Presence Of Micellar Aggregates Research Articles

Thermodynamics of Mixing of TEHDGA with Isodecanol in Dodecane: Effect of Equilibration with Aqueous Nitric Acid

The use of any new extractant requires the study of its tendency to form third phases. To understand the phase separation process it is important to have knowledge of the molecular scale phenomena present in the system. This includes the mixing of the substances and the behavior and nature of the aggregates. Here we report the mixing properties of N,N,N′,N′-tetra-(2-ethyl hexyl) diglycolamide (TEHDGA)–dodecane–isodecanol (in the absence and presence of micellar aggregates) which is recognized as a promising system for the separation of minor actinides through the conventional solvent extraction route. The nature of interactions between TEHDGA and isodecanol was investigated using several techniques, including density and speed of sound measurements, ultraviolet absorption spectroscopy and computational studies. The TEHDGA–isodecanol interaction was found to be favored over the inter-isodecanol interaction. On equilibrating the organic phase with nitric acid, some indication of pre-micellar aggregation was obtained. Increase of micellar aggregate size on addition of isodecanol was indicated.

Determining Critical Micelle Concentrations of Surfactants Based on Viscosity Calculations from Coarse-Grained Molecular Dynamics Simulations

Alternative methods for determining the critical micelle concentration (CMC) are proposed using coarse-grained molecular dynamics (MD) simulations. In the literature, the CMC value is commonly taken to be the “free” (unassociated) surfactant concentration in the presence of micellar aggregates given by MD simulations. In the present study, two surfactants with different head groups and the same alkyl tail, n-octyltrimethylammonium bromide (C8TAB) and sodium octyl sulfate (S8S), were used to calculate the CMC value. The CMC of surfactants can be calculated from the variation in the zero-shear-rate viscosity as a function of the surfactant concentration in both the premicellar and micellar regions. Linear slopes were obtained in both regions with increasing surfactant concentrations. The CMC values for C8TAB and S8S were determined from the intersection of the two lines and are in good agreement with experimental values.

Determination of the critical micelle concentration in simulations of surfactant systems.

Alternative methods for determining the critical micelle concentration (cmc) are investigated using canonical and grand canonical Monte Carlo simulations of a lattice surfactant model. A common measure of the cmc is the "free" (unassociated) surfactant concentration in the presence of micellar aggregates. Many prior simulations of micellizing systems have observed a decrease in the free surfactant concentration with overall surfactant loading for both ionic and nonionic surfactants, contrary to theoretical expectations from mass-action models of aggregation. In the present study, we investigate a simple lattice nonionic surfactant model in implicit solvent, for which highly reproducible simulations are possible in both the canonical (NVT) and grand canonical (μVT) ensembles. We confirm the previously observed decrease of free surfactant concentration at higher overall loadings and propose an algorithm for the precise calculation of the excluded volume and effective concentration of unassociated surfactant molecules in the accessible volume of the solution. We find that the cmc can be obtained by correcting the free surfactant concentration for volume exclusion effects resulting from the presence of micellar aggregates. We also develop an improved method for determination of the cmc based on the maximum in curvature for the osmotic pressure curve determined from μVT simulations. Excellent agreement in cmc and other micellar properties between NVT and μVT simulations of different system sizes is observed. The methodological developments in this work are broadly applicable to simulations of aggregating systems using any type of surfactant model (atomistic/coarse grained) or solvent description (explicit/implicit).

Amphiphilic azopolymers capable to generate photo-sensitive micelles

AbstractAmphiphilic macromolecular micelles are advantageous for drug delivery applications due to the decrease of side-effects, ease of screening drugs against degradation, long-term stability, targeted delivery and control of the amount of the released drug. A series of amphiphilic azo-polymers having a flexible or rigid main-chain were synthesized and characterized. The presence of chlorobenzyl side-groups allowed both the easy bonding of photo-sensitive or hydrophilic groups and good control of the degree of substitution. The chemical structure was confirmed by 1H-NMR. The critical concentration of aggregation (CCA) was calculated using the fluorescence emission spectrum of pyrene. The interest was focused on a preliminary study concerning the disaggregation capacity of micelles under UV irradiation. The presence of micellar aggregates was confirmed by DLS and SEM and different organization of the amphiphilic polymers was evidenced depending on polymers concentration and polymers structure. In low polymer concentrations in water predominantly globular aggregates were formed. The increase in concentration increased the polydispersity index due to the fusion of micelles and formation of associates of globular aggregates, inter-micellar associates (clusters) and vesicles.

An Efficient and Mild Procedure for the Preparation of Aldonic Acids via Oxidation of D-Sucrose by Employing N-Bromophthalimide Oxidant and Micellar System

Abstract The oxidation reactions of D-sucrose have been carried out with N-bromophthalimide in the presence of micellar aggregates at 45°C. The kinetics revealed first order dependence on N-bromophthalimide (NBP) and fractional order dependence on D-sucrose. Variation of mercuric acetate concentration has an insignificant effect on reaction rate. The stoichiometric ratio of NBP:D-sucrose was 1:2 and the oxidation product was aldonic acid confirmed by FeCl3–HCl test. The influence of salts on the reaction rate has also been studied. Phthalimide (NHP) and sulfuric acid (H2SO4) inhibit the rate. Thermodynamic and activation parameters have been evaluated and a mechanism consistent with the kinetic data has been proposed. Cetyltrimethylammonium bromide (CTAB) and TritonX-100 (TX-100) catalyze the reaction, while sodium dodecyl sulfate (SDS) inhibits the rate of reaction. The applicability of Berezin's model was tested to explain the observed micellar effects. The rate constants (kM) and binding constants (KS + KO) have been evaluated.

Unique role of hydrophilic ionic liquid in modifying properties of aqueous Triton X-100

Modification of important physicochemical properties of aqueous surfactant solutions can be achieved by addition of environmentally benign room temperature ionic liquids (ILs). While low aqueous solubility of "hydrophobic" ILs limits the amount of IL that may be added to achieve desired changes in the physicochemical properties, hydrophilic ILs do not have such restrictions associated to them. Alterations in the key physicochemical properties of aqueous solutions of a common nonionic surfactant Triton X-100 (TX100) on addition of up to 30 wt % hydrophilic IL 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) are reported. The presence of micellar aggregates in as high as 30 wt % [bmim][BF4]-added aqueous TX100 solutions is established by dynamic light scattering and fluorescence probe behavior. Increasing the concentration of [bmim][BF4] results in decrease in average micellar size and aggregation number and increase in critical micelle concentration, indicating an overall unfavorable aggregation process. Increase in the dipolarity and the microfluidity of the probe cybotactic region within the palisade layer of the micellar phase upon [bmim][BF4] addition implies increased water penetration and the possibility of TX100-[bmim][BF4] interactions. While the changes in some of the physicochemical properties indicate the role of [bmim][BF4] to be similar to a cosurfactant, the IL acts like a cosolvent as far as changes in other properties are concerned. Effectiveness of IL [bmim][BF4] in modifying physicochemical properties of aqueous TX100 is demonstrated.

In Search of Fully Uncomplexed Cyclodextrin in the Presence of Micellar Aggregates

The chemical behavior of beta-cyclodextrin/nonionic surfactant mixed systems has been investigated using the basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide as a chemical probe. The experimental results prove that at the cmc, there are significant quantities of uncomplexed beta-CD in equilibrium with the micellar aggregates. In contrast to the expected situation, the percentage of uncomplexed beta-CD in equilibrium with the micellar system increases on increasing the hydrophobicity of the surfactant molecule. This behavior is due to the existence of two simultaneous processes: complexation of surfactant monomers by cyclodextrin and the process of self-assembly to form micellar aggregates. The autoaggregation of surfactant monomers is expected to be more important than the complexation process in this mixed system. Varying the hydrophobicity of the surfactant monomer enabled us to determine that the percentages of uncomplexed cyclodextrin in equilibrium with the micellar system were in the range of 5-95%.

Dynamics of Solvent and Rotational Relaxation of Coumarin 153 in Room-Temperature Ionic Liquid 1-Butyl-3-methylimidazolium Hexafluorophosphate Confined in Brij-35 Micelles: A Picosecond Time-Resolved Fluorescence Spectroscopic Study

The dynamics of solvent and rotational relaxation of Coumarin 153 (C-153) in ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and in the ionic liquid confined in Brij-35 micellar aggregates have been investigated using steady-state and time-resolved fluorescence spectroscopy. We observed slower dynamics in the presence of micellar aggregates as compared to the pure IL. However, the slowing down in the solvation time on going from neat IL to IL-confined micelles is much smaller compared to that on going from water to water-confined micellar aggregates. The increase in solvation and rotational time in micelles is attributed to the increase in viscosity of the medium. The slow component is assumed to be dependent on the viscosity of the solution and involves large-scale rearrangement of the anions and cations while fast component is assumed to originate from the initial response of the anions during excitation. The slow component increases due to the increase in the viscosity of the medium and increase in fast component is probably due to the hydrogen bonding between the anions and polar headgroup of the surfactant. The dynamics of solvent relaxation was affected to a small extent due to the micelle formation.

Alternative Chemical Route to Mesoporous Titania From a Titanatrane Complex

High-purity, mesoporous titania was prepared by reaction of dimethylaminotitanatrane, [NMe2–Ti(OCH2CH2)3N] in the presence of micellar aggregates as templating agents followed by thermal treatments in the temperature range 350–450 °C. The powders were characterized by nitrogen adsorption–desorption isotherms, thermogravimetry–differential thermal analysis, Fourier transform infrared, field-emission scanning electron microscopy, and x-ray diffraction. Analysis of the morphological characteristics of titanium oxide powders calcined at 350 °C for 120 h and at 450 °C for 6 h showed the presence of a mesoporous structure, with an average pore size of about 3.5 nm. Firing temperatures above 450 °C caused the collapse of the mesoporous structure. Composite Nafion-based membranes, containing 5 wt% mesoporous titania fired at 450 °C as a filler were successfully prepared. Preliminary tests in a prototype direct methanol fuel cell demonstrated that the composite membrane allowed cell operation up to 145 °C, thus showing a significant performance improvement over pure Nafion.

Interactions between Poly(ethylene Oxide) and Sodium Dodecyl Sulfate in Elongational Flows

This work investigates the elongational flow of aqueous solutions of mixtures of a high-molecular-weight poly(ethylene oxide) (PEO) and sodium dodecyl sulfate (SDS). The formation of micellar aggregates of SDS along the PEO chain results in an increase in the strength of the extension thickening of the PEO solutions. This is especially pronounced under conditions in which the PEO molecules form transient entanglements in the flow field. The minimum PEO concentration required to form intermolecular entanglements is substantially reduced in the presence of micellar aggregates. This effect becomes quantitatively less important in solutions with NaCl, which suggests PEO coil contraction due to electrostatic screening of micellar aggregates. However, once extension thickening starts in the presence of NaCl, the growth of pressure drop is more abrupt than without salt, which suggests stronger interactions between PEO coils with attached aggregates. The critical aggregation concentrations of PEO/SDS and PEO/SDS/NaCl solutions agree with those reported in the literature, which were obtained by means of different experimental techniques. However, the saturation of the surfactant effect is attained at lower surfactant concentrations than the polymer saturation point previously reported. This might reflect a low sensitivity of the extension thickening effect to the amount of surfactant bound to the polymerchain as the saturation point is approached.

Photocatalytic degradation of carbaryl in aqueous TiO 2 suspensions containing surfactants

The effect of ionic and non-ionic aliphatic surfactants on the photocatalytic degradation of Carbaryl (1-naphtyl-N-methylcarbamate) in aqueous solutions containing suspended TiO 2 (anatase) particles, under irradiation with simulated AM1 solar light, was investigated. A neat inhibitory effect on the degradation rate was observed, depending on the nature of the surfactant and on the initial pH of the solution. The decay profiles of the primary process corresponded to the usual pseudo-first order kinetics for surfactant concentrations below the critical micellar concentration range, whereas a more complicate behaviour was observed in the presence of micellar aggregates. Mineralization of the pesticide to CO 2, NO 3 − and NH 4 + was evidenced also in the presence of added amphiphiles, suggesting the feasibility of photocatalytic treatment of surfactant-containing aqueous wastes.

Kinetics of the Acid Hydrolysis of Diazepam, Bromazepam, and Flunitrazepam in Aqueous and Micellar Systems

A kinetic study of the acid hydrolysis of aqueous diazepam, bromazepam, and flunitrazepam was carried out at 25 °C using a spectrophotometry method. For diazepam and flunitrazepam, the experimental pseudo first-order rate constant decreased as the acid concentration was increased. The contrary behavior was found in the case of bromazepam. A kinetic scheme that includes the hydrolysis reaction of both protonated and nonprotonated species of the drug can account for these results. Also, the kinetics of the acid hydrolysis of the same drugs in the presence of micellar aggregates [nonionic polyoxy- ethylene-23-dodecanol (Brij 35); cationic cetyl trymethyl ammonium bromide (CTAB); and anionic sodium decyl (SdeS), dodecyl (SDS), and tetradecyl (STS) sulfate] was studied at 25 °C. Negligible effects were observed in the cases of nonionic and cationic micelles. Anionic micelles produced an inhibitory effect in the reaction velocity. This effect increased as the hydrophobic nature of the surfactant increased. All these facts are interpreted quantitatively by means of a pseudophase model.

New amphoteric surfactants containing a 2-hydroxyalkyl group: IX. The pH dependence of micellar assemblies composed of amphoteric oligomeric and polymeric surfactants

A series of amphoteric oligomeric surfactants (AO) and amphoteric polymeric surfactants (AP) containing both a 2-carboxyethyl (CE) group and a 2-hydroxyalkyl (C 12-HA or C 14-HA) group has been studied. The bobbin-like molecular structure of the micelle formed by these surfactants poly{[ N-(2-carboxyethyl)- N′-(2-hydroxyalkyl)]aminoethylene} and the local movements of the molecular chain therein have been examined for pH dependence of 1H NMR spectroscopy on the CE HA ratio. From an analysis of chemical shifts and half-linewidths, the presence of micellar aggregates in a particular configuration has been inferred. The peaks of both ▪ and −CH 2COO groups shift to a higher field with increasing pH (alkaline side). The half-linewidth is broad on the acidic side and narrow on the alkaline side. The dissociation occurs and the bobbin structure becomes loose. The dissociation constant and bulk behavior are also discussed using the Henderson-Hasselbach equation.

Pseudo‐phase ion‐exchange model for micellar catalysis in the acid hydrolysis of vinyl ethers

AbstractThe rate of the perchloric acid hydrolysis of aqueous ethyl and butyl vinyl ethers at 25.0°C, in the presence of micellar aggregates [anionic, sodium dodecyl sulfate (SDS); cationic, cetyl trymethyl ammonium bromide (CTAB); and nonionic, polyoxyethylen23dodecanol, (Brij 35)], has been studied. Negligible effects were observed in the cases of cationic and nonionic micelles. Anionic micelles produce an enhancement in the reaction velocity, and the rate constants go through maxima with increasing SDS concentration. These maxima disappear in the presence of excess sodium perchlorate. All these facts are interpreted quantitatively by means of the pseudo‐phase ion‐exchange model.