Determination of vitamins A and E in milk samples by fluorescence in micellar media

The fat-soluble vitamins A and E in milk samples were determined by fluorescence at room temperature in an aqueous media of micellar solutions. Different types of surfactants were studied; the cationic hexadecyltrimethylammonium bromide (CTAB), the anionic sodium dodecylsulfate (SDS) and the non-ionic polyoxyethylene(23)laurylether (Brij 35). The detection limits ranged between 50 and 90 ng.L-1 for both vitamins in CTAB and Brij 35. The method has been applied to the determination of vitamins A and E in milk samples.     

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.     

A study on the hydrolysis of bis(nitrophenyl)phosphate catalyzed by N‐methyldiethanolamine‐Ce(III) complex

The hydrolysis of bis(p‐nitrophenyl)phosphate (BNPP) catalyzed by N‐methyldiethanolamine‐Ce(III) complex in the presence and absence of cetyltrimethylammonium bromide (CTAB) and Brij35 surfactants at pH 7.20 and 303 K has been studied. The experimental results indicate that N‐methyldiethanolamine‐Ce(III) complex remarkably accelerates the hydrolysis of BNPP. The observed first‐order rate constant of the hydrolysis of BNPP catalyzed by N‐methyldiethanolamine‐Ce(III) complex at pH 7.20 and 303 K is 1.22 × 10^?2 s^?1, which is 1.09 × 10⁹ times of that of spontaneous hydrolysis of BNPP at pH 7. It is close to the activity of natural enzyme. A general quantitative treatment of the catalytic reaction involved a ternary complex as M_mL_lS has also been proposed in this paper. Applying this method to the catalytic hydrolysis of BNPP, we have obtained its thermodynamic and kinetic parameters. CTAB and Brij35 surfactant micelles obviously influence the rate constants of the catalytic hydrolysis of BNPP. Brij35 micelles promote the catalytic hydrolysis of BNPP, while CTAB micelles inhibit it. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 687–692, 2004     

Surfactant-induced electroosmotic flow in microfluidic capillaries

Control of EOF in microfluidic devices is essential in applications such as protein/DNA sizing and high‐throughput drug screening. With the growing popularity of poly(methyl methacrylate) (PMMA) as the substrate for polymeric‐based microfludics, it is important to understand the effect of surfactants on EOF in these devices. In this article, we present an extensive investigation exploring changes in EOF rate induced by SDS, polyoxyethylene lauryl ether (Brij35) and CTAB in PMMA microfluidic capillaries. In a standard protein buffer (Tris‐Glycine), PMMA capillaries exhibited a cathodic EOF with measured mobility of 1.54 ± 0.1 (× 10^?4 cm²/V.s). In the presence of surfactant below a critical concentration, EOF was independent of surfactant concentration. At high concentrations of surfactants, the electroosmotic mobility was found to linearly increase/decrease as the logarithm of concentration before reaching a constant value. With SDS, the EOF increased by 257% (compared to buffer), while it was decreased by 238% with CTAB. In the case of Brij35, the electroosmotic mobility was reduced by 70%. In a binary surfactant system of SDS/CTAB and SDS/Brij35, addition of oppositely charged CTAB reduced the SDS‐induced EOF more effectively compared to nonionic Brij35. We propose possible mechanisms that explain the observed changes in EOF and zeta potential values. Use of neutral polymer coatings in combination with SDS resulted in 50% reduction in the electroosmotic mobility with 0.1% hydroxypropyl methyl cellulose (HPMC), while including 2% poly (N,N‐dimethylacrylamide) (PDMA) had no effect. These results will potentially contribute to the development of PMMA‐based microfluidic devices.     

Inhibition effect of {surfactant–substrate} aggregation on the rate of oxidation of reducing sugars by alkaline hexacyanoferrate(III)

The effect of cationic (cetyltrimethylammonium bromide, CTAB), anionic (sodium lauryl sulfate, NaLS), and nonionic (Brij‐35) surfactants on the rate of oxidation of some reducing sugars (xylose, glucose, and fructose) by alkaline hexacyanoferrate(III) has been studied in the temperature range from 35 to 50°C. The rate of oxidation is strongly inhibited in the presence of surfactant. The inhibition effect of surfactant on the rate of reaction has been observed below critical micelle concentration (CMC) of CTAB. In case of NaLS and Brij‐35, the inhibition effect was above CMC, at which the surfactant abruptly associates to form micelle. The kinetic data have been accounted for by the combination of surfactant molecule(s) with a substrate molecule in case of CTAB and distribution of substrate into micellar and aqueous pseudophase in case of NaLS and Brij‐35. The binding parameters (binding constants, partition coefficients, and free‐energy transfer from water to micelle) in case of NaLS and Brij‐35 have been evaluated with the help of Menger and Portnoy model reported for micellar inhibition. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 595–604, 2007     

Effect of self‐assemblies of various surfactants in their single and mixed states on the BZ oscillatory reaction

Micelles of different surfactants are well known to affect chemical equilibria and reactivities by selectively sequestering the reagent substrates through electrostatic and hydrophobic interactions. In this article, the effects of micelles of various surfactants on different parameters of the Ce(IV)‐catalyzed Belousov–Zhabotinsky (BZ) oscillatory reaction at 35°C in nonstirred closed conditions are studied by employing spectrophotometry and tensiometry. Surfactants used in this study are the cationics hexadecyltrimethylammonium bromide (CTAB) and pentamethylene‐1,5‐bis(N‐hexadecyl‐N,N‐dimethylammonium)bromide gemini (Gemini), anionic sodium dodecylbenzene sulfonate (SDBS), and nonionic Brij58, whereas the binary surfactant systems used are cationic–nonionic CTAB+Brij58 and anionic–nonionic SDBS+Brij58. The results revealed that the induction period shows a definite variation with increasing concentration of different surfactants above their critical micelle concentration (cmc). The amplitudes of oscillation and absorbance maxima and minima are enhanced in the presence of micelles of CTAB and Gemini surfactants, whereas micelles of SDBS and Brij58 have almost no effect on the nature of the oscillations. However, mixed micelles of CTAB+Brij58 and SDBS+Brij58 binary mixtures show a quite different effect on the overall behavior of the oscillations. The enhanced effect of CTAB and Gemini surfactants on the overall nature of oscillations has been attributed to the positive charge on the surface of their micelles and to some extent on the presence of nitrogen in their head group. The effect of mixed binary micelles may be attributed to their synergistic nature. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 659–668, 2010     

The separation of herbicides by micellar electrokinetic capillary chromatography

Summary A method for the separation of a number of herbicides consisting of chlorophenoxy acids by micellar electrokinetic capillary chromatography (MECC) was developed. Sodium dodecyl sulphate (SDS), Brij 35, cetyltrimethylammonium bromide (CTAB) and methanol were introduced into the buffers to investigate their effects on the separation of the herbicides. SDS combined with Brij 35 as the micellar agent was found to provide the best overall separation of these components.     

Effect of micelle composition on the formation of surfactant-templated polymer films

Surfactant-templated polymer films prepared from polyethylenimine (PEI), cetyltrimethylammonium bromide (CTAB), and octaethylene glycol monohexadecyl ether (C(16)E(8)) were examined and the effect of increasing the percentage of nonionic surfactant in the micelles measured using both surface and bulk-sensitive techniques. It was found that there is a strong interaction between CTAB and C(16)E(8), although no interaction between the C(16)E(8) and PEI was observed. Generally, increasing the percentage of C(16)E(8) in the micelles decreases both the thickness and degree of order in the films; however, it was observed, depending on the conditions, that films could still be formed with as little as 20% cationic surfactant. Experiments on the CTAB/Brij56/PEI system were also performed and these indicate that it is similar to the CTAB/C(16)E(8)/PEI system.     

Quenching of Pyrene Fluorescence in Premiceljar Solutions

Abstract

The quenching of the fluorescence intensity of pyrene by KBr has been measured in premicellar solutions of cetyltrimethylammonium bromide (CTAB), sodium lauryl sulfate (SLS) and polyoxyethylene 23-lauryl ether (Brij 35). The association of pyrene with premicellar aggregates is thought to bring the bromide ion closer to the fluorophore and hence results in a greater quenching effect. In 1.0 × 10^?4 M CTAB solutions there is the beginning of “protective” premicellar aggregation. At this stage, 13 times more bromide ion is needed to effect the same degree of quenching as in pure water.     

Synthesis and photocatalytic activity of co-doped mesoporous TiO2 on Brij98/CTAB composite surfactant template

Using composite surfactant templates, polyoxyethylene (20) oleyl ether (Brij98) and cetyl trimethyl ammonium bromide (CTAB), as structure-directing agents, N and La co-doped mesoporous TiO₂ complex photocatalysts were synthesized successfully. The micromorphology of co-doped mesoporous TiO₂ samples was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transformed infrared spectroscopy (FT-IR), energy-dispersive X-ray spectrometer (EDS) and N₂ adsorption-desorption measurements. The results indicated that the complex photocatalyst prepared with a molar ratio of Brij98:CTAB=1:1 showed a uniform pore size of ca. 7 nm and a high specific surface area (S_BET) of 279.0 m² g⁻¹, and exhibited the highest photocatalytic activity for degradation of papermaking wastewater under ultra-violet light irradiation. The chemical oxygen demand (CODc_r) percent degradation was about 73% in 12 h and chroma percent degradation was 100% in 8 h.     

Metallomicellar catalysis: effects of bridge-connecting ligands on the hydrolysis of PNPP catalyzed by Cu(II) complexes of ethoxyl-diamine ligands in micellar solution

The syntheses of three ligands are reported: N,N,N′,N′-tetra(2-hydroxyethyl)-1,3-propylene-diamine (1), N,N,N′,N′-tetra(2-hydroxyethyl)-1,10-decadiamine (2), N,N,N′,N′-tetra(2-hydroxyethyl)-1,4-xylyldiamine (3). The catalytic hydrolysis of p-nitrophenyl picolinate (PNPP) by the bivalent metal ion Cu(II) complexes of these ligands was studied kinetically in a buffered CTAB or Brij35 micellar solutions at 25 °C and different pH values. The results indicate that 1:2 and 2:1 complexes of these ligands and metal ion are the active species for the catalytic hydrolysis of PNPP in CATB and Brij35 micellar solutions. The ternary complex kinetic model for metallomicellar catalysis was employed to obtain the relative kinetic and thermodynamic parameters. The effects of the structure of the ligands and the microenvironment of reaction on the hydrolytic reaction of PNPP have been discussed in detail.     

Brij类表面活性剂与Laponite纳米颗粒的相互作用及其稳定乳液的研究

通过表面张力、Zeta电位和流变学参数的测定, 研究了聚氧乙烯烷基醚类非离子型表面活性剂(Brij 30和Brij 35)在合成锂皂石(Laponite)纳米颗粒表面的吸附及对Laponite水分散体系中颗粒间相互作用和体系粘度的影响. 结果表明, 这类表面活性剂能显著地吸附在Laponite颗粒表面上, 且吸附量随其分子中POE链长短而不同. 这种吸附没有改变Laponite粒子的带电性质, 但一定程度地降低了Laponite颗粒Zeta电位; 吸附也会减弱颗粒间的相互作用, 降低体系的粘度. 实验以Laponite和Brij为乳化剂, 制备了O/W型乳状液. 乳液稳定性变化和乳液粒径分布结果表明, 体系中Brij的浓度较低时, 乳液的性质主要是由Laponite颗粒决定的; 而Brij浓度较高时, 则主要取决于Brij表面活性剂. 高速剪切含Brij的Laponite水分散体系, 剪切后表面张力随时间的变化表明, 剪切作用会使得吸附在Laponite颗粒表面的Brij分子不同程度地解吸下来. 这也意味着乳液制备时, 高速剪切作用也会造成Brij分子自Laponite颗粒表面的脱附, 这可能是非离子表面活性剂与阳离子表面活性剂对负电固体颗粒稳定乳液影响不同的原因.     

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.     

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).     

Studies on Phenol Oxidation with H2O2 Catalyzed by Schiff Base Cobalt(II) Complexes in Micellar Solution

The two Schiff base cobalt(II) complexes, CoL¹ and CoL², were synthesized and characterized. The metallomicelle made up of the cobalt(II) complexes and surfactants (CTAB, LSS and Brij35), as mimic peroxidase metalloenzyme, were used in the catalytic oxidation of phenol by H₂O₂. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were studied. The acid effect of reaction system, structural effect of the complexes, and effect of temperature on the rate of the phenol oxidation catalyzed by the mimetic peroxidases have been discussed. The results showed that the schiff base cobalt(II) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme.     

Micellar Liquid Chromatography Study of Quantitative Retention–Activity Relationships for Antihypertensive Drugs

Use of micellar mobile phases in reversed-phase liquid chromatography (RPLC) results in hydrophobic and electrostatic sites for interaction. Modified stationary phases in micellar liquid chromatography (MLC) are structurally similar to biomembranes. To confirm this we focused on the effects of the type and concentration of surfactant (Brij 35, SDS, and CTAB) and mobile phase pH on the retention of antihypertensive drugs on modified C₁₈ stationary phases. Quantitative retention-activity relationships are proposed for the drugs and the different surfactants and compared with those obtained using aqueous–organic mobile phases. Finally, a correlation was obtained between the logarithm of retention factors (log k) and the toxicity (LD₅₀) of antihypertensive drugs. Revised: 14 September 2005 and 4 April 2006     

Simultaneous determination of fat- and water-soluble vitamins by microemulsion electrokinetic chromatography

A new procedure was developed for the simultaneous determination of water- and fat-soluble vitamins by microemulsion electrokinetic chromatography. Using microemulsions based on sodium dodecyl sulfate, Brij 35, 1-butanol, and heptane, 10 vitamins were separated (4 water-soluble and 6 fat-soluble) within 35 min. The efficiency of the separation was 800000 theoretical plates (effective capillary length, 40 cm). To enhance the selectivity, 2-propanol was used as a hydrophobizing addition into the microemulsion. The procedure was used for analyzing a kaolin-based vitamin premix. The use of microemulsion as an agent for extracting vitamins from the support considerably simplifies the sample preparation.     

Synergism and foaming properties in binary mixtures of a biosurfactant derived from Camellia oleifera Abel and synthetic surfactants

A biosurfactant, named tea saponin (TS), was isolated and purified from the defatted seed of Camellia oleifera Abel. The characterization of TS including molecular weight, glycosyl composition, and thermal behavior as well as the surface and foaming properties was conducted. The synergistic interactions of binary systems of CTAB-TS, SDS-TS, and Brij35-TS were investigated. The results show that TS had a weight-average molecular weight of 809.12 g mol(-1) and contained four aglycones of L-rhamnose, D-galactose, D-glucose, and D-glucuronic acid. The critical micelle concentration (cmc) of 2.242 mmol L(-1) and the minimum surface tension (γ(cmc)) of 43.5 mN m(-1) were determined for TS. Synergisms in surface tension reduction efficiency, in mixed micelle formation, and in surface tension reduction effectiveness were observed in CTAB-TS and SDS-TS systems, whereas that was not shown in Brij35-TS mixtures. The mixtures of TS with CTAB and SDS showed synergism in foaming efficiency, but this synergism did not exist in Brij35-TS system with respect to the surface properties. Nevertheless, there appears to be no significant correlation between foam stability and the surface properties.     

Solubilization of Aliphatic Carboxylic Acids (C3-C6) by Sodium Dodecyl Sulfate and Brij 35 Micellar Pseudophases

The apparent dissociation constants of 1-propanoic, 1-butanoic, 1-pentanoic and 1-hexanoic acids were obtained for the first time in Brij 35 micellar solutions with concentration from 0.03 to 0.20 mol⋅L⁻¹ and sodium dodecyl sulfate (SDS) micellar solutions with concentrations from 0.01 to 0.30 mol⋅L⁻¹. A pronounced effect of Brij 35 micelles on the acid-base properties of aliphatic acids was observed. The binding constants, K _b, of carboxylic acids to micellar pseudophases of SDS and Brij 35 were estimated within the framework of the pseudophase model. The dependences of Gibbs energies of transfer from water to the micellar pseudophases were constructed, and Gibbs energies were evaluated for methylene and carboxylic group transfers into Brij 35 and SDS micelles. Comparison of the Gibbs energies of methylene group transfer from water to Brij 35 and SDS suggests that the mechanisms of hydrocarbon group transfer into the core of nonionic and anionic micelles involving the same monomer hydrophobic tail length are similar.     

Effects of surfactant micelles on solubilization and DPPH radical scavenging activity of Rutin

The interaction of the antioxidant Rutin with the radical DPPH (2,2-diphenyl-1-picrylhydrazyl) in presence of cationic (CTAB, TTAB, DTAB), non-ionic (Brij78, Brij58, Brij35), anionic (SDS) and mixed surfactant systems (CTAB-Brij58, DTAB-Brij35, SDS-Brij35) has been followed by spectrophotometric and tensiometric methods to evaluate the DPPH radical scavenging activity (RSA) of Rutin in these model self-assembled structures. The results show that the solubilization capacity of various single surfactant systems for both DPPH as well as Rutin followed the order cationics > non-ionics > anionic. The radical scavenging activity of Rutin in the solubilized form was higher within ionic micelles than in non-ionic micelles. However, the antioxidant exhibited enhanced activity for the radical in mixed cationic-non-ionic micelles compared with any of the single component micelles. In contrast, anionic-non-ionic mixed micelles modulated the activity of Rutin in-between that seen for pure anionic and non-ionic micelles only.