染料与表面活性剂的相互作用

本文用光谱法研究了阴离子染料曙红(EY)与非离子表面活性剂TX-100)的相互作用, 得出相互作用常数K及与一个染料分子结合的表面活性剂分子数N, 也研究了两种添加剂(尿素, Na2SO4)及混合胶团对这种相互作用的影响并作了解释。     

表面张力法和电导法对比测定表面活性剂临界胶束浓度*

通过比较表面张力法和电导法测定阴离子表面活性剂十二烷基硫酸钠(SDS)和非离子表面活性剂辛基酚聚氧乙烯醚(TX-100)的临界胶束浓度的实验效果,明确了2种方法的优劣。 采用挂环法测试了不同浓度SDS和TX-100水溶液的表面张力,得到了它们的临界胶束浓度以及饱和吸附量、分子截面积;采用电导法研究上述2种表面活性剂溶液的电导率曲线,仅得到SDS的临界胶束浓度。与电导法相比,表面张力法得到的表面活性剂性质信息更多,应用更广泛。该实验使学生加深理解不同电性表面活性剂临界胶束浓度的性质及测定方法,明确不同方法的优缺点,扩大知识面,同时也提高学生处理数据的能力,为学生今后进一步学习应用表面活性剂打下良好基础。     

盐引发阴离子/非离子表面活性剂复配体系中囊泡自发形成

在无盐时, 阴离子表面活性剂十二烷基苯磺酸钠(SDBS)与非离子表面活性剂壬基酚聚氧乙烯(10)醚(TX-100)的复配体系中只有混合胶束存在, 而盐的加入即可以引发体系中囊泡的自发形成, 这使得囊泡的形成变得更加简单. 引发机理可以归因于盐对离子表面活性剂的极性头双电层的压缩作用, 减少了极性头的面积, 加上非离子表面活性剂的参与使得堆积参数P增加, 导致了半径更大的聚集体的形成. 制作了SDBS/TX-100/盐水拟三元相图, 通过目测和表面张力的变化确定了囊泡形成的带状区域, 并用负染色电镜(TEM)对囊泡进行了表征, 同时测定了盐度以及相同盐度下表面活性剂浓度对囊泡粒径的影响, 发现囊泡的粒径随着盐度的增加而增加, 而在同一盐度下, 囊泡的粒径基本不受表面活性剂浓度的影响.     

在金属-铬天青S铬合物可见光度法中表面活性剂-诱导变色的机理

——本文研究在Be~(2+)、Cu~(2+)和Al~(3+)的铬天青S(CAS)络合物可见光度法中,表面活性剂一诱导变色的机理。在阳离子表面活性剂(溴化十六烷基三甲铵、CTAB)存在下,对所有三种金属络合物,均观察到摩尔吸光系数的增加和最大吸收波长的红移。在非离子表面活性剂(TritonX-100,即TX-100)存在下,对Be~(2+)及Cu~(2+)的络合物,也观察到相同情况。在高离子强度时,发现阴离子表面活性剂(十二烷基硫酸钠,SDS)有类似的效应。在使用TX-100和SDS时,只涉及到严格意义下的胶束相互作用。而在使用CTAB时,既观察到包括表面活性剂单体在內的三元络合物的形成,也观察到了胶束相互作用,即在低浓度CTAB时,形成具有明确组成的络合物;到临界胶束浓度以上时,则为胶束相互作用。所有“表面活性剂增敏”体系的光谱都很类似,意味着生色团在三元络合物中和在胶束中有类似的微环境。     

表面活性剂对海藻酸钠稀水溶液剪切粘度的影响

通过粘度法考察了不同pH值时, 阴离子聚电解质海藻酸钠(NaAlg)与阴离子表面活性剂十二烷基硫酸钠(SDS)、阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、非离子表面活性剂辛基酚聚氧乙烯醚(TritonX-100)以及它们的复配体系的相互作用. 研究表明, 在酸性条件下, SDS和TritonX-100与NaAlg之间主要是疏水作用, 随着表面活性剂浓度的增加, 体系粘度下降直到基本不变, CTAB与NaAlg主要发生静电作用和疏水作用, 体系粘度随CTAB浓度的增加呈现先上升后下降的趋势. 在实验条件下, TritonX-100浓度为0.05 mmol·L-1时, SDS的加入, 使得NaAlg/TritonX-100体系的零剪切粘度下降, 而CTAB的加入, 在pH=3.0和5.0时, NaAlg/TritonX-100体系的零剪切粘度出现上升, 在pH=6.4时, 该体系零剪切粘度下降.     

光度法研究染料与非离子表面活性剂的相互作用

染料与表面活性剂的相互作用对纺织品的染色有重要影叫,一直是广泛研究的课题.近年来由于胶束增溶光度法的发展,它又引起了分析化学家的注意.但是现有的研究多集中于染料与电性相反的离子型表面活性剂的相互作用,且缺乏深入的定量研究.本文研究一种阴离子染料——漂蓝6B与非离子表面活性剂Triton X-100间的相互作用,用光度法定量地确定了二者的结合比,并进而研究了阴离子表面活性剂SDS对此种相互作用的影响.     

评价表面活性剂溶液泡沫性能的方法—真球气泡法北大核心CSCD

通过真球气泡法测定了不同价数和浓度的无机盐体系下十二烷基硫酸钠(SDS)表面活性剂溶液的表面张力和表面扩展黏度;通过Ross-Miles法测定了相应同一溶液的发泡力和泡沫稳定性;结果表明:SDS溶液的表面张力值随着各种无机盐浓度的增加而减小至不变,此时的无机盐浓度作为相对浓度100%来考察时,发现临界胶束浓度(CMC)值与添加盐的种类无关,只随无机盐的相对浓度的增加而减少;即CMC值随着无机盐的相对浓度的增加从不含无机盐时的8.3 mmol/L均收敛至最小值3.0 mmol/L;表面张力值和对应的发泡力值呈负线性关系,由此推断表面张力值可以评价发泡力;表面扩展黏度值和对应的泡沫稳定性值呈正线性关系,由此推断表面扩展黏度可以评价泡沫稳定性;无机盐种类对SDS表面活性剂发泡力和泡沫稳定性的影响力随阳离子价数(Na^(+)、Cu^(2+)、Fe^(3+))增加而增加。     

正负离子和表面活性剂对水解聚丙烯酰胺分子线团尺寸的影响及其作用机理

采用动态光散射(DLS)方法,研究了无机电解质正离子与负离子对部分水解聚丙烯酰胺(HPAM)分子线团尺寸的影响,也研究了阴离子型表面活性剂与非离子型表面活性剂对HPAM分子线团尺寸的影响.结果表明,无机电解质负离子对HPAM分子尺寸(分子流体力学直径(Dh))影响较小,而无机电解质正离子对Dh的影响较大,且影响程度随正离子浓度增大而减小.Ca2+、Mg2+、K+和Na+对Dh的作用强弱顺序为Mg2+>Ca2+>Na+>K+.当向聚合物溶液中加入阴离子型表面活性剂时,随表面活性剂浓度增大,Dh先减小,后增大,再减小.此外,由于强烈的静电斥力作用,阴离子型表面活性剂分子在聚合物分子表面吸附较弱,难形成"表面活性剂-聚合物"络合物,而非离子型表面活性剂会以类似于胶束聚集体的形式吸附在聚合物分子链上,形成"表面活性剂-聚合物"络合物,结果造成Dh随表面活性剂浓度增加而逐渐增大.     

某些硫碳菁染料在溴碘化银乳剂中聚集态的研究

本文应用三种不同晶形的溴碘化银乳剂(立方体、八面体和T-颗粒)和八种硫碳菁染料(大部分为内铵盐结构染料)进行了染料的聚集态的研究。试验结果表明,染料的J-聚集态的形成主要取决于染料的结构,其次依赖于卤化银的晶形。三种不同结构的表面活性剂对染料聚集态的形成均有影响,其中两性的表面活性剂最强,阴离子的表面活性剂次之,中性的表面活性剂最弱。二种中位甲基取代的硫碳菁染料的聚集态受表面活性剂影响最为明显,形成较强的J-态,而对其它六种染料的聚集态影响较小,J-聚集态稍有增强。     

表面活性剂对部分水解聚丙烯酰胺溶液抗盐性的影响

通过实验研究了阴离子表面活性剂(SDS)、非离子表面活性剂(OP-10)、两性表面活性剂(C12BE)浓度及KCl浓度对部分水解聚丙烯酰胺(阴离子型,HPAM)水溶液黏度的影响规律,进而分析各因素对聚合物溶液抗盐性的影响。实验结果表明:当表面活性剂浓度低于临界缔合浓度CAC时,聚合物溶液黏度变化不大;高于CAC后,随着表面活性剂浓度增大,聚合物溶液黏度急剧增加;当表面活性剂浓度达到聚合物饱和浓度PSP时,聚合物溶液黏度达到最大值;再加入阴离子和两性表面活性剂,将导致黏度降低,而加入非离子表面活性剂不再改变聚合物溶液的黏度,无机盐KCl对聚合物溶液有双重作用,低浓度KCl促进聚合物溶液黏度升高,高浓度KCl则导致聚合物溶液黏度急剧降低后趋于稳定,在相同KCl浓度下,三种表面活性剂的抗盐能力表现为:SDSOP-10C12BE。     

Interaction of Nonionic Surfactant Triton-X-100 with Ionic Surfactants

The interaction in two mixtures of a nonionic surfactant Triton-X-100 (TX-100) and different ionic surfactants was investigated. The two mixtures were TX-100/sodium dodecyl sulfate (SDS) and TX-100/cetyltrimethylammonium bromide (CTAB) at molar fraction of TX-100, α_TX-100 = 0.6. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), maximum surface excess concentration (Γ_max), and minimum area per molecule at the air/solution interface (A _min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were also determined. Mixtures of both TX-100/SDS and TX-100/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness.     

Influence of surfactants on the adsorption and elektrokinetic properties of the system: guar gum/manganese dioxide

The adsorption of non-ionic polysaccharide—guar gum (GG) in the presence or absence of the surfactants: anionic SDS, cationic CTAB, nonionic TX-100 and their equimolar mixtures SDS/TX-100, CTAB/TX-100 from the electrolyte solutions (NaCl, CaCl₂) on the manganese dioxide surface (MnO₂) was studied. The increase of GG adsorption amount in the presence of surfactants was observed in every measured system. This increase results from formation of complexes between the GG and the surfactant molecules. This observation was confirmed by the determination of the influence of GG on surfactants adsorption on the MnO₂ surface. The increase of GG adsorption on MnO₂ was the largest in the presence of the surfactant mixtures (CTAB/TX-100; SDS/TX-100) which is the evidence of the synergetic effect. The smallest amounts of adsorption were obtained in the presence of TX-100, which results from non-ionic character of this surface active agent. In the case of single surfactant solution CTAB has the best efficiency in increasing the amount of GG adsorption on MnO₂ which results from strong interactions with GG and also with the negatively charged surface of the adsorbent. In order to determine the electrokinetic properties of the system, the surface charge density of MnO₂ and the zeta potential measurements were performed in the presence of the GG macromolecules and the above mentioned surfactants and their mixtures. The obtained data showed that the adsorption of GG or GG/surfactants complexes on the manganese dioxide surface strongly influences the diffused part of the electrical double layer (EDL)—MnO₂/electrolyte solution, but has no influence on the compact part of the electric double layer. This is the evidence that the polymers chains are directly bonded with the surface of the solid and the surfactants molecules are present in the upper part of the EDL.     

Photophysics of xanthene dyes in surfactant solution

The spectral (both absorption and fluorescence) and photoelectrochemical studies of some anionic xanthene dyes namely erythrosine B, rose bengal and eosin have been carried out in micellar solution of cationic cetyl trimethyl ammonium bromide (CTAB), anionic sodium dodecyl sulphate (SDS) and neutral triton X-100 (TX-100). The results show that all these dyes form 1:1 electron-donor-acceptor (EDA) or charge-transfer (CT) complexes with TX-100, which acts as an electron donor. There is no interaction of these dyes with SDS, whereas the interaction with CTAB is mainly electrostatic in nature. In presence of TX-100, these dyes show enhancement of fluorescence intensity with a red shift and develop photovoltage in a photoelectrochemical cell. A good correlation has been found among the photovoltage generation in the systems consisting of these dyes and TX-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

Mutual influence of cetyltrimethylammonium bromide and Triton X-100 on their adsorption at the water–air interface

On the basis of surface tension values of the aqueous solution of cetyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) mixtures measured at 293 K as a function of CTAB or TX-100 concentration at constant TX-100 or CTAB concentration, respectively, the real surface area occupied by these surfactants at the water–air interface was established which is inaccessible in the literature. It appeared that at the concentration of the CTAB and TX-100 mixture in the bulk phase corresponding to the unsaturated monolayer at the water air-interface this area is the same as in the monolayer formed by the single surfactant at the same concentration as in the mixture. In the saturated mixed monolayer at this interface the area occupied by both surfactants is lower than that in the single surfactant monolayer corresponding to the same concentration in the aqueous solution. However, the decrease of the CTAB adsorption is lower than that of TX-100 and the total area occupied by the mixture of surfactants is also lower than that of the single one. The area of particular surfactants in the mixed saturated monolayer changes as a function of TX-100 and CTAB mixture concentration and at the concentrations close to CMC or higher the area occupied by both surfactants is the same. The changes of the composition of the mixed surface monolayer are connected with the synergetic effect in the reduction of the water surface tension by the adsorption of CTAB and TX-100 at the water–air interface. This effect was confirmed by the values of the standard Gibbs free energy of adsorption of both individual surfactants and their mixtures with different compositions in the bulk phase determined by using the Langmuir equation if RT instead of nRT was applied in this equation.     

Stability of manganese dioxide by guar gum in the absence or presence of surfactants

Stability of the manganese dioxide (MnO₂) suspensions by non-ionic guar gum (GG) in the absence or presence of the surfactants: anionic sodium dodecyl sulphate (SDS), cationic hexadecyltrimethylammonium bromide (CTAB) and non-ionic Triton X-100 (t-octylphenoxypolyethoxyethanol) and their equimolar mixtures (SDS/TX-100; CTAB/TX-100) was measured using turbidity. The obtained results of the manganese dioxide suspensions stability were discussed together with the adsorption data and with the data concerning the thicknesses of the adsorption layers. In order to gain more information about the structure of the electric double layer surface charge density and the zeta potential measurements were performed. The obtained results show that the addition of guar gum to the MnO₂ suspensions increases MnO₂ stability. The larger this increase is, the higher is the concentration of the polymer (concentration range 10–200 ppm). Moreover, the addition of single surfactants also causes the increase in the effectiveness of stabilizing the manganese dioxide suspensions. The reason for that is formation of multilayer complexes between the polymer and the surfactants. In such a system both the adsorption of polymer and the thickness of polymer adsorption layer increase. The greatest increase in the stability of MnO₂/GG suspensions was provided by the mixture of anionic and non-ionic surfactants due to a strong synergistic effect. Also, mixing the polymer and two surfactants reduces the stability of the suspension.     

Polarographic behavior of nicotinamide in surfactant media and its determination in cetyltrimethylammonium bromide surfactant system

The behavior of nicotinamide has been studied by differential pulse polarography and cyclic voltammetry in the presence of certain ionic and nonionic surfactants, viz. cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and Triton X-100 (TX-100). The cathodic peak potential (E(p(c))) and peak current (I(p(c))) of nicotinamide were found to be remarkably dependent on the charge and concentration of the surfactant. The presence of SDS and that of TX-100 cause a shift in peak potential and a change in peak current of nicotinamide. In the presence of the cationic surfactant, CTAB, an enhancement in the sensitivity of nicotinamide was observed. A sharp peak with more than two-fold increase in current was used to determine the limit of detection and linear working range using the differential pulse polarographic technique. The present method was successfully used for the simultaneous determination of nicotinamide and pyridoxine hydrochloride, and for the determination of nicotinamide in multivitamin pharmaceutical preparations.     

Interaction of poly(vinylpyrrolidone) with cationic and nonionic surfactants in aqueous solution studied by <Superscript>1</Superscript>H NMR

Aqueous solutions of surfactant at various concentrations with 0.2% poly(vinylpyrrolidone) (PVP) were studied by ¹H NMR methods, including relaxation time and self-diffusion coefficient measurements and two-dimensional nuclear Overhauser enhancement spectroscopy. Two surfactants were concerned: cationic cetyltrimethylammonium bromide (CTAB) and nonionic Triton X-100 (TX-100). In the presence of 0.2% PVP, the variation of the T ₂ values of CTAB protons is similar to that in the absence of PVP. Relaxation times of PVP protons are not significantly affected by the increasing concentration of CTAB. This indicates that no interaction between PVP and CTAB could be detected. However, in the presence of 0.2% PVP, TX-100 micelles are formed at a concentration lower than its normal critical micellization concentration. According to the results of relaxation time measurement of water protons, the presence of 0.2% PVP also induces the contraction of the hydrophilic layer of the TX-100 micelle. This indicates some interaction between PVP and TX-100, but the mechanism of this interaction needs further investigation.     

SURFACTANT MEDIATED POLYMERIZATION KINETICS OF ACRYLAMIDE USING CR(VI)-CYCLOHEXANONE REDOX SYSTEM

The effect of organized surfactants on the kinetics of acrylamide (AM) polymerization have been studied over a temperature range of 25–45°C using Cr (VI)-cyclohexanone (CH) redox system as initiator. The rate of polymerization, R_p(obs), as well as, the percentage of the monomer conversio were found to be increased with increasing the concentration of the anionic surfactant (SDS), above its CMC. But the cationic surfactant (CTAB) reduced the rate considerably at higher concentration, while non-ionic surfactant (TX-100) played no role on the rate. The effect of [Cr(VI)], [CH], [AM], [H+], and ionic strength on the rates have also been examined. The presence of 0.015M SDS decreased the overall activation energy of the polymerization by 6.28 k.Cal/ mole as compared to that in the absence of a surfactant. On increasing the SDS concentration, the viscosity average molecular weight was also found to increase. For the polymerization process, a mutable mechanistic scheme has been pro-posed.     

Spectral studies of N-nonyl acridine orange in anionic, cationic and neutral surfactants

The spectroscopic and photophysical properties of N-nonyl acridine orange - a metachromatic dye useful as a mitochondrial probe in living cells - are reported in water and microheterogeneous media: anionic sodium dodecylsulfate (SDS), cationic cetyltrimethylammonium bromide (CTAB) and neutral octylophenylpolyoxyethylene ether (TX-100). The spectral changes of N-nonyl acridine orange were observed in the presence of varying amount of SDS, CTAB and TX-100 and indicated formation of a dye-surfactant complex. The spectral changes were also regarded to be caused by the incorporation of dye molecules to micelles. It was proved by calculated values K(b) and f in the following order: K(bTX-100)>K(bCTAB)>K(bSDS) and f(TX-100)>f(CTAB)>f(SDS). NAO binds to the micelle regardless the micellar charge. There are two types of interactions between NAO and micelles: hydrophobic and electrostatic. The hydrophobic interactions play a dominant role in binding of the dye to neutral TX-100. The unexpected fact of the binding NAO to cationic CTAB can be explained by a dominant role of hydrophobic interactions over electrostatic repulsion. Therefore, the affinity of NAO to CTAB is smaller than TX-100. Electrostatic interactions play an important role in binding of NAO to anionic micelles SDS. We observed a prolonged fluorescence lifetime after formation of the dye-surfactant complex tau(SDS)>tau(TX-100)>tau(CTAB)>tau(water), the dye being protected against water in this environment. TX-100 is found to stabilize the excited state of NAO which is more polar than the ground state. Spectroscopic and photophysical properties of NAO will be helpful for a better understanding of the nature of binding and distribution inside mammalian cells.     

Ultrafast photoinduced electron transfer from dimethylaniline to coumarin dyes in sodium dodecyl sulfate and triton X-100 micelles

The primary steps of photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to five coumarin dyes are studied in an anionic micelle [sodium dodecyl sulfate (SDS)] and a neutral micelle [triton X-100 (TX-100)] using femtosecond upconversion. The rate of PET in micelle is found to be highly nonexponential. In both the micelles, PET displays components much faster (approximately 10 ps) than the slow components (180-2900 ps) of solvation dynamics. The ultrafast components of electron transfer exhibit a bell-shaped dependence on the free energy change. This is similar to Marcus inversion. The rates of PET in TX-100 and SDS micelle are, in general, faster than those in cetyltrimethylammonium bromide (CTAB) micelle. In the SDS and TX-100 micelle, the Marcus inversion occurs at -DeltaG0 approximately 0.7 eV which is lower than that (approximately 1.2 eV) in CTAB micelle. Possible causes of variation of PET in different micelles are discussed.