A spectroscopic study of water-soluble pyronin B and pyronin Y in Langmuir-Blodgett films mixed with stearic acid

Mono and multilayer of water-soluble pyronin B (PyB) and pyronin Y (PyY) mixed with stearic acid (SA) have been incorporated in Langmuir-Blodgett (LB) films. The surface pressure-area (π-A) isotherm studies pointed out that pure PyB and PyY are incapable of forming stable films at air-water interface and collapsed readily at low surface pressures. However, mixture of PyB or PyY with SA easily formed stable films at the air-water interface and they were easily transferred onto solid substrates. The average area per molecule of mixed films of PyB and PyY at the air-water interface was observed to decrease with increasing concentrations of PyB and PyY. The spectroscopic characteristics of PyB and PyY in chloroform, in SA containing chloroform and in LB films have also been investigated by using absorption and steady-state and time-resolved fluorescence spectroscopy techniques. The morphology of the LB film surfaces has been characterized by using atomic force microscopy (AFM).     

The molecular aggregation of pyronin Y in natural bentonite clay suspension

The molecular aggregation and spectroscopic properties of Pyronin Y (PyY) in the suspension containing natural bentonite clay were studied using molecular absorption, steady-state and time-resolved fluorescence spectroscopy techniques. Interaction between the clay particles and the cationic dye compounds in aqueous solution resulted in significant changes in spectral properties of PyY compared to its molecular behavior in deionized water at the same concentration. These changes were due to the formation of dimer and aggregate of PyY in the clay suspension as well as the presence of the dye monomer. The H-type aggregates of PyY in the clay suspension were identified by the observation of a blue-shifted absorption band of the dye compared to that of its monomer. In spite of diluted dye concentrations, the H-aggregate of PyY in the clay suspension was formed. The intensive aggregation in the clay suspension attributed to the localized high dye concentration on the negatively charged clay surfaces. Adsorption sites of PyY on the clay particles were discussed by deconvulated absorption and excitation spectra. Fluorescence spectroscopy studies revealed that the fluorescence intensity of PyY in the clay suspension is decreased by H-aggregates drastically. Moreover, the presence of H-aggregates in the clay suspension resulted in the decrease of fluorescence lifetime and quantum yield of PyY compared to those in deionized water.     

Protonated dye-surfactant ion pair formation between neutral red and anionic surfactants in aqueous submicellar solutions

Spectral and surface tension behavior of aqueous neutral red in the presence of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulfonate (SDSN) have been studied to understand the nature of the interactions in their submicellar concentration ranges. The variations in spectra and surface tension with variation in the concentrations of the surfactants suggest the formation of a 1:1 close-packed dye-surfactant ion pair, HNR⁺S⁻ between the acid form, HNR⁺ of the dye and the surfactant anion at very low concentrations of the surfactant below critical micelle concentration (cmc) of the pure surfactant. The dye-surfactant ion pair behaves like a nonionic surfactant having higher efficiency and lower cmc than that of the corresponding pure anionic surfactant. The ion pairs are adsorbed on the air/water interface at very low concentrations of the surfactant. As the concentration of the surfactant increases and the ion pairs form micelles of their own, the dye in the ion pair is protonated to form H₂NR²⁺S⁻. As the cmc of the pure surfactant is approached, the protonation equilibrium gradually reverses and pure surfactant ions gradually replace the ion pairs at the interface. Finally, a homogeneous monolayer of pure surfactant anions exists at the air/water interface and the dye remain solubilized in pure micelles above the cmc of the pure surfactant. The equilibrium constants, K_c for the close-packed protonated dye-surfactant ion pair (PDSIP) formation have been determined at varying pH. The submicellar interaction has been found to be stronger with SDS than SDBS. The plots of logarithm of K_c vs. pH have been found to be quite linear which consolidates the assumption of formation of the species, H₂NR²⁺S⁻. The interaction is driven by enthalpy as well as entropy.     

Analysis of fluorescence quenching of pyronin B and pyronin Y by molecular oxygen in aqueous solution

The fluorescence quenching of pyronin B and pyronin Y molecules by molecular oxygen in aqueous solution was studied by using steady-state and time-resolved fluorescence and UV-Vis absorption spectroscopy techniques. In order to understand the quenching mechanism, fluorescence decays, absorption and fluorescence spectra of the probes were recorded as a function of the oxygen concentration and temperature. The quenching was found to be appreciable and shows positive deviation in the Stern-Volmer representation obtained from the fluorescence intensity ratio. Fluorescence quenching constants (k_q) were calculated from the τ_o/τ vs. [Q] plots having linear correlation and compared with calculated diffusion-controlled rate constants (k_diff) values. Experimental results were in good agreement with the simultaneous dynamic and static quenching model.     

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.     

发光标记物——异硫氰酸曙红荧光的介质效应

详细研究了介质(pH、有机溶剂、表面活性剂) 对异硫氰酸曙红(Eosin-NCS)荧光的影响。结果表明,体系的pH和极性是影响Eosin-NCS荧光的两个主要因素。Eosin5-NCS在弱酸性介质中的荧光强度明显高于在弱碱性介质中的荧光强度,但荧光强度随溶液pH的变化较敏感,需要小心控制。表面活性剂与Eosin5-NCS的作用表现出明显的电性选择性, CTMAB对Eosin-NCS荧光的影响存在着单分子猝灭和胶束增敏作用两个过程; 当有CTMAB胶束存在时,Eosin-NCS在弱碱性介质中荧光强度可达到甚至超过其在弱酸性介质中的荧光强度。在高含量有机溶剂存在时,Eosin5-NCS荧光亦可显著增强,应充分利用这些特性。     

八丁氧基-2,3-萘酞菁铜(Ⅱ)的合成与UV光谱研究

采用分子碎片法合成了5,9,14,18,23,27,32,36-八丁氧基-2,3-萘酞菁铜,利用元素分析、红外及紫外可见光谱进行了表征。配合物的电子吸收光谱表明:新配制的氯仿溶液中萘酞菁铜的Q带H聚集体和单体的吸收峰在758、854nm处,5h后单体和H聚集体的吸收峰基本消失,出现了798和909nm的错位H/J聚集体以及960nm的J聚集体吸收,12h后主要以795nm的H聚集体形式存在。     

Molecular simulations of self-assembly processes of amphiphiles in dilute solutions: the challenge for quantitative modelling

We report on two recent developments in molecular simulations of self-assembly processes of amphiphilic solutions. We focus on the determination of micelle formation of ionic surfactants which exhibit the archetype of self-assembling compounds in solution. The first approach is centred on the challenge in predicting micellisation properties through explicit solvent molecular dynamics simulations. Even with a coarse-grained (CG) approach and the use of highly optimised software packages run on graphics processing unit hardware, it remains in many cases computationally infeasible to directly extract the critical micelle concentration (cmc). However, combined with a recently presented theoretical mean-field model this task becomes resolved. An alternative approach to study self-assembly is through implicit solvent modelling of the surfactants. Here we review some latest results and present new ones regarding capabilities of such a modelling approach in determining the cmc, and the aggregate structures in the dilute regime, that is currently not accessible through explicit solvent simulations, neither through atomistic nor through CG approaches. A special focus is put on surfactant concentration effects and surfactant correlations quantified by scattering intensities that are compared to recently published small-angle X-ray scattering data.     

A thermodynamic and photophysical study of the effects of thiourea on the micellar properties of aqueous sodium dodecyl sulphate solution

The micellar properties of sodium dodecyl sulphate (SDS) in aqueous thiourea solutions were investigated with the aim of studying the effect of thiourea on these properties. The critical micelle concentrations (cmc) and the degree of dissociation of the micelle were determined by the conductometric method over the temperature range 298–323 K for different concentrations of thiourea. The cmc values of the surfactant in the presence of thiourea were obtained by following the change in the relative intensities of vibrational fine structure of the pyrene fluorescence spectra. The aggregation numbers were determined by employing the static quenching fluorescence method. The cmc values in the presence of varying electrolyte concentrations (NaCl) were obtained with 8-anilinonaphthalene 1-sulphonate (ANS) as a fluorescence probe, and from these values the degree of dissociation was calculated. The mass action model was applied in the present study to obtain various thermodynamic parameters of micellization. All these properties were compared with the micellar properties of an aqueous urea/SDS system, and it was found that thiourea is a better demicellization agent.     

三氮吲哚Li嗪对增感染料吸收光谱和荧光谱的影响

本文研究了三氮吲哚Ｌｉ嗪（ＴＡＩ）对三种卤化银乳剂增感染料水溶液的吸收光谱和荧光光谱的影响，研究表明ＴＡＩ能使这些染料的各吸收峰强度增强，对容易形成了Ｊ聚集体的染料来说，更有利于其Ｊ态光谱吸收；当三氮吲哚Ｌｉ嗪的浓度达到一定值后，它能侃染料Ｈ聚集体分解成单分子，利用单分子光谱吸收，结果说明染料的荧光发射也随溶液中ＴＡＩ浓度的增大而增强，本文还讨论了产生这种现象的原因。     

Synthesis of Novel Fluorescent Cyclohexenone Derivatives and their Partitioning Study in Ionic Micellar Media

An approach is demonstrated toward the synthesis of four novel cyclohexenone derivatives (CDs) via a convenient route of Michael addition of ethyl acetoacetate. The molecular structures of CDs were confirmed by means of FT-IR, ¹H NMR, EIMS, UV and also by X-ray single crystal structure analysis. CDs are strongly fluorescent compounds and their fluorescent spectra exhibits intense violet fluorescence. To model the binding to biological membranes the behavior of CDs in micellar solutions of a cationic surfactant, cetyltrimethylammonium bromide (CTAB) and an anionic surfactant, sodium dodecylsulfate (SDS) has also been examined. The characteristics of partition and binding interactions of CDs with CTAB and SDS were investigated by UV-Visible and fluorescence spectroscopic techniques. Higher values of all mentioned interactions in case of CTAB, compared to SDS, indicate that there are greater interactions between the CDs and CTAB than with SDS.     

季铵盐表面活性剂溶液中阴离子偶氮染料的光谱研究

通过紫外-可见光谱法研究了阴离子偶氮染料甲基橙(MO)与3种季铵盐表面活性剂之间的相互作用.当表面活性剂浓度远低于临界胶束浓度(CMC)时,表面活性剂与染料形成聚集体,反映为吸收带蓝移并伴随着吸收强度下降.继续加入表面活性剂,引起染料在阳离子胶束中的特征吸收.当表面活性剂浓度达到CMC及以上时,混合溶液的λ<,max>...     

Diffusion coefficients of sodium dodecylsulfate in aqueous solutions and in aqueous solutions of β-cyclodextrin

Differential diffusion coefficients have been measured of sodium dodecylsulfate (SDS) in aqueous solutions of β-cyclodextrin (β-CD) at 298.15 K over the concentration range 0.001 M to 0.0817 M using a conductimetric cell and an automatic apparatus to follow the diffusion. The cell uses an open ended capillary method, while a conductimetric technique is used to follow the diffusion process by measuring the resistance of a solution inside the capillaries, at various recorded times. The β-CD is known to for strong 1:1 complexes with SDS, and the effect of this on the diffusion of this electrolyte was investigated. The presence of β-cyclodextrin can influence the diffusion coefficients of sodium dodecylsulfate both above and below the critical micelle concentration (cmc) of this surfactant. For concentrations of β-cyclodextrin of 0.001 mol dm⁻³ the behaviour of the diffusion of SDS in aqueous solutions is the same in the absence or the presence of β-cyclodextrin. In contrast, when the β-CD concentration is 0.016 mol dm⁻³ we obtain diffusion coefficients higher than those obtained in aqueous solutions. Further, we do not observe the dramatic decrease in diffusion normally found at the cmc of the surfactant. These results are interpreted in terms of the effect of incorporation of dodecylsulfate chains inside the cyclodextrin cavities.     

十二烷基硫酸钠对木瓜酶酶活性和构象的影响

采用紫外、荧光和圆二色等光谱技术研究了阴离子表面活性剂十二烷基硫酸钠（SDS）对木瓜酶酶活力及其构象变化的影响.结果表明：（1）SDS对木瓜酶酶活力的影响与pH有关,pH=8.00时,SDS对木瓜酶酶活力有增强作用,pH=6.30时,除了在SDS的临界胶束浓度（cmc）时木瓜酶酶活力得到增强外,其他浓度下SDS对木瓜酶酶活力没有影响,pH=9.50时,SDS对木瓜酶酶活力产生抑制作用.（2）SDS对木瓜酶的荧光产生淬灭,0.1cmc的SDS木瓜酶荧光峰红移,而SDS浓度≥1cmc后则使之蓝移;（3）当[SDS]＜cmc时,木瓜酶的α-螺旋、β-折叠、回转等有序结构的含量减少而无定形结构含量增加,当[SDS]＞cmc后,木瓜酶的α-螺旋、β-折叠构型含量有所增加,无定形构型含量则有所减少.有序结构的含量越大,酶活力越强.     

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.     

胶束中的若丹明6G荧光增强和激光行为

使用阴离子表面活性剂十二烷基硫酸钠 (SDS)有效的增强了若丹明 6G染料水溶液的荧光 ,在若丹明 6G浓度分别为 5 47× 10 -7和 5 47× 10 -4 mol·L-1时 ,最大增强比率分别为 1 95和 9 7。在后一浓度下SDS的加入使若丹明 6G染料激光阈值降低 ,能量转化效率提高。不加SDS时的激光阈值功率密度约为 6 5MW·cm-2 ,加入 4 1× 10 -2 mol·L-1的SDS后 ,激光阈值功率密度降为 0 8MW·cm-2 。泵浦光功率密度为 6 5MW·cm-2 时 ,能量转化效率达到 2 5 %。同时还观察到SDS的加入使溶液吸收谱、荧光谱和染料激光发生了红移。对以上现象的物理机制进行了讨论。     

Tunable energy transfer distributed feedback dye laser using pyronin B and crystal violet dye mixture

Using pyronin B and crystal violet dye mixture, the characteristics of energy transfer distributed feedback dye laser (ETDFDL) pumped by 532 nm Nd:YAG laser were investigated. The characteristics of donor DFDL and acceptor DFDL as well as the dependence of their pulse widths and output powers on pump power and acceptor concentrations were studied. The output energy of DFDL was measured at the emission peaks of donor and acceptor dyes for different pump powers and acceptor concentrations, and tunability was observed from 570 to 645 nm using prism dye cell arrangement.     

Effect of hydrophobicity of cationic carbocyanine dyes DiOC<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> on their binding to anionic surfactant micelles

The interaction of a series of cationic dialkyloxacarbocyanine perchlorate (DiOC _n ) dyes of different degrees of hydrophobicity with micelles of an anionic surfactant, sodium dodecylsulfate (SDS), has been studied spectrophotometrically in aqueous solutions. The Benesi–Hildebrand equation was used to calculate binding constants (K _b ) of the dyes to surfactant micelles, the fraction of dye bound to the micelles (f _mic ), and the standard free-energy change (ΔG ⁰) for the transfer of dye from the aqueous to micellar phase. It has been shown that the interaction of oppositely charged dye molecules and surfactant micelles is controlled by both electrostatic and hydrophobic interactions. A small increase in dye hydrophobicity due to lengthening of the hydrocarbon radical has been shown to cause an abrupt nonlinear increase of the fmic value. This points to a key role of hydrophobic interactions in the binding of dye molecules with the micelles.     

Premicellar and micelle formation behavior of aqueous anionic surfactants in the presence of triphenylmethane dyes: protonation of dye in ion pair micelles

The premicellar and micelle formation behaviors of four cationic triphenylmethane dyes, viz, Pararosaniline (RN), Crystal violet (CV), Ethyl violet (EV), and Malachite green (MG), in aqueous anionic surfactant solutions of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dodecyl sulfonate (SDSN) have been studied by spectral and surface tension measurements. The study was carried out within a pH range where the dyes are stable in their quinoid forms. The dyes have been found to form dye–surfactant ion pairs (DSIPs) with the surfactants, at the surfactant concentrations well below their critical micelle concentration, CMC*. The DSIPs behave like nonionic surfactants and form an air–water interfacial monolayer. The DSIPs have a lower critical micelle concentration (CMC_IP), greater efficiency, and lower effectiveness than the corresponding pure surfactants. As the surfactant concentration is increased below the CMC*, the DSIPs start forming micelles of their own where the dye gets protonated and exists as a protonated dye–surfactant ion pair (PDSIP) in the ion pair micelles. As the concentration of the surfactant exceeds the CMC* of the pure surfactant, the protonation reverses gradually with the dye remaining in the micelles in solubilized form and the DSIPs in the air–water interfacial monolayer are replaced by pure surfactants. The distorted helical isomeric form (isomer B) of the dyes is favored in the PDSIPs. Copyright © 2009 John Wiley & Sons, Ltd.     

阳离子激光染料吸附入聚合物/表面活性剂的薄膜

利用静电吸附技术将阳离子激光染料罗丹明6G(R6G)成功组装到预组装在石英衬底上聚电解质/表面活性剂的复合膜中. 聚丙烯胺盐酸盐(PAH)和十二烷基硫酸钠(SDS)分别作为阳离子和阴离子表面活性剂. 紫外可见吸收光谱表征揭示水溶液中仅形成H-型的R6G聚合物,而PAH/SDS/R6G薄膜同时存在H和J型两种R6G聚合物. R6G吸附动力学表明PAH/SDS/R6G复合薄膜两个聚集带的吸收强度比与用于制备PAH/SDS自组装薄膜的SDS溶液浓度无关. 原子力显微镜揭示R6G在PAH/SDS/R6G复合薄膜的