新取代苯基荧光酮试剂的合成及其性质的研究Ⅰ．新型取代苯基荧光酮的合成、提纯、鉴定及离解的研究

合成了３，５－二溴－４－氨基苯基荧光酮、４－偶氮变色酸苯基荧光酮、３，５－二溴－４－氨基变色酸苯基荧光酮、４偶氮肿Ⅰ苯基荧光酮、３，５－二溴－４－偶氮胂Ⅰ苯基荧光酮、４－偶氮间苯二酚苯基荧光酮、３，５－二溴－４－偶氮间并苯二酚苯基荧光酮和３，５－二溴－４－二甲氨基过溴化物苯基荧光酮等８种新有机试剂。对其进行了提纯和结构鉴定，并对试剂离解状态及离解常数进行了研究和测定。     

新取代苯基荧光酮试剂的合成及其性质的研究Ⅰ.：新型取代苯基…

合成了３，５－二溴－４－基苯基荧光酮、４－偶氮变色酸苯基荧光酮、３，５－二溴－４－氨基变色酸苯基荧光酮、４－偶氮胂Ⅰ苯基荧光酮、３，５－二溴－４－偶氮胂Ｉ苯基荧光酮、４－偶氮间苯二酚苯基荧光酮、３，５－二溴－４－偶氮间并苯二酚苯基荧光酮和３，５－二溴－４－二甲氨基过溴化物苯基荧光酮等８种新有机试剂。对其进行了提纯和结构鉴定，并对试剂离解状态及解常数进行了研究和测定。     

三苯二恶嗪荧光染料的合成与电子光谱性能

本文以４－氨基－４－苯基二苯醚和４－氨基－２－苯基二苯醚与四氯苯醌反应,合成了两个新结构三苯二恶嗪荧光染料。在五种肿瘤剂中测定了它们的吸收及荧光光谱,并讨论了溶剂极性对染料荧光光谱影响。     

三苯二噁嗪荧光染料的合成与电子光谱性能

本文以４－氨基－４’－苯基二苯醚和４－氨基－２’－苯基二苯醚与四氯苯醌反应,合成了两个新结构三苯二嗪荧光染料。在五种溶剂中测定了它们的吸收及荧光光谱,并讨论了溶剂极性对染料荧光光谱影响。     

荧光黄颜料的合成

本文以苊为原料经硝化、氧化、缩合、还原等工序合成了４－氨基－Ｎ－间甲苯基－１,８－萘二甲酰亚胺和４－氨基－Ｎ－邻甲苯基－１,８－萘二甲酰亚胺两种荧光黄颜色的荧光体,并对影响合成反应的诸因素进行了讨论。制得的两种化合物经光谱测定,证明有很好的荧光性能。     

几个双偶氮－8－氨基喹啉新衍生物的合成及其分析应用的研究

合成了４个５，８－二位双偶氮－８－氨基喹啉衍生物，它们是５－本基偶氮－８－（苯基偶氮氨基）喹啉（ＰＡＰＡＱ）、５－苯基偶氮－８－（４－羧基苯基偶氮氨基）喹啉（ＰＡＣＰＡＯ）、５－苯基偶氮－８－（４－溴苯基偶氮氨基）喹啉（ＰＡＢＰＡＱ）、５－苯基偶氮－８－（４－硝基苯基偶氮氨基）喹啉（ＰＡＮＰＡＱ）。用光度法测定ＴＰＡＰＡＱ和ＰＡＣＰＡＱ的酸离解常数。研究了它们与金属离子的光度和荧光性能。建立了一个光度法和一个荧光法测定铜的新方法。     

新型香豆素类荧光染料的合成研究

以７－二乙氨基－４－氯－３－甲醛基香豆素为基础合成了７只新型香豆素类的荧光染料。本类染料具有强烈的荧光，随着分子内π－共轭体系的增大，染料的色光从黄色增至红色。     

6—氯—2—[5—氯—2—（4—联苯磺酰氨基）]苯基—4—苯并恶嗪酮的合成和油？…

以邻氨基苯甲酸为原料，用盐酸－双水氯代法制得５－氯邻氨基苯甲酸，产率４０％，然后将固体联苯磺酰氯加入至－５－氯邻氨基苯甲酸的吡啶液中，合成出荧光发射波长为５５０ｎｍ的荧光剂６－氯－２－〖５－氯－２－（４－联苯磺酰氨基）苯基－４－苯并恶嗪酮，产率提高了２０％。并配制出了两种胶印油墨；黏度５．３２Ｐａ．ｓ，黏性４．６２，细芳１０μｍ；黏度３１．７５Ｐａ．ｓ，黏性１０．３０，细度１０μｍ。适用于有交 伯     

新型香豆素类荧光染料的合成研究

以７－二乙氨基－４－氯－３－甲醛基香豆素为基础合成了７只新型香豆素类的荧光染料。本类染料具有强烈的荧光。随着分子内π－共轭体系的增大，染料的色光从黄色增至红色。     

德国禁用若干化合物

德国禁用若干化合物德国已颁布有关的法令，禁止使用联苯胺、４－氨基联苯、４－氯－２．甲基苯胺、２－萘胺、４－氨基－３．２’－二甲基偶氮苯、２－氨基－４－硝基甲苯、对氯苯胺、２．４－二氨基苯甲醚、４．４’－二氨基二苯甲烷、３，３’－双氯联苯胺、３，３’－...     

Solubilisation study of water‐insoluble dye in cationic single/dimeric surfactant micelles: effect of headgroup,non‐polar tail,and spacer chain in aqueous and salt solution

The solubilisation of hydrophobic azo dye Orange OT in aqueous/salt solution in several cationic surfactant micelles was studied using UV‐vis spectroscopy. An attempt was made to correlate dye solubilising strength with adsorption/micellar characteristics. In our experiments we determined the change in solubilisation of hydrophobic dye when added to an aqueous solution of oppositely charged quaternary‐salt‐based cationic surfactants (conventional and gemini) and remarked on the probable location of the solubilised dye in the surfactant micelle. Results highlight the onset of dye solubilisation around the critical micelle concentration of each surfactant, which is influenced by the non‐polar tail, spacer, and polar headgroup, while no dye could be solubilised at concentrations below the critical micelle concentration. Orange OT solubilised almost linearly with increase in surfactant concentration at and above the critical micelle concentration. The change in colour intensity of the dye (darker below the critical micelle concentration, lighter at and above the critical micelle concentration) could be attributed to dye–surfactant interactions. Further dye solubilisation was observed in the presence of salt.     

罗丹明B与十二烷基硫酸钠胶团的相互作用

采用荧光光谱法研究了罗丹明B与阴离子表面活性剂十二烷基硫酸钠(SDS)胶团的相互作用以及无机盐的影响。结果表明,罗丹明B作为探针分子可以用来测定表面活性剂SDS在水溶液中的临界胶团浓度。两者之间的相互作用可用缔合常数Ka定量表示,体系中Ka值随着无机盐浓度的增大而增大,表明罗丹明B与SDS胶团的相互作用增大。     

Effect of position of ester group and temperature on critical micelle concentration of ester containing surfactants

The critical micelle concentrations of sodium sulfoalkyl alkanoates, C_nH_2n+1 COO(CH₂)_mSO₃Na (n=9, 10, and 11; m=2, 3, and 4), in aqueous solution were measured by an electro conductivity method from 15 to 50 C. Plots of critical micelle concentrations versus temperature show a minimum for all of the surfactants. Increasing the number of methylene groups between the ester and sulfonate groups in the surfactant molecule lowered the temperature at which the minimum critical micelle concentration was observed. When the percentage deviation of critical micelle concentration values obtained at different temperatures from critical micelle concentration values at 30 C was plotted as a function of the temperature, deviation in the range below 30 C increased with length of the hydrocarbon chain in the fatty acid portion of the surfactant, and decreased with the increase in length of the hydrocarbon chain situated between ester and sulfonate groups. These phenomena suggest that the change of interaction between the ester group and water molecule with the temperature is largely dependent on the position of the ester group in the alkyl chain of the surfactant. On the other hand, deviation values above 30 C increased with length of the hydrocarbon chain in the fatty acid portion and of the hydrocarbon chain situated between ester and sulfonate groups. These results indicate that interaction between the ester group and water molecule decreases with rise in temperature. The enthalpies, free energies, and entropies of micelle formation were calculated from temperature variation of critical micelle concentrations, and are consistent with current theories of the role of solvent in micelle formation.     

Influence of Nonionic Surfactant on Hydrolysis of Vinyl Sulfone Reactive Dye

Nonionic surfactants are widely used in reactive dyeing processes, and the interaction between surfactants and reactive dyes affect the hydrolytic property of reactive dyes. In this study, reactive brilliant blue KN‐R (C.I. reactive blue 19) was employed as a model dye, and fatty alcohol polyoxyethylene ether (AEO‐9) was selected as a model nonionic surfactant. The interaction was first investigated in aqueous solutions by a UV‐spectrophotometry method, then the effect of surfactant concentration on the hydrolytic behavior of KN‐R was studied using high performance liquid chromatography method. Below the critical micelle concentration, the surfactant served as dispersant; the hydrolysis of reactive dye was accelerated. However, when the concentration of surfactant was above its critical micelle concentration, the dye was solubilized into the micellar phase, which was revealed from the changes in absorbance intensity and wavelength of the maximum absorbance. This led to slowed hydrolysis of reactive dye. These findings are useful in understanding the effect of concentration of nonionic surfactant on the hydrolysis of vinyl sulfone reactive dyes.     

利用Gemini联接链上生色基团测定临界胶团浓度

利用Gemini表面活性剂分子聚集使联接链上生色基团吸光截面积增大的原理,发展了自吸收光谱测定水溶液中临界胶团浓度(CMC)的方法。实验测得C11pPHCNa水溶液(pH=12)的CMC值0．0891 mmol／L,与表面张力法测定的结果(CMC=0．0925 mmol／L)吻合。当这些分子聚集形成较完整胶团后造成联接链上生色基团的荧光猝灭,由此可测定形成较完整胶团的临界点(≈0．451 mmol／L)。     

Aqueous solution properties of disulfide-linked fluorinated gemini and cleaved monomeric thiol surfactants

We prepared a fluorinated gemini surfactant containing a disulfide bond in its spacer chain, [C?F??(CH?)?N(CH?)?CH?CH?SSCH?CH?N(CH?)?(CH?)?C?F??]2Cl, and its analogue with a hexamethylene spacer. Monomeric thiol surfactant, [C?F??(CH?)?N(CH?)?CH?CH?SH]Cl, was readily produced by the cleavage of the gemini surfactant using dithiothreitol in water. The critical micelle concentration was determined using surface tension, conductivity, and fluorescence probe methods. The critical micelle concentration of the monomeric surfactant was significantly larger than that of the gemini surfactant. The surface tension of aqueous solution for the cleaved monomeric thiol surfactant returned gradually to the original value through the formation of the disulfide bond via air oxidation.     

Influence of Spacer Nature on the Aggregation Properties of Anionic Gemini Surfactants in Aqueous Solutions

A series of anionic gemini surfactants with the same structure except the spacer nature have been studied. Their solution properties were characterized by the equilibrium surface tension and intrinsic fluorescence quenching method. The critical micelle concentrations (CMC), surface tension at cmc, C₂₀, and the micelle aggregation number (N) were obtained. The surface tension measurements indicate that these gemini surfactants have much lower cmc values and great efficiency in lowering the surface tension of water compared with those of conventional monomeric surfactants. Furthermore, the standard free energy of micellization for anionic gemini surfactants was also determined. The results showed that the nature of the spacer has an important effect on the aggregation properties of gemini surfactants in aqueous solutions. The surfactant with a hydrophilic, flexible spacer was more readily able to form micelle compared with the surfactant with a hydrophobic, rigid spacer, which leads to a lower CMC value, larger N, more negative free energy of micellization, and a more closely packed micelle structure.     

混合胶束对槲皮素荧光增强作用研究

研究发现,在六次甲基四铵-盐酸缓冲溶液中,阴离子表面活性剂十二烷基苯磺酸钠与阳离子表面活性剂十六烷基三甲基溴化铵形成的混合胶束对槲皮素的荧光强度有明显的增强作用。利用荧光光谱、共振光散射光谱、紫外吸收光谱研究了混合胶束对槲皮素的荧光增强机理。结果发现,混合胶束能为槲皮素提供更好的疏水环境,使槲皮素的吸收增强,进而使槲皮素的荧光增强。     

阳离子荧光敏感器的器件化问题研究

通过对石英玻片表面修饰，制作了联有多氨基链萘基的超薄膜荧光敏感器件，研究了它在镍、铜等金属离子水溶液及有机溶剂中的荧光猝灭现象。发现其荧光光谱无论在水或其他有机溶剂中都存在着单体和激基缔合物（excimer)的发射峰，当处于镍离子水溶液中时，其单体峰随离子浓度的增大出现了先增强后减弱的现象，而激基缔合物的发光峰则仅略有减弱但变化不大。在铜离子水溶液中其荧光的变化情况和镍离子有所不同，对单体荧光只能观察到强度减弱的趋势，而激基缔合物则变化不大。比较了未联结的敏感器化合物分子在有机溶剂中荧光被铜离子猝灭的行为，发现与其在器件表面时有很大的差别，表明其分子结构和构象也有很大的不同。     

Fluorescence technique for the determination of low critical micelle concentrations

A technique for determining low critical micelle concentrations (CMC) by means of a hydrophobic fluorescence probe has been developed. The amount of the fluorescent probe at the CMC is so small that the effect of the probe on micelle formation is negligible. The fluorescence intensity was measured at fixed dye/surfactant ratios, and it decreased with concentration. A quantity proportional to fluorescent quantum yield was calculated and found to be high for concentrations of surfactant above the CMC and almost zero below the CMC, giving a distinct break in the quantum yield vs. the concentration curve.