌ加成反应，合成出４个２－（２－羟苯甲酰基）－５－氧－５Ｈ－噻唑并［２，３－ｂ］嘧啶的衍生物。这些化合物结构经核磁共振光谱、紫外吸收光谱、红外光谱和元素分析均予以证实。     

吖啶类荧光探针与蛋白质相互作用的研究

文章研究3种新型吖啶类荧光探针(N-(2-二甲氨基)乙基-9-氯吖啶-4-甲酰胺(NCAF)、9-[(N-2-二甲氨乙基)吖啶-4-甲酰胺]-α-丙氨酸(NAFA)和4,9-二[N-(2-二甲氨基)乙基]-9-吖啶胺-4-甲酰胺(DNAF))与牛血清白蛋白(BSA)的相互结合作用机理。分别对3种吖啶类探针自聚集情况、与牛血清白蛋白结合常数KA和结合位点数n、热力学参数H、G以及S、能量转移效率E和结合距离R0进行比较,并对实验数据进行分析。研究了3种吖啶类探针对蛋白质内源荧光猝灭的猝灭机制和主要作用力类型,为进一步研究新的生物探针及其在生物大分子识别分析应用提供了一定的实验和理论支持。     

香豆素衍生物与碘Weng盐间的光诱导电子转移研究

研究了３种碘Ｗｅｎｇ盐对３种香豆素荧光的猝灭,发现猝灭曲线符合Ｓｔｅｍ Ｖｏｌｍｅｒ方程并且猝灭过程受扩散控制。研究证实了猝灭的机理是由于发生了光诱导电子转移。通过香豆素衍生物－碘Ｗｅｎｇ盐体系能在光照下引发甲基丙烯酸甲酯单体的聚合进一步证实了这种机理。尽管香豆素有较强的分子内电荷转移倾向,但由于碘Ｗｅｎｇ盐阳离子很强的拉电子能力,它们间还是能发生快速的电子转移。     

卤素离子对联有吖啶基三元共聚物薄膜的荧光猝灭

在合成了几种带不同组成比吖啶基三元共聚物的基础上，对其溶液和薄膜的吸收与荧光发光光谱进行了表征。研究了上述薄膜在含有卤素阴离子溶液中的荧光猝灭问题，发现含有不同吖啶组成比的薄膜对不同卤素离子具有不同的选择性，过多或过少吖啶含量的薄膜均对选择性的识别卤素阴离子不利，只有在某种特定组成条件下方能得到最佳、具有特征识别阴离子能力的薄膜器件。对所得结果进行了详细的讨论。     

Synthesis and photochemical behavior of 2-(N-acridonyl)ethyl methacrylate and its polymer

A polymerizable photosensitizer, 2-(N-acridonyl)ethyl methacrylate (AEMA), containing both aromatic ketone and aromatic tertiary amine moieties in the same molecule, was prepared by reaction of N-hydroxyethyl acridone (HEA) and methacryloyl chloride in the presence of triethylamine (TEA). HEA was obtained by reaction of acridone with ethylene carbonate. The photochemical behavior including photoinitiation and fluorescence properties of AEMA and its polymer P(AEMA) were studied. It was found that the photoinitiation efficiency of monomeric AEMA is lower than that of its polymer for the photopo-lymerization of acrylonitrile (AN) in DMF. By the kinetic study and the analysis of recorded electron spin resonance spectra of the photoinitiation systems of AEMA or AEMA-di-methylaminoethyl methacrylate (DMAEMA) trapped by 2-methyl-2-nitritopropane (MNP), the mechanism is deduced to be similar to that of the benzophenone-TEA system. The recorded fluorescence spectra show that AEMA and P(AEMA) possess a strong fluorescence emission peak at 410 and 439 nm, respectively. The concentration self-quenching effect was observed with maximum intensities at a concentration of 8.6 × 10⁻⁵ mol/L in DMF for both AEMA and P(AEMA). Even though AEMA has a tertiary amino group and an electron-deficient acrylic double bond in the same molecule, it did not display structural self-quenching effect as we reported previously. This may be due to the two benzene rings in acridone that lessen the electron-donating ability of the N atom. The fluorescence quenching of AEMA and P(AEMA) by electron-donating and electron-accepting compounds was also investigated. © 1996 John Wiley & Sons, Inc.     

L-半胱氨酸与牛血清白蛋白相互作用的荧光光谱分析

运用荧光猝灭光谱、同步荧光光谱探讨了L-半胱氨酸（L-Cys）与牛血清白蛋白（BSA）的相互作用,并计算了猝灭常数、结合常数、结合位点数以及3个热力学参数△H、△G和△S。结果表明,L-Cys使BSA的内源荧光发生猝灭,BSA的发射峰从350nm蓝移到347．5nm,荧光猝灭机制为动态猝灭;L-Cys与BSA之间的作用力主要为疏水作用力;L-Cys对BSA结构的微环境有一定的影响。     

Investigation of an N‐Butyl‐N‐(2‐Nitroxyethyl)Nitramine (BuNENA) Process: Identification of Process Intermediates,By‐Products and Reaction Pathways

A process for N‐butyl‐N‐(2‐nitroxyethyl)nitramine (BuNENA) was investigated: Step 1 involves N‐butyl‐ethanolamine addition to 98% HNO₃ to form a salt mixture; Step 2 is addition of acetic anhydride/acetyl chloride catalyst to the salt mixture. A number of potential intermediates, by‐products, and decomposition products from this process were identified/synthesized for use as analytical standards. BuNENA process reaction pathways/mechanisms were elucidated, including the nature of the amine salt solution formed in Step 1. In addition, potential pathways that could account for by‐product formation were elaborated. A study of the consumption of acetyl nitrate in Step 2 was undertaken to prevent its build‐up.     

荧光光谱法研究核黄素与牛血清白蛋白的相互作用

荧光光谱法研究了注射用核黄素(Riboflavin,Rf)与牛血清白蛋白(BSA)的相互作用.核黄素对BSA具有荧光猝灭作用,其猝灭方式为静态猝灭;在301和317K下用Stem-Volmer方程和热力学方程等处理实验数据,求出了结合常数KA、结合位点数n及热力学参数ΔG、ΔH和ΔS.核黄素与BSA之间的作用力主要为氢...     

High speed three-component photoinitiating systems composed of cyanine dyes borate salt and heteroaromatic thiols

Three heteroaromatic thiols (2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole) were investigated in regard to their abilities as a co-initiator in free radical polymerization induced by cyanine dye/borate salt photoinitiating system. The kinetic results shown that the new three-component photoinitiating systems are more effective than two-component ones. The mechanism of photochemical and chemical processes occurring during the irradiation of the three-component initiators was proposed on the basis of the laser flash photolysis. The addition to the cyanine dye borate salt of a second co-initiator (thiol) results in the generation besides butyl radical the second free radical which can start the polymerization chain reaction.     

反相微乳液聚合荧光高分子F-PAM

通过Span80-Tween80/异辛烷/FM(4-甲氧基-N-（2-N′,N′-二甲基氨基乙基）萘二甲酰亚胺烯丙基氯化铵）-AM（丙烯酰胺）-H₂O反相微乳液聚合,制备了AM和FM的荧光高分子聚合物（F-PAM）.采用透射电镜（TEM）、原子力显微镜（AFM）、激光纳米粒度仪、荧光分光光度计等测试手段,测定了荧光高分子聚合物（F-PAM）的粒子形态、粒径和粒径分布等微观结构及其荧光性能.试验结果表明：所制备的F-PAM为单分散、球形的纳米材料,平均粒径（D）在60～145 nm之间;F-PAM的激发波长和发射波长分别为381 nm和462 nm.F-PAM激发光谱与发射光谱呈较好的镜像对称关系;F-PAM的相对荧光强度随着其质量浓度的增加而增加,且F-PAM的浓度与其荧光强度呈很好的线性关系,其线性相关系数（R）为0.9953,F-PAM的检测下限为1.83 mg·L^-1.     

荜茇宁与牛血清白蛋白相互作用的研究

用荧光光谱及紫外光谱法研究生理条件下荜茇宁与生物大分子牛血清白蛋白(BSA)的相互作用.实验结果表明,荜茇宁与BSA形成基念复合物从而猝火BSA的内源性荧光,猝灭原因主要为静态猝灭和非辐射能量转移.根据Forster 偶极-偶极非辐射能量转移理论,确定荜茇宁与BSA有较强的相互作用,可以被蛋白质所储存和运输.荜茇宁与B...     

High performance of the linked visible photoinitiator for free radical polymerization based on erythrosine B derivative

A novel erythrosine B derivative linked with a tertiary amine used as a visible light initiator for free radical polymerization was synthesized and characterized. For comparison, the free hydrophobic erythrosine B derivative was also synthesized and its combination with the tertiary amine was used as the separated two component photoinitiator. The linked initiator exhibited higher photoinitiator efficiency in high viscosity monomer than in low viscosity one, compared with the separated counterpart. Especially, when it was combined with iodonium salt, the further promotion of the photoinitiator efficiency was observed, compared with the separated three component system. It was found that as iodonium salt together with tertiary amine was continuously added to the formula with the linked initiator, the photoinitiator efficiency was dramatically enhanced compared with the same addition to the formula with the separated counterpart, revealing the application potential of the linked initiator. And the continuous addition of either the iodium salt or the tertiary amine to the formula only leaded to the small size increase of the photoinitiator efficiency. These results suggested that there existed an interdependent relationship between iodonium salt and tertiary amine in promoting the photoinitiator efficiency of the dye/amine/iodonium salt system. For these, the corresponding synergistic mechanism was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42361.     

双水相萃取藻蓝蛋白的机理

采用荧光光谱的方法对双水相萃取藻蓝蛋白(PC)的机理进行了研究。不同分子量的聚乙二醇(PEG)对PC均有荧光猝灭作用。PEG与PC相互作用的热力学研究结果表明,PEG1000与PC的结合常数大于PEG2000和PEG4000,两者是熵驱动下的疏水作用力结合。不同的无机盐对PEG1000与PC结合的影响不同,其中Na₂SO₄使PEG1000-PC体系熵增效果最显著。同步荧光光谱的研究表明,PEG1000使PC色氨酸残基微环境的疏水性增强;Na₂SO₄通过促进PEG1000与PC的结合而使色氨酸残基微环境的疏水性进一步增强。单因素扫描实验的结果表明,PEG1000/Na₂SO₄体系双水相萃取纯化藻蓝蛋白(PC)的能力最强,符合PEG1000与PC分子相互作用的热力学规律。     

光谱法研究蛋白质与胆红素及铜的相互作用

应用荧光光谱研究了胆红素(BR)及铜与牛血清白蛋白(BSA)的相互作用机制.结果表明,BSA-BR的光谱图在有Cu2 存在时,发生了明显的变化,表明能够形成BSA-Cu2 -BR三元络合物.胆红素主要以静态猝灭的方式使得牛血清白蛋白荧光强度显著降低,胆红素和牛血清白蛋白主要凭借范德华力和氢键作用结合.测定了BSA-BR、BSA-Cu2 以及BSA-Cu2 -BR体系的组成和结合常数.探讨了铜离子及胆红素与牛血清白蛋白间的结合反应,阐明了铜离子浓度对胆红素和蛋白质结合的影响.