SDS胶束溶液在石油类污染物荧光光谱测量中的应用

提出了一种以十二烷基硫酸钠(SDS)胶束溶液为溶剂增溶、增敏、增稳石油类物质的新方法。研究了石油类物质的荧光强度随SDS胶束溶液浓度的变化规律,确定了其溶剂SDS胶束溶液的最佳浓度为0.1 mol·L-1。使用FLS920荧光光谱仪测量得到不同稀释浓度的汽油、柴油、煤油SDS胶束溶液的三维荧光光谱矩阵(EEMs),分析了瑞利(Rayleigh)散射、拉曼(Raman)散射以及仪器光谱特性对测量光谱的影响,经过光谱校正,建立了三种油的SDS胶束溶液在激发波长为250～400 nm、发射波长为260～500 nm范围内的三维荧光光谱图,并确定了在一定浓度范围内荧光强度与浓度具有良好的线性关系。在相同条件下,用同样的方法配制各种浓度汽油、柴油、煤油水溶液作对比,验证了SDS胶束溶液作为石油类物质的溶剂可以使水中石油类物质的溶解度增加、荧光强度增大、稳定性更好,实现了石油类物质可以不依赖于某些有毒溶剂萃取,又解决了其水中溶解度低不宜定量的问题。     

十二胺聚甘油醚表面活性剂的合成及光谱表征

十二胺与缩水甘油在碱催化下合成了不同聚合度的十二胺聚甘油醚表面活性剂,并以FTIR、ESI-MS、13CNMR进行了合成产品的光谱表征。用吊环法测定了该表面活性剂水溶液在25℃时的表面张力,考察了不同聚合度对其表面性质的影响。结果表明,十二胺二聚甘油醚、四聚甘油醚、六聚甘油醚水溶液的临界胶束浓度CMC（mmol/L）分别为0.32、0.055和0.20,先减小而后增大;最低表面张力γCMC（mN/m）分别为28.46、29.41和34.02,逐渐增大。     

Effect of surfactants on the aggregation of pyronin B and pyronin Y in aqueous solution

Molecular dynamics of pyronin B (PyB) and pyronin Y (PyY) in aqueous solution containing different surfactants were investigated by using absorption and fluorescence spectroscopy techniques. First, the interactions of PyB and PyY with the negatively charged surfactant sodium dodecyl sulphate (SDS) were investigated in the below and above critical micelle concentration (cmc). The H-aggregate formation of the dye compounds was observed for below the cmc of SDS surfactant. The absorbance of H-aggregate absorption band of PyB and PyY decreased according to the aggregate-monomer equilibrium by increasing SDS surfactant concentration towards the cmc. Therefore, equilibrium constants of the aggregate formation and oscillator strengths of monomer and aggregate of the dye compounds were calculated from spectral studies. Moreover, aggregate formation dynamics was discussed in terms of thermodynamic functions by using temperature studies. The interactions of PyB and PyY with the positively charged hexadecyltrimethylammonium bromide (CTAB) and neutral Triton X-100 (TX-100) were also studied and it was observed that there was no aggregate formation on the absorption and fluorescence spectra for below and above the cmc.     

Effect of surfactants on the spectrofluorimetric properties of zearalenone

The chemiluminescent properties of the estrogenic mycotoxin zearalenone in the presence of aqueous micellar media were investigated using steady state fluorescence techniques. Micelles of surfactants sodium dodecyl sulfate (SDS), hexadecyltrimethylammonium bromide (CTAB), and non-ionic Triton X-100 enhanced the fluorescence intensity of zearalenone in aqueous solutions. The binding constants have been determined and indicate zearalenone has the highest affinity for Triton X-100, followed by CTAB, and then by SDS. The encapsulation of zearalenone by the micelles studied is spontaneous and exothermic. The selective microenvironments provided by organized micellar systems offer an attractive medium to modulate fluorescence detection of zearalenone.     

Dielectric relaxation studies of alkanols solubilized by sodium dodecyl sulphate aqueous solutions

Considerable attention has been paid in recent years to the influence of alcohols on ionic micellar structures, alcohol co-surfactants most commonly employed in the preparation of microemulsions. Dielectric relaxation spectroscopy (DRS) is a versatile tool to monitor the dynamic process of such micellar systems. We report here the changes in the dielectric constant of the medium and the relaxation time of micellar solutions of sodium dodecyl sulphate (SDS) in water in the presence and absence of alkanols—hexan-1-ol, octan-l-ol, decan-l-ol and 1,2-ethanediol. The time domain dielectric data were obtained in the reflection mode in the frequency range of 10 MHz to 20 GHz using a HP54750A sampling oscilloscope and HP 54754A TDR plug-in-module. The sample is held at 303 K in a SMA cell with an effective pin length of 1.35 mm. We have determined the relaxation time (τ) using the Cole–Cole method. The relative viscosity ηr on the micellar solutions were also determined. The result shows that the dielectric constant increases linearly with SDS concentration in pure aqueous solutions up to 400 mM and decreases thereafter. The relaxation times are of the order of 15 ps to 25 ps and are far greater than that of Debye rotational relaxation of the monomer species. It is assigned to the dispersion step to water molecules surrounding to hydrophobic particles or the “bound water”. The addition of alcohols results in a linear increase in relaxation time in all the systems. As the concentration of SDS increases τ/ηr attains a near constant value showing that solubilization becomes more difficult at these concentrations. Our results show that the alcohol molecules are solubilized at the surface of the SDS micelle (i.e.) the micelle–water interface.     

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.     

HP-β-CD降低油田地层水中SDBS胶束对其检测光谱的干扰

采用同步荧光光谱法测定了十二烷基苯磺酸钠(SDBS)在不同浓度的羟丙基-β-环糊精(HP-β-CD)水溶液中的临界胶束浓度(cmc)。结果表明,同步荧光光谱法在扫描的波长差Δλ为25 nm 时,HP-β-CD不仅具有增强SDBS荧光强度的作用,同时还具有增加SDBS临界胶束浓度的特性。SDBS在水溶液中的标准摩尔吉布斯函变Δ_γGΘ_m随HP-β-CD浓度的增加而增大,表明了在水溶液中,相比于形成胶束,SDBS单体更容易与HP-β-CD形成包结物。SDBS与HP-β-CD包结物的job’s曲线表明了在水溶液中SDBS与HP-β-CD按摩尔计量比1∶1进行包结。按摩尔计量比1∶1加入HP-β-CD后,SDBS胶束对其检测光谱的干扰可显著降低,该定量标准曲线适用于检测临盘采油厂T5-X15和T9-X4两种水样中SDBS的含量(包括浓度大于cmc时),方法的回收率在100.5% ～101.2%之间。红外光谱及核磁共振氢谱分析结果表明包结物结构中SDBS分子的苯环基团位于HP-β-CD分子的大口径端。     

Micellar effects on the molecular aggregation and fluorescence properties of benzazole-derived push-pull butadienes

The absorption and fluorescence spectral behaviour of 1-(2-benzoxazolyl)-4-(p-dimethylaminophenyl)buta-1,3-diene and its benzothiazolyl analogue (abbreviated as BODB and BTDB, respectively) have been investigated in dioxane-water mixtures and micellar environments using steady-state techniques. In water, water-rich mixtures or premicellar solutions, BODB and BTDB tend to form molecular aggregates labelled as H-aggregates. These aggregates dissociate on adding surfactants forming micellized monomers. In all micellar media the fluorescence quantum yield is greatly enhanced along with a large hypsochromic shift. Also, in TX-100, CTAB and SDS both dienes show dual emission from the locally excited (LE) and intramolecular charge transfer (ICT) states. For BTDB in TX-100 and DODB in all solutions, the LE fluorescence predominates, while for BTDB in CTAB and SDS, the ICT fluorescence is the predominant. The fluorescence shifts suggest that the fluorescing molecules penetrate the core of the micellar unit in TX-100, whereas in CTAB and SDS they occupy the interfacial region. The binding constants and the micelle properties (such as polarity and CMC) have been determined using both dienes as probes.     

Ternary oil—water—amphiphile systems: self-assembly and phase equilibria

The micellization properties and phase behaviour of model ternary surfactant—oil—water systems were studied by grand canonical Monte Carlo simulations assisted by histogram reweighting techniques. Larson's lattice model was used for a symmetrical H₄T₄ surfactant, where H represents hydrophilic and T hydrophobic groups. In contrast to earlier studies, oil chains of variable length, from T to T₄, were studied and the effect of added oil on the critical micelle concentration (cmc) was determined quantitatively. It was found that the cmc decreases as the volume fraction of oil in the aqueous phase is increased. Longer oil chains have a stronger effect than shorter chains for the same volume fraction. The oil, tail and head density profiles were obtained for typical micelles. Simulation results for the density profiles indicate that long chain oils are almost exclusively located within the micellar aggregates, in agreement with single-chain mean-field theory predictions. Ternary phase diagrams were obtained both by simulations and by quasichemical theory. The results suggest that the critical micelle concentration line is directed towards the oil-lean corner of the three-phase triangle, if there is one present in the system. It was also found that the amount of oil that can be dissolved in the ternary system increases sharply at the surfactant critical micelle concentration, indicating that micellization greatly enhances oil solubility.     

Structural Transition in the Micellar Assembly: A Fluorescence Study

Structural transition can be induced in charged micelles by increasing the ionic strength of the medium. Thus, spherical micelles of sodium dodecyl sulfate (SDS) that exist in water at concentrations higher than the critical micelle concentration assume an elongated rod-like structure in the presence of an increased electrolyte concentration. This is known as sphere-to-rod transition. In this paper, we characterize the change in organization and dynamics that is accompanied by the salt-induced sphere-to-rod transition in SDS micelles using wavelength-selective fluorescence and other steady-state and time-resolved fluorescence parameters. Since the change in micelle organization during such structural transition may not be limited to one region of the micelle, we have selectively introduced fluorophores in two distinct regions of the micelle. We used two probes, N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (NBD-PE) and 25-[N-[(7-nitrobenz-2-oxa-1,3-diazol-4-yl)-methyl]amino]-27-norcholesterol (NBD-cholesterol), for monitoring the two regions of the micelle. NBD-PE monitors the interfacial region of the micellar assembly, while NBD-cholesterol acts as a reporter for the deeper regions of the micellar interior. Our results show that wavelength-selective fluorescence, in combination with other fluorescence parameters, offers a powerful way to monitor structural transitions induced in charged micelles. These results could be significant to changes in membrane morphology observed under certain physiological conditions.     

Spectrofluorimetric Determination of Second Critical Micellar Concentration of SDS and SDS/Brij 30 Systems

Potentially useful stead-state fluorimetric technique was used to determine the critical micellar concentrations (CMC(1) and CMC(2)) for two micellar media, one formed by SDS and the other by SDS/Brij 30. A comparative study based on conductimetric and surfacial tension measurements suggests that the CMC(1) estimated by the fluorimetric method is lower than the value estimated by these other techniques. Equivalent values were observed for SDS micelles without Brij 30 neutral co-surfactant. The use of acridine orange as fluorescent probe permitted to determine both CMC(1) and CMC(2). Based on it an explanation on aspects of micelle formation mechanism is presented, particularly based on a spherical and a rod like structures.     

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。     

NMR Self-diffusion Study of Amino Acid Ionic Liquids Based on 1-Methyl-3-Octylimidazolium in Water

In comparison with the conventional ionic liquids, water-miscible amino acid ionic liquids (AAILs) are considered as more biodegradable and biocompatible, less toxic, and as able to enhance the biomaterials stability. An application of some long-chain ionic liquids in catalysis, extraction, etc. requests the detailed analysis of ionic and water transport properties of their diluted aqueous solutions close to the area of its critical micelle concentration (cmc). In this work, the molecular transport properties of two 1-methyl-3-octylimidazolium-based AAILs, [C₈mim][Val], and [C₈mim][Leu] (with anions of l-Leucine or l-Valine), in the aqueous solutions were studied by measuring the self-diffusion coefficients and the solution’ viscosities in the temperature ranges 273–343 K at the AAIL’s concentrations below and above its cmc. The data on self-diffusion coefficients of water molecules and cations/anions of AAILs are discussed in terms of activation energies and of hydration effects. Above the cmc, the [C₈mim][Val] molecules demonstrate the strengthening effect on the solvent structure, while the molecules of [C₈mim][Leu] have structure-destructive effect. The results obtained for the relative dynamic viscosities show a decrease of micellar size with increasing temperature. In addition, it was found that the degrees of counterion binding for both AAILs are higher than for 1-methyl-3-octylimidazolium halides.     

FT-EPR study of photoionization in micellar solutions

Fourier Transform EPR (FT-EPR) was used to study the formation and decay of free radicals produced by photoionization of phenothiazine (PTH) solubilized in aqueous SDS and Triton X-100 micellar solutions in the absence and presence of electron acceptors. CIDEP spectra produced by PTH photoionization in micellar solution differ from those found in homogeneous solution. The effect is attributed to changes in relative importance of single-photon, singlet excited state, and biphotonic, triplet excited state, photoionization. With quinone acceptors present in the bulk aqueous phase, photoionization of PTH in SDS, results in instantaneous formation of quinone anion radicals that carry the spin polarization of the precursor hydrated electrons. If the acceptor is anchored in the micelle, electron capture cannot compete with electron escape into the aqueous phase. Instead, anion radicals are formed primarily by reductive quenching of³PTH*. This process gives rise to a spectrum that is attributed to long-lived spin-correlated radical pairs, [PTH⁺…Q^?].     

Micelle-Enhanced Spectrofluorimetric Method for Determination of Cyproheptadine Hydrochloride in Tablets: Application to In-Vitro Drug Release and Content Uniformity Test

A highly sensitive and simple spectrofluorimetric method was developed for the determination of cyproheptadine hydrochloride (CYP) in its pharmaceutical formulations. The proposed method is based on the investigation of the fluorescence spectral behaviour of CYP in a sodium dodecyl sulphate (SDS) micellar system. In aqueous solution, the fluorescence intensity of CYP was greatly enhanced (150 %) in the presence of SDS. The fluorescence intensity was measured at 410 nm after excitation at 280 nm. The fluorescence–concentration plot was rectilinear over the range 0.2–2.0 μg/mL, with lower detection limit of 0.06 μg/mL. The proposed method was successfully applied to the assay of commercial tablets as well as content uniformity testing. The application of the proposed method was extended to test the in-vitro drug release of CYP tablets, according to USP guidelines. The results were statistically compared with those obtained by official USP method and were found to be in good agreement.     

EPR Spin Probe Study of New Micellar Systems

Molecular dynamics, structure, and phase state of two new micellar systems were investigated using spin-probe electron paramagnetic resonance spectroscopy. While the local mobility of the new cationic long-chain detergents varies in micelles in a minor way when the length of a chain increases from 16 to 22 carbon atoms, the order parameter increases noticeably. The latter is caused by gain of hydrophobic interactions. It is worthwhile to note that the incorporation of the two hydroxyl groups into the polar head group of the C22 detergent influences particularly on the molecular dynamics and phase state of an aqueous solution of the detergent. Furthermore, not only the local mobility decreases and ordering factor increases, but also the phase state of the system changes, being transited from the solid to the micellar (liquid) state. Addition of the KCl salt in an aqueous solution of the long-chain detergents results in a decrease of local mobility and increase of ordering factor. The phase transitions are found to be caused by the addition of the salt. The cationic monomer [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate was shown to decrease the critical concentration of micelle formation of the anionic detergent sodium dodecyl sulfate (SDS). Most likely this is because, being the counterion, the cationic monomer forms a dense layer around the SDS micelle. Binding of SDS micelle with the monomer strongly reduces the local mobility of the detergent.     

Chemiluminescence of phthalhydrazide derivatives in organized media: Interactions with surfactants and cyclodextrins

The chemiluminescent oxidation of some phthalhydrazide derivatives, luminol (LUM), isoluminol (ISOL), N-(4-aminobutyl)-N-ethylisoluminol (ABEI) and N-(6-aminohexyl)-N-ethylisoluminol (AHEI), has been carried out in micellar media and in the presence of natural cyclodextrins (CDs), using Co(II) as catalyst and H₂O₂ as oxidant. The cationic cetyltrimethylammonium bromide (CTAB) and, in a lesser extent, the anionic sodium dodecyl sulfate (SDS) produce quenching in the chemiluminescence (CL) of all the luminophores at concentrations above the cmc, whereas slight enhancements are attained with the non-ionic pentaethylene glycol monododecyl ether (C₁₂E₅). On the contrary, the incorporation of the CDs to the reaction produces a remarkable intensification of the CL. Binding of the luminophores to the macrocycles and the micelles has been studied by Pulsed-Gradient-Spin-Echo-NMR (PGSE-NMR) and fluorescence anisotropy. The cationic CTAB decreases the emission mainly due to charge compensation as a result of the association of the luminophores and the luminescent intermediates to the micelles. The presence of the alkyl substituents of ABEI and AHEI provides an additional hydrophobic contribution to the binding process. SDS quenches this reaction as the micelles retain Co(II) on their anionic layer. The protection and stabilization of these luminophores or their luminescent intermediates provided by the cavities of the CDs make this family of cyclic oligosaccharides much more suitable agents than the surfactants for enhancing the CL in aqueous media for this specific reaction.     

NMR法研究短链芳烃及其衍生物在胶束中的增溶作用

本文应用高分辨¹H-NMR谱和相图,研究了十种短链芳烃及其衍生物,在十二烷基硫酸钠胶束中的增溶作用,获得这些增溶物在胶束中的增溶位置和增溶量的详细结果。这对了解这一类增溶物的增溶机理有实际意义。     

Investigations into the spectral and luminescent properties of methylphenols in neutral and ionic forms in aqueous micelle solutions

The special features of the absorption and fluorescence spectra of some substituted phenols (2-, 4-methylphenol and 2-amino-4-methylphenol) in aqueous micelle solutions are investigated on addition of an alkali and acid. A fluorescence band of 4-methylphenol in the anion form is detected in the presence of a cation surfactant. The fluorescence efficiency of 4-methylphenol in the presence of the triton X100 micelle decreases in comparison with aqueous solutions. It is established that the quantum yield of fluorescence of 2-methylphenol in the presence of N-cetyltrimethyl ammonium bromide (CTAB) increases in comparison with the aqueous solution (ϕ_fl = 0.25 and 0.17, respectively). The constant of fluorescence quenching for methylphenol in aqueous micelle solutions by the alkali is two orders of magnitude higher than by the acid. The proton-acceptor properties of 2-amino-4-methylphenol are higher than of 4-methylphenol. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 54–61, November, 2005.     

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.