Effects of urea on the microstructure and phase behavior of aqueous solutions of polyoxyethylene surfactants

Membrane proteins are made soluble in aqueous buffers by the addition of various surfactants (detergents) to form so-called protein-detergent complexes (PDCs). Properties of membrane proteins are commonly assessed by unfolding the protein in the presence of surfactant in a buffer solution by adding urea. The stability of the protein under these conditions is then monitored by biophysical methods such as fluorescence or circular dichroism spectroscopy. Often overlooked in these experiments is the effect of urea on the phase behavior and micellar microstructure of the different surfactants used to form the PDCs. Here the effect of urea on five polyoxyethylene surfactants - n-octylytetraoxyethylene (C(8)E(4)), n-octylpentaoxyethylene (C(8)E(5)), n-decylhexaoxyethylene (C(10)E(6)), n-dodecylhexaoxyethylene (C(12)E(6)) and n-dodecyloctaoxylethylene (C(12)E(8)) - is explored. The presence of urea increases the critical micelle concentration (CMC) of all surfactants studied, indicating that the concentration of both the surfactant and urea should be considered in membrane protein folding studies. The cloud point temperature of all surfactants studied also increases with increasing urea concentration. Small-angle neutron scattering shows a urea-induced transition from an elongated to a globular shape for micelles of C(8)E(4) and C(12)E(6). In contrast, C(8)E(5) and C(12)E(8) form more globular micelles at room temperature and the micelles remain globular as the urea concentration is increased. The effects of increasing urea concentration on micelle structure are analogous to those of decreasing the temperature. The large changes in micelle structure observed here could also affect membrane protein unfolding studies by changing the structure of the PDC.     

Synthesis and Surface Active Properties of Gemini Cationic Surfactants and Interaction with Anionic Azo Dye (AR52)

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, ¹H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.     

Calibration of vapor pressure osmometers for molecular weight measurement

Experimental molecular weights in the range 200 to 100,000 Daltons have been determined by vapor pressure osmometry using three different solvents. For all values in excess of 10,000, molecular weights were also determined by membrane osmometry. The general agreement found for molecular weights determined under a variety of conditions, leads to the conclusion that values as high as 100,000 Daltons can be determined by at least one type of vapor pressure osmometer when it is calibrated with a material of 200 Daltons. Thermistor self-heating and diffusion in the liquid phase are shown to be unimportant for this particular instrument.     

Activity of horseradish peroxidase in aqueous and reverse micelles and back‐extraction from reverse‐micellar phases

Studies on the activity of the enzyme horseradish peroxidase (HRP) have been carried out in micellar as well as reverse‐micellar media. The activity of the enzyme was studied in the presence of different classes of surfactants – ionic as well as non‐ionic. In aqueous media, the activity of the enzyme varied depending on whether the concentration of the surfactant used was above or below the critical micellar concentration (CMC). The enzyme was also studied in reverse‐micellar systems. HRP was introduced into the reverse micellar phase by the injection method and its activity within the reverse micelles was determined. The effect of water to surfactant ratio (W_o) on activity within reverse micelles was studied, and an almost two‐fold increase in activity was seen when the enzyme was encapsulated within reverse micelles of aqueous phase fractional hold‐up (?) of 0.0072 (v/v) consisting of sodium bis‐(2‐ethylhexyl) sulfosuccinate (AOT) in isooctane at a W_o of 20. The activity of HRP was measured over a wide range of AOT concentrations having different W_o values. Back‐extraction of HRP from these reverse micelles was carried out at varying ionic strengths of phosphate buffer. Back extraction was found to be highest at pH 7.0 in 40 mol m^?3 phosphate buffer and 100 mol m^?3 sodium chloride. © 2001 Society of Chemical Industry     

Solubilization of selected polycyclic aromatic compounds by nonionic surfactants

Solubilization of selected polycyclic aromatic compounds (PAC) by biodegradable nonionic surfactants, Tergitol 15-S-X (X=7 or 9) and Neodol 25–7, was investigated and correlated with micellar properties of these surfactants. These PAC include dibenzofuran, phenanthrene, acenaphthene, fluoranthene, and 9-chloroanthracene. Tergitol surfactants are mixtures of secondary ethoxylated alcohols, and Neodol 25–7 is a mixture of similar species but has the alcohol group in the primary position. These surfactants have the same chain length of hydrophobic tails and similar numbers of ethylene oxides. The results show that the Neodol surfactant yields micelles having larger hydrophobic core volume and renders a higher solubilization capacity for the PAC solubilizates in comparison with Tergitol surfactants. In general, aggregation numbers and micellar sizes both increase at elevated temperatures still below the cloud point. The micellewater partition coefficients of these PAC by the nonionic surfactants were well correlated to their octanol-water partition coefficients. Moreover, an estimated log K _ow value of 9-chloanthracene is 4.78.     

Influence of breakup and reformation of micelles on surfactant diffusion in pure and mixed micellar systems

Pulsed field gradient (PFG) NMR technique was used to study diffusion of surfactant ions in the following two micellar systems: (i) aqueous solution of an anionic surfactant sodium dodecyl sulfate (SDS), and (ii) aqueous solution of a mixture of SDS and a small amount of the cationic surfactant N-dodecyltrimethylammonium bromide (C₁₂TAB). PFG NMR measurements provided separate sets of data on diffusion of SDS and C₁₂TAB surfactant ions for a broad range of diffusion times. For each type of surfactants at least two components with different effective diffusivities were observed at sufficiently small diffusion times. The faster component was assigned to the surfactants that experience breakup or reformation of micelles during the diffusion time of the PFG NMR measurement, while the slower component was assigned to the surfactants that did not participate in such events during the diffusion time. The observed changes of the fractions and diffusivities of these components with increasing diffusion time were found to be in a qualitative agreement with such assignment. Fundamental understanding of surfactant diffusion in micellar system is important due to an increasing use of such systems for synthesis of porous materials where micelles are used as templates as well as for many other applications.     

Solubilization of octafluoronaphthalene by mixed micelles of fluorocarbon and hydrocarbon surfactants in aqueous solutions

Solubilization of octafluoronaphthalene (OFN) by fluorocarbon and hydrocarbon surfactants in aqueous solutions has been examined to investigate the effects of mixing surfactants and added salt. Diethylammonium perfluoronanoate (DEAPFN) micelles have the most solubilization power toward OFN. The difference in micellar solubilization power will be caused by the hydrophobicity of ionic groups and micellar size. Large positive synergistic effects on solubilization behavior were observed in the DEAPFN-diethylammonium tetradecyl sulfate mixed micellar systems. Solubilization of OFN depended on the concentrations of added salt and the aggregation number, that is, the micellar size.     

Catalytic asymmetric hydrogenation in micellar media with amphiphilic and non-amphiphilic ligands

The transfer of a homogeneous catalytic hydrogenation catalyst into an aqueous micellar system was investigated. In case of the asymmetric hydrogenation activity and enantioselectivity were enhanced in water due to the addition of surfactants. A variation of the microheterogenization in water was realized with new amphiphilic ligands derived from Brij (polyoxyethylene ethers) and PPM (4-diphenylphosphino-2-diphenylphosphinomethyl-pyrrolidine). The substrate could be solubilized in the micellar assemblies. Best results were observed in mixed micelles: the enantioselectivity achieved 96% ee. New practical aspects are given by use of polymerized surfactants which we prepared by polymerization of assemblies.     

嵌段式共聚物胶团在萃取分离中的应用

本文以嵌段式共聚物表面活性剂为对象，介绍了聚合物胶团概念、聚合物胶团的萃取分离作用原理和过程．讨论了聚合物表面活性剂加港特性以及萃取过程中放团再生等因素对萃取分离的影响．对聚合物胶团分离技术的研究将促进表面活性剂科学、膜分离技术的发展，在工业上具有良好的应用前景．     

Polymeric surfactants for enhanced oil recovery. Part I—critical micelle concentration of some ethoxylated alkylphenol—formaldehyde nonionics

Four low molecular weight nonionic polymeric surfactants were prepared by condensing octyl-, dodecyl-, tetradecyl- and hexadecylphenol with para-formaldehyde, and then reacting the resulting resins with ethylene oxide to obtain products with the desired degree of ethoxylation. The molecular weights of the prepared alkylphenol-formaldehyde resins (prior to ethoxylation) were determined by vapour pressure osmometry. The surface tensions of aqueous solutions of these nonionic polymeric surfactants were determined by using the spinning drop method. Plotting the surface tensions obtained versus the logarithm of concentrations resulted in two lines: the pre-CMC (CMC = critical micelle concentration) line (the linear portion below the CMC value) and the post-CMC line (the linear portion above the CMC value). Least squares regression analysis was performed to get the best equation for each of the two lines. Solving these two equations simultaneously resulted in the value of the CMC and the corresponding surface tension (γ_CMC) for each surfactant of the four polymeric nonionic groups. The CMC values obtained for these polymeric surfactants are of the same order of magnitude obtained for monomeric and other polymeric nonionic surfactants.     

Micellization of a di‐block copolymer in ethylene glycol and its utilization for suspension of carbonaceous nanostructures

Suspensions of carbonaceous nanoparticles (NPs) in ethylene glycol (EG) can be used as colloidal inks for additive manufacturing and nano‐fluids for heat‐transfer applications. While micellar solutions of surfactants are often used for suspension of the NPs in water, micellization of surfactants in EG is suppressed as compared to aqueous solutions and a well‐defined critical micellization concentration (CMC) is often not observed. Unlike the surfactants, a di‐block copolymer comprising a poly(ethylene glycol) monomethylether methacrylate (PEGMA) segment, 2‐(diethylaminoethyl) methacrylate (DEAEMA) and butyl methacrylate (BMA), poly(O950)‐b‐(DEAEMA‐co‐BMA) was found to assemble into spherical micelles in EG. Surface tension measurements show a well‐defined CMC that depends on the volume fraction of EG. Cryogenic transmission electron microscopy and dynamic light scattering show the presence of spherical micelles with a diameter that reduces with the volume fraction of EG. The micellar solutions were further used for suspending carbonaceous NPs of different geometry and characteristic dimensions: C₆₀ fullerenes, multi‐walled carbon nanotubes, and nanodiamonds. The flow behavior of the suspensions exhibits a relatively low viscosity and mostly Newtonian behavior due to strong interaction between the NPs and the micelles. These suspensions may be used as colloidal inks for two‐dimensional and three‐dimensional printing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46518.     

反胶团酶催化研究新进展

评述了近年来反胶团酶催化研究的新进展。在AOT/异辛烷反胶团中加入非离子型表面活性剂如Tween 85、小相对分子质量聚乙二醇等可有效降低酶与表面活性剂间的静电和疏水作用 ,显著提高酶的活性。对AOT进行化学修饰及合成结构与磷脂类似的新表面活性剂以用其构建新的反胶团体系 ,酶的活性较常用的AOT/异辛烷反胶团体系有显著提高。在反胶团酶反应动力学研究中考虑水含量或底物在反胶团表面吸附的影响等 ,提出了进一步研究的设想 ,包括开发新型表面活性剂以进一步提高酶的活性和稳定性及有利于产物分离     

Reverse Micellar Encapsulation of d‐ and l‐Enantiomers of Some Aromatic α‐Amino Acids and Nucleobases by Glucose‐Derived Non‐ionic Gemini Surfactants in Neat n‐Hexane

Novel carbohydrate‐based non‐ionic gemini surfactants consisting of two sugar head groups, two hydrophobic tails having chain lengths of C12, C14, and C16 and a flexible –(CH₂)₆– spacer were synthesized and investigated for their reverse micellar encapsulation properties. The head groups of the geminis comprise glucose entities (with reducing function blocked in a cyclic acetal group) connected through C‐6 to tertiary amines. These surfactants were explored for reverse micellar encapsulation of d ‐ and l ‐enantiomers of aromatic α‐amino acids viz. histidine (His), phenylalanine (Phe), tyrosine (Tyr) and tryptophan (Trp) in neat n‐hexane. Similar studies were carried out for encapsulation of nucleobases viz. adenine (Ade), guanine (Gua), thymine (Thy), cytosine (Cyt) and Uracil (Ura). Reverse micellar studies revealed that aromatic α‐amino acids were encapsulated in the sequence His>Tyr>Phe>Trp. In most cases, a difference in the degree of encapsulation of d ‐ and l ‐enantiomers of aromatic amino acids in reverse micellar phases of gemini amphiphiles in neat n‐hexane, was revealed. For Tyr, l ‐enantiomer was better encapsulated than its antipode, i.e., d ‐enantiomer but for Trp, d ‐enantiomer was better encapsulated then l ‐enantiomer. In the case of nucleobases, Ura was found selectively encapsulated by reverse micelles formed by these new amphiphiles.     

Polymerization of micelle-forming monomers: Mechanistic study and characterization of the systems before and after polymerization

Cationic surfactants bearing a polymerizable styryl headgroup and a variable alkyl chain with 8–16 carbon atoms have been synthesized. Their aqueous solutions have been characterized by the surfactant critical micellar concentration (CMC) and aggregation number using electrical conductivity, spectrofluorimetry and time-resolved fluorescence quenching. The photoinitiated polymerization of these surfactants in the micellar state led to stable and transparent or slightly bluish systems. The kinetics of polymerization were measured by dilatometry and were found to be close to those obtained for styrene emulsion polymerization. A mechanism of polymerization is proposed and discussed in terms of micellar dynamics. The polymerized systems, p(Cn-STY), and the recovered polymers were characterized by means of several complementary techniques. The polymers have high molecular weights (3 × 10⁵-3 × 10⁶), which indicates that the initial micellar structure is not preserved upon polymerization. The structure of the polymerized systems depends on the alkyl chain length of the surfactant. The p(C16-STY) systems exhibit a structure similar to that of a polysoap with intramolecular hydrophobic microdomains whereas the p(C8-STY) systems behave like classical polyelectrolytes.     

Study of the Antioxidative Properties of Several Amino Acid-Type Surfactants and their Synergistic Effect in Mixed Micelle

Cysteine and methionine, two sulfur-containing amino acids (AA), were introduced in their surfactant forms as potential antioxidants. The antioxidative (AOX) properties of lauroyl methionine (C12-Met) and lauroyl cysteine (C12-Cys) was investigated by means of the oxygen radical absorbance capacity assay. Both the surfactants exhibited excellent AOX behavior at the premicellar state and micellar medium. The AOX behavior was found to be comparable for both the surfactants at their premicellar states. However, in micellar medium, C12-Met showed better AOX property than C12-Cys. The AOX power of the surfactants was compared with other previously developed AA-type surfactants. The order of the AOX power was found to be: C12-tryptophan > C12-tyrosine ≈ C12-methionine ≈ C12-cysteine > C12-histidine at the premicellar state and C12-tryptophan > C12-tyrosine > C12-methionine > C12-cysteine > C12-histidine at the micellar state. C12-Cys displayed lower AOX property in micellar medium due to its dimer formation tendency. Based on the HPLC and UPLC-Q-TOF-MS analysis, the dimer formation of C12-Cys was found to be accelerated due to the micellar environment and results into negative synergistic effect on other aromatic AA-type surfactants. However, the presence of C12-His in the micellar solution of C12-Cys resulted no synergistic effect due to stronger H-bonding between the surfactants and resulting less dimer formation.     

Electrospinning of chitosan-poly(ethylene oxide) blend nanofibers in the presence of micellar surfactant solutions

Nanofibers were fabricated by electrospinning a mixture of cationic chitosan and neutral poly(ethylene oxide) (PEO) at a ratio of 3:1 in aqueous acetic acid. Chitosan ((1 → 4)-2-amino-2-deoxy-β-d-glucan) is a multifunctional biodegradable polycationic biopolymer that has uses in a variety of different industrial applications. Processing conditions were adjusted to a flow rate of 0.02 ml/min, an applied voltage of 20 kV, a capillary tip-to-target distance of 10 cm and a temperature of 25 °C. To further broaden the processing window under which nanofibers are produced, surfactants of different charge were added at concentrations well above their critical micellar concentrations (cmc). The influence of viscosity, conductivity and surface tension on the morphology and physicochemical properties of nanofibers containing surfactants was investigated. Pure chitosan did not form fibers and was instead deposited as beads. Addition of PEO and surfactants induced spinnability and/or yielded larger fibers with diameters ranging from 40 nm to 240 nm. The presence of surfactants resulted in the formation of needle-like, smooth or beaded fibers. Compositional analysis suggested that nanofibers consisted of all solution constituents. Our findings suggest that composite solutions of biopolymers, synthetic polymers, and micellar solutions of surfactants can be successfully electrospun. This may be of significant commercial importance since micelles could serve as carriers of lypophilic components such as pharmaceuticals, nutraceuticals, antimicrobials, flavors or fragrances thereby further enhancing the functionality of nanofibers.     

Fluorocarbon-hydrocarbon interactions in interfacial and micellar systems

The interactions of fluorocarbons and hydrocarbons in liquid mixtures are known to be highly nonideal. Recent research has indicated that the unusual characteristics of such interactions have a significant influence on the behavior of many interfacial and micellar systems in which such interactions occur. Results from several different studies are presented. These involve (a) properties of partially fluorinated surfactants and lipids, including comments on the use of fluorine substituted groups as spectroscopic probes; (b) surface tensions of nonideal mixtures of liquid fluorocarbons and hydrocarbons and their interfacial tensions against water; (c) adsorptions of fluorocarbon and hydrocarbon surfactants to air/water, hexane/water, and perfluorohexane/water interfaces and a comparison of relative affinities; (d) formation of mixed micelles of fluorocarbon and hydrocarbon surfactants and evidence of partial miscibility of micelles; (e) comparison of adsorption of fluorocarbon and hydrocarbon surfactants to graphon; and (f) comparison of wetting of hydrocarbon-like solids by aqueous solutions of fluorocarbon and hydrocarbon surfactants.     

Solubilization of Aromatic Hydrocarbons in Ethylene Oxide-Propylene Oxide Triblock Micelles: Location of Solubilizate and its Effect on Micelle Size from 2D NMR and Scattering Techniques

The solubilization of benzene and toluene in micellar solutions and the effects on the micellization and micelle size of ethylene oxide-propylene oxide triblock copolymers were investigated by dynamic light scattering (DLS), small angle neutron scattering (SANS), and 2D NMR spectroscopy. The copolymeric surfactants have the same size as the middle hydrophobic polypropylene oxide block (Mol. Wt. 3250) and varying polyethylene oxide end blocks (30, 40 and 50%). The solubilization and the properties of the micelles in the presence of the solubilizates were investigated; the results reveal that the more hydrophobic copolymer showed better solubilization. The cloud points of the copolymers decreased in the presence of oils; the depression in the cloud point is due to the formation of an electron donor–acceptor complex. DLS shows that the effect of benzene is dominated at high oil concentration. SANS data show that the micelles remain spherical in shape and that the micellar core size does not change with higher benzene concentration; observed changes in the low scattering vector region could be because of some small amount of benzene clusters formed at higher benzene concentration. Finally, the locus of solubilization of the oils in the copolymer micelles was determined via 2D NMR experiments. In all cases, significant nuclear Overhauser effect spectroscopy (NOESY) cross peaks were observed that appeared to correlate well with the expected loci of these solubilizates in micelles. Hence, the noninvasive NOESY technique provides important information on the location of the aromatic solubilizates in these copolymer micelles that depends on the structure of the oils.     

Experimental Study of CMC Evaluation in Single and Mixed Surfactant Systems, Using the UV–Vis Spectroscopic Method

In this study, the critical micellar concentration (CMC) of anionic, cationic and nonionic surfactants was determined using the UV–Vis spectroscopic method. Sodium lauryl sulfate (SDS) as anionic, hexadecyl-trimethyl-ammonium bromide as cationic, tert-octylphenol ethoxylates TOPEON (with N = 9.5, 7.5 and 35) and lauryl alcohol ethoxylate (23EO) as nonionic surfactants have been used. Concentration of surfactants varies both from below and above the CMC value in the pyrene solution. In addition, the amount of the CMC was determined using the values from the data obtained from the graph of absorbance versus concentration of surfactants. A comparative study was conducted between the results of the present study and the literature which shows a good agreement, in particular for TOPEO9.5 and LAEO23. Furthermore, the CMC value of SDS (as an ionic surfactant) in the presence of nonionic surfactants was also examined. The result reveals that with addition of small amount of nonionic surfactant to the anionic SDS surfactant, a decline in the CMC value of the anionic–nonionic system relative to the CMC of pure anionic surfactant was observed. In addition and for the first time, the effect of UV irradiation on the size of the micelle formations was studied. It was found that UV irradiation causes the formation of smaller micelles which is of prime concern in membrane technology.     

Solubilisation of dyes by surfactant micelles. Part 3; A spectroscopic study of azo dyes in surfactant solutions†

A spectroscopic study (UV–vis and adsorption) has been made of the interactions of select model azo dyes with a range of surfactant types or their mixtures both above and below their respective critical micelle concentrations. All surfactants inhibit adsorption of the dyes to cotton above their critical micelle concentrations due to incorporation in micelles. However, formation of 1;1 complexes between dyes and cationic or zwitterionic surfactants in sub‐micellar regions results in enhanced deposition on cotton. It is shown that attractive or repulsive electrostatic interactions play a key role in dye binding to micelles. Unusually, spectra of complexes formed between the dye and cationic surfactant are typical of those of the azo tautomeric form as opposed to the hydrazone form that is prevalent in aqueous media. Addition of anionic surfactant to micellar solutions of nonionic or zwitterionic surfactants results in successive displacement of dye from the respective micelles, i.e. binding is competitive.