苯甲醇对CTAB/KBr胶束体系流变性及CTAB分子1HNMR谱影响的研究

报道了苯甲醇对CTAB/KBr胶束体系粘度的影响,利用1HNMR法研究了苯甲醇在CTAB胶束中的增溶位置.结果表明,在KBr盐溶液中,随着苯甲醇的加入,0.01mol/LCTAB胶束体系的粘度增大至最大值.对CTAB分子的1HNMR分析表明,少量的苯甲醇增溶在棒状胶束的界面,促使胶束体积增大和相互缠结,体系的粘度随之增大;当苯甲醇浓度较高时,将增溶在胶束的栅栏层靠近极性头一侧,胶束发生棒-球转变和解缠,体系的粘度降低.     

正戊醇对CTAB/KBr胶束体系流变性的影响

报道了正戊醇对CTAB/KBr胶束体系流变性的影响。结果表明：在0.01mol.dm^-^3CTAB(十六烷基三甲基溴化铵)溶液中,正戊醇促使CTAB/KBr胶束体系的粘度增大至一最大值,然后降低在0.08mol.dm^-^3CTAB/KBr的溶液中,正戊醇能促使该胶束体系呈现粘弹性。根据动态荧光法测定的胶束聚集对以上结果进行了解释。     

直链醇对反胶束体系中木素过氧化物酶催化活性的影响

根据研究发现, 在有醇作助表面活性剂的CTAB反胶束中木素过氧化物酶(LiP)不能表现活力, 而在水介质中CTAB对LiP的催化活性影响又不是很大. 为了揭示其中醇的影响, 本工作就不同碳链长度的醇对LiP酶催化性能的影响进行了研究. 由于CTAB反胶束体系中醇浓度较高, 且碳原子数大于4的直链醇在水中的溶解度又很小, 为此采用了LiP可在其中显示催化活性的CTAB正胶束、AOT反胶束和Brij30反胶束作介质, 通过研究这些介质中不同链长的醇对LiP催化活力的影响, 来探讨CTAB反胶束中木素过氧化物酶(LiP)不能表现活力的原因. 结果表明, 不管表面活性剂聚集体的结构、电性质及反胶束大小如何, 只要醇的浓度超过500 mmol•L^－1 (丁醇≥1200 mmol•L^－1), LiP在上述原本可显示活力的介质中均无催化活性. 据此推测CTAB反胶束中木素过氧化物酶(LiP)不能表现活力的原因主要是由助表面活性剂醇造成的.     

Inclusion Complex of β-cyclodextrin with CTAB in Aqueous Solution

Cetyltrimethylammonium bromide (CTAB)/potassium bromide (KBr) micellar system has been used as a viscosity probe to study the inclusion complexation between β-cyclodextrin (β-CD) and CTAB. Viscosity measurements show that the inclusion complexation between β-CD and CTAB may cause the breakdown of CTAB/KBr wormlike micelles, resulting in the decrease of the solution viscosity. The viscosity minimum at C_β-CD/C_CTAB=2 indicate the molecular ratio of host molecule to guest molecule is 2:1 in the β-CD/CTAB inclusion complex.     

Catalytic action of CTAB/KBr/C9OH micellar media on the basic hydrolysis of crystal violet

The kinetics of basic hydrolysis of crystal violet (CV) in CTAB/KBr/C₉OH micellar media was investigated under pseudo-first-order conditions. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of CV at 590?nm. It was observed that the pseudo-first-order rate constant increases with increase in C₀. The enhancement of reaction rate with C₀ is explained on the basis of dependence of reaction rate on micellar morphology. Further, the viscosity and DLS analysis supports nonanol-induced morphological transitions. Fluorescence spectroscopy has been used to understand dye–micelles interactions. The enhancement of fluorescence intensity of CV with C₀ suggests an increase in dye–micelles interaction with C_0. The concentration of surfactant and salt had a marked effect on reaction rate. The inhibition of reaction rate at high concentration of surfactant and salt is due to the ionic competition of OH^? and Br^? ions for the reaction center. The influence of [OH^?] on CV hydrolysis was also investigated. The results show that the pseudo-first-order rate constant, k’, increases linearly with hydroxide ion concentration, indicating first-order dependence on [OH^?].     

NMR study on solubility of benzyl alcohol and its transfer free energy from D_2O to cationic micelle

A new kind of surfactant, [CnH_(2n+1)OCH2CH(OH)CH2N(CH3)3]Cl (n=12, 14, 16) was synthesized. The solubility of benzyl alcohol in micellar solutions was determined by 1H NMR method. The results indicate that the length of alkyl chains of surfactant affects the solubility of ben-zyl alcohol in 2.5 × l0~(-2) mol/L micellar solutions. The solubility of benzyl alcohol per liter of micellar solution is 0.095 mole for n=12, 0.115 mole for n=14, 0.165 mole for n=16. The transfer free energy of benzyl alcohol from aqueous phase to micellar phase is -24.29 kJ/mol for n=12, -24.37 kJ/mol for n=14, -24.49 kJ/mol for n=16.     

Dynamic light scattering study of cetyltrimethylammonium bromide aqueous solutions

Cetyltrimethylammonium bromide (CTAB) aqueous solutions are studied by dynamic light scattering method in a wide concentration range covering the first and second critical micelle concentrations (CMC₁ and CMC₂, respectively). Nonmonotonic and ambiguous behavior of diffusion coefficients D with an increase in concentrations above CMC1 is revealed. An increase in the D values in the first decade of CTAB concentration above CMC1 agrees with known published data for aqueous solutions of ionic surfactants. It is shown that an increase in the ionic strength of solution with the addition of KBr leads to a decrease in the positive slope of the dependence of diffusion coefficients on CTAB concentration up to zero at 0.05 M KBr. Two relaxation processes corresponding to large and small D values are simultaneously observed in micellar solutions, beginning with 0.03 M CTAB concentration. The data obtained are compared with published data, as well as with the results of viscosity measurements. The performed analysis indicates that the observed relaxation processes are explained by the coexistence of spherical and nonspherical micelles. It is established that micelles acquire a cylindrical shape at CTAB concentrations ranging from 0.2 to 0.25 M. Hydrodynamic radii and lengths of micelles are calculated.     

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.     

PNPP Cleavage Catalyzed by Schiff Base Mn(III) Complexes Containing Polyether Side Chains in CTAB Micellar Solutions

Two Schiff base Mn(III) complexes containing polyether side chain were synthesized and characterized. The catalytic hydrolysis of p‐nitrophenyl picolinate (PNPP) by the two complexes in the buffered CTAB micellar solution in the pH range of 6.60–8.20 was investigated kinetically in this study. The influences of acidity, temperature, and structure of complex on the catalytic cleavage of PNPP were also studied. The mechanism of PNPP hydrolysis catalyzed by Schiff base manganese(III) complexes in CTAB micellar solution was proposed. The relative kinetic and thermodynamic parameters were determined. Comparied with the pseudo‐first‐order rate constant (k ₀) of PNPP spontaneous hydrolysis in water, the pseudo‐first‐order rate constants (k _obsd) of PNPP catalytic hydrolysis are 1.93×10³ fold for MnL¹ ₂Cl and 1.06×10³ fold for MnL² ₂Cl in CTAB micellar solution at pH=7.00, T=25°C, and [S]=2.0×10^?4mol · dm^?3, respectively. Furthermore, comparing the k _obsd of PNPP catalytic hydrolysis by metallomicelles with that of PNPP hydrolysis catalyzed only by metal complexes or CTAB micelle at the above‐mentioned condition, metallomicelles of MnL₂(L=L¹, L²) Cl/CTAB exhibit notable catalytic activities for promoting PNPP hydrolysis, and MnL¹ ₂Cl/CTAB system is superior in promoting cleavage of PNPP relative to MnL² ₂Cl/CTAB system under the same experimental conditions. The results indicate that the rate of PNPP catalytic cleavage is influenced by the structures of the two complexes, the acidity of reaction systems, and the solubilization of PNPP in CTAB micelles.     

Micellae catalysis of the oxidation of 1,4-dihydro-nicotinamides by methylene blue part 2

The oxidation of 1-R-1,4-dihydronicotinamides (1a: R = benzyl, 1b:R = octyl, 1c:R = cetyl) by methylene blue has been studied in the presence of micelles of cetyltrimethylammonium bromide (CTAB), polyoxyethylene[23]lauryl ether (Brij^® 35) and sodium dodecylbenzenesulfonate (SDBS). In CTAB, a small rate enhancement was observed below the cmc, followed by a gradual decrease above the cmc. Brij 35 has little effect on the reaction rate. The rate vs. concentration profile in SDBS shows a very sharp maximum near the cmc for 1b and 1c, whereas a more moderate increase in rate is observed for 1a. The effects are analyzed in terms of the pseudophase model for micellar catalysis, and it appears that the observed rate enhancements can be completely ascribed to increments of the reactant concentration in the micellar pseudophase. Comparison with rate effects in sodium dodecylsulfate (SDS) micelles reveals that the reaction in SDBS micelles proceeds in a more polar environment. This provides kinetic evidence that the aryl moiety in SDBS allows a deeper penetration of water molecules into the micelle, thus giving rise to a more open surface for SDBS micelles than for SDS micelles.     

Light absorption in solutions of cetyltrimethylammonium and cetylpyridinium bromides

Absorption of monochromatic light in solutions of cetyltrimethylammonium (CTAB) and cetylpyridinium (CPB) bromides has been studied in the wavelength λrange of 190–1000 nm. The investigation has been performed at 30°C and surfactant concentrations ranging from 5 × 10^?5 to 3.5 × 10^?3 M. Spectra of solutions of LiBr, KBr, and CTAB in the premicellar concentration region have been shown to coincide with each other. They are unimodal, and the heights of their maxima at λ_max ≈ 193 nm depend on Br^? concentration alone. In contrast to CTAB solutions, the UV spectra of CPB solutions are characterized by the presence of two absorption maxima near λ_max1 = 191 nm and λ_max2 = 259 nm, as well as a shoulder at 210–218 nm. Their existence is caused by the presence of both Br^? anions and CP⁺ cations in the solutions. The dependences of the integral absorption in the examined wavelength range on CPB concentration exhibit inflections both in the premicellar region and upon the transition to micellar solutions, with these inflections characterizing the critical dimerization and micellization concentrations, respectively. For CTAB, this regularity has only been observed at the critical micellization concentration. The data on the concentration dependence of the light absorption have resulted in the proposal of a method for determining the degree β of counterion binding by micelles of ionic surfactants. The β values calculated for CTAB and CPB are equal to 0.89 ±0 0.1.     

Kinetics of basic hydrolysis of tris(1,10‐phenanthroline)iron(II) in macromolecular assemblies of CTAB

The kinetics of basic hydrolysis of tris(1,10‐phenanthroline)iron(II) has been carried out in aqueous, N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) micellar, and CTAB reverse micellar media by UV–visible spectroscopy system. The reaction follows the overall second‐order kinetics; first order in each Fe(II) complex and the base (^?OH). CTAB micelles catalyze the reaction rate through the adsorption of the Fe(II) complex and the hydroxyl ions on the micellar surface. In the reverse micellar medium, interesting physicochemical features are observed. Being ionic nature of reactants, both the reactants prefer to stay and react inside the water pool in place of the hydrophobic environment. The rate increases with w, that is, the size of the water pool, attains a maximum value at w = 8.33, and then decreases. But the rate increases as the concentration of surfactant increases at fixed w values. For a better explanation of the kinetic data, the activation parameters, standard enthalpy of activation (Δ^?H°), standard entropy of activation (Δ^?S°), and energy of activation (E_a) were determined. All kinetic data corroborate the proposed mechanism. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 579–589, 2011     

Multiresidue Analysis of Pesticides in Environmental Waters by Capillary Electrophoresis Using Simultaneous UV and Electrochemical Detection

A rapid multiresidue method has been developed for the analysis of eight pesticides (triazines, triazinones and ureas) in environmental waters. A simple end‐column electrochemical detector was used in combination with an available commercial capillary electrophoresis instrument with UV detection. The determination of these pesticides using micellar electrokinetic capillary chromatography (MEKC) with dual electrochemical and UV detection is the first time reported. In both detection systems, a linear range was obtained for the eight pesticides, concentrations lower than 5.0×10^?5 mol L^?1, in 0.020 mol L^?1 boric acid at pH 8.3 and containing 0.025 mol L^?1 of sodium dodecylsulfate, to obtain selectivity in the additional separation by micellar distribution process. Under these conditions a lower detection limit than 2.0×10^?6 mol L^?1 (0.15 pmol of pesticide) was achieved for the most of them. The eight pesticides are resolved in less than 14 min.     

THE EFFECT OF SURFACTANT MICELLES ON THE ALKALINE HYDROLYSIS OF DIMETHYLFORMAMIDE

The alkaline hydrolysis of dimethylformamide has been studied at 40'C in micellar solutions of single surfactant (CTAB. SDS. Brij 35) with the analog thermoanalytical curve method of thermokinetics. A kinetic equation of micellar catalysis under the condition of highter reactant concentration than micellar concentration ([S]>[M]) has been derived from the pseudophase model of micellar catalysis and some relative assumptions, The kinetic parameters. k_m, k_2mand the association constant of reactant with micelle K₁, have been calculated in this way. the results indicate that these surfactant micelles exhibit catalytic effect on the reaction. This is attributed to the micropolarity and local concentration effect of micelles.     

Determination of Vitamins A and E Exploiting Cloud Point Extraction and Micellar Liquid Chromatography

Cloud point extraction and micellar chromatographic methods were developed for determination of vitamins A and E. The stationary phase was C18 and the mobile phase was 3.00% (w/v) SDS, 15.0% (v/v) butyl alcohol and 0.02 mol L^?1 phosphate buffer solution at pH 7.0. The retention times for vitamins A and E were 9.6 and 13.0, respectively. The extraction solution was 100 mmol L^?1 Triton X-100, 650 mg NaCl and 1.0% ascorbic acid at 70°C for 30 min. The method is precise (r.s.d. < 7%), the linear range was from 5.0 up to 360.0 mg L^?1 for both vitamins. Recovery test showed recuperation between 90.2 and 99.2%, and LOD and LOQ of 0.234 and 0.108 mg L^?1, 0.780 and 0.360 mg L^?1 to vitamins A and E were found.     

Electroanalytical Method for Determining Pyrogallol in Biodiesel in the Presence of a Surfactant

A sensitive, straightforward electroanalytical method for determining pyrogallol (PY) in biodiesel in the presence of a surfactant was developed using a voltammetric technique and screen‐printed electrodes. The influence of surfactant addition (sodium dodecyl sulfate (SDS), Triton X‐100 (TX‐100), cetyltrimethylammonium bromide (CTAB), tetrabutylammonium iodide (TBAI), tetrabutylammonium bromide (TBAB), or tetraethylammonium bromide (TEAB)) on the supporting electrolyte (0.04 mol L^?1 Britton? Robinson buffer) was evaluated. Only CTAB significantly increased the oxidation peak current. Under optimal conditions, the method demonstrated linearity over the concentration range of 0.8–9.0×10^?6 mol L^?1, with limits of detection and quantification of 4.9×10^?7 and 1.5×10^?6 mol L^?1, respectively. The results were satisfactory, relative to those obtained using high‐performance liquid chromatography (HPLC).     

Influence of Gold Nanoparticles of Varying Size in Improving the Lipase Activity within Cationic Reverse Micelles

Herein, we report the effect of gold nanoparticles (GNPs) in enhancing lipase activity in reverse micelles of cetyltrimethylammonium bromide (CTAB)/water/isooctane/n‐hexanol. The size and concentration of the nanoparticles were varied and their specific roles were assessed in detail. An overall enhancement of activity was observed in the GNP‐doped CTAB reverse micelles. The improvement in activity becomes more prominent with increasing concentration and size of the GNPs (0–52 μM and ca. 3–30 nm, respectively). The observed highest lipase activity (k₂=1070±12 cm³ g^?1 s^?1) in GNP‐doped CTAB reverse micelles ([GNP]: 52 μm, ca. 20 nm) is 2.5‐fold higher than in CTAB reverse micelles without GNPs. Improvement in the lipase activity is only specific to the GNP‐doped reverse micellar media, whereas GNP deactivates and structurally deforms the enzyme in aqueous media. The reason for this activation is probably due to the formation of larger‐sized reverse micelles in which the GNP acts as a polar core and the surfactants aggregate around the nanoparticle (‘GNP pool’) instead of only water. Lipase at the augmented interface of the GNP‐doped reverse micelle showed improved activity because of enhancement in both the substrate and enzyme concentrations and increased flexibility in the lipase conformation. The extent of the activation is greater in the case of the larger‐sized GNPs. A correlation has been established between the activity of lipase and its secondary structure by using circular dichroism and FTIR spectroscopic analysis. The generalized influence of GNP is verified in the reverse micelles of another surfactant, namely, cetyltripropylammonium bromide (CTPAB). TEM, dynamic light scattering (DLS), and UV/Vis spectroscopic analysis were utilized to characterize the GNPs and the organized aggregates. For the first time, CTAB‐based reverse micelles have been found to be an excellent host for lipase simply by doping with appropriately sized GNPs.     

Effects of Nonpolar Solvents on the Solubilization of Pepsin into Bis(2-Ethylhexyl) Sodium Sulfosuccinate and Cetyltrimethylammonium Bromide Reverse Micelles

Solubilization of pepsin by bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and cetyltrimethylammonium bromide (CTAB) reverse micelles has been studied at 20C. Isooctane, cyclohexane and hexane were used as solvents, and n-butanol, amyl alcohol and hexanol were used as cosurfactants for CTAB. AOT concentrations were varied from 50 to 500 mM and pepsin concentrations were varied from 2 to 10 mg-mL^–1. At 250 mM, AOT can solubilize more than 85% of the Pepsin in each solvent. The effect of aqueous-phase pH on the solubilization of Pepsin has been studied from pH 1 to 8. The maximum solubilization of pepsin was observed below the isoelectric point (pI = 1.5) of the protein at pH 1.0 with 300 mM of AOT. The CTAB solutions were prepared by dissolving CTAB in isooctane with varying concentrations (0–100% v/v) of n-butanol, amyl alcohol or hexanol cosurfactants. It was found that 5% cosurfactant with 100 mM of CTAB was sufficient to solubilize more than 90% of the total pepsin. Pepsin solubilization by AOT reverse micelles increases with increasing polarizability and molar volume of the solvents.     

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.     

STUDIES ON THERMOKINETICS(XVI) THE KINETICS OF THE POLYMERIZATION OF ACRYLAMIDE IN MICELLAR SOLUTION

The kinetics of the polymerization of acrylamide in aqueous solution and CTAB micellar solution initiated by sodium sulfite has been investigated with the theory and method of thermokinetics for n order reactions with equal concentration in this paper. The influence of initiator and CTAB concetrations on molecular weight of polyacrylamide has been discussed.The second—order rate constants of this reaction at 30 and 40°C in aqueous solution are 0. 112and 0. 0262dm³ mol^-1s^_1, respectively. The activation energy,based on measurements at these two temperatures,is 66. -4kJ mol^-1. The ratio k2√n in CTAB micellar solution is smaller than that in aqueous solution. The rate of forming radical in micellar solution has been decreased.