邻苯二甲酸二甲酯胶束增溶过程的NMR研究

胶束的增溶作用，可通过X射线，紫外光谱以及核磁共振潜等进行研究.Eriksson等［‘］用NMR法研究了芳香烃在CTAB表面活性剂胶束溶液中的增溶作用.李干佐等问用NMR法研究了件二甲苯和末甲醇在SDS表面活性剂胶束溶液中的增溶作用.然而，关于既非亲油也非亲水的某些小的极性分子的     

Interaction of gums (guar, carboxymethylhydroxypropyl guar, diutan, and xanthan) with surfactants (DTAB, CTAB, and TX-100) in aqueous medium

The interaction of surfactants dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB), and p-tert-octylphenoxypolyoxyethylene (9.5) ether (TX-100) with guar (Gr), carboxymethylhydroxypropyl guar (CMHPG), diutan (Dn), and xanthan (Xn) gums has been studied employing conductometry, tensiometry, microcalorimetry, viscometry, and atomic force microscopy (AFM) techniques. Both weak and strong interactions were observed. CTAB interacted stronger than DTAB with the gums. The surfactant-gum interaction process was enhanced by the presence of borate ions in the solution; the borate ion itself also manifested interaction with the surfactants comparable with that of water-soluble polymers polyvinyl alcohol, polyoxyethylene, and so forth. Viscometric results supported configurational changes of the gum molecules by interaction with surfactants. The geometry of the pure gums and their CTAB interacted products in the dried states was ascertained from AFM measurements; spherical and prolate shapes were observed for pure gums, and distorted states were observed for their surfactant complexed species. Detailed topological features of these entities were ascertained.     

Interaction of acridine orange and sodium poly-α, L-glutamate

Summary The interaction of acridine orange and sodium poly-, L-glutamate in the pH range of 3.8–6.8 was studied by a spectral method and viscosity measurement. From the binding data, the molar change in entropy, enthalpy and the number of binding sites on polymer were calculated. The values of S° were positive. S° for binding decreasing extensively in pH range of 5.0. These results are explained by the transition of helix coil of the polymer. The intrinsic viscosity reduction in the presence of the dye, in pH 3.8 is due to the formation of dye bridges between the polymer helix.

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Zusammenfassung Die Wechselwirkung zwischen Natriumsalz-, L-Glutamin-Säure wurde mit den Methoden der Spektroskopie und der Viskositätsmessung untersucht. Aus den Bindungsdaten wurde die molare Änderung von Entropie und Enthalpie und die Zahl der Brückenstellen des Polymeren berechnet. Die Werte von S° sind positiv. Für die Binding ergibt sich für S° eine starke Verminderung im Bereich pH 5.0. Diese ist durch die Änderung der Konformation der Polymerketten (Helix Knäuel-Umwandlung) zu erklären.

     

Synergistic adsorption of Triton X-100 and CTAB surfactants at the toluene + water interface

Equilibrium interfacial tension measurements at 25.0 °C of the toluene + water system with two widely used surfactants, octylphenol decaethylene glycol ether (Triton X-100) and cetyl trimethyl ammonium bromide (CTAB) having concentrations much lower than their CMC were performed. According to the obtained parameters from the Szyszkowski equation, Triton has higher adsorption tendency than of CTAB. The results obtained for surfactants mixtures are analyzed by the theory of non-ideal interactions in binary mixtures (NIBMs) and the interfacial composition and the interaction parameter in the mixed adsorbed monolayer are determined. The attractive interaction shows a maximum value at nearly equal surfactants bulk mole fraction. The synergism is achieved for Triton bulk mole fractions of 0.30 and higher, and the highest degree of synergism (40.6%) is found for the bulk mole fraction of 0.52 with the lowest investigated constant interfacial tension of 28.0 mN m⁻¹. A correlation was developed for variation of the interaction parameter with bulk mole fraction.     

Interaction of surfactants and aminoindophenol dye

The interaction of dye and surfactants was studied by their spectroscopic and surface properties. Large bathochromic shift (15 nm) in the absorption spectrum was found for aminoindophenol dye at high pH in cationic surfactant, while there is no significant shift in anionic, zwitterionic and nonionic surfactant solutions. The static and dynamic surface properties show there is strong interaction in mixture of cationic surfactant and aminoindophenol dye. Interaction of dye and surfactants on surface and in solution is correlated to the intensity of dye deposition on fiber. The charge complex formation between cationic surfactant and aminoindophenolic dye delays the dye diffusion into keratin fiber. The stronger is the dye/surfactant interaction, the lower dye deposition and diffusion become.     

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.     

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_b TX-100 > K_b CTAB > K_b SDS 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 τ_SDS > τ_TX-100 > τ_CTAB > τ_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.     

Mixed micelle behavior of Pluronic L64 and Triton X-100 with conventional and dimeric cationic surfactants

The mixed micellar properties of a triblock copolymer, Pluronic L64, (EO)13(PO)30(EO)13, and a nonionic surfactant, Triton X-100, in aqueous solution with conventional alkyl ammonium bromides and their dimeric homologues were investigated with the help of fluorescence and cloud point measurements. The composition of mixed micelles and the interaction parameter, beta, evaluated from the critical micelle concentration (cmc) data for different mixtures using Rubingh's and Motomura's theories are discussed. It has been observed that the mixed micelle formation between monomeric/dimeric alkyl ammonium bromides and L64 was due to synergistic interactions which increase with the increase in hydrophobicity of the cationic component. On the other hand, synergistic mixing was observed in the mixed micelles of Triton X-100 and monomeric cationic surfactants, the magnitude of which decreases slightly with the increase in hydrophobicity of the cationic component. Antagonistic interactions were observed in the case of Triton X-100 and dimeric cationic surfactants.     

A Photochemical Study of Uranyl Ion Interaction with the Triton X-100 Micellar System

This is a report on the spectroscopic characteristics of UO²⁺₂in the excited state in Triton X-100 micellar medium. It also indicates some important results of viscosity and surface tension measurements of the system which have direct relevance to the spectroscopic investigation in the excited state. The quenching of the UO²⁺₂fluorescence due to Triton X-100, upon micellization in the aqueous medium, reveals two kinds of microenvironments of the fluorophore from the Stern–Volmer plot. This has been verified by flash photolytic measurements. A blue shift of the quenched emission spectrum is ascribed to the collisional encounter of UO²⁺₂with the head groups of Triton X-100.     

Adsorption of anionic methyl orange dye by polyaniline,poly(o-methylaniline) and poly(o-methoxyaniline)

This study reports the effect of substituents in the ortho position of polyaniline on the adsorption capacity to remove the anionic dye methyl orange (MO) from an aqueous solution. The aim of this study is the synthesis of polyaniline (PANI) and its derivatives, poly-o-methylaniline (poly-o-toluidine, POT) and poly-o-methoxyaniline (poly-o-anisidine, POA) for the adsorption removal of MO dye. All polymers were obtained by oxidative polymerization of the corresponding monomers and characterized by scanning electron microscopy (SEM) and infrared spectroscopy (IR). The average particle size of the polymer was about 200 nm. The effect of various parameters such as pH, temperature, adsorption time and initial concentration was analyzed. It was found that the adsorption capacity for dye removal increases from 50.68 to 222.56 mg g⁻¹ for PANI, from 16.89 to 66.57 mg g⁻¹ for POT, and from 97.26 to 532.54 mg g⁻¹ for POA with an increase in the initial dye concentration from 5 up to 50 mg L⁻¹. For all polymers, the equilibrium state of MO adsorption was reached in 50 min. The results showed that MO adsorption on PANI, POT, and POA is well described by a pseudo second order kinetic model. Isothermal studies have shown that adsorption is in good agreement with the Langmuir isotherm model, as evidenced by higher values of correlation coefficients. Based on the data of thermodynamic studies, it was concluded that MO adsorption on PANI, POT, and POA is spontaneous and endothermic.     

Investigation of SDS, DTAB and CTAB micelle microviscosities by electron spin resonance

Electron spin resonance spectroscopy (ESR) of the nitroxide labelled fatty acid probes (5-, 16-doxyl stearic acid) was used to monitor the micelle microviscosity of three surfactants at various concentrations in aqueous solution: sodium dodecyl sulphate (SDS), dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB). At low surfactant concentration, there is no micelle, the ESR probe is dissolved in water/surfactant homogeneous phase and gives his microviscosity. At higher surfactant concentration, an abrupt increase in microviscosity indicates the apparition of micelles and, the solubilization of the probes in micelles. The microviscosity of the three surfactants, in a large surfactant range, was obtained as well as the critical micelle concentration (CMC). The microviscosity increased slightly with the increase in surfactant concentration. Phosphate buffer lowered the CMC value and generally increased the microviscosity.     

The Influence of Triton X-100 on Protolytic Properties of Aminomethylated Calix[4]resorcinarene and Its Interaction with Copper(II)

The influence of Triton X-100 (concentration 5 mM) on acid-base properties of aminomethylated calix[4]resorcinarene (H₈L) containing alkyl (R¹ = C₁₁H₂₃) and dimethylaminomethyl (R² = CH₂N(CH₃)₂) substituents and interaction of H₈L with copper(II) is studied by potentiometry and mathematical simulation of equilibria in solutions. It is found that the presence of a nonionic surfactant favors the aggregation of H₈L (the degree of aggregation is higher than four), whereas, in 80% isopropanol at the same pH ≈ 10.2, a neutral species of the compound is only dimerized. The addition of Triton X-100 affects both the composition and stability of formed copper(II) complexes. The fraction of the highly charged tetranuclear [Cu₄(H₄L)]⁴⁺ complex sharply decreases. The formation of a large amount of [Cu(H₇L)]⁺ complex appears to be preferable compared to [Cu(H₈L)₂]²⁺ complex containing two ligands in the coordination sphere (pH ≈ 5.7). An enhancement of the acidic properties of protonated species of the compound and a decrease in the apparent constants of H₈L-copper(II) complex formation in Triton X-100 solutions compared to those in water-alcohol solutions are attributed to the formation of mixed micelles.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 527–533.Original Russian Text Copyright © 2005 by Sal’nikov, Boos, Ryzhkina, Lukashenko, Tiforova.     

Micellization and mixed micellization of cationic gemini (dimeric) surfactants and cationic conventional (monomeric) surfactants: Conductometric,dye solubilization,and surface tension studies

In the present study, we have investigated the self-association, mixed micellization, and thermodynamic studies of a cationic gemini (dimeric) surfactant, hexanediyl-1,6-bis(dimethylcetylammonium bromide (16-6-16)) and a cationic conventional (monomeric) surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of pure (16-6-16 and CTAB) and mixed (16-6-16+CTAB) surfactants was measured by electrical conductivity, dye solubilization, and surface tension measurements. The surface properties (viz., C₂₀ (the surfactant concentration required to reduce the surface tension by 20 mN/m), Π_CMC (the surface pressure at the CMC), Γ_max (maximum surface excess concentration at the air/water interface), A_min (the minimum area per surfactant molecule at the air/water interface), etc.) of micellar (16-6-16 or CTAB) and mixed micellar (16-6-16+CTAB) surfactant systems were evaluated. The thermodynamic parameters of the micellar (16-6-16 and CTAB) and mixed micellar (16-6-16+CTAB) surfactant systems were also evaluated.     

Wettability of ionic surfactants SDS and DTAB on wheat (Triticum aestivum) leaf surfaces

Abstract

Due to the important use of pesticide formulation, it is necessary to make it clear how ionic surfactant effect the wettability at leaf surface. In this work, we used the sessile drop method to study the wettability of SDS and DTAB on wheat leaf surfaces at different leaf stages, and reveal the relationship between surfactants structures and leaf stages of wheat leaf surfaces on wettability behavior. Results showed that few surfactant molecules adsorbed at the interface at low concentrations. With the concentration increased, the surfactant replaced the air layer partially within the nano/micro structure of leaf surfaces. When the concentration exceeded to CMC, the adsorption of surfactant molecules was saturated at both air-liquid interface and solid-liquid interface, the wetting state was still the transitional state between Cassie-Baxter’s and Wenzel’s state. In all concentrations, the adhesional tension and surface tension showed the linear relationship and the slope values were all below ?1, suggesting there were more surfactant molecules adsorbed at the solid-liquid interface than the liquid-air interface. As SDS is a common wetting agent and DTAB is a common fungicide in agrochemical, this study will provide potential guidance in practical application of pesticide solutions in leaf surface wetting.     

Interaction of (hydroxypropyl) cellulose with anionic surfactants in dilute regime

(Hydroxypropyl)cellulose (HPC) dilute aqueous solutions in the presence of sodium cholate (CS), sodium deoxycholate (DC), and sodium dodecylsulphate (SDS) were investigated. The hydrophobicity parameter (I ₁/I ₃) from fluorescence has shown a critical aggregation concentration (CAC) lower than the critical micellar concentration (CMC). One or two breakpoints were observed in the curve conductivity vs surfactant concentration. The thermodynamic parameters of aggregation (, and ) and the degree of counterion dissociation were calculated. Evidences for the secondary aggregation of CS/water system were found. The relative viscosity increases for HPC/bile salt solutions only at high surfactant concentrations, whereas for HPC/SDS, it passes through a maximum. The cloud points of both HPC/bile salt solutions at higher surfactant concentrations reach a temperature plateau value around 324 K, while for HPC/SDS, it exceeds 373 K at low SDS concentrations. Dynamic light scattering has demonstrated that the surfactants bind to HPC already at concentrations lower than CAC.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Interaction of sodium dodecylsulfate (SDS) with homoionic montmorillonites: adsorption isotherms and metal-ion release

The interaction of dodecylsulfate anions (DS^–) with homoionic Ca-, Mg-, Ni-, Cu-, Cd-, Pb- and Fe-montmorillonites were investigated. Mg- and Cd-montmorillonite do not adsorb DS^–, and an anion exchange at the edges of the clay mineral does not take place. Three different adsorption processes are identified on the other montmorillonites: i) Fe-montmorillonite is covered with amorphous iron hydroxide, and DS^–-anions are bound at positively charged sites. ii) On Ca- and Pb-montmorillonite DS^– is precipitated as Me(DS)₂. iii) On Ni- and Cu-montmorillonite DS^– forms ion pairs with the cations on the surface. In all cases DS^– is not bound above the CMC but the metal ions are mobilized from the surface either by solubilization of the precipitates or by formation of mixed micelles.     

聚吖啶橙修饰电极的电化学行为及其对肾上腺素的电催化性能

研究了聚吖啶橙 (POAO)修饰电极及其电化学性能 ,并用于肾上腺素 (EP)的电化学测定。EP在POAO修饰电极上产生一灵敏的氧化峰 ,与裸玻碳电极 (GCE)相比 ,其峰电位负移了 2 30mV ,明显降低了EP的氧化过电位。在pH 6 .0的磷酸氢二钠 柠檬酸缓冲溶液中 ,氧化峰电流与EP的浓度在 4 .5× 10 - 7～ 9.2× 10 - 5mol L范围内呈良好的线性关系 ,检出限为 1.0× 10 - 9mol L。可用于实际样品中EP的测定