荧光增白剂VBL与阳离子Gemini表面活性剂溶液的光谱研究

研究了荧光增白剂VBL在阳离子Gemini表面活性剂相互作用的紫外光谱和荧光光谱。当加入表面活性剂浓度较低时,由于VBL和表面活性剂单体形成离子缔合物,紫外吸收下降,荧光发生静态猝灭;进一步加大表面活性剂的浓度到形成胶束时,由于胶束微环境的影响,使VBL的紫外吸收和荧光光谱增强;当表面活性剂的浓度远大于CMC(1.25×10-5mol/L,25℃)时,这种变化趋缓。结果表明,在合适的表面活性剂浓度下,荧光增白剂VBL与阳离子Gemini表面活性剂之间存在强的相互作用。     

稳态荧光探针法研究槐糖脂生物表面活性剂的胶束化行为

应用稳态荧光探针法测定了非离子生物表面活性剂槐糖内脂临界胶束浓度(CMC)和胶束聚集数(N_agg),并考察了添加无机电解质和短链脂肪醇对槐糖内酯CMC的影响。结果表明,槐糖内酯的CMC为1.3×10-4 mol·L-1,并随加入电解质浓度的升高而略有降低,外加短链脂肪则使其CMC值升高;在4~8倍的CMC浓度范围内,槐糖内酯溶液N_agg随其浓度增大而增大,但胶束聚集数较小,为4~8个;激光纳米粒径结果显示槐糖内酯胶束动态直径较大且分布较为集中,平均约为90 nm。槐糖内酯胶束具有聚集数小而直径大的特点,表明该生物表面活性剂所形成的胶束排列较为松弛。     

表面活性剂对HPTS荧光的单分子猝灭及胶束作用

研究了各种表面活性剂存在下,8-羟基-1,3,6-三磺酸芘钠盐(HPTS)的荧光光谱,结果表明、表面活性剂对其荧光特性的影响可分为两种类型:单分子猝灭(CMC以下)和胶束作用(CMC以上)。它们分别服从相应的Stern-Volmer稳态猝灭和溶质-胶束作用线性方程。按导出方程对应作图,求得CTMAB的单分子猝灭常数K=2.4×10~5L/mol;CTMAB胶束和TX100胶束对HPTS的键合常数分别为7.4×10~5L/mol和7.0×10~3L/mol。阴离子表而活性剂十二烷基硫酸钠,由于其电性与HPTS阴离子电性的不相容性,对HPTS荧光未见明显影响。     

球状胶束中表面活性剂脱附的离子调控机制

建立耦合伞状采样的粗粒度分子动力学方法,研究球状胶束中表面活性剂分子的脱附过程,揭示表面活性剂聚集数、盐种类及浓度对表面活性剂脱附过程的影响机制。发现球状胶束半径及偏心率均随聚集数增加而增大,盐浓度的影响主要取决于抗衡离子的半径和吸附特性,半径更大、吸附更强的水杨酸根离子对胶束结构的影响更为显著;基于伞状采样方法获得了表面活性剂脱附自由能、脱附时间等关键参数,发现球状胶束中表面活性剂脱附自由能和脱附时间均随聚集数和盐浓度呈非单调变化,揭示其主要机制为离子吸附引起的静电屏蔽作用;发现自由能在表面活性剂脱附过程中起主导作用,结合胶束热力学理论发展了临界胶束浓度预测方法,获得了临界胶束浓度下胶束尺寸的分布范围。     

荧光探针法研究N-月桂酰基-N''-羟乙基乙二胺乙酸盐的微极性

用荧光光谱法测定Ⅳ-月桂酰基-Ⅳ'-羟乙基乙二胺乙酸盐(两性乙酸钠)的微极性.芘的荧光强度随着两性乙酸钠浓度的增加而减小,其第一峰(I1)和第三峰(I3)的强度随两性乙酸钠浓度的增加先降低,到达一定浓度后,趋于稳定.由芘的I1/I3与浓度关系可以得出两性乙酸钠的临界胶束浓度(CMC值大约为11.03mmol/L),与表面张力法(1.02mmol/L)测定结果一致.同时研究了无机盐的加入对芘的I1/I3值的影响,无机盐的加人使芘的I1/I3值减小,即无机盐的加入使芘所处的微环境极性减小.     

荧光探针法研究N-月桂酰基-N′-羟乙基乙二胺乙酸盐的微极性

用荧光光谱法测定N-月桂酰基-N′-羟乙基乙二胺乙酸盐(两性乙酸钠)的微极性。芘的荧光强度随着两性乙酸钠浓度的增加而减小,其第一峰(I1)和第三峰(I3)的强度随两性乙酸钠浓度的增加先降低,到达一定浓度后,趋于稳定。由芘的I1/I3与浓度关系可以得出两性乙酸钠的临界胶束浓度(CMC值大约为1.03mmol/L),与表面张力法(1.02mmol/L)测定结果一致。同时研究了无机盐的加入对芘的I1/I3值的影响,无机盐的加入使芘的I1/I3值减小,即无机盐的加入使芘所处的微环境极性减小。     

硫杂杯[4]芳烃基胶束自组装荧光探针的结构性质及检测性能的研究

水体中重金属污染因威胁生态环境和人类健康而被受广泛关注。荧光探针由于具有快速高效检测重金属的特性,一直是该领域的研究热点。通常,荧光探针在结构上包括对待测物质起识别作用的受体和能产生信号响应的荧光体,并逐步形成了内在型、共轭型、系综型和模板辅助自组装型等四种结构类型。近年来,基于受体和荧光体在表面活性剂胶束内自组装而形成的胶束自组装型荧光探针因结构简单、易于制备、能直接应用于水环境等特点逐渐受到重视。以对铜离子具有优异结合性能的对叔丁基硫杂杯[4]芳烃（TCA）为受体,以芘、荧蒽、蒽、菲、苝等分子为荧光体,通过表面活性剂胶束自组装制备针对Cu2+检测的胶束自组装型荧光探针,采用参比法测定了胶束自组装荧光探针的荧光量子产率,采用稳态荧光法测定了胶束聚集数,同时通过计算荧光猝灭率分别考察了荧光体种类、复配表面活性剂等因素对该探针的Cu2+检测性能的影响情况。实验结果显示,采用十二烷基硫酸钠（SDS）、曲拉通100（TX-100）、聚氧乙烯月桂醚（Brij35）等三种不同的表面活性剂对探针荧光体的荧光量子产率产生了明显影响,测得的荧光探针荧光量子产率介于0.25~0.47,且三者逐渐增大,说明表面活性剂改变了胶束内荧光分子芘所处微环境的极性,且不同类型表面活性剂对微环境极性的影响程度有所差异,微环境极性的增强对极性更大的激发态芘具有更强的稳定作用。而受体TCA的加入对荧光体所处微环境极性影响较小,未对荧光量子产率产生较大影响。但TCA的加入使探针的胶束聚集数明显减少,这归因于具有两亲性的受体TCA分子通过胶束自组装进入并分散在表面活性剂分子层中,形成共胶束结构,从而改变了表面活性剂分子的聚集状态。荧光体变更对荧光探针的Cu2+检测性能有显著影响,在同样条件下,以荧蒽、蒽、菲作为荧光体的探针检测Cu2+所得到的荧光猝灭率远高于芘、苝,这主要是因为不同荧光体在从激发态返回基态时辐射跃迁所释放能量不同,其能量与受体TCA识别Cu2+所需能量之间的匹配度越高,荧光猝灭率越大。不同类型的表面活性剂之间的复配能明显提升荧光探针检测性能,当非离子/阴离子、非离子/阳离子型复配表面活性剂之间的复配比例分别为7∶3和1∶1时荧光猝灭率达到最大值,且均高于单一表面活性剂时的荧光猝灭率。这说明不同类型表面活性剂复配的最佳比例存在较大差异,但均有效地增强了受体与荧光体的分散性及自组装性能,提高了对Cu2+的检测性能。研究结果将为新型胶束自组装荧光探针的设计和应用提供数据参考。     

表面活性剂敏化稀土荧光探针对环丙沙星药物的测定研究

稀土铽离子能与环丙沙星形成络合物,并发射铽离子的特征荧光,加入表面活性剂SDBS能大大增强体系的荧光强度,由此建立了表面活性剂敏化的铽离子荧光探针测定环丙沙星的方法。用1 cm 石英比色池在激发波长为300 nm, 发射波长为545 nm处测定其荧光强度。在最佳测试条件为pH=8.0～8.5, Tb3+ 浓度为5.0×10-5 mol·L-1, SDBS浓度为8.0×10-4 mol·L-1时,环丙沙星的浓度与体系的荧光强度呈线性关系,线性范围为2.0×10-8 mol·L-1～2.5×10-6 mol·L-1, 相关系数为0.999 6,检出限为4.0×10-9 mol·L-1。该法可用于不同剂型环丙沙星药物的测定。     

胶束体系中荧光素与四溴荧光素间能量转移条件及模型研究

研究了阳离子表面活性剂(CSAA)在水溶液中与阴离子酸性染料四溴荧光素(TBF)的荧光反应,发现当CSAA单体与TBF形成离子缔合物时,TBF的荧光发生猝灭,而CSAA胶束与TBF作用又会产生一个新的、更强的荧光。进而研究了阳离子表面活性剂CTMAB及CPB胶束体系中酸性阴离子荧光染料荧光素与四溴荧光素间的能量转移条件。表明只有在带相反电荷的CSAA形成的胶束中,阴离子染料间的能量转移才可能发生,在2/3临界胶束浓度(CMC)时能量转移效率达到最大。并推测了胶束体系中染料间能量转移模型及染料间能量转移的一般规律。     

荧光光谱法检测非水体系中蒽和芘

用荧光光谱法检测建立了非水体系中蒽和芘的测试方法,蒽和芘的检测线性范围分别为5.6×10^-9—2.8×10^-6mol/L和4.9×10^-8—1.47×10^-6mol/L,相关系数为0.99959和0.99822,检出限分别为0.356ng/mL,5.230ng/mL,回收率分别为86.61%—98.66%和96.60%—115.80%。考察了常见离子、时间以及温度对荧光强度的影响,结果表明,常见离子对分析检测干扰均不大,可忽略,在2h、5—55℃温度范围内,对荧光强度影响较弱,故此分析检测方法对温度的适应范围较宽。方法可直接用于食品、饮料、酒产品等非水体系中的蒽和芘的测定。     

Spectroscopic investigations on the interaction of an anionic probe with nonionic micelles of Igepal surfactants in aqueous media

The behaviour of the anionic dye 8-anilino-1-napthalenesulfonic acid ammonium salt, or ANS, in aqueous solutions containing the Igepal series of polyoxyethylene nonionic surfactants was investigated using fluorescence spectroscopic technique. The interactions of the dye with the nonionic surfactants were examined in micellar media, to prevent dye aggregate formation and to ensure maximum dye and surfactant interaction. From the relative fluorescence enhancements, binding constants of the dye to the surfactant micelles and aggregation numbers of the micelles were determined. The aggregation numbers were also separately determined by static fluorescence quenching of pyrene by cetylpyridinium chloride in aqueous surfactant mixtures at a fixed concentration of surfactant, and compared with the value obtained from the present investigation of the interaction of the micelles with the ANS probe. The values of binding constants, micropolarity values sensed by pyrene and the Stern–Volmer constants for quenching of pyrene fluorescence by cetylpyridinium chloride were correlated with the number of ethylene oxide groups in the Igepal series.     

高斯多峰拟合用于烷基葡萄糖苷临界胶束浓度测量

报道了可见吸收光谱线型的高斯多峰拟合用于新型非离子表面活性剂烷基葡萄糖苷(APG),如辛基-β-D-葡萄糖单苷(C₈G₁)和癸基-β-D-葡萄糖单苷(C10G₁)的临界胶束浓度(CMC)的测定。具体作法是以结晶紫(crystal violet,CV)为探针,测量一系列不同浓度的APG-CV水溶液体系的可见吸收光谱。其光谱特征是CV单体吸收峰598～609 nm和二聚体吸收峰538～569 nm叠合在一起。用高斯多峰拟合法实现了体系可见光谱吸收叠合峰的分峰、峰面积(积分吸光度)、频移及半高宽等光谱线型参数计算。单体和二聚体峰面积比(相对积分吸光度A₂/A₁)、频移(Δλ)及半高宽(w₁,w₂)对APG浓度图形在CMC处发生突变。首次发现可见吸收光谱线型参数半高宽对APG聚集行为敏感,并成功用于APG的CMC测量。     

Light scattering and fluorescence probe studies on micellar properties of Triton X-100 in KCl solutions

The effect of KCl on micelle formation and structure of Triton X-100 (TX-100) was investigated by using combined static and dynamic light scattering measurements, together with the fluorescence probe technique. An analysis of the light scattering data, including hydrodynamic radius and micellar aggregation number, accounted for both micelle growth and hydration. Fluorescence studies using pyrene as a probe were carried out to determine the critical micelle concentration (CMC) as a function of solution composition. In addition, with the aim of gaining information on the possible changes in the micro-environmental properties of TX-100 micelles, fluorescence probe studies, including intermolecular pyrene excimer formation and fluorescence polarization of coumarin 6 associated with micelles, were carried out. It was found that the addition of electrolyte induces a decrease in the CMC and an increase in both aggregation number and hydration. However, complementary data of partial specific volume and cloud point of the surfactant suggested that the main contribution to micellar hydration is due to water mechanically trapped in the micelle. Fluorescence measurements do not indicate changes in the micellar micropolarity, probably due to modifications of the solubilization site of the probe caused by the micellar growth. Both pyrene excimer formation and fluorescence polarization of coumarin 6 revealed an increase in microviscosity with electrolyte addition, which is consistent with increased micellar hydration.     

多组分水溶液中的石油磺酸盐与OP—10的荧光发射光谱

含苯氧基的非离子型和阴离子型表面活性剂在一定激发波长下可发出特定波长的荧光，在稀溶液中荧光发射强度与其浓度成正比，不受溶液里存在的其他物质的影响，在适当条件下相互之间也无影响。本文报道了用荧光检测复合驱油体系中的ＯＰ１０、石油磺酸盐和ＯＰ１０＋石油磺酸盐的结果。此法选择性高，灵敏度高，操作简便，可望用于复合驱油体系中表面活性剂的分析、研究。     

Surfactant fluorescence in the study of aggregation and clouding

The intrinsic fluorescence of Triton X-114 and Igepal CO-630 was used to monitor the aggregation behavior of micellar solutions of these surfactants. The response to changes in surfactant concentration, increases in temperature up to and beyond the cloud point, and addition of an ionic surfactant (SDS) was monitored. The intrinsic fluorescence was used to measure aggregate anisotropy as a function of SDS concentration and temperature. Relative aggregate abundance showed a minimum at the CMC, confirming the existence of premicellar assemblies. Structural differences in the hydrophobic portions of the two nonionic surfactants led to vastly different packing in their aggregates. The addition of SDS produced smaller, more closely packed micelles.     

基于NaGdF_4∶Eu纳米粒子的荧光猝灭测定痕量Cu~(2+)

采用水热法合成了柠檬酸盐修饰的水溶性NaGdF4:Eu荧光纳米粒子,粒子溶液荧光强度稳定.实验发现,Cu2+外对合成粒子的荧光有猝灭作用,据此可建立用NaGdF4:Eu荧光探针测定痕量Cu2+的新方法.实验确定NaGdF4:Eu的浓度为1.0×10-3 mol·L-1,溶液的pH值为10.0.考察了其他常见离子对粒子荧光性能的影响,其中Fe3+使荧光发生猝灭,用三乙醇胺可消除Fe3+的干扰.标准曲线的线性回归方程为I=532-0.685c,相关系数r为-0.998 4,线性范围为3.33×10-6～1.33×10-4 mol·L-1,检出限为8.9×10-7 mol·L-1,对浓度为6.0×10-5 mol·L-1的Cu2+溶液平行测定11次,RSD为0.62%.以上结果表明,方法的线性范围较宽,灵敏度和精密度较高.测定了茶叶样品中铜含量,测定结果和原子吸收法测定结果相一致.分析Cu2+对粒子荧光猝灭的机理认为,Cu2+和粒子表面的柠檬酸根发生化学结合,改变了粒子表面的结构和组成,导致其荧光发生猝灭.     

Role of the head group on the mixed micellization process in binary systems containing a sugar-based surfactant: decanoyl- N -methylglucamide

The mixed micelles of nonionic decanoyl-N-methylglucamide (MEGA-10) with the anionic sodium dodecyl sulphate (SDS), the cationic dodecyltrimetylammonium bromide (DTAB), and the nonionic octaoxyethylene monododecyl ether (C₁₂E₈) have been studied using the fluorescence probe technique. The critical micelle concentration of the three mixed systems in the whole composition range were determined by the pyrene 1:3 ratio method, and the experimental results were analysed in the context of the pseudophase separation model, by using the regular solution theory. It was found that the mixed micelles containing the anionic surfactant are more stable than the pure micelles. This fact was attributed to the occurrence of ion–dipole interactions between the head groups of the component surfactants in the mixed micelle. The static quenching method was used to determine the mean aggregation number of pure and mixed micelles. It was found that whereas mixed micelles containing SDS show a positive deviation from the ideal behaviour, those constituted by DTAB deviate negatively. This different tendency was interpreted on the basis of both steric and electrostatic interactions. The evolution of the microstructure of the mixed micelles upon the participation of the co-surfactant was followed through the micropolarity and microviscosity of the mixed systems. Although the micropolarity studies do not allow definite conclusions, the microviscosity assays indicate that the participation of the co-surfactant induces the formation of less ordered micelles, this effect being more pronounced in the case of mixtures with the anionic surfactant.     

功能性CdTe量子点荧光增敏法测定对苯二胺

以CdT e量子点作为荧光探针,基于荧光增敏法对对苯二胺进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH 7.6的0.2m ol/LN a2HPO4-N aH2PO4缓冲液中,反应时间为15m in,对苯二胺浓度为6.0×10-6—1.8×10-5m ol/L范围时,其线性回归方程为ΔF=75.64＋7.95C（10-6m ol/L）,相关系数和检出限分别为0.9989和2.1×10-8m ol/L。该方法检出限低,灵敏度高,为对苯二胺的测定提供了新的选择。