Condensation of <Emphasis Type="Italic">p</Emphasis>-Dimethylaminocinnamaldehyde with Aniline and Substituted Anilines in Micellar Media

Optimal conditions were found for the reactions of aniline and its hydroxy-, carboxy-, methyl-, and nitro-substituted derivatives with p-dimethylaminocinnamaldehyde in the presence of sodium dodecyl sulfate micelles in the pH range 1–6. A correlation was revealed between the optimal pH value pK _a of aromatic amines. The reaction in the model system aniline-p-dimethylaminocinnamaldehyde-sodium dodecyl sulfate in micelles formed by anionic surfactants is accelerated more than 1000-fold due to increased concentration of the reactive species in sodium dodecyl sulfate micelles.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 288–294.Original Russian Text Copyright © 2005 by Doronin, Chernova, Gusakova.     

Quenching of zinc phthalocyanine excited states by viologen surfactant assemblies——The influence of microenvironment

A series of functional surfactants of N-alkyl-N'-butyl viologens has been synthesized.The quenching of excited singlet and triplet states of zinc phthalocyanine was studied in DMSOand in mixed micelles containing the functional surfactant as one and cationic cetyl trimethylam-monium bromide(CTAB),anionic sodium dodecylsulfate(SDS)and neutral TX-100 surfactantas the other component.Fluorescence quenching and laser photolysis studies indicate that thefunctional surfactants are solubilized at different sites in micelles,the process depends on chainlength and exerts great influence on the quenching of zinc phthalocyanine excited states.     

Phase behavior in mixtures of cationic and anionic surfactants in aqueous solutions

Phase behavior of cationic/anionic surfactant mixtures of the same chain length (n=10, 12 or 14) strongly depends on the molar ratio and actual concentration of the surfactants. Precipitation of catanionic surfactant and mixed micelles formation are observed over the concentration range investigated. Coacervate and liquid crystals are found to coexist in the transition region from crystalline catanionic surfactant to mixed micelles.The addition of oppositely charged surfactant diminishes the surface charge density at the mixed micelle/solution interface and enhances the apparent degree of counterion dissociation from mixed micelles. Cationic surfactants have a greater tendency to be incorporated in mixed micelles than anionic ones.     

Test films for test-determinations on the base of reagents, immobilized in gelatinous gel

Gelatinous solidified layers of the photographic film were used for the immobilization of analytical reagents for detection and determination of reductants and primary aromatic amines. It was shown, that the films with immobilized iron(III)-Dipy or iron(III)-Phen complexes as test films for reductants and films with immobilized aldehydes (vanillin, p-dimethylaminobenzaldehyde) as the test films for primary aromatic amines can be used. The improving of reagents immobilization in the presence of sodium dodecylsulfate micelles was obtained. Metrological characteristics of visual detection and photometric determination using test films were evaluated on the basis of statistical approach and investigation of detection probability distribution in the concentration range of unreliable reaction. The suggested test films for the determination of ascorbic acid, analgin (dipyrone), novocaine and streptocide in drugs were examined successfully.     

Investigation on the basic hydrolysis of crystal violet in mixed reverse micelles formed with AOT and nonionic surfactants

 The kinetics and thermodynamics of the basic hydrolysis of crystal violet (CV) in mixed reverse micelles formed with anionic surfactant AOT and nonionic surfactants have been investigated. It was found that the mixed reverse micelles had inhibitory effects on CV hydrolysis compared with the normal aqueous solution, and the equilibrium constant K of the reaction in mixed reverse micellar systems is smaller than that in pure water. The influence of water content and surfactant composition in reverse micelles on the second-order rate constant k ₁ of the positive reaction, on the first-order rate constant k _-1 of the reverse reaction, as well as on the equilibrium constant K of the reaction has been studied, and the results obtained were interpreted in terms of the nature of surfactants and the properties of microenvironment where the reaction took place. Received: 24 October 1997 Accepted: 18 March 1998     

Microstructure of un-neutralized hydrophobically modified alkali-soluble emulsion latex in different surfactant solutions

At low pH conditions and in the presence of anionic, cationic, and nonionic surfactants, hydrophobically modified alkali-soluble emulsions (HASE) exhibit pronounced interaction that results in the solubilization of the latex. The interaction between HASE latex and surfactant was studied using various techniques, such as light transmittance, isothermal titration calorimetry, laser light scattering, and electrophoresis. For anionic surfactant, noncooperative hydrophobic binding dominates the interaction at concentrations lower than the critical aggregation concentration (CAC) (C < CAC). However, cooperative hydrophobic binding controls the formation of mixed micelles at high surfactant concentrations (C > or = CAC), where the cloudy solution becomes clear. For cross-linked HASE latex, anionic surfactant binds only noncooperatively to the latex and causes it to swell. For cationic surfactant, electrostatic interaction occurs at very low surfactant concentrations, resulting in phase separation. With further increase in surfactant concentration, noncooperative hydrophobic and cooperative hydrophobic interactions dominate the binding at low and high surfactant concentrations, respectively. For anionic and cationic surfactant systems, the CAC is lower than the critical micelle concentration (CMC) of surfactants in water. In addition, counterion condensation plays an important role during the binding interaction between HASE latex and ionic surfactants. In the case of nonionic surfactants, free surfactant micelles are formed in solution due to their relatively low CMC values, and HASE latexes are directly solubilized into the micellar core of nonionic surfactants.     

New anionic gemini surfactant based on EDTA accessible by convenient synthesis

A straightforward, broadly applicable synthetic strategy to anionic dimeric (“gemini”) surfactants is demonstrated, reacting ethylenediamine tetraacetic acid (EDTA) dianhydride with fatty amines. Characteristic surfactant properties in water are examined for the model compound based on N-methyldodecylamine. The new dimeric surfactant exhibits a low value for the critical micellization concentration (cmc < 10⁻⁴ mM), low surface tension at the cmc, and an enhanced solubilization capacity in comparison with a monomeric reference surfactant, sodium laurate. In particular, solutions of the gemini surfactant are remarkably stable in hard water, compared to conventional carboxylate surfactants.     

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     

Shape and Structure Formation of Mixed Nonionic–Anionic Surfactant Micelles

Aqueous solutions of a nonionic surfactant (either Tween20 or BrijL23) and an anionic surfactant (sodium dodecyl sulfate, SDS) are investigated, using small-angle neutron scattering (SANS). SANS spectra are analysed by using a core-shell model to describe the form factor of self-assembled surfactant micelles; the intermicellar interactions are modelled by using a hard-sphere Percus–Yevick (HS-PY) or a rescaled mean spherical approximation (RMSA) structure factor. Choosing these specific nonionic surfactants allows for comparison of the effect of branched (Tween20) and linear (BrijL23) surfactant headgroups, both constituted of poly-ethylene oxide (PEO) groups. The nonionic–anionic surfactant mixtures are studied at various concentrations up to highly concentrated samples (ϕ ≲ 0.45) and various mixing ratios, from pure nonionic to pure anionic surfactant solutions. The scattering data reveal the formation of mixed micelles already at concentrations below the critical micelle concentration of SDS. At higher volume fractions, excluded volume effects dominate the intermicellar structuring, even for charged micelles. In consequence, at high volume fractions, the intermicellar structuring is the same for charged and uncharged micelles. At all mixing ratios, almost spherical mixed micelles form. This offers the opportunity to create a system of colloidal particles with a variable surface charge. This excludes only roughly equimolar mixing ratios (X≈ 0.4–0.6) at which the micelles significantly increase in size and ellipticity due to specific sulfate–EO interactions.     

Interfacial and micellar properties of anionic azo dye-surfactant binary systems

The association of an anionic dye C.I. Reactive Orange 16 (RO16) and different types of surfactants, i.e., anionic surfactant sodium dodecylsulfate, nonionic surfactants poly(oxyethylene) ethers (C _m POE₁₀, m = 12, 16, and 18; C₁₂POE _n , n = 4, 10, and 23), was investigated using tensiometry in a certain micellar concentration range. RO16 was shown to aggregate in water when its concentration is above the threshold value. The surface tension lowering and critical micellar concentration (CMC) values were interpreted on the same grounds as those for surfactants mixtures. The tensiometric measurements of dye-surfactant systems are carried out as a function of the molar concentration of solution at 25°C. Using Rubingh’s regular solution theory, the values of interaction parameters were found to be negative for all studied binary mixtures. These negative values indicate that there is an attractive interaction of the surfactants in mixed micelles and reflect synergistic behavior of a mixture. In all studied systems, deviations from ideal behavior were observed depending on the type of surfactant. Interaction parameters calculated using regular solution theory are changed from −2.62 to −12.43. The smallest deviation from ideal behavior is obtained for the RO16-C₁₂POE₄ mixed system; i.e., in the case when nonionic surfactant has the shortest alkyl chain and the smallest number of ethylene oxide units. The text was submitted by the authors in English.     

Kinetics of hydrolysis of procaine in aqueous and micellar media

The kinetics of alkaline hydrolysis of procaine under the pseudo–first‐order condition ([OH^?] ? [procaine]) has been carried out. N,N‐Diethylaminoethanol and p‐aminobenzoate anion were obtained as the hydrolysis product. The rate of hydrolysis was found to be linearly dependent upon [NaOH]. The addition of cationic cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DDTAB) and tetradecyltrimethylammonium bromide, and anionic sodium dodecyl sulfate (SDS) micelles inhibited the rate of hydrolysis. The maximum inhibitive effect on the reaction rate was observed for SDS micelles, whereas among the cationic surfactants, CTAB inhibited most. The variation in the rate of hydrolysis of procaine in the micellar media is attributed to the orientation of a reactive molecule to the surfactant and the binding constant of procaine with micelles. The rate of hydrolysis of procaine is negligible in DDTAB micelles. The observed results in the presence of cationic micelles were treated on the basis of the pseudophase ion exchange model. The results obtained in the presence of anionic micelles were treated by the pseudophase model, and the various kinetic parameters were determined. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 1–9, 2013     

Flocculation of anionic surfactant micelles in the presence of hydrocarbons

Adsorptive micellar flocculation (AMF) is a surfactant-based separation process based on the flocculation of micelles of suitable anionic surfactants by Al³⁺. The micelles form large amorphous flocs which can be removed by filtration, which is attractive because soluble pollutants are captured by the floc, thus providing a simple separation method. As the primary aim of AMF is the removal of anionic pollutants from aqueous streams, it is important to investigate the influence of the various substances which may affect it. This article discusses the influence of the presence of insoluble hydrocarbons on the flocculation of micelles of the anionic surfactant dodecyl sulfate by Al³⁺. The ratio between surfactant remaining in solution and total surfactant and the ratio between Al³⁺ and surfactant in the flocculate are determined in systems composed of an aqueous solution containing a constant dodecyl sulfate concentration of 0.05 M and a variable Al³⁺ concentration and an organic phase (decane) with phase volume ratios of decane/water ranging from 0 (no decane) to 0.15. The flocculation is only slightly affected by the presence of decane for decane/solution ratios below 0.05, while the effect (lower flocculated fraction) is more marked above this ratio. Received: 25 October 1999/Accepted: 7 February 2000     

Computational Investigations of a pH-Induced Structural Transition in a CTAB Solution with Toluic Acid

In this work, molecular dynamics simulations were performed to study the pH-induced structural transitions for a CTAB/p-toluic acid solution. Spherical and cylindrical micelles were obtained for aqueous surfactants at pH 2 and 7, respectively, which agrees well with the experimental observations. The structural properties of two different micelles were analyzed through the density distributions of components and the molecular orientations of CTA⁺ and toluic acid inside the micelles. It was found that the bonding interactions between CTA⁺ and toluic in spherical and cylindrical micelles are very different. Almost all the ionized toluic acid (PTA⁻) in the solution at pH 7 was solubilized into the micelles, and it was located in the CTA⁺ headgroups region. Additionally, the bonding between surfactant CTA⁺ and PTA⁻ was very tight due to the electrostatic interactions. The PTA⁻ that penetrated into the micelles effectively screened the electrostatic repulsion among the cationic headgroups, which is considered to be crucial for maintaining the cylindrical micellar shape. As the pH decreased, the carboxyl groups were protonated. The hydration ability of neutral carboxyl groups weakened, resulting in deeper penetration into the micelles. Meanwhile, their bonding interactions with surfactant headgroups also weakened. Accompanied by the strengthen of electrostatic repulsion among the positive headgroups, the cylindrical micelle was broken into spherical micelles. Our work provided an atomic-level insights into the mechanism of pH-induced structural transitions of a CTAB/p-toluic solution, which is expected to be useful for further understanding the aggregate behavior of mixed cationic surfactants and aromatic acids.     

A theoretical analysis of micelle-mediated transport through porous membranes

A novel method is proposed for the purpose of controlled release of a sparingly water soluble compound. The solubility of a sparingly water soluble compound can be increased by addition of a sufficient amount of surfactant to form micelles. The flux of the compound across a porous membrane can be enhanced if the membrane has pores larger than the micelle size so that the compound-loaded micelles can diffuse simultaneously, and micelle-mediated transport occurs. The membrane permeability of the micelle is a monotonically decreasing function of the ratio of the size of the micelle to the membrane pore size (R_m/R_p). However, the solubilizing capacity of the micelle increases with increasing size of the micelle. These opposing effects influence the transport and may result in an optimum flux of the solubilizate at a particular size of the micelle. In the determination of the optimum surfactant molecule, the concept of the hydrophilic-lipophilic balance (HLB) is employed in order to have stable aqueous solutions of the surfactants. For a family of nonionic surfactants solubilizing the hydrophobic and hydrocarbon substance n-heptane, it is shown that there exists a maximum flux of the solubilizate at a value of R_m/R_p within the limitation of the HLB. The release rates over a long period of time are nearly constant for micelles close to the optimum size for a given pore size.     

Biosensing of Aromatic Amines in Reversed Micelles with Self‐Generation of Hydrogen Peroxide at Glucose Oxidase‐Peroxidase Bienzyme Electrodes

The amperometric biosensing of aromatic amines using a composite glucose oxidase (GOD)‐peroxidase (HRP) biosensor in reversed micelles is reported. Rigid composite pellets of graphite and Teflon, in which GOD and HRP were coimmobilized by simple physical inclusion, were employed for the biosensor design. This design allows the in situ generation of the H₂O₂ needed for the enzyme reaction with the aromatic amines, thus preventing the negative effect that the presence of a high H₂O₂ concentration in solution has on HRP activity. The H₂O₂ in situ generation is performed by oxidation of glucose catalyzed by GOD. The effect of the composition of the reversed micelles, i.e., the nature of the organic solvent used as the continuous phase, the nature and concentration of the surfactant used as emulsifying agent, the aqueous 0.05 mol L^?1 phosphate buffer percentage used as the dispersed phase, and the glucose concentration in the aqueous phase, on the biosensor response was evaluated. Reversed micelles formed with ethyl acetate, a 5% of phosphate buffer (pH 7.0) containing 3.0×10^?3 mol L^?1 glucose, and 0.1 mol L^?1 AOT (sodium dioctylsulfosuccinate), were selected as working medium. Well‐defined and reproducible amperometric signals at 0.00 V were obtained for p‐phenylenediamine, 2‐aminophenol, o‐phenylenediamine, m‐phenylenediamine, 1‐naphthylamine, o‐toluidine and aniline. The useful lifetime of one single biosensor was of 60 days. The trend in sensitivity observed for the aromatic amines is discussed considering the effect of their structure on the stabilization of the radicals formed in the enzyme reaction which are electrochemically reduced. The behavior of the composite bienzyme electrode was also evaluated in a FI (flow injection) system using reversed micelles as the carrier. The suitability of the composite bienzyme electrode for the analysis of real samples was demonstrated by determining aniline in spiked carrots.     

Iron salts catalyzed synthesis of β-N-substituted aminoacrylates

The direct condensation of amines with β-ketoesters to produce functional enamine derivatives has been investigated with iron Lewis acid catalysts. FeCl₃·6H₂O shows good catalytic activity and makes possible the chemo- and stereoselective formations of (Z)-enamine derivatives from aliphatic and aromatic primary amines under mild conditions.     

A “one-pot” synthesis of α-(p-toluenesulfonyl)-aminobenzylphosphinodipeptide derivatives containing a P?N bond

With acetyl chloride as the solvent, the condensation reaction of p-toluenesulfonamide, an aromatic aldehyde and phenyldichlorophosphine given a reactive intermediate, α-(p-toluenesulfonyl)-aminobenzylphosphinic chloride, which reacts with glycine ethyl ester to give the corresponding phosphinopeptide (6) containing a P? N bond directly.     

ZINC TETRAPHENYLPORPHYRIN-SENSITIZED PHOTOREDUCTION OF ANTHRAQUINONESULFONATE IN AQUEOUS MICELLAR SOLUTIONS*

Abstract— Zn-tetraphenylporphyrin (ZnTPP), solubilized in non-ionic surfactant micelles, was found to sensitize photoreductions of some sodium anthraquinonesulfonatesz in the presence of ascorbic acid under anaerobic conditions. The reaction rate was increased by the addition of an anionic surfactant, while retardation was observed with a cationic surfactant. The pH-reaction rate profiles showed maxima located in the order corresponding to pK_a-values for the semiquinone of each anthraquinone-sulfonate. A reaction scheme involving the formation of ZnTPP⁺ at the primary step, followed by back-reduction with ascorbic acid, is proposed. The reaction scheme is in good agreement with the results of flash photolysis. The surfactant micelles are suggested to aid the charge-separation between the ionic species just after the redox reaction involving the photoexcited ZnTPP and anthraquinonesulfonates.     

Study on Binding Properties of Poorly Soluble Drug Trimethoprim in Anionic Micellar Solutions

Binding and distribution properties of trimethoprim (TMP) in the presence of various anionic surfactants; sodium octyl sulfate (C₈SO₄Na), sodium decyl sulfate (C₁₀SO₄Na), sodium lauryl sulfate (C₁₂SO₄Na), and sodium tetradecyl sulfate (C₁₄SO₄Na) has been studied by conductivity, spectrophotometry and surface tension measurements. The surface properties of anionic surfactants, that is, maximum surface excess concentration (Γ _max ) and minimum area per surfactant molecule (A _min ) at the air/water interface have been evaluated in the absence and presence of TMP using Gibbs adsorption isotherm. From conductivity data the ionization degree and counterion binding parameter have been obtained. Spectrophotometric experiments were used to determine binding constants of TMP to anionic micelles. With the increasing alkyl chain of surfactants, the interaction becomes stronger, which shows the importance of hydrophobic forces and incorporation of TMP molecules to the pure micelles of anionic surfactants increased. The results obtained from the surface tension and conductometric studies have been correlated with those obtained from the spectroscopic studies and binding tendency of TMP to anionic micelles followed the order as: C₁₄SO₄Na > C₁₂SO₄Na > C₁₀SO₄Na > C₈SO₄Na. From these results, the study of the interaction TMP in different anionic micellar solutions provided information about the characteristics of binding properties of poorly soluble drugs.     

Rheological properties of the aqueous solution for fluorocarbon‐containing hydrophobically modified sodium polyacrylic acid with various surfactants

The interaction of fluorocarbon‐ containing hydrophobically modified sodium polyacrylic acid (FMPAANa) (0.5 wt%) with various surfactants (anionic, nonionic and cationic) has been investigated by rheological measurements. Different rheological behaviors are displayed for ionic surfactants and nonionic surfactants. Fluorinated surfactants have stronger affinity with polyelectrolyte hydrophobes comparing with hydrogenated surfactants. The hydrophobic association of FMPAANa with a cationic surfactant (CTAB) and a fluorinated nonionic surfactant (FC171) is much stronger than with a nonionic surfactant (NP7. 5) and an anionic surfactant (FC143). Further investigation of the effects of temperature on solution properties shows that the dissociation energy E_m is correlated to the strength of the aggregated junctions.