Average Aggregation Number Research Articles

Hierarchical Structures in Amphiphilic Random Copolymer Solutions

Surveying the theory of associating polymer solutions, we have applied the theory to aqueous solution systems of two amphiphilic random copolymers to reveal the hierarchical structure in the solutions. The two random copolymers form uni-core flower micelles comprising of 2 and 8 copolymer chains in dilute solution. However, a part of hydrophobic groups are outside the micellar core and act as binding sites for higher-order aggregation of micelles progressing with increasing the copolymer concentration. The aggregates of flower micelles are bimodal: the major fast relaxation mode component with mw (the weight average aggregation number) of the order of 10 and the minor slow relaxation mode component with mw of order of 10 3 . The viscosity enhancement of the copolymer solutions with increasing the concentration mostly arises from the growth of the major fast mode aggregate.

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.

Effects of Organic Solvent Addition on the Aggregation and Micellar Growth of Cationic Dimeric Surfactant 12-3-12,2Br-

The micellization and micellar growth of cationic dimeric surfactant propanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide, 12-3-12,2Br-, have been studied in several water-organic solvent mixtures. The organic solvents were ethylene glycol, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, acetonitrile, dioxane, formamide, and N,N-dimethylformamide. Results showed that the aggregation process was less favored in the binary mixtures than in pure water, which was explained by considering the influence of the solvophobic effect on micellization. The addition of organic solvents was accompanied by a diminution in the average aggregation number, Nagg, of the dimeric micelles. This diminution was due to the decrease in the interfacial Gibbs energy contribution, Delta G0interfacial, to the Gibbs energy of micellization caused by the decrease in the hydrocarbon/bulk-phase interfacial tension. As a result of the micelle size diminution, the concentration at which the sphere-to-rod transition occurred, C*, was higher in the mixtures than in pure water. Micelle size reduction is accompanied by a decrease in the ionic interactions and in the extra packing contribution to the deformation of the surfactants tails, making the formation of cylindrical micelles less favorable.

Dilution method study on the interfacial composition, thermodynamic properties and structural parameters of W/O microemulsions stabilized by 1-pentanol and surfactants in absence and presence of sodium chloride

The phase behaviors, interfacial composition, thermodynamic properties and structural characteristics of water-in-oil microemulsions under varied molar ratio of water to surfactant ( ω) at 303 K and also by varying temperatures at a fixed ω ( = 40 ) by mixing with 1-pentanol and decane or dodecane in absence and presence of sodium chloride have been studied by the method of dilution. The surfactants used were cetyl pyridinium chloride (CPC), sodium dodecyl sulfate (SDS) and polyoxyethylene (23) lauryl ether (Brij-35). The compositions of 1-pentanol and the surfactant at the interfacial region, the distribution of 1-pentanol between the interfacial region and the continuous oil phase, and the effective packing parameter ( P eff ) at the threshold level of stability have been estimated. The thermodynamics of transfer of 1-pentanol from the continuous oil phase to the interface have been evaluated. The structural parameters viz. radii of the droplet ( R e ) and the waterpool ( R w ), effective thickness of the interfacial layer ( d I ), average aggregation numbers of surfactants ( N ¯ s ) and the cosurfactant (1-pentanol) ( N ¯ a ) and the number of droplets ( N d ) have also been estimated. The prospect of using these w/o microemulsions for the synthesis of nanoparticles with small size, have been discussed in the light of the radii of the droplet, and waterpool, the extent of variation of effective thickness of the droplet under varied molar ratio of water to surfactant and temperature. An attempt has been made to rationalize the results in a comprehensive manner.

Thermodynamics investigation of a series of metalloporphyrazine-bovine serum albumin complexes

The equilibrium binding of the tetra-cationic complexes ( N , N ′, N ″, N ‴-tetra-methyltetra-2,3-pyridinoporphyrazinato)copper(II), ([ Cu (2,3- TMTPPA )]4+), ( N , N ′, N ″, N ‴-tetra-methyltetra-3,4-pyridinoporphyrazinato)copper(II), ([ Cu (3,4- TMTPPA )]4+), (( N , N ′, N ″, N ‴-tetra-methyltetra-3,4-pyridinoporphyrazinato)cobalt(II), ([ Co (3,4- TMTPPA )]4+) and (( N , N ′, N ″, N ‴-tetra-methyltetra-3,4-pyridinoporphyrazinato)zinc(II), ([ Zn (3,4- TMTPPA )]4+) with bovine serum albumin (BSA) has been studied in phosphate buffer pH = 7.0 and at various temperatures using multi-spectroscopy techniques. The results of resonance light scattering (RLS) studies represent no aggregate formation of porphyrazine in the surface of BSA and low tendency of these porphyrazine for aggregate formation. The binding constants and binding stoichiometries were determined by analyzing of optical absorption spectra of porphyrazine complexes at various concentration of BSA using SQUAD software. The results show that the best fitting corresponds to a 1:1 complex model between BSA and porphyrazines. The thermodynamic parameters were calculated by van't Hoff equation at various temperatures. The data indicate that the process is entropy driven suggesting that hydrophobic interactions play a considerable role in the complex formation. The binding of porphyrazine complexes to BSA quenches fluorescence emission of BSA via a dynamic mechanism and the quenching process obeys a linear Stern-Volmer relationship. The average aggregation number of BSA, which has been calculated from the analysis of fluorescence quenching data, indicates the absence of any porphyrazine induced aggregation of BSA due to its interaction with porphyrazine complexes. Fluorescence studies also indicate that porphyrazine is bound to site I of BSA placed in sub-domain IIA, where tryptophan 214 is located.

Aggregation behaviour of n-alkyl-β- d-glucopyranoside + water + alcohol mixtures

The formation and properties of aggregates in aqueous n-alkyl-β- d-glucopyranoside (C XG 1) + n-alcohol mixtures are investigated theoretically, with particular emphasis on: (1) micellar size and shape; (2) critical micelle concentration; (3) partition of alcohols between micelles and intermicellar solution. In order to check the theoretical results some critical micelle concentrations were estimated using dynamic surface tension measurements. Utilizing a statistical-thermodynamic mixed micelle formation model, developed by Nagarajan and Ruckenstein, expressions for the chemical potentials of each of the solution components are obtained and used, along with the principle of multiple-chemical equilibrium, to calculate the micellar size distribution and the chemical composition of the mixed micelles. All calculations were performed taking a divariante distribution with respect to the aggregation number and with respect to the chemical composition, completely into account. The model contains no adjustable parameter. For energetic reasons the n-alkyl-β- d-glucopyranoside form in pure water and in presence of alcohol spherical bilayer vesicles. The predicted values of the critical micelle concentration are in satisfactory quantitative agreement with experimental values obtained by dynamic surface tension measurements. The number-average aggregation number of the mixed micelles runs through a minimum as function of the alcohol concentration. The alcohol molecules will be incorporated into the aggregates according their overall concentration. The penetration of the alcohol in the micelles does not depend on the chain length of the surfactant molecules.

Conductivities, Volumes, Fluorescence, and Aggregation Behavior of Ionic Liquids [C4mim][BF4] and [Cnmim]Br (n = 4, 6, 8, 10, 12) in Aqueous Solutions

Densities, conductivities, and polarity indexes of pyrene for aqueous solutions of a series of ionic liquids [C(n)mim]Br (n = 4, 6, 8, 10, 12) and [C4mim][BF4] have been determined at 298.15 K as a function of ionic liquid concentrations. It was shown that possible aggregation appeared for the ionic liquids in aqueous solutions except for [C4mim]Br. The critical aggregation concentration (CAC) of the ionic liquids, the ionization degree of aggregates (beta), the standard Gibbs energy of aggregation (Delta G(m)(o)), the limiting molar conductivity (Lambda(m)(o)), and the standard partial molar volume (V(m)(o)) for the ionic liquids were derived from the experimental data. The dependence of the CAC, Delta G(m)(o), Lambda(m)(o), and V(m)(o) on the length of the alkyl chain of the cations was examined. It was further suggested from volumetric data that a micelle was formed for [C8mim]Br, [C10mim]Br, and [C12mim]Br in aqueous solutions. Their apparent molar volumes at the critical micelle concentration (V Phi,CMC), apparent molar volumes in the micelle phase (V(Phi)(mic)), and the change of their apparent molar volume upon micellization (Delta V Phi,m) were calculated by application of the pseudophase model of micellization. In addition, the average aggregation number of [C(n)mim]Br (n = 8, 10, 12) has been determined by the steady-state fluorescence quenching technique, and predicted from a simple geometrical mode. It is found that the experimental values are in good agreement with the predicted ones.

Stability and State of Aggregation of Aqueous Fibrinogen and Dipalmitoylphosphatidylcholine Lipid Vesicles

The stability and state of aggregation of aqueous fibrinogen (FB) and dipalmitoylphosphatidylcholine (DPPC) vesicles in water or buffer at 25 degrees C were studied with dynamic light scattering (DLS), UV-vis spectroturbidimetry (ST), and cryo-transmission electron microscopy (cryo-TEM). In water, when 1000 ppm (0.10 wt %) DPPC dispersions were prepared with a protocol including extensive sonication, they contained mostly vesicles and were quite clear, transparent, and stable for at least 30 days. FB mixtures with water (0.075 wt %) were quite unstable and biphasic. They formed large aggregates which eventually precipitated. The addition of DPPC vesicles into these unstable FB dispersions reversed FB aggregation and precipitation and produced stable translucent microdispersions. The inferred lipid/protein aggregates were limited in size, with average diameters ranging from 200 to 300 nm. In buffer, DPPC dispersions were also clear and quite stable, with average dispersed particles diameter of ca. 90 nm. FB dissolved in aqueous buffer and formed transparent and stable solutions. Adding salt to an aggregated FB dispersion in water reversed the aggregation. FB aggregated and redissolved in the presence of the citrate and after the citrate was removed. There was no effect of citrate (present in FB initially) in the FB aggregation or redissolution. FB molecules in buffer form dimers or higher aggregates. Their average aggregation number is 2, determined with Rayleigh scattering analysis of turbidity data. The average hydrodynamic diameter of FB solutions from DLS was 30 nm. Mixing a stable FB solution in buffer and a stable DPPC dispersion in buffer produced highly unstable mixtures, in which large aggregates precipitated. These results have implications in understanding the interactions of lipids and proteins in many biological applications and food processing applications.

Phase Behavior of Aqueous Polyion-Surfactant Ion Complex Salts: Effects of Polyion Charge Density

The effect of varying the fraction of charged monomer units of the polyion in aqueous polyion-oppositely charged surfactant complex salts has been investigated. The complex salts used were based on cetyltrimethylammonium (C16TA+) with three different polymeric counterions: poly(acrylate) (PA-) or poly(acrylate) copolymerized with either dimethylacrylamide (PA-/DAM) or N-isopropylamide (PA-/NIPAM). The charge density of the polyion was varied by either adding poly(acrylic) acid (PAA) to the C16TAPA complex salt (annealed charges) or by varying the fraction of uncharged units in the C16TAPA/DAM or C16TAPA/NIPAM complex salts (quenched charges). The formed phases were studied visually between crossed polarizers and by small angle X-ray scattering (SAXS). Both types of complex salts (annealed and quenched) formed hexagonal phases at high fractions of charged monomers and low water contents. Upon increasing the water content, a cubic phase of the Pm3n space group was found. Upon further addition of water, a miscibility gap with the cubic phase in equilibrium with pure water was found. Decreasing the fraction of charged monomers in the annealed complex salt resulted in an increase of the curvature of the surfactant aggregates. Only at very low (<0.05) fractions of charged monomers did the packing of the surfactant aggregates lose long-range order, and eventually, the miscibility gap disappeared. For the quenched complex salts, the changes upon decreasing the fraction of charged monomers in the polyion were similar, but the loss of long-range order occurred at much higher fractions of charged monomers. The average surfactant aggregation number in the surfactant aggregates, which was similar for the annealed and quenched systems, decreased when the fraction of charged monomers was decreased.

Kinetics of Anionic Polymerization of Polybutadienyl Lithium in Benzene: An Osmotic Effect on Propagation Process

The kinetics of the polymerization (propagation) process of protonated polybutadienyllithium (hPB) in a nonpolar solvent, deuterated benzene (dBz), was examined with 1H NMR. An oligomeric, deuterated butadienyllithium (oBLi) was utilized as an initiator in order to avoid a contamination of the initiation process to the NMR data. The hPBLi chains mostly formed aggregate with an average aggregation number f ≍ 4 through Li at their ends. The residual monomer fraction φ(t) did not rigorously exhibit the single-exponential decay with time t expected for the conventionally considered propagation through the dissociated chains, φ(t)=exp(−t/τ) with τ={f/Kd[I]0}1/f/kp (Kd = association/dissociation equilibrium constant, kp = propagation rate constant, [I]0 = molar concentration of initiator at time 0). This deviation from the conventional behavior appeared to be due to competing propagation mechanism through the transiently fused aggregates (suggested from the 7Li NMR data): This fusion-aided propagation should have been osmotically suppressed on an increase of the hPB concentration (decrease of φ) to give the deviation. The propagation was found to be also retarded in the presence of chemically inert deuterated polybutadiene (dPB) chains that just tuned the osmotic environment for the aggregates, lending support to the molecular idea of the osmotic effect on the propagation. Furthermore, the φ(t) data in the absence/presence of the dPB chains were semi-quantitatively described by a simple model considering the competition of the propagation mechanisms through the fused 2f-mer aggregates and dissociated chains, with the former mechanism vanishing in the late stage of propagation. These results suggested a non-negligible contribution of the fused aggregates to the polymerization kinetics in particular in the early stage.

Effects of Ethylene Glycol Addition on the Aggregation and Micellar Growth of Gemini Surfactants

Micellization of three didodecyl dicationic dibromide gemini surfactants with different methylene spacer lengths, 12-s-12,2Br- where s = 3-5 methylene groups, has been investigated in water-ethylene glycol, EG, mixtures with weight percentages of EG up to 50%. Subsequently, effects of the addition of the organic solvent on the micellar growth of these surfactants and on the surfactant concentration range where sphere-to-rod transitions occur were studied by means of steady-state and time-resolved fluorescence quenching and spectroscopic measurements. Results show that an increase in the weight percentage of ethylene glycol added to aqueous 12-s-12,2Br- (s = 3-5) micellar solutions causes the sphere-to-rod transition to occur at higher surfactant concentrations than in pure water. The diminution in the average aggregation number, N(agg), when wt % EG increases, provoked by the decrease in the interfacial Gibbs energy contribution to DeltaG degrees M, is the main factor responsible for this observation. The decrease in N(agg) is accompanied by a decrease in the ionic interactions and the extra packing contribution to the deformation of the surfactants tails, making formation of cylindrical micelles less favorable. Besides, an increase in the solvent content and polarity of the interfacial region does not favor formation of direct ion pairs, decreasing the tendency of micelles to grow.

A Small-Angle Scattering Study on Equilibrium Clusters in Lysozyme Solutions

We use small-angle scattering experiments to investigate the structural properties of aqueous lysozyme solutions under conditions where the existence of equilibrium clusters has recently been demonstrated (Nature 2004, 432, 492). We also discuss the possible emergence of a low angle scattering contribution, which recently attracted interest due to its appearance in solutions of various proteins. We demonstrate that in lysozyme solutions under our experimental conditions such rising low q intensities can only be observed under special circumstances and can thus not be attributed to the existence of a universal long-range attraction. We then focus on the structural properties of the equilibrium clusters as a function of protein concentration, temperature, and ionic strength. We show that the experimental structure factors obtained from the scattering measurements exhibit the typical cluster-cluster peak q(c) reflecting the mean distance between charged clusters as well as a monomer-monomer peak q(m), which represents the nearest neighbor shell of monomers within a single cluster. The underlying principle for the formation of these structures is the coexistence of two opposing forces, a short-range attraction and a long-range repulsion due to residual charges. We can quantitatively analyze our scattering data by applying a simple equilibrium cluster model and calculate an average cluster aggregation number, N(c). The thus obtained cluster aggregation number increases linearly with volume fraction. We also observe an increasing N(c) as temperature decreases and as the screening of residual charges increases. We point out the importance of the existence of equilibrium clusters and the universality of this phenomenon for self-assembling processes observed in nature. Finally, we discuss the limitations of our simple globular cluster model in view of recent findings from computer simulations.

Mesoscopic simulation of self-assembly in surfactant oligomers by dissipative particle dynamics

Self-assembling properties of surfactant oligomers in an aqueous medium is simulated by dissipative particle dynamics (DPD). The critical micellar concentration (CMC) of dimeric (oligomerization = 2) and trimeric (oligomerization = 3) surfactant is much lower than their single-chain counterpart. All surfactants form spherical micelles at the concentration not far above their CMC. The transition from spherical to cylindrical micelles exhibits with increasing surfactant concentration. Lamellar micelles will appear with further increasing the surfactant concentration. For dimeric and trimeric surfactants, cylindrical micelles transform into extremely long “wormlike” or “threadlike” micelles before the transition to lamellar micelles. These results are in qualitative agreement with laboratory experiment. Average aggregation numbers (AN) of micelles increase with a power law of AN ∼ c α when the surfactant concentration c≫ CMC. The self-diffusion coefficients will drop with a power law of D ∼ c − α when wormlike micelles are formed.

Monte Carlo Simulations of Micellization in Model Ionic Surfactants: Application to Sodium Dodecyl Sulfate

A lattice model for ionic surfactants with explicit counterions is proposed for which the micellization behavior can be accurately determined from grand canonical Monte Carlo simulations. The model is characterized by a few parameters that can be adjusted to represent various linear surfactants with ionic headgroups. The model parameters have a clear physical interpretation and can be obtained from experimental data unrelated to micellization, namely, geometric information and solubilities of tail segments. As a specific example, parameter values for sodium dodecyl sulfate were obtained by optimizing for the solubility of hydrocarbons in water and the structural properties of dodecane. The critical micelle concentration (cmc), average aggregation number, degree of counterion binding, and their dependence on temperature were determined from histogram reweighting grand canonical Monte Carlo simulations and were compared to experimental results. The model gives the correct trend and order of magnitude for all quantities but underpredicts the cmc and aggregation number. We suggest ways to modify the model that may improve agreement with experimental values.

In situ probing of insulin aggregation in chromatography effluents with spectroturbidimetry

Probing protein aggregation in situ is quite important for analyzing and developing chromatographic protein purification processes. A spectroturbidimetry method with a photodiode array detector is developed and tested for probing insulin aggregation in solution and determining the aggregation number, n m . All aggregates examined are in the Rayleigh light scattering regime, where the turbidity between 400 and 350 nm is proportional to λ −4 . Insulin at 25 °C in 3.5 N acetic acid is mainly monomeric (non-aggregated). At 25 °C and lower acetic acid concentrations, from 0.1 to 1 N, the average insulin aggregation number n m ranges from 2.9 to 1.6. Aggregates, with n m = 2 – 3 , are found in 2.6 N acetic acid with 20 vol% acetonitrile. In 0.8 N acetic acid with 20 vol% denatured ethanol, n m = 1.2 . At 4 °C, as acetic acid concentration decreases from 3.5 to 0.1 N, n m decreases from 2.4 to 1.8. In 2.8 N acetic acid with 20 vol% denatured ethanol at 4 °C, insulin exists mainly in monomer form. In situ probing of size exclusion chromatography, SEC, effluents in 3.5 N acetic acid at 4 °C shows n m = 1.6 at the fronting portion (a mixture of monomers and dimers or other oligomers) and n m = 1.1 (mostly monomers) at the tailing portion of the main peak. In another example, for LysPro-insulin in reversed phase chromatography at 4 °C, complex elution patterns and broad peaks are due to substantial aggregation. For a linear gradient of acetonitrile from 10 to 60 vol% at 4 °C, n m ranges from 2.2 to 12, in order of elution. For a linear gradient of ethanol from 30 to 50 vol% at 4 °C, n m ranges from 14 to 27, in order of elution. Analytical HPLC results at 25 °C imply that the aggregates are reversible.

Flocculation and percolation in reversible cluster-cluster aggregation

Off-lattice dynamic Monte-Carlo simulations were done of reversible cluster-cluster aggregation for spheres that form rigid bonds at contact. The equilibrium properties were found to be determined by the life time of encounters between two particles (te). te is a function not only of the probability to form or break a bond, but also of the elementary step size of the Brownian motion of the particles. In the flocculation regime the fractal dimension of the clusters is df=2.0 and the size distribution has a power law decay with exponent tau=1.5. At larger values of te transient gels are formed. Close to the percolation threshold the clusters have a fractal dimension df=2.7 and the power law exponent of the size distribution is tau=2.1. The transition between flocculation and percolation occurs at a characteristic weight average aggregation number that decreases with increasing volume fraction.

A small-angle neutron scattering study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles

Mixed micelle of protonated or deuterated sodium dodecyl sulfate (SDS and SDSd25, respectively) and poly(propylene oxide) methacrylate (PPOMA) are studied by small-angle neutron scattering (SANS). In all the cases the scattering curves exhibit a peak whose position changes with the composition of the system. The main parameters which characterize mixed micelles, i.e., aggregation numbers of SDS and PPOMA, geometrical dimensions of the micelles and degree of ionisation are evaluated from the analysis of the SANS curves. The position q max of the correlation peak can be related to the average aggregation numbers of SDS–PPOMA and SDSd25–PPOMA mixed micelles. It is found that the aggregation number of SDS decreases upon increasing the weight ratio PPOMA/SDS (or SDSd25). The isotopic combination, which uses the “contrast effect” between the two micellar systems, has allowed us to determine the mixed micelle composition. Finally, the SANS curves were adjusted using the RMSA for the structure factor S ( q ) of charged spherical particles and the form factor P ( q ) of spherical core–shell particle. This analysis confirms the particular core–shell structure of the SDS–PPOMA mixed micelle, i.e., a SDS “core” micelle surrounded by the shell formed by PPOMA macromonomers. The structural parameters of mixed micelles obtained from the analysis of the SANS data are in good agreement with those determined previously by conductimetry and fluorescence studies.

Polymerization of Anionic Wormlike Micelles

Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

Effect of hexanol on the reversed micelles of Span 85 modified with Cibacron Blue F-3GA for protein solubilization

Sorbitan trioleate (Span 85) modified with Cibacron Blue F-3GA (CB) was used as an affinity surfactant (CB-Span 85) to form affinity-based reversed micelles in n-hexane. It was found that the addition of hexanol to the reversed micellar system resulted in a significant increase in water content and hydrodynamic radius of the affinity-based reversed micelles. Moreover, the reversed micelles with hexanol revealed broader aggregation number distribution and larger average aggregation number than the reversed micelles without hexanol addition. This is considered to be due to the decreases in the micellar curvature and rigidity of the micellar interfacial layer and the increase in the micellar interfacial fluidity. Consequently, the solubilization capacity of lysozyme increased about 70% in the reversed micellar solution with 3 vol% hexanol. On the other hand, the capacity of BSA was only 30% increased under the same conditions due to its larger molecular size than lysozyme. Kinetic analysis revealed that the increase in the micellar interfacial fluidity in the presence of hexanol resulted in faster release of lysozyme from the micelles, thus leading to an increase of the overall volumetric mass transfer coefficient in the back extraction.

Aggregation behavior and chromonic liquid crystal properties of an anionic monoazo dye

X-ray scattering and various optical techniques are utilized to study the aggregation process and chromonic liquid crystal phase of the anionic monoazo dye Sunset Yellow FCF. The x-ray results demonstrate that aggregation involves pi-pi stacking of the molecules into columns, with the columns undergoing a phase transition to an orientationally ordered chromonic liquid crystal phase at high dye concentration. Optical absorption measurements on dilute solutions reveal that the aggregation takes place at all concentrations, with the average aggregation number increasing with concentration. A simple theory based on the law of mass action and an isodesmic aggregation process is in excellent agreement with the experimental data and yields a value for the "bond" energy between molecules in an aggregate. Measurements of the birefringence and order parameter are also performed as a function of temperature in the chromonic liquid crystal phase. The agreement between these results and a more complicated theory of aggregation is quite reasonable. Overall, these results both confirm that the aggregation process for some dyes is isodesmic and provide a second example of a well-characterized chromonic system.