Influence of urea additives on micellar morphology/protein conformation

The present study highlights the fact that the effect of additives (urea, monomethylurea, thiourea) on the supramolecular assemblies and proteins is strikingly similar. To investigate the effect, a viscometeric study on sphere-to-rod transition (s-->r) was undertaken in a system (3.5% tetradecyltrimethylammonium bromide+0.05 M NaBr + 1-pentanol [P.M. Lindemuth, G.L. Bertand, J. Phys. Chem. 97 (1993) 7769]) in the presence and absence of the said additives. [1-pentanol] needed for s-->r (i.e. [1-pentanol]s-->r) was determined from the relative viscosity versus [1-pentanol] profiles. It was observed that the additives preponed as well as postponed s-->r depending upon their nature and concentrations. These effects are explained in terms of increased polarity of the medium and the adsorption ability of urea/monomethylurea on the charged surfactant monomers of the micelle. In case of thiourea, postponement of s-->r was observed throughout which is attributed to its structure. To derive an analogy between micelles and proteins the additive-induced conformational changes of the protein, bovine serum albumin (BSA) was taken to monitor secondary structural changes and tryptophanyl fluorescence. A marked increase in secondary structure (far-UVCD) and increased tryptophanyl fluorescence with a marked blue shift in lambdamax was observed in presence of low concentrations of urea or alkylurea. This indicates that a more compact environment is created in presence of these additives, if added judiciously. Addition of thiourea to BSA caused a marked quenching without any significant change in lambdamax. The large decrease in tryptophanyl emission in presence of low thiourea concentrations seems to be specific and related to thiourea structure as no corresponding changes were observed in urea/alkylurea. All these effects pertaining to protein behavior fall in line with that of morphological observations on the present as well as surfactant systems studied earlier [S. Kumar, N. Parveen, Kabir-ud-Din, J. Phys. Chem. B 108 (2004) 9588].     

Spectroscopic probing of the effect of alkanols on the properties of the head group region in reverse micelles of AOT-heptane-water

The effects of addition of alkanols (ethanol, n-hexanol, and 3-ethyl-3-pentanol) on the micropolarity and microviscosity of the head group region in reverse micelles of AOT-heptane-water have been investigated by fluorescence probing methods (ANS fluorescence yield and TMADPH fluorescence anisotropy), complemented by the use of the solvatochromic probe E(T)(30) in absorption spectroscopy. For all the alkanols considered, ANS fluorescence in AOT reverse micelles (at W=3) is quenched by additive incorporation, being the effect elicited almost independent of the alkanol chain length and topology. As sensed by the E(T)(30) parameter, the micropolarity of the micelle surface increases, remains unmodified, and decreases upon addition of ethanol, 3-ethyl-3-pentanol, and hexanol, respectively. While ethanol barely modifies the fluorescence anisotropy of TMADPH, 3-ethyl-3-pentanol and n-hexanol addition strongly decrease it. The similarity of the tendencies of ANS data to TMADPH anisotropies and the differences between ANS data and E(T)(30) values would indicate that, at least for 3-ethyl-3-pentanol and n-hexanol, microviscosity, rather than micropolarity, must be considered to interpret the effect of the alkanols upon the fluorescent behavior of ANS.     

Effect of urea on the enzymatic activity of a lipase entrapped in AOT-heptane-water reverse micellar solutions

A study has been made of the effect of urea upon the hydrolysis of 2-naphthyl acetate (2-NA) catalyzed by lipase from Rhizopus arrhizus in AOT-heptane-water reverse micellar solutions at pH 7. The partition constants, K, of 2-NA between n-heptane and aqueous urea solutions in the absence of micelles were also determined. It was found that K decreases when the concentration of urea increases. In aqueous solution the rate of hydrolysis of 2-NA catalyzed by lipase is dependent on the concentration of urea (at a given 2-NA concentration). This result can be due to a decrease in the magnitude of the association of lipase with 2-NA and/or to changes in the reaction rate of the lipase-2-NA complex. The modifications of the enzymatic activities elicited by addition of urea show a lineal correlation with K, emphasizing the relevance of hydrophobic effects in the loss of activity. Nevertheless, the slope of the line is higher than one, suggesting that changes in the conformation of the enzyme would be also important. Addition of urea to the micellar solutions provokes a decrease of the enzyme activity. From the dependence of the reaction rate with AOT concentration, the partition constant of 2-NA between n-heptane and the micelles, K(p), was obtained. In the presence of 2 M urea a value of K(p)=0.33 M(-1) was derived. This value is lower than that measured in the absence of urea (Aguilar et al., Arch. Biochem. Biophys. 388 (2001) 231), indicating that incorporation of urea to the micellar interface produces a decrease of the association of 2-NA with the micelles. From a comparison of the results obtained in the micellar solution and in aqueous solution, it is concluded that the enzyme is more resistant to denaturation by urea in the micellar solution than in aqueous solution. Furthermore, at intermediate urea concentrations (2 M), the additive produces an increase in the Michaelis constant (K(M)) without a significant decrease (or even a small increase) in the catalytic rate constant (k(cat)).     

Stabilizing effect of low concentrations of urea on reverse micelles

Urea is a well-known destabilizing agent for biopolymers like proteins and molecular aggregates like micelles and reverse micelles. Several theories have been proposed to explain the destabilizing/denaturing effect of urea. In this work, we present evidence for a stabilizing effect of a low concentration (<1 M) of urea incorporated in the central pool of AOT/n-heptane/water reverse micelles. Static light-scattering experiments were performed to measure (w0)cr--the molar ratio of water to AOT beyond which the micelles become unstable--as a function of the concentration of urea in the central water pool. The stabilizing effect of urea is reflected in an increase in the value of (w0)cr at low urea concentrations over that in the absence of urea. Dynamic light-scattering experiments show that the hydrodynamic radius of the micelles is smaller at low urea concentrations (<1 M) than in the absence of urea. Size-distribution analysis shows that for w0=20 the microemulsion containing 0.5 M urea in its pool is significantly more monodisperse than that containing no urea. Temperature-dependent studies in the range 15-65 degrees C indicate that the magnitude of this stabilizing effect decreases with increasing temperature, vanishing at temperatures higher than 65 degrees C. A model is proposed to explain the above results.     

On the molecular mechanism of stabilization of proteins by cosolvents: role of Lifshitz electrodynamic forces

Several ionic and nonionic additives are known to affect structural stability of proteins in aqueous solutions. At a fundamental level, the mechanism of stabilization or destabilization of proteins by cosolvents must be related to three-body interactions between the protein, additive, and the water medium. In this study, the role of the Lifshitz-van der Waals electrodynamic interaction between various additives (sucrose, glycerol, urea, poly(ethylene glycol)-200, betaine, taurine, proline, and valine) and bovine serum albumin (BSA) in water medium was examined. The electrodynamic interaction energy was attractive for all of the additives studied here when both far ultraviolet and infrared relaxations of the additives were included in their dielectric susceptibility representations. However, when only the infrared contribution was included for structure stabilizers and both far ultraviolet and infrared contributions for the structure destabilizers, the resulting electrodynamic interaction energy (E/kT) followed the structure stabilizing and/or destabilizing behavior of the additives; that is, the interaction was attractive for urea and PEG200 (structure destabilizers), whereas it was repulsive for sucrose, glycerol, betaine, taurine, alanine, valine, and proline (structure stabilizers). The electrodynamic interaction energy E/kT at any given surface-to-surface separation distance between the additives and BSA was positively correlated (r(2) = 0.92) with the experimental thermal denaturation temperature (T(d)) of BSA in 1 M solutions of the additives. These analyses provided a mechanistic basis for the experimental observations of exclusion of the structure-stabilizing additives from the protein-water interface and binding of the structure-destabilizing additives to the protein surface. The role of water structure in the three-body electrodynamic interaction is discussed. It is hypothesized that in the case of additives that enhance water structure the hydration shells formed around the additives effectively dampen the contribution of ultraviolet frequencies to the dielectric susceptibility of the additives and thus impart repulsive electrodyanamic interaction between the additive and the protein, whereas the opposite occurs in the case of additives that breakdown the hydrogen-bonded structure of water.     

碱性溶液中锌电极缓蚀的研究

研究了硝酸铅（Pb(NO3)2）和十二烷基苯磺酸钠（SDBS）及二者组成的复合添加剂对在3mol•L-1 KOH溶液中锌电极电化学行为的影响, 结果表明:两种添加剂均具有一定的缓蚀作用,而其复合添加剂的协同效应、缓蚀效果最佳.     

Hydrotropic salt promotes anionic surfactant self-assembly into vesicles and ultralong fibers

Molecular self-assembly has become a versatile approach to create complex and functional nanoarchitectures. In this work, the self-assembly behavior of an anionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a hydrotropic salt (benzylamine hydrochloride, BzCl) in aqueous solution is investigated. Benzylamine hydrochloride is found to facilitate close packing of surfactants in the aggregates, inducing the structural transformation from SDBS micelles into unilamellar vesicles, and multilamellar vesicles. The multilamellar vesicles can transform into macroscale fibers, which are long enough to be visualized by the naked eye. Particularly, these fibers are robust enough to be conveniently separated from the surfactant solution. The combined effect of non-covalent interactions (e.g., hydrophobic effect, electrostatic attractions, and π-π interactions) is supposed to be responsible for the robustness of these self-assembled aggregates, in which π-π interactions provide the directional driving force for one-dimensional fiber formation.     

Equilibrium surface adsorption behavior in complex anionic/nonionic surfactant mixtures

Neutron reflectivity (NR) and small angle neutron scattering (SANS) have been used to investigate the equilibrium surface adsorption behavior and the solution microstructure of mixtures of the anionic surfactant sodium 6-dodecyl benzene-4 sulfonate (SDBS) with the nonionic surfactants monododecyl octaethylene glycol (C12EO8) and monododecyl triiscosaethylene glycol (C12EO23). In the SDBS/C12EO8 and SDBS/C12EO23 solutions, small globular mixed micelles are formed. However, the addition of Ca2+ ions to SDBS/C12EO8 results in a transition to a vesicle phase or a mixed vesicle/micellar phase for SDBS rich compositions. In contrast, this transition hardly exists for the SDBS/C12EO23 mixture, and occurs only in a narrow composition region which is rich in SDBS. The adsorption of the SDBS/C12EO8 mixture at the air-solution interface is in the form of a mixed monolayer, with a composition variation that is not consistent with ideal mixing. In water and in the presence of NaCl, the nonideality can be broadly accounted for by regular solution theory (RST). At solution compositions rich in SDBS, the addition of Ca2+ ions results in the formation of multilayer structures at the interface. The composition range over which multilayer formation exists depends upon the Ca2+ concentration added. In comparison, the addition of a simple monovalent electrolyte, NaCl, at the same ionic strength does not have the same impact upon the adsorption, and the surface structure remains as a monolayer. Correspondingly, in solution, the mixed surfactant aggregates remain as relatively small globular micelles. In the presence of Ca2+ counterions, the variation in surface composition with solution composition is not well described by RST over the entire composition range. Furthermore, the mixing behavior is not strongly correlated with variations in the solution microstructure, as observed in other related systems.     

Studies on the Interaction of SDS with Gelatin in Presence of Urea Derivatives

The interactions of an anionic surfactant sodium dodecyl sulfate (SDS) in presence of urea and its derivatives with different percentage compositions of gelatin solutions were investigated by viscosity, conductivity, Fourier transform infrared spectroscopy (FTIR) and circular dichroism (CD) spectroscopic measurements at 35°C. The additives used were urea (U), thiourea (TU), mono methyl urea (MU), dimethyl urea (DMU), and tetra methyl urea (TMU). Circular dichroism spectroscopy reveals the linear decrease in molar ellipticity as the concentration of urea (and its derivatives) increases, without any change in the conformation of gelatin. This is contrary to the expected denaturation of gelatin in presence of urea. FTIR studies probe the characteristic effect of additive, thiourea on the gelatin-SDS system. The transition of gelatin from an unfolded state to the folded one has some resemblance to micelle formation because both processes are governed by the same basic intermolecular and ionic forces. In this work, we present an evidence for the stabilizing effect of urea and its alkyl derivatives in moderate concentration ranges of surfactant and gelatin.     

Unlike surfactant–polymer interactions of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate with water-soluble polymers

Single and mixed micelle formation by sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS) and their mixtures in pure water and in the presence of water-soluble polymers such as Synperonic 85 (triblock polymer, TBP), hydroxypropylcellulose (HPC), and carboxymethylcellulose sodium salt (CMC) were studied with the help of conductivity, pyrene fluorescence, cyclic voltammetry, and viscosity measurements. Conductivity measurements showed a single aggregation process for pure surfactants and their mixtures both in pure water as well as in the presence of water-soluble polymers. Triple breaks corresponding to two aggregation processes for SDS, SDBS, and their mixture in the presence of TBP were observed from fluorescence measurements. The first one demonstrated the critical aggregation process due to the adsorption of surfactant monomers on TBP macromolecule. The second one was attributed to the participation of surfactant–polymer aggregates formed at the first one, in the micelle formation process. The aggregation number ( N _agg) of single and mixed micelles and diffusion coefficient ( D) of electroactive probe were computed from the fluorescence and cyclic voltammetry measurements, respectively. Both parameters, along with the viscosity results, indicated stronger SDS–polymer interactions in comparison to SDBS–polymer interactions. Mixed surfactant–polymer interactions showed compensating effects of both pure surfactants. The nature of mixed micelles was found to be ideal in all cases, as evaluated by applying the regular solution and Motomura's approximations.     

Micellae catalysis of the oxidation of 1,4-dihydro-nicotinamides by methylene blue part 2

The oxidation of 1-R-1,4-dihydronicotinamides (1a: R = benzyl, 1b:R = octyl, 1c:R = cetyl) by methylene blue has been studied in the presence of micelles of cetyltrimethylammonium bromide (CTAB), polyoxyethylene[23]lauryl ether (Brij^® 35) and sodium dodecylbenzenesulfonate (SDBS). In CTAB, a small rate enhancement was observed below the cmc, followed by a gradual decrease above the cmc. Brij 35 has little effect on the reaction rate. The rate vs. concentration profile in SDBS shows a very sharp maximum near the cmc for 1b and 1c, whereas a more moderate increase in rate is observed for 1a. The effects are analyzed in terms of the pseudophase model for micellar catalysis, and it appears that the observed rate enhancements can be completely ascribed to increments of the reactant concentration in the micellar pseudophase. Comparison with rate effects in sodium dodecylsulfate (SDS) micelles reveals that the reaction in SDBS micelles proceeds in a more polar environment. This provides kinetic evidence that the aryl moiety in SDBS allows a deeper penetration of water molecules into the micelle, thus giving rise to a more open surface for SDBS micelles than for SDS micelles.     

Emulsion polymerization of styrene using an alkali-soluble random copolymer as polymeric emulsifier

An alkali-soluble random copolymer (ASR), poly(styrene/α-methylstyrene/acrylic acid), was used as a polymeric emulsifier in the emulsion polymerization of styrene. The calorimetric technique was applied to study the kinetics of emulsion polymerization of styrene using ASR and a conventional ionic emulsifier, sodium dodecyl benzenesulfonate (SDBS). ASR could form aggregates like micelles, and the solubilization ability of the aggregates was dependent on the neutralization degree of ASR. The rate of polymerization in the ASR system was lower than that in the SDBS system. This result can be explained by the creation of a hairy ASR layer around the particle surface, which decreases the diffusion rate of free radicals through this region. Although a decrease in particle size was observed, the rate of polymerization decreased with increasing ASR concentration. The higher the concentration of ASR is, the thicker and denser ASR layer may be, and the more difficult it would therefore be for radicals to reach the particle through this layer of ASR. The rate of polymerization decreased with increasing the neutralization degree of ASR. The aggregates with high neutralization of ASR are less efficient in solubilizing the monomer and capturing initiator radicals than that of the lower neutralization degree, which leads to decrease in rate of polymerization. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2865–2872, 1998     

Ionic liquid-induced unprecedented size enhancement of aggregates within aqueous sodium dodecylbenzene sulfonate

Physicochemical properties of aqueous micellar solutions may change in the presence of ionic liquids (ILs). Micelles help to increase the aqueous solubility of ILs. The average size of the micellar aggregates within aqueous sodium dodecylbenzene sulfonate (SDBS) is observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM) to increase in a sudden and drastic fashion as the IL 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]) is added. Similar addition of [bmim][PF(6)] to aqueous sodium dodecyl sulfate (SDS) results in only a slow gradual increase in average aggregate size. While addition of the IL [bmim][BF(4)] also gives rise to sudden aggregate size enhancement within aqueous SDBS, the IL 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF(4)]), and inorganic salts NaPF(6) and NaBF(4), only gradually increase the assembly size upon their addition. Bulk dynamic viscosity, microviscosity, dipolarity (indicated by the fluorescent reporter pyrene), zeta potential, and electrical conductance measurements were taken to gain insight into this unusual size enhancement. It is proposed that bmim(+) cations of the IL undergo Coulombic attractive interactions with anionic headgroups at the micellar surface at all [bmim][PF(6)] concentrations in aqueous SDS; in aqueous SDBS, beyond a critical IL concentration, bmim(+) becomes involved in cation-π interaction with the phenyl moiety of SDBS within micellar aggregates with the butyl group aligned along the alkyl chain of the surfactant. This relocation of bmim(+) results in an unprecedented size increase in micellar aggregates. Aromaticity of the IL cation alongside the presence of sufficiently aliphatic (butyl or longer) alkyl chains on the IL appear to be essential for this dramatic critical expansion in self-assembly dimensions within aqueous SDBS.     

Location of solubilizate in water-AOT-isooctane systems using positron lifetime spectroscopy

In the present work, positrons have been used as a probe to locate the interaction site of the additive molecules in a membrane mimetic system similar to reverse micelles. The systems investigated are water-AOT Aerosol OT [Sodium bis(2-ethylhexyl) sulfosuccinate)-isooctane solutions. Positron lifetime measurements have been performed in water-AOT-isooctane solutions containing chloroform and dichloromethane, respectively, as additives. The choice of these additives is based on their physiological importance. A comparison of the behavior of positron annihilation parameters in surfactant solutions containing the additives with that in systems without them has been made. It has provided some information about the location of the interaction site of the additive molecules in these solutions. In chloroform, the additive molecules tend to migrate from the bulk solvent to the aggregates and are adsorbed either at the interface or close to it. The dichloromethane molecules, on the other hand, tend to get distributed near the hydrocarbon tail of the AOT molecules closer to the bulk solvent.     

Aqueous block copolymer-surfactant mixtures and their ability in solubilizing chlorinated organic compounds. A thermodynamic and SANS study

Within the topic of surfactant enhanced solubilization of additives sparingly soluble in water, volumetric, solubility, conductivity, and small-angle neutron scattering (SANS) experiments on mixtures composed of alpha,omega-dichloroalkane, surfactant, copolymer, and water were carried out at 298 K. The triblock copolymers (ethylene oxide)132(propylene oxide)50(ethylene oxide)132 (F108) and (ethylene oxide)76(propylene oxide)29(ethylene oxide)76 (F68) were chosen to investigate the role of the molecular weight keeping constant the hydrophilic/hydrophobic ratio. The selected surfactants are sodium decanoate (NaDec) and decyltrimethylammonium bromide (DeTAB) with comparable hydrophobicity and different charged heads. The alpha,omega-dichloroalkanes were chosen as contaminant prototypes. For the water + surfactant + copolymer mixtures, both the volume and the SANS results straightforwardly evidenced that (1) monomers of NaDec and copolymer unimers generate small mixed aggregates, (2) monomers of DeTAB combined with copolymer unimers do not form aggregates, and (3) unimeric copolymer is solubilized into NaDec and DeTAB micelles. The alpha,omeaga-dichloroalkanes presence induces the F108 aggregation even at very low copolymer composition. The addition of surfactant disintegrates the F108 aggregates and, consequently, the additive is expelled into the aqueous phase. Once F108 is in the unimeric state, it forms copolymer-micelle aggregates which incorporate the oil. In the case of F68 both the volumetric and the SANS data reveal that the additive does not alter the copolymer unimeric state. Moreover, they show that for the aqueous DeTAB-F68 system the additive trapping in both the copolymer-micelle aggregate and the pure micelles takes place being enhanced in the former aggregate in agreement with solubility experiments. For the NaDec-F68 mixtures, an additional solubilization process in the premicellar copolymer-surfactant microstructures occurs. SANS and conductivity data show that the additive incorporation into the mixed and the pure micelles does not essentially influence the structural properties of the aggregates.     

Effect of self‐assemblies of various surfactants in their single and mixed states on the BZ oscillatory reaction

Micelles of different surfactants are well known to affect chemical equilibria and reactivities by selectively sequestering the reagent substrates through electrostatic and hydrophobic interactions. In this article, the effects of micelles of various surfactants on different parameters of the Ce(IV)‐catalyzed Belousov–Zhabotinsky (BZ) oscillatory reaction at 35°C in nonstirred closed conditions are studied by employing spectrophotometry and tensiometry. Surfactants used in this study are the cationics hexadecyltrimethylammonium bromide (CTAB) and pentamethylene‐1,5‐bis(N‐hexadecyl‐N,N‐dimethylammonium)bromide gemini (Gemini), anionic sodium dodecylbenzene sulfonate (SDBS), and nonionic Brij58, whereas the binary surfactant systems used are cationic–nonionic CTAB+Brij58 and anionic–nonionic SDBS+Brij58. The results revealed that the induction period shows a definite variation with increasing concentration of different surfactants above their critical micelle concentration (cmc). The amplitudes of oscillation and absorbance maxima and minima are enhanced in the presence of micelles of CTAB and Gemini surfactants, whereas micelles of SDBS and Brij58 have almost no effect on the nature of the oscillations. However, mixed micelles of CTAB+Brij58 and SDBS+Brij58 binary mixtures show a quite different effect on the overall behavior of the oscillations. The enhanced effect of CTAB and Gemini surfactants on the overall nature of oscillations has been attributed to the positive charge on the surface of their micelles and to some extent on the presence of nitrogen in their head group. The effect of mixed binary micelles may be attributed to their synergistic nature. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 659–668, 2010     

Retention prediction in reversed-phase liquid chromatography systems with methanol/water mobile phases containing different alkanols as additives

In an effort to gain enhancement of selectivity in reversed-phase liquid chromatography, retention was tuned in this study by introducing short and medium straight-chained-length alkanol additives (methanol (MeOH), ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol or 1-heptanol) at low concentrations in mobile phases containing MeOH as the main organic solvent. A six-parameter retention model considering simultaneously the contents of the main organic modifier and of the alcohol additive as well as of the number of alkyl chain of additive was developed by a direct combination of equations expressing separately a linear dependence of the retention upon each of these factors. The effectiveness of the above model was tested in the retention prediction of a mixture of six alkylbenzenes under isocratic conditions with mobile phases containing as an additive any member of the homologues series of alkanols (with 1-7 carbon atoms) at different low concentrations in a wide range of MeOH-water mixtures. The prediction was excellent in all cases even when the alkanol additives used in experiments for the fitting procedure are different than those used in chromatographic runs done for testing the prediction ability of the proposed model.     

Urea-induced demicellization of Pluronic L64 in water

The micellar behavior of a polyethylene oxide block–polypropylene oxide block–polyethylene oxide copolymer Pluronic L64 in aqueous urea solutions (urea concentrations 0, 1, 2, 3, 4, and 6 M) by physical methods, viz. cloud point and viscosity, spectral techniques (Fourier transform infrared, fluorescence, and nuclear magnetic resonance), differential scanning calorimetry, and dynamic light scattering is reported. The presence of urea causes an increase in the clouding temperature, critical micellization temperature, and the structural transition (spherical micelles to ellipsoid/rod) temperature; different methods showed good agreement. Urea induces demicellization of L64, enhancing accumulation of water molecules surrounding micelles. L64 micelles show growth at high temperatures, but this micellar transition is suppressed by urea, as proven by calorimetric and viscometric methods. The results are discussed in terms of the molecular mechanism underlying the effects of urea.     

表面活性剂对驱油聚合物界面剪切流变性质的影响

利用双锥法研究了表面活性剂十二烷基苯磺酸钠(SDBS)和十六烷基三甲基溴化铵(CTAB)对油田现场用部分水解聚丙烯酰胺(PHPAM)和疏水改性聚丙烯酰胺(HMPAM)溶液的界面剪切流变性质的影响,实验结果表明:HMPAM分子通过疏水作用形成界面网络结构,界面剪切复合模量明显高于PHPAM.SDBS和CTAB通过疏水相互作用与HMPAM分子中的疏水嵌段形成聚集体,破坏界面网络结构,剪切模量随表面活性剂浓度增大明显降低.同时,界面膜从粘性膜向弹性膜转变.低SDBS浓度时,少量SDBS分子与PHPAM形成混合吸附膜,界面膜强度略有升高;SDBS浓度较高时,界面层中PHPAM分子被顶替,吸附膜强度开始减弱.阳离子表面活性剂CTAB通过静电相互作用中和PHPAM分子的负电性,造成聚合物链的部分卷曲,从而降低界面膜强度.弛豫实验结果证实了表面活性剂破坏HMPAM网络结构的机理.     

Mixed adsorption of poly(vinylpyrrolidone) and sodium dodecylbenzenesulfonate on kaolinite

The mixed adsorption of the nonionic polymer poly(vinylpyrrolidone) (PVP) and the anionic surfactant sodium dodecylbenzenesulfonate (SDBS) on kaolinite has been studied. Both components adsorb from their mixture onto the clay mineral. The overall adsorption process is sensitive to the pH, the electrolyte concentration, and the amounts of polymer and surfactant. Interpretation of the experimental data addresses also the patchwise heterogeneous nature of the clay surface. In the absence of PVP, SDBS adsorbs on kaolinite by electrostatic and hydrophobic interactions. However, when PVP is present, surfactant adsorption at 10(-2) M NaCl is mainly driven by charge compensation of the edges. The adsorption of PVP from the mixture shows similar behavior under different conditions. Three regions can be distinguished based on the changing charge of polymer-surfactant complexes in solutions with increasing SDBS concentration. At low surfactant content, PVP adsorbs by hydrogen bonding and hydrophobic interactions, whereas electrostatic interactions dominate at higher surfactant concentrations. Over the entire surfactant concentration range, polymer-surfactant aggregates are present at the edges. The composition of these surface complexes differs from that in solution and is controlled by the surface charge.