Surfactant-induced amorphous aggregation of tobacco mosaic virus coat protein: a physical methods approach

The interactions of non-ionic surfactant Triton X-100 and the coat protein of tobacco mosaic virus, which is an established model for both ordered and non-ordered protein aggregation, were studied using turbidimetry, differential scanning calorimetry, isothermal titration calorimetry, and dynamic light scattering. It was found that at the critical aggregation concentration (equal to critical micelle concentration) of 138 x 10(-6) M, Triton X-100 induces partial denaturation of tobacco mosaic virus coat protein molecules followed by protein amorphous aggregation. Protein aggregation has profound ionic strength dependence and proceeds due to hydrophobic sticking of surfactant-protein complexes (start aggregates) with initial radii of 46 nm. It has been suggested that the anionic surfactant sodium dodecyl sulfate forms mixed micelles with Triton X-100 and therefore reverses protein amorphous aggregation with release of protein molecules from the amorphous aggregates. A stoichiometric ratio of 5 was found for Triton X-100-sodium dodecyl sulfate interactions.     

Self-aggregation and supramolecular structure investigations of Triton X-100 and SDP2S by NOESY and diffusion ordered NMR spectroscopy

The self-aggregation and supramolecular micellar structure of two surfactants in aqueous solution, the anionic surfactant SDP2S (sodium dodecyl dioxyethylene-2 sulfate) and the nonionic surfactant Triton X-100 (octylphenol-polyoxyethylene ether with 9.5 ethoxy groups), were investigated by NMR spectroscopy. The critical micellar concentration (CMC), the size, and shape of the aggregates were determined by diffusion ordered NMR spectroscopy (DOSY), while 2D NOESY NMR spectra were used to study the mutual spatial arrangement of surfactant molecules in the aggregated state. A nonlinear increase of the micellar hydrodynamic radius, indicating possible sphere-to-rod shape transition, was found for SDP2S at higher surfactant concentrations. Triton X-100 micelles were found to be almost spherical at low surfactant concentrations, but formation of ellipsoid shaped particles and/or micellar aggregation was observed at higher concentrations. The NOESY data show that at low concentration Triton X-100 forms a two-layer spherical structure in the micelles, with partially overlapping internal and external layers of Triton X-100 molecules and no distinct hydrophilic-hydrophobic boundary.     

Diffusion in surfactant solutions

The diffusion coefficients in water of Triton X-100 and sodium dodecyl sulfate were measured as a function of concentration using the Taylor dispersion technique. For Triton X-100, a nonionic surfactant, the diffusion coefficient drops from 7.4 × 10^-7 cm²/sec at 0.45 g/liter to 6.45 x 10^-7 cm²/sec at 5 g/liter. The diffusion coefficient of methyl yellow solubilized in Triton X-100 is close to that of the surfactant. This behavior is quantitatively consistent with a chemical equilibrium between monomer and micelle. For sodium dodecyl sulfate, an anionic surfactant, the diffusion coefficient increases from 1.76 x 10^-6 cm²/sec at 0.01 M to 4.53 x 10^-6 cm²/sec at 0.125 M. The increase is less when 0.1 M NaCl is added. The diffusion coefficient of the methyl yellow solubilized by the SDS is significantly less than that of the surfactant, particularly at low ionic strength. This behavior can be quantitatively explained by including electrostatic coupling between monomer, micelle, and counterion.     

Spectrofluorimetric Determination of 2-Naphthol in A Pharmaceutical Shampoo Using Anionic SDS Micellar Media

Abstract

Fluorescent characteristics of 2-naphthol were studied in aqueous solution and in micellar solutions of sodium dodecyl sulfate (SDS), hexadecyl-trimethylammonium bromide (HDTB), and Triton X-100. The enhancement of 2-naphthol fluorescence in SDS neutral solutions was used to establish a method for the determination of 2-naphthol. The method was applied in a medicinal shampoo.     

Surfactant effects on the spectrophotometry of the gadolinium—chrome azurols complex

Increased molar absorptivities and red-shifted absorbance maxima were noted only upon the addition of cetylpyridinium chloride (CPC), a cationic surfactant. A 1:2:4 gadolinium/chrome azurol S/CPC complex was forned but dissociated at [CPC]/ [Gd³⁺] > 4 apparently because gadolinim(III) was displaced from this complex by additional surfactant monomers. Ternary complexes having different stoichiometries formed in the presence of excess dye. Sodium dodecyl sulfate (SDS), an anionic suffactant, induced dissociation of the binary complex at micellar concentrations, suggesting that dissociation resulted from adsorption of Gd³⁺ cations on the negatively charged micellar surface. Addition of Triton X-100, a nonionic surfactant, had little effect at either micellar or submicellar concentrations. These results confirm that complex stability is an important factor in the use of surfactants as sensitizers in quantitative spectrophotometry.     

表面活性剂中DNA构象变化的研究

以荧光探针法研究了表面活性剂与小牛胸腺DNA的相互作用，结果表明：阳离子表面活性剂主要通过静电引力和疏水方式与DNA作用；阴离子表面活性剂与DNA之间存在静电排斥力，两者之间的相互作用不太明显；而非离子表面活性剂与DNA的相互作用类似于有机溶剂对DNA的影响，即通过溶液的极性、粘度和介电常数来影响DNA的构象，表面活性剂使得DNA构象发生较大的变化，预示了它可能使DNA的生物功能发生较大的变化。     

A Study on the Location and Aggregation of Tetrahydrophenylporphyrin with a Single Hexadecyl Chain in Triton X-100 Micelle

The location and aggregation of 5,10,15-tris(4-hydroxyphenyl)-20-(hexadecyloxyphenyl)porphyrin (P) in nonionic polyoxyethylene (9.5) octylphenol (Triton X-100) micelle solutions were studied by means of UV–Vis and fluorescence spectra. P forms premicelle surfactant–porphyrin aggregates when the surfactant concentration is below and approaching the CMC. In Triton X-100 micelle solutions, different types of H-aggregates of P were formed when the concentration of P is higher than 3.9×10^-6?mol?dm^-3. As the bulk pH is changed, a transfer process for the porphyrin moiety in Triton X-100 micelle occurs. In neutral Triton X-100 micelle solutions, P may be located at the inner layer of the micelle; in basic conditions, the porphyrin moiety may transfer to the outer surface of the micelle. The kinetic study of porphyrin complexed with Cu(II) in Triton X-100 micelle solutions shows that the metalation rate could be controlled by changing the pH.     

TIME-RESOLVED SPECTROSCOPIC STUDIES ON PHOTOPHYSICAL PROPERTIES OF BENOXAPROFEN IN MICELLAR SOLUTIONS: AN INTRAMICELLAR FLUORESCENCE QUENCHING

The micellar dependencies of the photophysical properties of benoxaprofen (BXP), a 2-phenyl benzoxazole derivative, have been investigated using fluorescence spectroscopy and laser flash photolysis techniques. The fluorescence of BXP in aqueous solution has been observed to be remarkably quenched upon addition of a surfactant, cetyltrimethyl ammonium bromide (CTAB) or Triton X-100, in contrast to its enhancement in sodium dodecyl sulfate (SDS) micellar solution. Time-resolved fluorescence measurements show that the fluorescence decays biexponentially in the micellar solution, indicating the relaxation of micellar environments surrounding the excited BXP. The major component of fluorescence lifetimes in CTAB or Triton X-100 micellar phase is even shorter (330–427ps) than in SDS micellar phase (731 ps). The nonradiative decay constants are significantly larger (ca 3.0 times 10⁹ s^?1) in the CTAB or Triton X-100 micellar phase than in SDS micelles by a factor of ca 10. The major nonradiative decay is interpreted to be the internal conversion due to nuclear geometric change of BXP in the first excited singlet state. This is consistent with the observation that the quantum yields of intersystem crossing are very low (less than 0.01) in the micellar solutions as determined by the laser flash photolysis technique. The laser-induced transient absorption spectrum of BXP in CTAB or Triton X-100 micellar solution shows that the decay kinetics of the transients in CTAB or Triton X-100 are significantly different from first order kinetics in SDS.     

Solution properties of hydrophobically modified acrylamide-based polysulfobetaines in the presence of surfactants

Polymer–surfactant interactions in aqueous solutions of a acrylamide-based, hydrophobically modified polysulfobetaine (ADS) containing 3-[N-(2-methacryloxylethyl)-N,N-dimethylammonio]-propane sulfonate and stearyl methylacrylate, with sodium dodedyl sulfate (SDS), N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), and Triton X-100 were studied using surface tension, rheology, Rayleigh light scattering, and dynamic laser light scattering techniques. The purpose of this study was to highlight the influences of the surfactant structure and the nature of the surfactant head group on the polymer–surfactant interactions. The results show that the interaction and association between ADS and surfactants are distinctly varied depending on surfactant type and surfactant concentration. SDS produced the strongest interactions with ADS, while DTAB and Triton X-100 interact with ADS to a lesser degree, which is attributed to surfactant structure and the nature of the surfactant head group. For SDS and DTAB, there are two driving forces for the complexation of the polymer and surfactants, resulting from the electrostatic interaction and the hydrophobic association. However, for the nonionic surfactant Triton X-100, only hydrophobic association predominated in the interaction between ADS and the surfactant. The mechanism and reconstruction of the polymer–surfactant complexes have been evaluated and discussed.     

Factors Influencing Electroanalytical Measurements In Aqueous Surfactant Media

Abstract

Surfactant solutions of sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and Triton X-100, have been studied for their utility as media for electroanalytical measurements. Each medium possesses a wide potential window with low background currents within which electrochemical measurements can be conducted. the potential windows at a glassy carbon electrode are +1.2 to -1.6 V for 0.1 M TEAP/SDS, 0.1 M NaCl/0.1 M SDS and 0.1 M NaCl/1.2% Triton X-100, and +0.6 to -1.6 V for 0.1 M NaCl/32 mM CTAB (V vs. Ag/AgCl (3M NaCl)). the M(II/I) redox couples of [ReCdmpe)₃]^2+/+ and [Tc(dmpe)₃]^2+/+ were used as electrochemical probes of each surfactant medium. Results are discussed In terms of the solubilization and interaction of the complexes with the micellar environment. Several factors are described which affect the general shape of the voltammograms as well as the observed values of E^o'; these include (i) the structure of the micelle as influenced by the supporting electrolyte, (ii) the electrostatic affinity of the probe complex for the micellar environment and (iii) the solubilization of each component of the redox couple in the micelle.     

Magnetic Relaxation Probing of the State of Diheptyl Dithiophosphate Ions in Water and Aqueous Triton X-100 Solutions

The nuclear magnetic relaxation was used to study the state of diheptyl dithiophosphoric acid (D7DTP, L₇) anions in water and aqueous solutions of the nonionic surfactant, Ttiton X-100, at 298 K in the presence of paramagnetic probes, Mn²⁺ions. It was found that increase in the spin-lattice relaxation rate of water protons is caused by formation of simple and mixed (with surfactant) aggregates of D7DTP. Unlike the Mn²⁺–sodium dodecyl sulfate –Triton X-100 system, studied previously an influence of a probe concentration was found at surfactant concentration close to the CMC. It was suggested that two types of mixed species containing diheptyl dithiophosphate ions, Mn(II), and nonionic surfactant can be formed: micellar aggregates, {Mn(L₇)₂(TX)}, and polynuclear associates, [Mn _x (L₇) _y (tx) _z ]. The associates likely contain surfactant in the form of monomers (tx).     

疏水缔合共聚物与表面活性剂的界面相互作用

采用界面张力弛豫法研究了疏水缔合聚合物聚丙烯酰胺/2-乙基己基丙烯酸酯[P(AM/2-EHA)]在正辛烷-水界面上的扩张粘弹性质, 考察了不同类型表面活性剂十二烷基硫酸钠(SDS)、聚环氧乙烯醚(Tx-100)和十六烷基三甲基溴化铵(CTAB)对其界面扩张性质的影响. 研究发现, 界面上的表面活性剂分子可以与聚合物的疏水嵌段形成类似混合胶束的聚集体, 表面活性剂分子与聚集体之间存在快速交换. 这种弛豫过程的特征时间远比分子在体相与界面间的扩散交换时短. 当界面面积增大时, 上述混合胶束中的表面活性剂分子能快速释放, 在界面层内原位快速消除界面张力梯度, 从而大大降低界面扩张弹性. 界面上的CTAB分子与聚合物链节上的负电中心通过较强的电荷吸引作用形成复合物. 当界面面积增大时, 上述混合胶束中的CTAB分子释放较慢, 界面张力梯度较大. 非离子表面活性剂Tx-100分子量较大, 扩散速率较慢, 它在界面上与聚集体间的交换比阴离子表面活性剂SDS慢, 其特征时间约为0.9 s.     

EXPERIMENTAL CHARACTERIZATION OF FLUOROCARBON-MODIFIED POLYACRYLAMIDE/SURFACTANT AQUEOUS SOLUTIONS

The interaction between surfactants and fluorocarbon-modified polyacrylamide (FC-PAM) in aqueous solutionswas evaluated by rheological means and fluorescence spectroscopy and was found to be strong regardless of the surfactant'snature. Two representative surfactants, anionic sodium dodecyl sulfate (SDS) and nonionic Triton X-100, were used. The origin of the interaction and its dependence on the surfactant concentration were discussed.     

Regulatory role of surfactants in the kinetics of glucose oxidase-catalyzed oxidation ofd-glucose by ferrocenium andn-butylferrocenium ions

The effect of micelles of different surfactants (cationic, anionic, and neutral) on the kinetics of the glucose oxidase-catalyzed reduction of ferrocenium cations RFc⁺ (R=H, Buⁿ) byd-glucose was studied by spectrophotometry. In micellar media of Triton X-100 and sodium dodecyl sulfate (SDS), the Michaelis dependence of the reaction rate on the HFc⁺ concentration is observed, while this dependence has an extreme character in cationic micelles of cetyltrimethylammonium bromide (CTAB). The nature and concentration of surfactants of all types have a slight effect on the rate of reduction of HFc⁺. The level of enzymatic activity is approximately equal in the case of Triton X-100 and CTAB and is considerably lower in the SDS micelles. On going from HFc⁺ to BuⁿFc⁺, the reaction rate is maximum in the cationic CTAB micelles, the anionic SDS micelles exhibit almost no activity, and the activity has an intermediate value in neutral micelles of Triton X-100. The conditions are presented under which the micellar medium controls the catalytic activity of glucose oxidase with respect to ferrocenium cations. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1795–1801, October, 1997.     

Evaluation of surfactant assisted pressurized liquid extraction for the determination of glycyrrhizin and ephedrine in medicinal plants

Surfactant assisted pressurized liquid extraction (PLE) with a laboratory made system was applied for the extraction of glycyrrhizin in Radix glycyrrhizae/liquorice and ephedrine in Ephedra sinica. The proposed system set-up for this current work was simpler as no heating and back pressure regulator was required. Extraction with surfactant assisted PLE was carried out dynamically at a flow of 1.5 mL min⁻¹, at room temperature, under an applied pressure of 10-20 bar with an extraction time of 45-50 min. The extraction efficiencies of the proposed method using surfactants such as sodium dodecyl sulfate (SDS) and Triton X-100 were compared with sonication using organic solvent for different batches of medicinal plants materials. For the determination of glycyrrhizin in R. glycyrrhizae, the extraction efficiencies of surfactant assisted PLE with SDS and Triton X-100 was observed to be comparable with sonication. The method precision was found to vary from 1.6 to 2.6% (R.S.D., n = 6) on different days. For ephedrine in E. sinica, surfactant assisted PLE with SDS was found to give higher extraction efficiencies compared to Triton X-100. The overall method precision for surfactant assisted PLE with SDS for ephedrine in E. sinica was found to vary from 1.5 to 4.1% (R.S.D., n = 6) on different days. The marker compounds present in the various medicinal plant extracts were determined by gradient elution HPLC. Our data showed the possibility of PLE at room temperature and the advantages of eliminating the use of organic solvents in the extraction process.     

Daunomycin binding to detergent micelles: a model system for evaluating the hydrophobic contribution to drug-DNA interactions

The interaction of daunomycin with sodium dodecyl sulfate and Triton X-100 micelles was investigated as a model for the hydrophobic contribution to the free energy of DNA intercalation reactions. Measurements of visible absorbance, fluorescence lifetime, steady-state fluorescence emission intensity, and fluorescence anisotropy indicate that the anthraquinone ring partitions into the hydrophobic micelle interior. Fluorescence quenching experiments using both steady-state and lifetime measurements demonstrate reduced accessibility of daunomycin in sodium dodecyl sulfate micelles to the anionic quencher iodide and to the neutral quencher acrylamide. Quenching of daunomycin fluorescence by iodide in Triton X-100 micelles was similar to that seen with free daunomycin. Studies of the energetics of the interaction of daunomycin with micelles by fluorescence and absorbance titration methods and by isothermal titration calorimetry in the presence of excess micelles revealed that association with sodium dodecyl sulfate and Triton X-100 micelles is driven by a large negative enthalpy. Association of the drug with both types of micelles also has a favorable entropic contribution, which is larger in magnitude for Triton X-100 micelles than for sodium dodecyl sulfate micelles. The thermodynamic profile for the interaction of daunomycin with both types of micelles is characteristic of the "nonclassical" hydrophobic effect. The enthalpy for the interaction of daunomycin with sodium dodecyl sulfate micelles increases nonlinearly with temperature, indicating a positive (and temperature dependent) heat capacity change. The binding isotherm for daunomycin association with sodium dodecyl sulfate micelles was cooperative, with a Hill coefficient of 1.6. The cooperative behavior and the positive heat capacity change suggest that the drug alters micelle size or imposes order on the hydrocarbon interior of the micelle.     

Partitioning behavior of silica in the Triton X-100/dextran/water aqueous biphasic system

The partitioning behavior of silica particles was investigated in the Triton X-100/dextran/water system. It was found that both electrostatic effects and interactions between phase-component species and the solid surface played important roles in determining the distribution of solids. Silica partition was highly pH-dependent, which was interpreted in terms of the pH dependence of the Triton X-100/SiO(2) interaction and the weak acidity of dextran. The presence of sodium dodecyl sulfate (SDS) moved the particles from the top surfactant-rich phase to the interface and the bottom phase, while dodecyltrimethylammonium bromide (DTAB) had the opposite effect. These trends are attributable to the electrostatic interaction between the charged mixed micelles in the top phase and the particles and to the fact that the ionic surfactants modified the adsorption density of the nonionic surfactant on silica.     

Flow-Injection Analysis of Pyridoxine Hydrochloride by Coupling with the Diazonium Ion of p-Sulfanilic Acid

ABSTRACT

A flow-injection (FI) procedure is proposed for the determination of pyridoxine. In the FI manifold, a solution of p-sulfanilic acid in a micellar medium of N-cetylpyridinium chloride (NCPC) was diazotized with nitrite in acidic medium, and the pH was then adjusted to 7 with monohydrogenphosphate; the sample was injected into this stream and the absorbance measured at 450 nm. The surfactant catalyzed the derivatization reaction and enhanced the sensitivity of the FI procedure.

Consequently, the addition of toxic mercury(II) acetate, used in the conventional procedure performed in non-micellar medium, was no longer required. The signals obtained with other surfactants, such as sodium dodecyl sulfate or Triton X-100, were smaller. Under optimized FI conditions, the calibration curve was linear from the limit of detection, 5×10^?5 M, up to 1×10^?3 M, and the sampling frequency was 60 h^?1. The procedure was applied to the determination of pyridoxine hydrochloride in commercial pharmaceutical preparations, with recoveries close to 100%.     

Surface Property of Nonionic Surfactant Triton X-100 in an Ionic Liquid

A common nonionic surfactant Triton X-100 was dissolved in a commercial ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄). The surface tension of the bmimBF₄ solution was decreased with increasing the content of surfactant Triton X-100, a similar phenomenon with aqueous solution systems. Dynamic surface properties of Triton X-100 in bmimBF₄ were measured. It was found that pure IL solvents need rearrangement at the air-bmimBF₄ interface during the beginning stage of absorption. Moreover, the adsorption model was found to be in accord with the diffusion-controlled adsorption mechanism, and further, the dilute bmimBF₄ solutions are close to the diffusion-controlled adsorption.     

Voltammetric determination of piroxicam in micellar media by using conventional and surfactant chemically modified carbon paste electrodes

A method for piroxicam determination based on adsorptive stripping voltammetric techniques, using conventional and chemically modified carbon paste electrodes in micellar media, is described. The employed surfactants were sodium dodecyl sulfate (SDS), Triton X-100, Triton X-405, Tween 80 and Brij 30. However, the purpose of this paper is, at present, to research the use of surfactants as carbon paste modifier because one of the mechanisms of hydrophobic drugs ad-accumulation on the carbon paste electrode is based on the chemical affinity. Besides, because of the water piroxicam insolubility, a special aqueous medium, such as a surfactant solution above its c.m.c. was used, this micellar media being very advantageous in relation to the use of organic or aqueous-organic media, in order to dissolve the studied drug and to remove the problems derived from the organic solvents use. In addition, a piroxicam ad-accumulation increase, on surfactant modified carbon paste electrode, with the surfactant mass incorporated into the electrode, was observed.