Properties of mixed micelles of cationic gemini surfactants and nonionic surfactant triton X-100: effects of the surfactant composition and the spacer length

The mixed micelles of cationic gemini surfactants C12C(S)C12Br2 (S=3, 6, and 12) with the nonionic surfactant Triton X-100 (TX100) have been studied by steady-state fluorescence, time-resolved fluorescence quenching, electrophoretic light scattering, and electron spin resonance. Both the surfactant composition and the spacer length are found to influence the properties of mixed micelles markedly. The total aggregation number of alkyl chains per micelle (N(T)) goes through a minimum at X(TX100)=0.8. Meanwhile, the micropolarity of the mixed micelles decreases with increasing X(TX100), while the microviscosity increases. The presence of minimum in N(T) is explained in terms of the competition of the reduction of electrostatic repulsion between headgroups of cationic gemini surfactant with the enhancement of steric repulsion between hydrophilic headgroups of TX100 caused by the addition of TX100. The variations of micropolarity and microviscosity indicate that the incorporation of TX100 to the gemini surfactants leads to a more compact and hydrophobic micellar structure. Moreover, for the C12C3C12Br2/TX100 mixed micelle containing C12C3C12Br2 with a shorter spacer, the more pronounced decrease of N(T) at X(TX100) lower than 0.8 may be attributed to the larger steric repulsion between headgroups of TX100. Meanwhile, the increase of microviscosity and the decrease of micropolarity are more marked for the C12C12C12Br2/TX100 mixed micelle, owing to the looped conformation of the longer spacer of C12C12C12Br2.     

Photophysical study of 3-acetyl-4-oxo-6,7-dihydro-12H-indolo[2,3-a]quinolizine in biomimetic reverse micellar nanocavities: a spectroscopic approach

Photophysical properties of 3-acetyl-4-oxo-6,7-dihydro-12H-indolo[2,3-a]quinolizine (AODIQ), a bioactive molecule, has been investigated in well-characterized, monodispersed biomimicking nanocavities formed by sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in heptane using steady-state and picosecond time resolved fluorescence and fluorescence anisotropy. The emission behavior of AODIQ is very much dependent upon the water/surfactant mole ratio (W), i.e., on the water pool size of the reverse micellar core. AODIQ exhibits a sharp decrease in fluorescence anisotropy with increasing W, implying that the overall motional restriction experienced by the molecule is decreased with increased hydration. Some of the depth-dependent relevant fluorescence parameters, namely, fluorescence maxima and fluorescence anisotropy (r), have been monitored for exploiting the distribution and microenvironment around the probe in the reverse micelles. Fluorescence spectral position and fluorescence quenching studies suggest that the probe does not penetrate into the reverse micellar core; rather it binds at the interfacial region. Quantitaive estimates of the micropolarity and microviscosity at the binding sites of the probe molecule have been determined as a function of W.     

Nonionic surfactants: a key to enhance the enzyme activity at cationic reverse micellar interface

The primary objective of the present study is to understand how the different nonionic surfactants modify the anisotropic interface of cationic water-in-oil (W/O) microemulsions and thus influences the catalytic efficiency of surface-active enzymes. Activity of Chromobacterium viscosum lipase (CV-lipase) was estimated in several mixed reverse micelles prepared from CTAB and four different nonionic surfactants, Brij-30, Brij-92, Tween-20, and Tween-80/water/isooctane/n-hexanol at different z ([cosurfactant]/[surfactants]) values, pH 6 (20 mM phosphate), 25 degrees C across a varying range of W0 ([water]/[surfactants]) using p-nitrophenyl-n-octanoate as the substrate. Lipase activity in mixed reverse micelles improved maximum up to approximately 200% with increasing content of non-ionic surfactants compared to that in CTAB probably due to the reduced positive charge density as well as plummeted n-hexanol (competitive inhibitor of lipase) content at the interfacial region of cationic W/O microemulsions. The highest activity of lipase was observed in CTAB (10 mM) + Brij-30 (40 mM)/isooctane/n-hexanol)/water system, k2 = 913 +/- 5 cm3 g-1 s-1. Interestingly, this observed activity is even higher than that obtained in sodium bis (2-ethyl-1-hexyl) sulfosuccinate (AOT)/n-heptane reverse micelles, the most popular W/O microemulsion in micellar enzymology. To ascertain the influence of non-ionic surfactants in improving the activity of surface-active enzymes is not limited to lipase only, we have also investigated the catalytic activity of Horseradish peroxidase (HRP) in different mixed W/O microemulsions. Here also following the similar trend as observed for lipase, HRP activity enhanced up to 2.5 fold with increasing concentration of nonionic surfactants. Finally, the enzyme activity was correlated with the change in the microenvironment of mixed reverse micelles by steady-state fluorescence study using 8-anilino-1-napthalenesulphonic acid (ANS) as probe.     

Aggregation of Sodium 2,4,5-(tri-n-Alkyl)-benzene Sulfonates in Aqueous Solution: Micellization and Microenvironment Characteristics Studied by Electron Paramagnetic Resonance and Steady-State Fluorescence Quenching

The aggregation behaviors and microenvironmental characteristics of five sodium tri-n-alkylbenzene sulfonates (STABS) micelles have been investigated by electron paramagnetic resonance (EPR) and steady-state fluorescence quenching (SSFQ) techniques. The results indicated that the micropolarity of STABS micelles was less sensitive to the increase of the alkyl chain length, and showed slight decrease with the increasing solution concentration. The microviscosity of STABS micelles increased with the increase of the long alkyl chain length, decreased with the increase of the short alkyl chain length, and exhibited little increase when increase the solution concentration. The salinity of added inorganic salt exhibited obvious effect on the decrease of micropolarity and increase of microviscosity of STABS. These results suggested that these different alkyl chains showed different effects on the micellization of STABS and the salinity's effect was even bigger.     

Effect of sphere to rod transition on the probe microenvironment in sodium dodecyl sulphate micelles: A time resolved fluorescence anisotropy study

The effect of different hydrotropic salts on the microenvironment at the anionic head group region of sodium dodecyl sulphate (SDS) micelle has been studied through time-resolved fluorescence anisotropy measurements of a solubilized probe, coumarin-153 (C153). The organic cations of the hydrotropic salts used in this study, i.e. aniline hydrochloride (AHC) and o-, m- and p-toluidine hydrochlorides (OTHC, MTHC and PTHC, respectively), differ in their charge to size ratio and hydrophobicity. Present study utilizes the sensitivity of the fluorescence technique to understand the changes in the micropolarity and microviscosity experienced by the fluorescent probe, C153, solubilized in the micellar Stern layer, on addition of different hydrotropic salts. Significant changes are observed in the rotational relaxation dynamics of the probe with increasing concentration of the salts. The changes in the rotational relaxation dynamics clearly reflect the sphere to rod transition in the SDS micelles and correspond nicely with the reported results from dynamic light scattering measurements. The growth behavior of SDS micelles is found to be sensitive to the hydrophobicity of the organic cations. The charge to size ratio of the organic cations also indicated to play a role in inducing the sphere to rod transition in the SDS micelles. The interesting observation made from this study is that the sphere to rod transition of SDS micelles is largely facilitated by the presence of the hydrotropic salts and such a transition is successfully indicated by the simple fluorescence anisotropy measurements of a probe in the micelle carried out in the presence of different hydrotropic salts.     

Comparison of microenvironments of aqueous sodium dodecyl sulfate micelles in the presence of inorganic and organic salts: a time-resolved fluorescence anisotropy approach

Microenvironments of aqueous sodium dodecyl sulfate (SDS) micelles was examined in the presence of additives such as sodium chloride and p-toluidine hydrochloride (PTHC) by monitoring the fluorescence anisotropy decays of two hydrophobic probes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and coumarin 6 (C6). It has been well-established that SDS micelles undergo a sphere-to-rod transition and that their mean hydrodynamic radius increases from 19 to 100 A upon the addition of 0.0-0.7 M NaCl at 298 K. A similar size and shape transition is induced by PTHC at concentrations that are 20 times lower compared to that of NaCl. This study was undertaken to find out how the microviscosity of the micelles is influenced under these circumstances. It was noticed that the microviscosity of the SDS/NaCl system increased by approximately 45%, whereas there was a less than 10% variation in the microviscosity of the SDS/PTHC system. The large increase in the microviscosity of the former system with salt concentration has been rationalized on the basis of the high concentration of sodium ions in the headgroup region of the micelles and their ability to strongly coordinate with the water present in this region, which decreases the mobility of the probe molecules.     

Micropolarity of sodium bis(2-ethylhexyl) sulfosuccinate reverse micelles prepared in supercritical ethane and near-critical propane

The micropolarity of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles prepared in supercritical ethane and near-critical propane has been determined in terms of a solvent polarity parameter, E _T(30) values, by using absorption probes, 1-ethyl-4-methoxycarbonyl pyridinium iodide and 2,6-diphenyl-4-(2,4,6-triphenylpyridinio)-phenolate as a functions of pressure and the molar ratio of water to AOT, W ₀, at a constant temperature of 310 K. The micropolarity comparable to that of ethanol was observed for reverse micelles containing water of W ₀ = 2. The micropolarity increased with the water content and became independent of pressure after the system changed to a one-phase reverse micelle solution. For a given W ₀ value, no difference in the micropolarity was noticed in the micelles prepared in ethane and propane. Phase behaviour investigations have revealed that complete dissolution of 50 mM AOT occurred at 20 MPa in supercritical ethane, while a much lower pressure of 1 MPa was required in near-critical propane. The amount of water solubilized in reverse micelles formed in supercritical ethane was relatively low, reaching a W ₀ value of 7 at 36 MPa. In contrast, the amount of water solubilized in near-critical propane reverse micelles was W ₀ = 11 at a much lower pressure of 6 MPa. A higher pressure was required to solubilize larger amount of water in reverse micelles prepared in both ethane and propane. Received: 9 October 1998 Accepted in revised form: 12 February 1999     

Characterization of the fluorescence emission properties of prodan in different reverse micellar environments

We have examined the steady state and time resolved fluorescence emission properties of the hydrophobic fluorescence probe, prodan, in three representative reverse micellar systems formed by the surfactants poly(oxyethylene) (tetramethylbutyl) phenylether (Triton X-100, neutral), cetyl trimethylammonium bromide (CTAB, cationic) and sodium bis-(2-ethylhexyl) sulfosuccinate (AOT, anionic) in organic solvent media containing different concentrations of water. The results obtained from the experiments indicate conspicuous dependence of the emission behaviour of prodan on the type of surfactant used and the water/surfactant molar ratio (w0). The nature of the emission profiles, along with relevant parameters namely emission maximum (lambda(em)max), anisotropy (r) and lifetime (tau) data are used to infer the distribution and microenvironments of the prodan molecules in the reverse micelles at different w0 values. Furthermore, quantitative estimates have been obtained for the polarities (in terms of the empirical polarity parameter E(T)(30)) of the sites of solubilization of the fluorophore in different reverse micellar systems.     

Micropolarity and microviscosity of Pluronics L62 and L64 core–shell aggregates in water at various concentrations and additives examined by absorption and fluorescence probes

The microstructure of aggregates formed in aqueous solutions of the triblock copolymers poly(ethylene oxide) (PEO)–poly(propylene oxide)–PEO, Pluronics L62 and L64, and the effect of additives (n-butanol, n-hexanol, and o-xylene) on the local polarity and viscosity were investigated using several absorption and fluorescence probes with different hydrophilic/hydrophobic trade-offs. The absorption probe was 2,2,6,6-tetramethylpiperidine-1-oxyl and the fluorescence probes pyrene (P), 1-anilinonaphthalene-8-sulfonic acid (ANS), 1,10-bis(1-pyrene) decane (PD), and N-[5-(dimethylamino)naphthalene-1-sulfonyl]hexadecylamine (Dansyl). The specific absorption and fluorescence parameters, sensitive to changes in micropolarity and microviscosity, were related to the hydration calibration curves carried out in homogeneous tetraethylene glycol/water mixtures. Thus, the effective local hydration of the molecular probe solubilized in the guest aggregate was quantified, and at the same time, the probe location is established with respect of the corona and core aggregate. The ANS and PD probes evidence differences in microviscosity and track the effect of the block copolymer structure and additive concentration on microviscosity.     

Heat capacity of associated systems. Experimental data and application of a two-state model to pure liquids and mixtures

The predictions from a recently reported (J. Chem. Phys. 2004, 120, 6648) two-state association model (TSAM) have been tested against experimental data. The temperature, T, and pressure, p, dependence of the isobaric heat capacity, C(p), for three pure alcohols and the temperature dependence at atmospheric pressure of the excess heat capacity, C(p)(E), for four alcohol + ester mixtures have been measured. The branched alcohols were 3-pentanol, 3-methyl-3-pentanol, and 3-ethyl-3-pentanol, and the mixtures were 1-butanol and 3-methyl-3-pentanol mixed with propyl acetate and with butyl formate. These data, together with literature data for alcohol + n-alkane and alcohol + toluene mixtures, have been analyzed using the TSAM. The model, originally formulated for the C(p) of pure liquids, has been extended here to account for the C(p)(E) of mixtures. To evaluate its performance, quantum mechanical ab initio calculations for the H-bond energy, which is one of the model parameters, were performed. The effect of pressure on C(p) for pure liquids was elucidated, and the variety of C(p)(E)(T) behaviors was rationalized. Furthermore, from the C(p) data at various pressures, the behavior of the volume temperature derivative, (deltaV/deltaT)(p), was inferred, with the existence of a (deltaV/deltaT)(p) versus T maximum for pure associated liquids such as the branched alcohols being predicted. It is concluded that the TSAM captures the essential elements determining the behavior of the heat capacity for pure liquids and mixtures, providing insight into the macroscopic manifestation of the association phenomena occurring at the molecular level.     

Diffusion Coefficients and Structure Properties of Triton X-100/ n-C6H13OH/H2O System

Abstract

The diffusion coefficients of Triton X-100 micelles with different shape are determined by cyclic voltammetry without any probe. The first CMC (3.2 × 10^?4 mol-L^minus;1) and the second CMC (1.3 × 10^minus;3 mol-L^minus;1) of Triton X-100 micelles arc obtained, and the mechanism of electrochemical reaction for Triton X-100 is deduced, When n-hexanol is added, the diffusion coefficient of Triton X-100 micelles with different shape increases, but the solubilization fraction of n-hexanol decreases in spherical micelles and is almost constant in rodlike ones. However, the micropolarity of micelles decreases in both spherical and rodlike micelles. Furthermore, the diffusion coefficient of Triton X-100 micelles with different shape increases with temperature and the diffusion activation energy increases with n-hexanol content.     

荧光探针法和电子自旋共振技术研究干扰基团对烷基苯磺酸钠聚集行为的影响

利用稳态荧光探针法和电子自旋共振技术测定多烷基苯磺酸钠的临界胶团浓度(cmc)、胶团聚集数(N_agg)、胶团的微极性和微粘度.当干扰基团增加时,烷基苯磺酸钠的临界胶团浓度减少,胶团聚集数减少,胶团微粘度降低,胶团的微极性增强.     

Fluorescence probing investigation of the mechanism of formation of MSU-type mesoporous silica prepared in fluoride medium

The mechanism of formation of a MSU-type siliceous material from tetraethyl orthosilicate (TEOS) in the presence of the nonionic surfactant tergitol T-15-S-12, sulfuric acid, and sodium fluoride has been investigated using mainly fluorescence probing techniques and, to a lesser extent, dynamic light scattering (DLS) and 29Si NMR spectroscopy. The tergitol micelles present in the systems obtained by progressively generating the reaction mixture giving rise to the mesostructured material by adding to an appropriate tergitol solution sulfuric acid, TEOS, and NaF were characterized by fluorescence probing (micelle aggregation number, micropolarity, and microviscosity) and also by dynamic light scattering (apparent micelle diameter). 29Si NMR experiments were also performed on selected systems after hydrolysis of the TEOS. The fluorescence probing techniques were also used to follow the changes of micelle characteristics with time during the evolution of the full reaction mixture from a limpid solution to a system containing a minor amount of condensed siliceous material. The synthesized solid material was characterized by X-ray diffraction and nitrogen adsorption-desorption analyses. The micelle aggregation number N was found to change only little, and the micropolarity remained constant when going from the tergitol solution to the full reaction mixture. The results of DLS measurements agree with this finding. Besides, while the condensation of silica took place after addition of NaF, the N value increased only very little with time up to the point where a small amount of mesostructured material precipitated out. These results indicate that the interaction between tergitol micelles and the siliceous species formed in the system by the hydrolysis of TEOS and also between micelles and the growing siliceous species must be very weak. As in our previous studies of the mechanism of formation of MCM41-type material from sodium silicate in the presence of cetyltrimethylammonium bromide, it appears that the locus of formation of the mesostructured material is not the micelle surface but the bulk phase. Micelles only act as reservoirs of surfactant providing surfactant monomer that binds to the growing siliceous species.     

The nature of the micellar stern region as studied by reaction kinetics. 2

The nature of rate-retarding effects of cationic micelles on the water-catalyzed hydrolyses of a series of para-substituted 1-benzoyl-1,2,4-triazoles (1a-f) and 1-benzoyl-3-phenyl-1,2,4-triazole (2) has been studied using kinetic methods. A comparison is drawn between medium effects in the micellar Stern region and in model solutions for the micellar Stern region. Simple model solutions involving concentrated aqueous solutions of a small ionic molecule resembling the surfactant headgroup, as reported before,(1) were improved. New model solutions for alkyltrimethylammonium bromide micelles contain both tetramethylammonium bromide (TMAB), mimicking micellar headgroups, and 1-propanol, mimicking hydrophobic tails. The rate-retarding effect of micelles on the hydrolysis of 1a-f and 2 is caused by the high concentration of headgroups as well as by hydrophobic tails in the Stern region where 1a-f and 2 bind to the micelle. Individual contributions of these interactions are quantified. Rate-retarding effects found for different probes, with different sensitivities for interactions as they occur when the probe binds to the micellar Stern region, as well as the micellar Stern region's micropolarity as reported by the E(T)(30) probe, are satisfactorily reproduced by new model solutions containing both TMAB and 1-propanol.     

Tetradecyltrimethylammonium bromide water-in-oil microemulsions: dependence of the minimum amount of alkanol required to produce a microemulsion with the alkanol and organic solvent topology

The amount of alcohol required to produce a microemulsion in a quaternary water-in-oil system was evaluated for a series of alcohols and hydrocarbon solvents of different size or topology. It was observed that the amount of n-hexanol and n-decanol required was similar in all the solvents considered. On the other hand, considerably higher concentrations of the branched alcohols (2,4-dimethyl-3-pentanol and 3-ethyl-3-pentanol) were required to produce the microemulsion, irrespective of the solvent topology (n-hexane or 2,2,4-trimethylpentane). From an analysis of the change in the analytical alcohol concentration with the surfactant concentration the amounts of alcohol present at the microaggregates' surface at the point of microemulsion formation were obtained. It is concluded that the high amounts of branched alcohols required are due to both less efficient incorporation at the interface and the larger number of alcohol molecules per surfactant required to stabilize the microemulsion.     

顺磁共振和紫外光谱法研究SDS-PEO体系的相互作用

合成更疏水的自旋探针4 羰基 2,2,6,6 四甲基哌啶氮氧自由基 2,4 二硝基苯腙.用顺磁共振（ESR）和紫外光谱法研究了十二烷基硫酸钠（SDS） 0.5 ％(w,质量分数)聚氧乙烯（PEO）体系的分子间相互作用. ESR结果表明,此水溶液体系的微极性随SDS浓度增大而减小,并且SDS与PEO聚集体具有更加紧密的堆积结构使其结合处具有较大的微粘性, SDS与PEO间的相互作用导致PEO分子链伸展. UV表明自旋探针分子可能靠近胶束的表面存在, 2,4 二硝基苯肼基团可能位于靠近SDS的硫酸根基团,定向于SDS胶束的表面,氮氧自由基基团短距离渗透到SDS胶束的碳氢核.     

Poly(ethylene glycol)-b-poly(epsilon-caprolactone) and PEG-phospholipid form stable mixed micelles in aqueous media

Novel mixed polymeric micelles formed from biocompatible polymers, poly(ethylene glycol)-b-poly(epsilon-caprolactone) (PEG(5000)-b-PCL(x)) and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-methoxy poly(ethylene glycol) (PEG-DSPE), possess small size and high thermodynamic stability, raising their potential as long circulating carriers in the context of delivery of antineoplastic and antibiotic drugs. Formation of mixed polymeric micelles was confirmed using size exclusion chromatography and 1H NMR NOESY. Steady-state fluorescence measurements revealed depressed critical micellar concentrations indicative of a cooperative interaction between component hydrophobic blocks, which was quantified using the pseudophase model for micellization. Steady-state fluorescence measurements indicated that the mixed polymeric micelle cores possess intermediate micropolarity and high microviscosity. Pulsed field gradient spin-echo measurements were used to characterize micellar diffusion coefficients, which agree well with those obtained using dynamic light scattering. NOE spectra suggested that the hydrophobic polymer segments from individual components are in close proximity, giving evidence for the formation of a relatively homogeneous core. Contrary to one-component PEG(5000)-b-PCL(x) micelles, the mixed polymeric micelles could incorporate clinically relevant levels of the poorly water soluble antibiotic, amphotericin B (AmB). AmB encapsulation and release studies revealed an interesting composition-dependent interaction of the drug with the mixed polymeric micelle core.     

Aggregation of sodium 1-(n-alkyl)naphthalene-4-sulfonates in aqueous solution: micellization and microenvironment characteristics

In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.     

全氟辛酸钠与十二烷基三甲基溴化铵混合胶束微环境性质的NMR,ESR研究

应用表面张力法、NMR法和ESR法研究了全氟辛酸钠(SPFO)-十二烷基三甲基溴化铵(DTAB)混合体系水溶液胶束形成及混合胶束的微环境性质(微观粘度、微观极性等)。结果表明, 碳氟表面活性剂碳氟链和碳氢表面活性剂碳氢链之间具有强烈的相互作用, DTAB与SPFO在水溶液中形成混合胶束。DTAB与SPFO混合体系的表面活性高于单一的DTAB或SPFO, 混合体系cmc较单一的DTAB和SPFO低。DTAB与SPFO混合胶束的微观粘度较DTAB胶束的大, 而微观极性较DTAB的小。