Comparative studies on reaction of bis(p‐nitrophenyl) phosphate and α‐nucleophiles in cationic micellar media

We studied the cleave of bis(p‐nitrophenyl) phosphate (BNPP) over a pH range of 7.0–12.0 in the presence of cationic micelles of cetyldiethylethanolammonium bromide, cetyldimethylethanolammonium bromide, cetylpyridinium bromide, cetyltrimethylammonium bromide, and cetylpyridinium chloride by using different α‐nucleophiles, viz acetohydroxamate, benzohydroxamate, salicylhydroxamate, butane‐2,3‐dione monooximate, and α‐benzoin oximate ions. With the use of α‐nucleophiles in cationic micellar media, the hydrolytic cleavage of BNPP was found to be approximately 10⁵‐fold faster than its spontaneous hydrolysis. All reactions followed pseudo‐first‐order kinetics. The effect of various concentrations of cationic micelles for the reaction of BNPP and α‐nucleophiles has been studied. The variation of k_obs values of the reactions depends on the micellar structure, that is, head groups, hydrophobic tail length, and counter ion. Copyright © 2012 John Wiley & Sons, Ltd.     

Role of cationic gemini surfactants toward enhanced ninhydrin–tryptophan reaction

In this paper we report the effect of dicationic ‘gemini’ surfactants (CH₃)₂C₁₆H₃₃N⁺? (CH₂)_m? N⁺C₁₆H₃₃(CH₃)₂, 2Br^? (where m = 4, 5, 6) on the reaction of ninhydrin with DL ‐tryptophan. The gemini surfactant micellar media are comparatively more effective than their conventional monomeric counterpart cetyltrimethylammonium bromide (CTAB) micelles. Also, whereas typical rate constant (k_ψ) increase and leveling‐off regions, just like CTAB, are observed with geminis, the latter produce a third region of increasing k_ψ at higher concentrations. These subsequent increases are ascribed to changes in micellar morphologies, consistent with changes in ¹H NMR line widths. Quantitative kinetic analysis of the rate constant–[surfactant] data has been performed on the basis of modified pseudophase model. Copyright © 2007 John Wiley & Sons, Ltd.     

Small-angle neutron scattering studies of nonionic surfactant: Effect of sugars

Micellar solution of nonionic surfactantn-dodecyloligo ethyleneoxide surfactant, decaoxyethylene monododecyl ether [CH₃(CH₂)₁₁(OCH₂CH₂)₁₀OH], C₁₂E₁₀ in D₂O solution have been analysed by small-angle neutron scattering (SANS) at different temperatures (30, 45 and 60° C) both in the presence and absence of sugars. The structural parameters like micelle shape and size, aggregation number and micellar density have been determined. It is found that the micellar structure significantly depends on the temperature and concentration of sugars. The micelles are found to be prolate ellipsoids at 30° C and the axial ratio of the micelle increases with the increase in temperature. The presence of lower concentration of sugar reduces the size of micelles and it grows at higher concentration of sugar. The structure of micelles is almost independent of the different types of sugars used.     

Structural investigation of viscoelastic micellar water/CTAB/NaNO<Subscript>3</Subscript> solutions

A highly viscoelastic worm-like micellar solution is formed in hexadecyltrimethylammonium bromide (CTAB) in the presence of sodium nitrate (NaNO₃). A gradual increase in micellar length with increasing NaNO₃ was assumed from the rheological measurements where the zero-shear viscosity (η ₀) versus NaNO₃ concentration curve exhibits a maximum. However, upon increase in temperature, the viscosity decreases. Changes in the structural parameters of the micelles with addition of NaNO₃ were inferred from small angle neutron scattering measurements (SANS). The intensity of scattered neutrons in the low q region was found to increase with increasing NaNO₃ concentration. This suggests an increase in the size of the micelles and/or decrease of intermicellar interaction with increasing salt concentration. Analysis of the SANS data using prolate ellipsoidal structure and Yukawa form of interaction potential between micelles indicate that addition of NaNO₃ leads to a decrease in the surface charge of the ellipsoidal micelles which induces micellar growth. Cryo-TEM measurements support the presence of thread-like micelles in CTAB and NaNO₃.      

Mixed micellization study of ibuprofen (sodium salt) and cationic surfactant (conventional as well as gemini)

Herein, we have studied the interaction between cationic surfactant (conventional [myristyltrimethylammonium bromide, MTAB] as well as gemini surfactant 1, 4‐butanediyl‐α, ω‐bis(dimethyltetradecylammonium bromide) (14‐4‐14)) and anti‐inflammatory sodium salt of ibuprofen (IBU) drug in aqueous solutions by using tensiometry method at 298.15 K. The means of the interaction of drugs by added foreign materials is of paramount importance in the drug delivery. Ibuprofen is used for the relief of pain, fever, and swelling. From this study we have evaluated different parameters, for example, critical micelle concentration (cmc), micellar mole fraction of mixed micelles/mixed interface (X₁^m/X₁^σ), micellar/surface interaction parameter (β^m/β^σ), activity coefficients (f₁^m/f₁^σ and f₂^m/f₂^σ) of the mixed micelles/mixed interface, excess Gibbs free energy of mixed monolayer/mixed micelle formation ( $\mathrm{\Delta }{G}_{\mathrm{ex}}^{\mathrm{\sigma }}$/ $\mathrm{\Delta }{G}_{\mathrm{ex}}^{\mathrm{m}}$), surface excess concentration (Γ_max) etc. and discussed in detail. The micellar interaction parameter (β^m) was determined from the critical micelle concentration values of the pure surfactant (MTAB/14‐4‐14) and IBU (cmc₁ and cmc₂) and the mixed system (cmc) using the Rubingh's model. In addition to this, various other parameters such as packing parameters of amphiphiles in the micelles (P), volume contribution of the hydrophobic chain (V₀), and its effective length (l_c), have also been calculated. The value of micellar mole fraction ( $X_1^{\mathrm{m}}$) is found to be more for IBU + 14‐4‐14 mixtures as compared to IBU + MTAB mixtures at lower mole fraction and vice versa at a higher mole fraction of surfactant. The ΔG^o_m and ΔG^o_ads values for all studied systems were found out to be negative, ie, micellization, as well as adsorption processes, are found to be energetically favorable.     

Spherical polyelectrolyte block copolymer micelles: Structural change in presence of monovalent salt

Spherical polyelectrolyte block copolymer micelles were investigated as a function of added NaCl salt concentration using Small-Angle Neutron Scattering (SANS) and Light Scattering (LS). The micelles are formed by the self-association of charged-neutral copolymers made of a long deuterated polyelectrolyte moiety (NaPSS_d)₂₅₁ and a short hydrophobic moiety (PEP)₅₂. In presence of salt, the core shape and the aggregation number of the micelles are not affected. The hydrodynamic radius of the micelle is found to be identical to the radius of the whole micelle deduced from neutron scattering and thus the hydrodynamic radius is a valid measure of the corona thickness. At the lowest salt concentrations investigated the thickness of the corona, R_s, remains essentially constant and a contraction is observed above an added-salt concentration c_s of 2×10^-2 M where this crossover concentration corresponds to the average ionic strength of the free counterions in the corona. The contraction takes place while maintaining a rod-like behavior of the chains at short scale and obeys to: R_s c_s^-0.18. The exponent 0.18 suggests an electrostatic persistence length proportional to the Debye screening length.     

Counterion condensation in ionic micelles as studied by a combined use of SANS and SAXS

We report a combined use of small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) to the study of counterion condensation in ionic micelles. Small-angle neutron and X-ray scattering measurements have been carried out on two surfactants cetyltrimethylammonium bromide (CTABr) and cetyltrimethylammonium chloride (CTACl), which are similar but having different counterions. SANS measurements show that CTABr surfactant forms much larger micelles than CTACl. This is explained in terms of higher condensation of Br⁻ counterions than Cl⁻ counterions. SAXS data on these systems suggest that the Br⁻ counterions are condensed around the micelles over smaller thickness than those of Cl⁻ counterions.     

Aggregation Behavior of Monomeric Surfactants and a Gemini Cationic Surfactant by NMR and Computer Simulation Data

Aggregation of decyltrimethylammonium bromide and cetyltrimethylammonium bromide (CTAB) in D₂O has been studied. Spin–lattice relaxation time and self-diffusion coefficient of surfactant molecules were measured at concentrations below and above surfactant critical micelle concentration. The aggregation properties of conventional surfactant, CTAB, examined by nuclear magnetic resonance (NMR) and molecular dynamic (MD) simulation, were compared with the properties of double-tail analog, N,N,N′,N′-tetramethyl-N,N′dihexadecyl-1,4-butan di-ammonium di-bromide (BCTA). Both NMR and computer simulation methods suggest that micellization is a stepwise process and the pre-micellar aggregates take place in a solution at concentration below critical micelle concentration. According to MD simulation Gemini surfactant, BCTA, forms worm-like micelles, whereas CTAB, which may be considered as its “monomer”, forms only elongated micelles.     

Temperature and concentration effects on decyltrimethylammonium micelles in water

Wide-angle neutron scattering experiments combined with Empirical Potential Structural Refinement modelling have been used to study the detailed structure of decyltrimethylammonium bromide (C₁₀TAB) micelles at two different temperatures; 25°C and 50°C and two concentrations; 0.4 and 0.8?M in water. At higher temperature, the micelles become smaller, and fewer counterions bind to the micelle surfaces, however, the headgroup positions are more ordered, possibly due to crowding in the smaller micelles. At higher concentration, the models suggest the micelles become elongated, although the aggregations numbers are smaller than those at the lower concentration. The smaller micelles found in 0.8?M solutions have more hydrated headgroups and lower counterion binding than the ellipsoidal micelles found in 0.4?M C₁₀TAB solutions.     

Conductometric and fluorometric studies of sodium dodecyl sulphate in aqueous solution and in the presence of amino acids

The critical micelle concentration (CMC) of sodium dodecyl sulphate (SDS) in pure water and in the presence of amino acids (0.01, 0.02 and 0.03 mol kg^?1), L-valine (Val) and L-leucine (Leu) was determined from conductometric and fluorometric methods using pyrene as luminescence probe. Depression in the CMC at low concentration of amino acids is attributed to the increased hydrophobic–hydrophobic interaction between the non-polar groups of the surfactant, while, at high concentration, amino acids bind strongly with the anion, DS^?, head groups of SDS, thereby, delaying the micelle formation, resulting in increased CMC. A pronounced decrease in the CMC, while a marked increase in λ⁰₊, with decrease in the solvated radius (rather than crystal radius) of the counterions is observed. Negative values of ΔG⁰_m and ΔH⁰_m indicate that micellisation of SDS in the presence of amino acids is thermodynamically spontaneous and exothermic. Highest negative value of ΔH⁰_m in 0.01 m Val, with lowest CMC value, shows that 0.01 m aqueous Val is the most suitable medium favouring the micellisation of SDS. Decrease in I₁/I₃ from Val to Leu confirms the relative hydrophobicity of two amino acids. The observed values of the packing parameter, P, of SDS in water and in aqueous amino acids suggest that micelles formed are spherical in nature.     

Role of gemini surfactants (m‐s‐m type; m = 16, s = 4–6) on the reaction of [Zn(II)‐Gly‐Phe]+ with ninhydrin

In the present paper, reaction of zinc‐glycylphenylalanine ([Zn(II)‐Gly‐Phe]⁺) with ninhydrin has been investigated in gemini (m‐s‐m type; m = 16, s = 4–6) surfactants at temperature (70 °C) and pH (5.0). Monitoring the appearance of product at 400 nm was used to follow the kinetics, spectrophotometrically. The order of the reaction with respect to [Zn(II)‐Gly‐Phe]⁺ was unity while with respect to [ninhydrin] was fractional. The reaction constants involved in the mechanism were obtained. In addition to the rate constant (k_Ψ) increase and leveling‐off regions are observed with the geminis, just like as seen with conventional surfactant hexadecyltrimethylammonium bromide (CTAB), the former produced a third region of increasing k_Ψ at higher concentrations. A close agreement between observed and calculated rate constants was found under varying experimental conditions. A suitable mechanism consistent with the experimental findings has been proposed. Copyright © 2014 John Wiley & Sons, Ltd.     

Self-Diffusion of Ionic Surfactants and Counterions in Premicellar and Micellar Solutions of Sodium,Lithium and Cesium Dodecyl Sulfates as Studied by NMR-Diffusometry

Self-diffusion of surfactants and counterions in premicellar and micellar solutions of sodium, lithium and cesium dodecyl sulfates has been examined by nuclear magnetic resonance (NMR)-diffusometry. Self-diffusion of surfactants obeys as a whole the well-known two-site exchange model in which surfactants diffuse as micelles and non-micellized molecules in monomer and dimer forms. To explain self-diffusion of counterions, the model which takes into account their diffusive motion about the surface of micelles is proposed. It is shown that this phenomenon contributes considerably to charge transfer in micellar solutions. Estimation of surface diffusion of counterions about the micellar surface is made on the basis of experimental results on self-diffusion of surfactants and counterions, the data obtained on critical micelle concentration and the degree of counterion binding.     

Role of the head group on the mixed micellization process in binary systems containing a sugar-based surfactant: decanoyl- N -methylglucamide

The mixed micelles of nonionic decanoyl-N-methylglucamide (MEGA-10) with the anionic sodium dodecyl sulphate (SDS), the cationic dodecyltrimetylammonium bromide (DTAB), and the nonionic octaoxyethylene monododecyl ether (C₁₂E₈) have been studied using the fluorescence probe technique. The critical micelle concentration of the three mixed systems in the whole composition range were determined by the pyrene 1:3 ratio method, and the experimental results were analysed in the context of the pseudophase separation model, by using the regular solution theory. It was found that the mixed micelles containing the anionic surfactant are more stable than the pure micelles. This fact was attributed to the occurrence of ion–dipole interactions between the head groups of the component surfactants in the mixed micelle. The static quenching method was used to determine the mean aggregation number of pure and mixed micelles. It was found that whereas mixed micelles containing SDS show a positive deviation from the ideal behaviour, those constituted by DTAB deviate negatively. This different tendency was interpreted on the basis of both steric and electrostatic interactions. The evolution of the microstructure of the mixed micelles upon the participation of the co-surfactant was followed through the micropolarity and microviscosity of the mixed systems. Although the micropolarity studies do not allow definite conclusions, the microviscosity assays indicate that the participation of the co-surfactant induces the formation of less ordered micelles, this effect being more pronounced in the case of mixtures with the anionic surfactant.     

An isothermal titration calorimetry study of the interactions between an oxyphenylethylene/oxyethylene diblock copolymer and sodium dodecyl sulfate

Interactions between the diblock copolymer S₁₅E₆₃ and the surfactant sodium dodecyl sulfate (SDS) have been investigated by isothermal titration calorimetry (ITC) in the temperature range 10–40°C. At 20°C, the block copolymer is associated into micelles with a hydrodynamic radius of 11.6?nm, which is composed of a hydrophobic styrene oxide (S) core and a water-swollen oxypolyethylene (PEO) corona. The copolymer/surfactant system has been studied at a constant copolymer concentration of 0.25?wt% and over a wide range of surfactant concentration, from 7.5?×?10^?6 up to 0.3?M. The titration calorimetric data for SDS in the temperature range 10–20°C presents a first endothermic increase indicating the formation of mixed copolymer rich-surfactant micelles. From that point, important differences in the ITC plots for surfactant titrations in the presence and in the absence of the copolymer are present. A shallow second endothermic peak is assigned to the interaction between SDS molecules and copolymer molecules resulting from the beginning of micelle disruption. An exothermic peak indicates the end of this disruption where only SDS micelles attached to single copolymer monomers are present, as shown by DLS in a previous paper. At higher temperatures in the range 25–40°C, the first endothermic maximum is not totally shown because interactions between surfactant and block copolymer start at very low SDS concentrations. Moreover, the second endothermic peak is absent and the exothermic minimum is less pronounced as a consequence of the increased micellization of the block copolymer.     

Aggregation and microenvironmental properties of gemini and conventional mixed surfactants systems: A fluorometric study

Aggregation behavior of cationic gemini (hexanediyl-1,5-bis(dimethylcettylammonium bromide) (16-5-16)) surfactant with conventional single chain surfactants cetyltrimethylammonium bromide (CTAB) and tetradecyltrimethylammonium bromide (TTAB) were studied with the help of fluorescence measurements. Fluorescence probe is a proficient technique for examining the surfactant-surfactant interaction and aggregation. The micelle aggregation number (N _agg) was measured using steady-state fluorescence quenching method. The micelle aggregation numbers of binary combinations fall between those of constituent surfactants. The micropolarity (I ₁/I ₃), binding constant (K _sv) and dielectric constant (D _exp) of mixed systems were determined from the ratio of peaks intensity in the pyrene fluorescence spectrum. The I ₁/I ₃ values were found to be more than >1, showing more polar environment around pyrene in the mixed micelle as compared to the pure micelles.     

Effect of hydrophobicity of cationic carbocyanine dyes DiOC<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> on their binding to anionic surfactant micelles

The interaction of a series of cationic dialkyloxacarbocyanine perchlorate (DiOC _n ) dyes of different degrees of hydrophobicity with micelles of an anionic surfactant, sodium dodecylsulfate (SDS), has been studied spectrophotometrically in aqueous solutions. The Benesi–Hildebrand equation was used to calculate binding constants (K _b ) of the dyes to surfactant micelles, the fraction of dye bound to the micelles (f _mic ), and the standard free-energy change (ΔG ⁰) for the transfer of dye from the aqueous to micellar phase. It has been shown that the interaction of oppositely charged dye molecules and surfactant micelles is controlled by both electrostatic and hydrophobic interactions. A small increase in dye hydrophobicity due to lengthening of the hydrocarbon radical has been shown to cause an abrupt nonlinear increase of the fmic value. This points to a key role of hydrophobic interactions in the binding of dye molecules with the micelles.     

Premicellar and micelle formation behavior of aqueous anionic surfactants in the presence of triphenylmethane dyes: protonation of dye in ion pair micelles

The premicellar and micelle formation behaviors of four cationic triphenylmethane dyes, viz, Pararosaniline (RN), Crystal violet (CV), Ethyl violet (EV), and Malachite green (MG), in aqueous anionic surfactant solutions of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dodecyl sulfonate (SDSN) have been studied by spectral and surface tension measurements. The study was carried out within a pH range where the dyes are stable in their quinoid forms. The dyes have been found to form dye–surfactant ion pairs (DSIPs) with the surfactants, at the surfactant concentrations well below their critical micelle concentration, CMC*. The DSIPs behave like nonionic surfactants and form an air–water interfacial monolayer. The DSIPs have a lower critical micelle concentration (CMC_IP), greater efficiency, and lower effectiveness than the corresponding pure surfactants. As the surfactant concentration is increased below the CMC*, the DSIPs start forming micelles of their own where the dye gets protonated and exists as a protonated dye–surfactant ion pair (PDSIP) in the ion pair micelles. As the concentration of the surfactant exceeds the CMC* of the pure surfactant, the protonation reverses gradually with the dye remaining in the micelles in solubilized form and the DSIPs in the air–water interfacial monolayer are replaced by pure surfactants. The distorted helical isomeric form (isomer B) of the dyes is favored in the PDSIPs. Copyright © 2009 John Wiley & Sons, Ltd.     

Non-ideal behavior of mixed micelles of cationic gemini surfactants with varying spacer length and anionic surfactants: A conductimetric study

Mixtures of cationic and anionic surfactants (catanionic mixtures) are often highly non-ideal, exhibiting strong synergism in their interfacial properties, manifested for instance in significant reduction of the mixture critical micelle concentration (cmc) and enhanced adsorption onto surfaces. The magnitude of such effects is of fundamental interest and has important application-related uses (e.g. in detergent formulation). In this work, the micellization process of mixtures of cationic gemini surfactants of the alkanediyl-α,ω-bis(alkyl dimethylammonium bromide) type, denoted by 12–n–12 (where n is the spacer length), with several common anionic surfactants has been investigated by electric conductivity. For the purpose of comparison, cationic–cationic mixtures, where dodecyltrimethylammonium bromide is the second cationic surfactant, have also been investigated. The cationic/anionic mixtures show relatively significant deviations from ideal behavior, depending on the structure of the gemini surfactant and the anionic surfactant. The interaction parameter β₁₂, within Rubingh's non-ideal model for mixed micelles, has been calculated for each mixture, as well as the mixed micelle composition as a function of mixture composition. The observed synergism in the different mixtures is interpreted in terms of the molecular structure of the surfactants and corresponding head–head and chain–chain interactions.     

Behavior of Sodium Lauroyl Sarcosinate in Solution and Binary Mixtures by Means NMR

Measurements of the ¹H and ¹³C chemical shifts as well as ¹H spin–lattice relaxation times of sodium lauroyl sarcosinate (SLAS) in aqueous solutions and mixed binary systems with co-surfactants were carried out at various concentrations. It will be shown that changes in the chemical shifts for the N–CH₂ groups in SLAS with increasing surfactant concentration can be used to estimate the ratio p _cis /p _trans of cis- and trans-isomers. The relative fraction p _trans of molecules in trans-configurations increases the most in a narrow concentration range 0.007–0.034 mol/l, i.e., at the transition from the monomeric state to the micelle. The ratio p _cis /p _trans asymptotically decreases with increasing concentration, reaching a constant value at concentrations significantly above the critical micelle concentration. Thus, the ratio can be related to the process of micellization. If micellization takes place, the cis-isomer starts to transform into trans-isomer because the trans-isomer is more favorable in micelles. Because of the smaller cross section of the polar group region, the trans-conformation can be more easily incorporated into the micelle. In summary, the occurrence of micellar aggregates at low SLAS concentration in mixed systems can be clearly inferred from the nuclear magnetic resonance spectra.     

Rapid and controlled transformation of nitrate in water and brine by stabilized iron nanoparticles

Highly reactive zero-valent iron (ZVI) nanoparticles stabilized with carboxymethyl cellulose (CMC) were tested for reduction of nitrate in fresh water and brine. Batch kinetic tests showed that the pseudo first-order rate constant (k _obs) with the stabilized nanoparticles was five times greater than that for non-stabilized counterparts. The stabilizer not only increased the specific surface area of the nanoparticles, but also increased the reactive particle surface. The allocation between the two reduction products, NH₄ ⁺ and N₂, can be manipulated by varying the ZVI-to-nitrate molar ratio and/or applying a Cu–Pd bimetallic catalyst. Greater CMC-to-ZVI ratios lead to faster nitrate reduction. Application of a 0.05 M HEPES buffer increased the k _obs value by 15 times compared to that without pH control. Although the presence of 6% NaCl decreased k _obs by 30%, 100% nitrate was transformed within 2 h in the saline water. The technology provides a powerful alternative for treating water with concentrated nitrate such as ion exchange brine.