Role of cholesterol in functional association between K(+)-Cl(-) cotransporter-3a and Na+,K(+)-ATPase

The conformation of amyloid-beta peptide (Aβ) determines if toxic aggregates are formed. The peptide structure by its turn depends on the environment and molecule-molecule interactions. We characterized the secondary structure of Aβ-(1-40) in surfactant solutions and interacting with monolayers. The peptide adopts β-sheet structure in solutions of ionic surfactants at sub-micelle concentrations and α-helix in the presence of ionic micelles. Uncharged micelles induce β-sheets. Aβ-(1-40) alters the critical micelle concentration value of the non-ionic surfactant, underlining hydrophobic interactions. At ionic monolayers the peptide forms β-sheets when its concentration at the surface is high enough. These results suggest that only electrostatic interactions of charged micelles that surround completely the peptide are able to induce non-aggregated α-helix structure.     

Study of the Formation and Solution Properties of Worm-Like Micelles Formed Using Both N-Hexadecyl-N-Methylpiperidinium Bromide-Based Cationic Surfactant and Anionic Surfactant

The viscoelastic properties of worm-like micelles formed by mixing the cationic surfactant N-hexadecyl-N-methylpiperidinium bromide (C₁₆MDB) with the anionic surfactant sodium laurate (SL) in aqueous solutions were investigated using rheological measurements. The effects of sodium laurate and temperature on the worm-like micelles and the mechanism of the observed shear thinning phenomenon and pseudoplastic behavior were systematically investigated. Additionally, cryogenic transmission electron microscopy images further ascertained existence of entangled worm-like micelles.     

Chirality of reverse micelles

Four chiral analogues of the surfactant Aerosol-OT (AOT) have been synthesized and characterized. All of them form reverse micelles in apolar solvents in the w₀ range 0–30 (w₀ = [water]/[tenside]). Reverse micellar solutions have been investigated by UV absorption and circular dichroism spectroscopies with the aim of clarifying whether the formation of the macromolecular micellar structure induces the appearance of new chromophoric bands or perturbs the existing ones. Methanolic solutions of the surfactants, in which no micellar aggregates are formed, were taken as references. One of the products 1(S),1′(S)-dimethylbisheptylsulphosuccinate sodium salt (MH-AOT) was capable of forming reverse micelles of relatively high water content (w₀ up to 40) and this process was accompanied by a specific increase in the intensity of the circular dichroism band associated with the ester absorbance of the molecule. As no concomitant changes were seen in the UV absorbance spectrum, it was concluded that this observation reflected conformational events occurring within the surfactant rather than chromophoric perturbation. These results are qualitatively similar to those found recently for lecithin reverse micelles which, however, form gels at sufficiently high water contents. The chiroptical properties of these supramolecular aggregates are compared with those of covalent macromolecular systems such as polypeptides.     

Determination of Benzalkonium Chloride Partition in Micelle Solutions Using Ultrafiltration Method

The objectives of this study were to determine the concentrations of free benzalkonium chloride (BAC) and apparent partitions coefficients (K _m) in micelle solutions and to explore its application in formulation development. Ultrafiltration (UF) was carried out using 10K Nanosep® devices and centrifugation at 5,000 rpm for 5 min. The separation of free BAC from micellar solutions was also conducted using ultracentrifugation (UC) method for the comparison with UF method. Capillary electrophoresis method was used for the identification of micelles. Results showed that a UF method was applicable for quantitatively evaluating BAC–micelle interaction in micellar solutions. Unlike UF, UC could not completely separate free BAC from the micelles. The free BAC concentrations in the micelle solutions decreased with increasing surfactant concentrations. Among polysorbate 80, cremophor EL, and tyloxapol, BAC had the highest K _m in polysorbate 80 solutions. The K _m was significantly lower in non-buffered aqueous solutions than that in citric buffers. Moreover, increasing surfactant concentrations led to reducing antimicrobial activity. The UF is a rapid and accurate method that minimally alters the micellar equilibrium for the determination of free BAC and K _m in micellar solutions. In conclusion, free BAC concentration, which is a function of surfactant type, surfactant concentration, and ion strength of solution, is likely associated with the antimicrobial activity.     

Assessing bioavailability of the solubilization of organic compound in nonionic surfactant micelles by dose–response analysis

It is uncertain in some extent that organic compounds solubilized in micelles of a nonionic surfactant aqueous solution are bioavailable directly by the microbes in an extractive microbial transformation or biodegradation process. In this work, a dose–response method, where a bioequivalence concept is introduced to evaluate the synergic toxicity of the nonionic surfactants and the organic compounds, was applied to analyze the inhibition effect of organic compounds (naphthalene, phenyl ether, 2-phenylethanol, and 1-butanol) in nonionic surfactant Triton X-100 micelle aqueous solutions and Triton X-114 in aqueous solutions forming cloud point systems. Based on the result, a mole solubilization ratio of organic compounds in micelle was also determined, which consisted very well with those of classic semi-equilibrium dialysis experiments. The results exhibit that bioavailability of organic compounds solubilized in micelles to microbial cells is negligible, which provides a guideline for application of nonionic surfactant micelle aqueous solutions or cloud point systems as novel media for microbial transformations or biodegradations.     

Tuning micelles of a bioactive heptapeptide biosurfactant via extrinsically induced conformational transition of surfactin assembly

We have studied the effects of extrinsic environmental conditions on the conformation of surfactin, a heptapeptide biosurfactant from Bacillus subtilis, in aqueous solutions. It has been made clear that temperature, pH, Ca²⁺ ions and the synthetic nonionic surfactant hepta-ethylene glycol (C₁₂E₇) affect the conformation of surfactin in aqueous solutions. The β-sheet formation reached a maximum at 40°C both in presence and absence of (C₁₂E₇) and the nonionic surfactant enhances the β-sheet formation even at 25°C. Ca²⁺ induced the formation of a-helices and caused this transition at 0.3 mm with surfactin monomers or at 0.5 mm with surfactin micelles, but above these transition concentrations of Ca²⁺ β-sheets were observed. In micellar solution the β-sheet structure was stabilized at pH values below 7 or upon addition of Ca²⁺ in concentrations above 0.5 mm . Our results indicated that the bioactive conformation of surfactin is most likely the β-sheets when the molecules are assembled in micelles. The β-sheet structure in micelles could be retained by tuning the micelles. Surfactin micelles could be tuned in the bioactive conformation by manipulating pH, temperature, Ca²⁺ or (C₁₂E₇) concentrations in surfactin solutions. Our results strongly indicated that Ca²⁺ and other molecules (such as C₁₂E₇) may function as directing templates in the assembly and conformation of surfactin in micelles. Thus, we suggest environmental manipulation and template-aided micellation (TAM) as a new approach for preparing predesigned micelles, microemulsions or micro-spheres for specific application purposes. © 1998 European Peptide Society and John Wiley & Sons, Ltd.     

Characterization of the solubilization of lipid bilayers by surfactants

This communication addresses the state of aggregation of lipid-detergent mixed dispersions. Analysis of recently published data suggest that for any given detergent-lipid mixture the most important factor in determining the type of aggregates (mixed vesicles or mixed micelles) and the size of the aggregate is the detergent to lipid molar ratio in these aggregates, herein denoted the effective ratio, R_e. For mixed bilayers this effective ratio has been previously shown to be a function of the lipid and detergent concentrations and of an equilibrium partition coefficient, K, which describes the distribution of the detergent between the bilayers and the aqueous phase. We show that, similar to mixed bilayers, the size of mixed micelles is also a function of the effective ratio, but for these dispersions the distribution of detergent between the mixed micelles and the aqueous medium obeys a much higher partition coefficient. In practical terms, the detergent concentration in the mixed micelles is equal to the difference between the total detergent concentration and the critical micelle concentration (cmc). Thus, the effective ratio is equal to this difference divided by the lipid concentration. Transformation of mixed bilayers to mixed micelles, commonly denoted solubilization, occurs when the surfactant to lipid effective ratio reaches a critical value. Experimental evaluation of this critical ratio can be based on the linear dependence of detergent concentration, required for solubilization, on the lipid concentration. According to the ‘equilibrium partition model’, the dependence of the ‘solubilizing detergent concentration’ on the lipid concentration intersects with the lipid axis at −1/K, while the slope of this dependence is the critical effective ratio. On the other hand, assuming that when solubilization occurs the detergent concentration in the aqueous phase is approximately equal to the critical micelle concentration, implies that the above dependence intersects with the detergent axis at the critical micelle concentration, while its slope, again, is equal to the critical effective ratio. Analysis of existing data suggests that within experimental error both these distinctively different approaches are valid, indicating that the critical effective ratio at which solubilization occurs is approximately equal to the product of the critical micelle concentration and the distribution coefficient K. Since the nature of detergent affects K and the critical micelle concentration in opposite directions, the critical (‘solubilizing’) effective ratio depends upon the nature of detergent less than any of these two factors.     

Solubilization capacity of nonionic surfactant micelles exhibiting strong influence on export of intracellular pigments in Monascus fermentation

In this study, perstractive fermentation of intracellular Monascus pigments in nonionic surfactant micelle aqueous solution had been studied. The permeability of cell membrane modified by nonionic surfactant might have influence on the rate of export of intracellular pigments into its extracellular broth while nearly no effect on the final extracellular pigment concentration. However, the solubilization of pigments in nonionic surfactant micelles strongly affected the final extracellular pigment concentration. The solubilization capacity of micelles depended on the kind of nonionic surfactant, the super‐molecule assembly structure of nonionic surfactant in an aqueous solution, and the nonionic surfactant concentration. Elimination of pigment degradation by export of intracellular Monascus pigments and solubilizing them into nonionic surfactant micelles was also confirmed experimentally. Thus, nonionic surfactant micelle aqueous solution is potential for replacement of organic solvent for perstractive fermentation of intracellular product.     

Interaction between covalent DNA gels and a cationic surfactant

The interaction of covalently cross-linked double-stranded (ds) DNA gels and cetyltrimethylammonium bromide (CTAB) is investigated. The volume transition of the gels that follows the absorption of the oppositely charged surfactant from aqueous solution is studied. As do other polyelectrolyte networks, DNA networks form complexes with oppositely charged surfactant micelles at surfactant concentrations far below the critical micelle concentration (cmc) of the polymer-free solution. The size of the absorbed surfactant aggregates is determined from time-resolved fluorescence quenching (TRFQ). At low surfactant concentrations, small discrete micelles (160 < N < 210) are found, whereas large micelles (N > 500) form at surfactant concentrations of 1 mM. When the DNA is in excess of the surfactant, the surfactant binding is essentially quantitative. The gel volume decreases by 90% when the surfactant to DNA charge ratio, beta, increases from 0 to 1.     

The effect of surfactants on the aggregation state of amphotericin B

We have studied the effect of two surfactants, one non-ionic, lauryl sucrose (LS) and the other ionic, sodium deoxycholate (DOC), on the aggregation state of amphotericin B (AmB) and its selectivity towards ergosterol and cholesterol. It is shown that the addition of these surfactants has very similar effects on the AmB micelles. Below the critical micellar concentration of the surfactants, mixed micelles with AmB are first formed as a result of the penetration of the surfactant molecules into the AmB micelles. At higher concentrations of the surfactant molecules, the micellar structure is completely destroyed and AmB is found as monomers in solution. When the concentration of the surfactant is further increased, micelles of the surfactant molecules are built up, AmB remaining in monomeric form. However, the critical micellar concentration of LS is modified by the presence of AmB in solution, while that of DOC is not affected, thereby indicating that the interactions of AmB with LS are stronger than those of DOC with AmB. We also show that both surfactants enhance the selectivity of the AmB binding to sterols at exactly the concentrations of the surfactants which induce the monomerization of the antibiotic. It is observed that the maximal selectivity is found at a concentration of the surfactants corresponding to their particular CMC in presence of the antibiotic.     

Lysozyme activity in the presence of nonionic detergent micelles

The effect of a nonionic surfactant, polyoxyethylenesorbitan monolaurate (Tween 20), on the hen egg-white lysozyme catalyzed lysis of a dried cell suspension of Micrococcus lysodeikticus is analysed. A rate enhancement of up to 70% is observed in the presence of surfactant at concentrations above the critical micelle concentration. This activity increase may be explained by postulating the existence of a micelle-enzyme complex in which enzyme molecules are bound to micelles with preferential orientation of their active sites. The reaction is found to be second order with respect to substrate. A mechanism is postulated in which a substrate particle is assumed to be an energy-furnishing collision partner to the enzyme-substrate complex. This mechanism correlated data over a wide range of enzyme and substrate concentrations. Data from kinetic, ultrafiltration, ultraviolet, and fluorescence studies provide convincing evidence for the existence of a micelle-lysozyme complex. The results suggest that it is possible that immobilized enzymes mat in general be more reactive than corresponding free enzymes.     

Effects of cationic micelles on the rate of reaction of p-nitrophenyl esters with dihydrolipoic acid and dihydrolipoylamido derivatives

Dihydrolipoic acid (DHLA) 2a and its surfactant derivatives, trialkyl(2-lipoylamidoethyl) ammonium salts 2b-c, have been investigated, mainly in micellar solutions of cetyltrimethyl-ammonium bromide (CTABr), as esterolytic reagents toward p-nitrophenyl esters. The origins of the observed kinetic effects are discussed, and the reactivity of these reagents are compared with that of other thiolytic systems. The results indicate that DHLA, although not a surfactant, is effectively comicellized by CTABr, and micelles of CTABr and DHLA are among the most effective esterolytic systems, at moderately alkaline pHs, so far reported.     

Microstructures formed in aqueous solutions of a hydrophobically modified nonionic cellulose derivative and sodium dodecyl sulfate: a fluorescence probe investigation

The association behavior of hydrophobically modified ethyl hydroxyethyl cellulose (HM-EHEC) and its interaction with the anionic surfactant sodium dodecyl sulfate (SDS) has been studied in the dilute concentration regime. Steady-state fluorescence probe techniques have been utilized to obtain microstructural information of the system properties and combined with macroscopic bulk information from equilibrium dialysis experiments in order to determine binding isotherms of SDS to HM-EHEC. HM-EHEC was found to self-associate and form polymeric micelles in semi-dilute aqueous solutions. c^* for the self-association process was determined to be approximately 0.4%. The microviscosity of the polymeric micelles is much higher, and the micropolarity slightly higher, than that of ordinary SDS micelles. The onset of interaction between HM-EHEC and SDS was evidenced by a simultaneous strong increase in microviscosity and decrease in micropolarity upon successive addition of SDS. There is a minor, noncooperative SDS binding to the HM-EHEC starting from low concentrations of SDS (<5 mM) followed by a highly cooperative binding region at SDS concentrations ≥5 mM. The polymer–surfactant aggregates are rigid and hydrophobic with a maximum in microviscosity in the noncooperative binding region at a very low degree of SDS-adsorption.     

Recovery of proteins and amino acids from reverse micelles by dehydration with molecular sieves

A new method is presented to precipitate proteins and amino acids from reverse micelles by dehydrating the micelles with molecular sieves. Nearly complete precipitation is demonstrated for alpha-chymotrypsin, cytochromec, and trytophan from 2-ethylhexyl sodium sulfosuccinate (AOT)/isooctane/water reverse micelle solutions. The products precipitate as a solid powder, which is relatively free of surfactant. The method does not require any manipulation of pH, ionic strength, temperature, pressure, or solvent composition, and is applicable over a broad range of these properties. This general approach is compared with other techniques. This general approach is compared with other techniques for the recovery of biomolecules from reverse micelles. (c) 1994 John Wiley & Sons, Inc.     

Mixed micelles of sphingomyelin and phosphatidylcholine with nonionic surfactants. Effect of temperature and surfactant polydispersity.

Mixed micelle formation of the polydisperse nonionic surfactant Triton X-100 as well as its homogeneous analogue, p-(1,1,3,3-tetramethylbutyl)-phenoxynonaoxyethylene glycol (OPE-9), with bovine brain sphingomyelin or dipalmitoyl phosphatidylcholine has been characterized by column chromatography on 6% agarose. At 40 degrees C, mixtures of OPE-9 and either sphingomyelin or dipalmitoyl phosphatidylcholine give a narrow size distribution for mixed micelles. A this temperature the size distribution of Triton X-100-containing mixed micelles is complicated because of the polydispersity of the oxyethylene chains. At 20 degrees C narrow size distributions are observed for mixed micelles of sphingomyelin/Triton X-100 and sphingomyelin/OPE-9 up to at least 0.06 mol fraction of lipid. For dipalmitoyl phosphatidylcholine this is observed only with OPE-9. At intermediate mol fractions of lipid (around 0.25), two populations of mixed micelles exist for sphingomyelin/Trition X-100, sphingomyelin/OPE-9, and dipalmitoyl phosphatidylcholine/OPE-9. At high mol fractions of lipid only one population of mixed micelles again exists. At 20 degrees C, sphingoymelin forms a clear solution with Triton X-100 and OPE-9 to a lipid mol fraction of at least 0.46 and 0.67, respectively. Dipalmitoyl phosphatidylcholine forms a clear solution with OPE-9 to a lipid mol fraction of at least 0.57 at the same temperature. Triton X-100 and dipalmitoyl phosphatidylcholine do not form stable, clear solutions at 20 degrees C unless the lipid mol fraction is extremely low. These results show that surfactant polydispersity and temperature are important determinants in the solubilization of lipids by nonionic surfactants. It is also shown that pure surfactant micelles and lipid/surfactant mixed micelles do not co-exist in the same solution.     

Conformational and phase transitions in DNA—photosensitive surfactant solutions: Experiment and modeling

DNA binding to trans‐ and cis‐isomers of azobenzene containing cationic surfactant in 5 mM NaCl solution was investigated by the methods of dynamic light scattering (DLS), low‐gradient viscometry (LGV), atomic force microscopy (AFM), circular dichroism (CD), gel electrophoresis (GE), flow birefringence (FB), UV–Vis spectrophotometry. Light‐responsive conformational transitions of DNA in complex with photosensitive surfactant, changes in DNA optical anisotropy and persistent length, phase transition of DNA into nanoparticles induced by high surfactant concentration, as well as transformation of surfactant conformation under its binding to macromolecule were studied. Computer simulations of micelles formation for cis‐ and trans‐isomers of azobenzene containing surfactant, as well as DNA‐surfactant interaction, were carried out. Phase diagram for DNA‐surfactant solutions was designed. The possibility to reverse the DNA packaging induced by surfactant binding with the dilution and light irradiation was shown. © 2014 Wiley Periodicals, Inc. Biopolymers 103: 109–122, 2015.     

In Situ emulsification and mobilization of gasoline range hydrocarbons using surfactants

In this article the conditions that govern surfactant‐enhanced emulsification and mobilization of petroleum hydrocarbons in soil are reviewed. The effect of soil properties, groundwater constituents, and differing surfactant solutions on the emulsification process is discussed. A constant head soil flushing apparatus used to characterize surfactant‐enhanced mobilization of m‐xylene is described. Data showing the effect of surfactant‐enhanced mobilization on m‐xylene removal efficiency in washed sand is presented. Flushing solutions were used at concentrations from below to well above the critical micelle concentration (CMC) of the surfactants used. Removal efficiencies are shown to vary with surfactant concentration and with surfactant type. Flushing solutions of anionic, nonionic, and anionic/nonionic surfactant mixtures were evaluated.     

Effect of a commercial alcohol ethoxylate surfactant (C<Subscript>11-15</Subscript>E<Subscript>7</Subscript>) on

Biodegradation of poorly soluble polycyclic aromatic hydrocarbons (PAHs) has been a challenge in bioremediation. In recent years, surfactant-enhanced bioremediation of PAH contaminants has attracted great attention in research. In this study, biodegradation of phenanthrene as a model PAHs solubilized in saline micellar solutions of a biodegradable commercial alcohol ethoxylate nonionic surfactant was investigated. The critical micelle concentration (CMC) of the surfactant and its solubilization capacity for phenanthrene were examined in an artificial saline water medium, and a type of marine bacteria, Neptunomonas naphthovorans, was studied for the biodegradation of phenanthrene solubilized in the surfactant micellar solutions of the saline medium. It is found that the solubility of phenanthrene in the surfactant micellar solutions increased linearly with the surfactant concentrations, but, at a fixed phenanthrene concentration, the biodegradability of phenanthrene in the micellar solutions decreased with the increase of the surfactant concentrations. This was attributed to the reduced bioavailability of phenanthrene, due to its increased solubilization extent in the micellar phase and possibly lowered mass transfer rate from the micellar phase into the aqueous phase or into the bacterial cells. In addition, an inhibitory effect of the surfactant on the bacterial growth at high surfactant concentrations may also play a role. It is concluded that the surfactant largely enhanced the solubilization of phenanthrene in the saline water medium, but excess existence of the surfactant in the medium should be minimized or avoided for the biodegradation of phenanthrene by Neptunomonas naphthovorans.     

Immobilization ofArthrobacter simplex cells in thermally reversible hydrogels: Comparative effects of organic solvent and polymeric surfactant on steroid conversion

Summary Organic solvents have sometimes been used to increase the solubility of water insoluble substrates for steroid transformation using immobilized whole cells, even though the cell viability is often damaged. Polymeric surfactants which form micelles in aqueous solutions could be used instead of organic solvents to solubilize the steroid. We have successfully utilized this approach by employing a poly(dimethyl siloxane)-poly(ethyleneoxide) (PDMS-PEO) block copolymer surfactant to enhance conversion of hydrocortisone to prednisolone by immobilizedArthrobacter simplex cells, without deactivation of the immobilized cells.     

Formulation and Characterization of Phytophenol-Carrying Antimicrobial Microemulsions

Phytophenols were solubilized in nonionic surfactant micelles to form antimicrobially active and thermodynamically stable microemulsions. Formulation of phytophenols in microemulsions has previously been shown to improve their antimicrobial activity in model microbiological and food systems. Carvacrol and eugenol were incorporated in micellar solutions of two nonionic surfactants (Surfynol® 485W and Surfynol® 465) by mixing at room temperature. Particle size of formed microemulsions was determined by dynamic light scattering, and structural information about the mixed micellar system was obtained by nuclear magnetic resonance spectroscopy (NMR). Uptake of carvacrol and eugenol in surfactant micelles as determined by ultrasonic velocity measurements was very rapid, e.g., below the maximum additive concentration, the phytophenols were completely solubilized in the micelles in less than 30 min. Depending on the surfactant–phytophenol combination, the self-assembled surfactant–phytophenol aggregates had mean particle diameters between 3 and 17 nm. Elucidation of the structure of aggregates by 1H NMR studies indicated that micelles had a “bracket-like” structure with phytophenols being located inside the palisade layer of the micelle in direct contact with adjacent surfactant monomers. Encapsulation of phytophenols in surfactant micelles enables the incorporation of large amounts of hydrophobic antimicrobials in aqueous phases. Formulation of antimicrobial microemulsions may thus offer a means to deliver high concentrations of phytophenols to the bacterial surfaces of foodborne pathogens to affect kill.