The effect of surfactant micelles on the dissociation constants and transition points and transition intervals of acid-base indicators

The effects of cetyltrimethylammonium (CTAB), sodiumdodecylsulfate (SDS) and pol(oxyethylene)(9.5)p-(1,1,3,3-tetramethyl; Triton X-100) on the dissociation constants, transition points and transition intervals of thymol blue and bromothymol blue were studied. The experimental results indicated that surfactant micelles remarkably affected dissociation constants, transition points and transition intervals of the acid-base indicators, and the application ranges of acid-base indicators became wider and the titration accuracy increased when an appropriate surfactant micellar solution was chosen as a titration medium.     

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.     

Spectrophotometric study of interaction and solubilization of procaine hydrochloride in micellar systems

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, K_x, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (K_x = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (K_b = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.      

维生素A在胶束溶液中衰变动力学及机理研究

利用紫外光谱方法测定了维生素A及其乙酸酯在不同胶束水溶液中的衰变速率常数和衰变活化参数. 数据显示, 维生素A及其乙酸酯在阴离子胶束溶液SDS中的衰变速度要远大于在阳离子胶束溶液CTAB和中性胶束溶液TX-100中的衰变速度. 机理分析表明, 维生素A及其乙酸酯在水溶液中的衰变是经过先质子化, 再脱去一分子水或乙酸生成碳正离子中间体, 碳正离子再脱去质子, 经重排后得到最终产物脱水维生素A.     

Quantitating the association of charged molecules with ionic micelles

We have studied micelles comprised of cationic (CTAB) and anionic (SDS) surfactants through the interactions of solution phase anionic disodium fluorescein (DSF) and cationic rhodamine 110 (R110) dyes with perylene sequestered within the micelles. Fluorescence lifetime measurements monitor energy transfer between the nonpolar optical donor within the micelle and ionic probes in the surrounding solution. The efficiency of this process is mediated by the extent to which the ionic dyes interact with the micelle palisade layer, and our fluorescence lifetime data allow us to determine the association constants for acceptor-micelle interactions.     

Separation of Six Pyridoncarboylxic Acid Derivatives by Micellar and Microemulsion Electrokinetic Chromatography

Micellar electrokinetic chromatography (MEKC) and microemulsion electrokinetic chromatography (MEEKC) are two kinds of electrokinetic capillary chromatography (EKC), which are characterized of high solubilization capacity and separation efficiency. In our previous work, some polar organic compounds and hydrophobic neutral compounds were separated successfully by EKC1-3. In this paper, these methods were used for separating six pyridoncarboylxic acid derivatives with similar structures. T…     

Effect of ionic micellar medium on kinetics and mechanism of oxidation of bovine serum albumin: A pulse radiolysis study

Effect of protein–micelle interaction on bovine serum albumin (BSA) oxidation by trichloromethyl peroxyl radical (CCl₃O₂^·) in anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethyl ammonium bromide (CTAB) micellar media has been studied using nanosecond pulse radiolysis technique. Viscosity measurement and light scattering studies have suggested that SDS and CTAB micelles produce BSA–micelle aggregates of different sizes and polydispersity. Oxidation kinetics and transients have been affected both by anionic SDS and cationic CTAB micelles but in a different manner. Tryptophanyl-CCl₃O₂^· adduct radical to tyrosyl radical transformation in BSA has been observed in anionic SDS micelles but not in cationic CTAB micelles. Similar studies have also been done with tryptophan and tyrosine amino acids, which undergo oxidation in BSA. The study suggests that Coulombic and hydrophobic interactions between micelles and protein affect the structure of the protein to shield its functional amino acids, like tryptophan and tyrosine, to neutral oxidizing radical.     

Studies on the Interaction of Surfactants with Cationic Dye by Absorption Spectroscopy

The interaction of methyl violet, a cationic dye, with various surfactants, viz. anionic (SDS), nonionic (Triton X-100), and cationic (CTAB), has been investigated spectrophotometrically in submicellar and micellar concentration range. While in the submicellar concentration region of SDS the higher aggregates of the dye are found, in the micellar concentration region the monomer of the dye predominates. With nonionic surfactant the dye is solubilized primarily as the monomer. CTAB produces no perturbation to the visible spectra of the dye. In the presence of strong electrolytes such as NaNO(3) and NaCl the dye aggregates are formed at a much lower SDS concentrations. Copyright 2000 Academic Press.     

Pseudo-phase ion-exchange model for micellar catalysis in the acid hydrolysis of vinyl ethers

The rate of the perchloric acid hydrolysis of aqueous ethyl and butyl vinyl ethers at 25.0°C, in the presence of micellar aggregates [anionic, sodium dodecyl sulfate (SDS); cationic, cetyl trymethyl ammonium bromide (CTAB); and nonionic, polyoxyethylen? 23? dodecanol, (Brij 35)], has been studied. Negligible effects were observed in the cases of cationic and nonionic micelles. Anionic micelles produce an enhancement in the reaction velocity, and the rate constants go through maxima with increasing SDS concentration. These maxima disappear in the presence of excess sodium perchlorate. All these facts are interpreted quantitatively by means of the pseudo-phase ion-exchange model.     

卵清蛋白与离子型表面活性剂的相互作用

本文通过荧光光谱法、紫外-可见吸收光谱法和透射电镜并结合电导率测定分别研究了水中卵清蛋白与阴离子表面活性剂十二烷基硫酸钠（SDS）和阳离子表面活性剂十二烷基三甲基溴化铵（DTAB）和十六烷基三甲基溴化铵（CTAB）之间的相互作用。研究结果表明卵清蛋白可以增加SDS和CTAB的临界胶束浓度,但对DTAB的临界胶束浓度没有影响。阴离子表面活性剂可以使卵清蛋白构象完全伸展,而阳离子表面活性剂却不具备此种作用。表面活性剂单体与卵清蛋白的相互作用强于表面活性剂胶束与卵清蛋白的相互作用。     

The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

表面胶团修饰电极电化学测定双酚A的增敏机理及抗污性能研究

分别以2种阴离子表面活性剂(SDS、SDBS)、3种季铵盐阳离子表面活性剂(CTAB、TTAB、DTAB)和2种季铵盐型双子表面活性剂(12-3-12、12-4-12)修饰碳糊电极。通过原子力显微镜、接触角以及分析物在电极表面的电化学行为探讨了不同表面活性剂在电极表面的吸附情况,推测在浓度大于临界胶束浓度(CMC)时,季铵盐型阳离子表面活性剂CTAB、TTAB、12-3-12和12-4-12在碳糊电极表面形成了圆柱形的表面胶团,而DTAB和SDS可能是饱和单分子层吸附。以BPA为分析物,研究了表面活性剂修饰电极对BPA的电化学增敏机理,结果表明修饰电极对双酚A(BPA)的电化学增敏作用主要是因为表面胶团对BPA的增溶作用,表面活性剂和BPA间的阳离子-π作用是表面胶团增溶BPA的主要原因。     

THE EFFECTS OF MIXED MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in mixed micellar solutions of surfactants, initiated by NaHSO₃ has been studied at 20 and 3Q° C with time variable method of thermokinetics for 1. 5-order reaction. The results indicate that the mixed micellar systems of cationic or anionic with zwitterionic surfactants (SLS/ CTAB, SLS/ TTAB, SLS/ SDS) and cationic with nonionic surfactants (Brij 357sol; CTAB, Bri-J35/TTAB, Brij35/ DTAB) have catalytic effect on the polymerization in the order, at 20° C. SLS/ SDS SLS/ TTAB SLS/ CTAB Brij35/ CTAB at 30° C SLS/ SDS SLS/ TTAB≈ / CTAB Bri-j35/ DTAB= sBrij35/ TTAB as Brij35/ CTAB, while Brij35/ SDS mixed micellar system has inhibition. These effects are attributed to the effect of the Stern layer of mixed micelles on the step of initiator (HSOT) to form free radical.     

Effect of CTAB and SDS micelles on the excited state equilibria of some indole probes

The absorption and fluorescence spectral characteristics of some biologically active indoles have been studied as a function of acidity and basicity (H_/pH/H(o)) in cationic (cetyltrimethylammonium bromide, CTAB), anionic (sodium dodecylsulphate, SDS) and aqueous phases at a given surfactant concentration. The prototropic equilibrium reactions of these probes have been studied in aqueous and micellar phases and apparent excited state acidity constant (pK(a)(*)) values are calculated. The probes show formation of different species on changing pH. Various species present in water, CTAB and SDS have been identified and the equilibrium constants have been determined by Fluorimetric Titration method. The fluorescence spectral data suggest the formation of oxonium ion through the excited state proton transfer reaction in highly acidic media and formation of photoproducts due to the base catalyzed auto-oxidative reaction in basic aqueous solutions. Variations in the apparent pK(a)(*) value have been observed in different media. The change in the apparent pK(a) values depends upon the solubilising power of the micelles, as well as on the location of the protonating site in the molecule. The observation about increase in pK(a)(*) values in SDS and decrease in CTAB compared to pure water for various equilibria is consistent with the pseudophase ion-exchange (PIE) model.     

Depletion flocculation of latex dispersion in ionic micellar systems

The flocculation behavior of anionic and cationic latex dispersions induced by addition of ionic surfactants with different polarities (SDS and cetyltrimethylammonium bromide (CTAB)) have been evaluated by rheological measurements. It was found that in identical polar surfactant systems with particle surfaces of SDS + anionic lattices and CTAB + cationic lattices, a weak and reversible flocculation has been observed in a limited concentration region of surfactant, which was analyzed as a repletion flocculation induced by the volume-restriction effect of the surfactant micelles. On the other hand, in oppositely charged surfactant systems (SDS + cationic lattices and CTAB + anionic lattices), the particles were flocculated strongly in a low surfactant concentration region, which will be based on the charge neutralization and hydrophobic effects from the adsorbed surfactant molecules. After the particles stabilized by the electrostatic repulsion of adsorbed surfactant layers, the system viscosity shows a weak maximum again in a limited concentration region. This weak maximum was influenced by the shear rate and has a complete reversible character, which means that this weak flocculation will be due to the depletion effect from the free micelles after saturated adsorption.     

The study of the partitioning mechanism of methyl orange in an aqueous two-phase system

An aqueous two-phase system of dodecyl triethylammonium bromide (C₁₂NE, cationic surfactant) and sodium dodecyl sulfate (SDS, anionic surfactant) mixture is proposed for the extraction of some dyes and porphyrin compounds. Transparent two phase-systems are formed when the surfactant concentrations and C₁₂NE/SDS ratios are in certain regions. In this study, the aqueous two phase-systems were prepared by mixing 0.1 mol l⁻¹ C₁₂NE and SDS with a molar ratio of 1.7:1.0. The results showed that negatively charged chlorophyll (sodium copper chlorophyllin) and positively charged dye (methyl violet) were efficiently extracted into the upper phase. The negatively charged methyl orange (pH>7) was moved into the upper phase mostly while amphoteric methyl orange (pH<3) was distributed in the two phases uniformly. Except for hydrophobic force, charge interaction between solute and surfactant also play an important role in the extraction process.     

Crystal modification of calcium sulfate dihydrate in the presence of some surface-active agents

The effect of surface-active agents (surfactants), as additives, on the crystallization of gypsum was studied under conditions of the simulated dihydrate process of phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 degrees C, and the turbidity of the reaction mixture was measured at different time periods to determine the induction time of gypsum crystal formation. Two types of surfactants, namely, cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant were added to investigate their effects on the crystallization of gypsum. Addition of CTAB decreased the induction time and increased the growth efficiency, while addition of SDS increased the induction time and decreased the growth efficiency compared with the baseline (without additives). The surface energy increased with CTAB and decreased with SDS compared with the baseline. The percentage of fine crystals decreased in the presence of CTAB and increased in the presence of SDS compared with the baseline. Gypsum morphology changed from needle-like in the absence of additives to tabular in the presence of CTAB.     

UV-Visible Spectrometric Study and Micellar Enhanced Ultrafiltration of Alizarin Red S Dye

Ultraviolet spectrometric study of alizarin red S (ARS) showed the substantial change in dye spectra by cationic CTAB as compared to anionic SDS and nonionic TX-100 surfactant. High spectral change by CTAB confirms the anionic nature of ARS dye and thus ARS-CTAB complex formation takes place due to electrostatic force of attraction. A little spectral change by SDS is the result of similarly charged repulsive forces that overcome weak hydrophobic-hydrophobic interaction between dye and surfactant micelles. TX-100 exhibited moderate spectral effect responsive to weak hydrophobic-hydrophobic interaction alone. MEUF study of ARS dye justified the spectral changes and dye rejection percentage (R) decreases in the following order: cationic > nonionic > anionic surfactant. Permeate flux (J) slightly decreases in presence of CTAB and it remains virtually constant for both SDS and TX-100. Addition of copper salt (i.e., CuCl₂) in dye-CTAB complex solution, favors rejection (%) removing dye and copper simultaneously via micellar enhanced ultrafiltration.     

Tetraiodophenolsulfonphthalein as a spectral substitute to characterize the complexation between cationic and anionic surfactant

The complexation of cetyltrimethylammonium bromide (CTAB) with sodium dodecyl sulfate (SDS) with sodium dodecyl benzene sulfonate (SDBS), with tetraiodophenolsulfonphthalein (TIPST) as a spectral substitute was investigated at pH 5.89 and 8.30 by the microsurface adsorption--spectral correction (MSASC) technique. The aggregations of TIPST, SDS, and SDBS on CTAB obeyed the Langmuir isothermal adsorption. The aggregates TIPST-CTAB, TIPST2-CTAB3, SDS3-CTAB2, and SDBS3-CTAB2 were formed at 20 degrees C and the binding constants of all the aggregates were determined. The replacement of TIPST-binding CTAB monomer with SDS or SDBS at pH 5.89 was applied to the quantitative determination of anionic detergent (AD) in water with satisfactory recovery.     

Studies on bio-antioxidants--micellar effects on the reduction of nitroxides by vitamin C

The kinetics of reduction of nitroxides including 4-hydroxy-TEMPO, 4-methoxy-TEMPO and 4-hexanoyloxy-TEMPO, which are of different lipophilicities, by vitamin C in cationic, non-ionic and anionic micelles, i.e. CTAB, Triton X-100 and SDS, respectively, have been studied by FSR spectroscopy by a stopped-flow technique. A mechanism for the reaction conducted in micelles is proposed and the rate constants for the elementary reactions are evaluated. It is found that the rates of single electron transfer reactions involving the nitroxides are dependent on the nature of the micelle and the lipophilicity of the nitroxide. The rates are increased in CTAB, decreased in SDS, whereas unaffected in Triton X-100. And the greater the lipophilicity of the nitroxide, the more pronounced the rate variation. As high as a 3600-fold increase in the rate was observed for 4-hexanoyloxy-TEMPO in CTAB over that in SDS. The micellar effects are rationalized on the basis of analysis of parameters and line shape of the ESR spectra for the nitroxides in the micelles.