Structure of Hydrogen and Hydrophobically Bonded Amphiphilic Copolymer with Poly(methacrylic acid) Complexes as Revealed by Small Angle Neutron Scattering

We study by SANS the structure of intermolecular complexes formed through hydrogen bonding and hydrophobic interactions between poly(methacrylic acid) (PMA) and a neutral copolymer surfactant (PEO-PPO-PEO). The contrast variation method enables us to probe the structure factor of each polymer in the complex and their cross structure factor. The number of copolymer chains, which results from the cooperative action of hydrogen bonding and hydrophobic interactions increases as the charge of the polyacid decreases. The aggregation preserves the micellar core-corona organization of the copolymer and shrinks the polyacid chains which adopt a similar compact structure. Finally, the structure of the aggregates is compared to that of PEO-PMA homopolymer complex observed by SANS.     

Relaxation properties and complex formation of copolymers of 2-deoxy-2-methacrylamido-D-glucose and unsaturated acids

With the use of polarized luminescence, relaxation times characterizing the intramolecular mobility of luminescent labeled copolymers of 2-deoxy-2-methacrylamido-D-glucose and unsaturated acids in solutions are determined in both nonionized and ionized states. Elements of the secondary structure typical for poly(methacrylic acid) are formed in copolymers with a high content of methacrylic acid (≥50 mol %) in their nonionized state. This structure is destroyed during ionization. Equilibrium stability constants for complexes of the copolymers with cationic surfactants are determined. Quantitative characteristics of the effects of the surfactant and copolymer structures and the ionic strength of solution on complex formation are estimated.     

Solubilization of Polycyclic Aromatic Compounds into n-Decyltrimethylammonium Perfluorocarboxylate Micelles

Solubilization of polycyclic aromatic compounds in aqueous dilute solutions of three cationic amphiphiles was studied. The maximum additive concentrations (MACs) of the aromatic compounds were constant below their critical micelle concentrations (cmcs) and monotonically increased above the cmcs. The first stepwise association constants (K(1)) between a solubilizate monomer and a vacant micelle were evaluated from the MACs for the solubilizates using the mass action model for solubilization into micelles in the dilute solution. The standard Gibbs energy changes of solubilization (DeltaG degrees ) were calculated from K(1), and the enthalpy and entropy changes of solubilization were estimated from the temperature dependence. MACs of each surfactant at the same surfactant concentration above the cmc were different depending on the cmc, but there was little difference in the DeltaG degrees values. Some differences appeared in the enthalpy and entropy values in accordance with their micellar size or degrees of counterion binding to micelles. DeltaG degrees for solubilization decreased linearly with carbon number of aromatic solubilizate for each micellar solution. Copyright 2000 Academic Press.     

Probing solubilization sites in block copolymer micelles using fluorescence quenching

The solubilization sites provided by micelles formed by a diblock copolymer with one neutral hydrophobic block, polystyrene, and one charged hydrophilic block, poly(acrylic acid) or poly(methacrylic acid), have been studied by fluorescence quenching of pyrene by polar and nonpolar quenchers. Pyrene solubilized into these micelles is distributed between the inner corona and the micelle core. The fraction of pyrene residing in the inner corona is almost unity for star micelles, where the corona-forming blocks are larger than the core-forming blocks, and around 0.5 for crew-cut micelles where the opposite situation prevails. The kinetics of the quenching process depends on the pyrene location, i.e. is static in the micelle core, and largely dynamic in the inner corona at low quencher concentration. The rate constants for fluorescence quenching by nitromethane are shown to increase with increasing pH.     

Binding of a surfactant counterion to low-charge-density poly(acrylic acid) and poly(methacrylic acid)

The binding of a cationic surfactant, dodecylpyridinium (C12Py) chloride, with a low-charge-density poly (methacrylic acid) (PMA) was investigated in buffer solutions under the condition of constant pH. The binding isotherms with PMA consisted of two and three steps at a pH lower and higher than 3.2, respectively. Bindings in the first step were independent of pH and this step was considered to correspond to the solubilization of the hydrocarbon chains of C12Py into the nonpolar region of the compact form of PMA. This is the indication of the compact form from the binding isotherm. At pH higher than 3.2, the second step was discriminated and it depended on the pH. In the third step, a sharp rise in the degree of binding (β) was observed accompanying the solubilization of the precipitates of the PMA–C12Py complex. The binding with poly(acrylic acid) (PAA) and PMA in conventional unbuffered NaCl solutions was also examined and the pH profile of the solution during the binding process was determined. In the case of unbuffered NaCl solutions, the binding with PAA took place cooperatively at the critical association concentration (cac). The binding isotherm consisted of two steps and the pH decreased with the increase in β. The binding isotherm of PMA, on the other hand, consisted of three steps: the pH decreased slightly in the first step and considerably in the second step with the increase in β but it increased with β in the third step, exhibiting a pH minimum around 3.2. The binding in the first step coincided with that obtained in the buffered solutions. Linear relationships between β and the pH were found for both polymers. In the case of PMA, no cac was observed in both buffered and unbuffered NaCl solutions. Received: 24 January 2001 Accepted: 23 May 2001     

Novel temperature‐responsive water‐soluble copolymers based on 2‐hydroxyethylacrylate and vinyl butyl ether and their interactions with poly(carboxylic acids)

Novel water‐soluble amphiphilic copolymers have been synthesized by free radical copolymerization of 2‐hydroxyethylacrylate with vinyl butyl ether. In water these copolymers exhibit lower critical solution temperature, which depends on the content of hydrophobic vinyl butyl ether units. The interaction between these copolymers and poly(acrylic acid) or poly(methacrylic acid) in aqueous solutions results in formation of interpolymer complexes stabilized by hydrogen bonds and hydrophobic interactions. An increase in hydrophobicity of the copolymers leads to the enhancement of their complex formation ability with respect to poly(acrylic acid) and poly(methacrylic acid). Poly(methacrylic acid) forms stronger complexes with the copolymers when compared with poly(acrylic acid). The complexes exhibit dual sensitivity to pH‐ and temperature and this property may be easily adjusted regulating the strength of interaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 195–204, 2006     

Effects on the micellar solubilization of organic compounds by surfactant micelles. I. Length of carboxylic side chains in aromatic acids

The semiequilibrium dialysis method has been used to determine solubilization equilibrium constants and activity coefficients of benzoic, phenylacetic, and hydrocinnamic acids (solubilizate) in micelles of the cationic surfactant hexadecylpyridinum chloride (cetylpyridinium chloride) in 0.1M HCl aqueous solutions. Methods described previously were employed to infer the concentrations of monomeric organic solute and surfactant on both sides of the dialysis cell. Values of the apparent solubilization constant K of the neutral acids have been correlated with mole fractions of the acid in the micelle X_A, where K=X_A/[monomeric acid]. The activity coefficients of both acid and surfactant were obtained, consistent with the Gibbs-Duhem equation. The solubilization constants of all three acids are nearly the same, indicating that there is no significant effect owing to the presence of one or more methylene groups between the carboxylate and the phenyl groups of benzoic acid. The solubilization constants also decrease appreciably, and the activity coefficients of the acids increase, as the mole fraction of the acid in the micelle increases.     

Adsorption of nonionic surfactants on cellulose surfaces: adsorbed amounts and kinetics

Kinetic and equilibrium aspects of three different poly(ethylene oxide) alkylethers (C12E5, C12E7, C14E7) near a flat cellulose surface are studied. The equilibrium adsorption isotherms look very similar for these surfactants, each showing three different regions with increasing surfactant concentration. At low surfactant content both the headgroup and the tail contribute to the adsorption. At higher surface concentrations, lateral attraction becomes prominent and leads to the formation of aggregates on the surface. The general shape of the isotherms and the magnitude of the adsorption resemble mostly those for hydrophilic surfaces, but both the ethylene oxide and the aliphatic segments determine affinity for the surface. The adsorption and desorption kinetics are strongly dependent on surfactant composition. At bulk concentrations below the CMC, the initial adsorption rate is attachment-controlled. Above the CMC, the micellar diffusion coefficient and the micellar dissociation rate play a crucial role. For the most hydrophilic surfactant, C12E7, both parameters are relatively large. In this case, the initial adsorption rate increases with increasing surfactant concentration, also above the CMC. For C12E5 and C14E7 there is no micellar contribution to the initial adsorption rate. The initial desorption kinetics are governed by monomer detachment from the surface aggregates. The desorption rate constants scale with the CMC, indicating an analogy between the surface aggregates and those formed in solution.     

Effect of polymer nature on the structure and properties of gel composites with incorporated bentonite particles

Composite gels based on polyacrylamide and poly(N-isopropyl acrylamide) with incorporated sodium bentonite particles are synthesized. It is shown that the presence of hydrophobic isopropyl groups in a polymer molecule promotes the subsequent formation of highly ordered aggregates of clay and cetylpyridinium chloride in a gel composite. An increase in temperature results in the collapse of composite gels based on poly(N-isopropyl acrylamide); however, no marked changes in the structure of lamellar aggregates of clay and surfactant are observed. It is revealed that the gel can stabilize lamellar structures formed in organoclay suspension prior to the incorporation into swollen polymer network.     

Solubilization of silica nanoparticles in alkanes and poly(α-olefin)s by functionalized polyisobutylene oligomers

Covalent and noncovalent chemical methods that use oligomeric lipophilic agents to solubilize silica nanoparticles in heptane and poly(α-olefin) (EPAO) solvents are described. While only modest solubilization efficiencies are seen with an octadecyl group, a variety of terminally functionalized polyisobutylene (PIB) derivatives are more efficient. Both covalent and noncovalent chemistry was found to be effective. Covalent modification solubilized up to 34 wt% of silica nanoparticles (SiNPs) as stable solutions in heptane or PAOs. Noncovalent modification was however more effective, solubilizing up to 70% of SiNPs in heptane or PAOs. The most successful covalent approach used PIB oligomers containing terminal triethoxysilane groups to covalently modify SiNPs. Alternatively, SiNPs that were first functionalized with amine groups could be solubilized in heptane or PAOs with polyisobutylene containing sulfonic acid groups using acid–base chemistry. Studies of these and other solubilization chemistry was also carried out using fluorescent labels, studies that confirmed the gravimetric analyses of the heptane-solubilized SiNPs. Transmission electron microscopy of a PAO solution of these solutions showed that these SiNPs were present as small aggregates dispersed in the PAOs.     

Photophysical and conformation properties of luminescent-labeled star poly-2-isopropyl-2-oxazolines based on octa-<Emphasis Type="Italic">tert</Emphasis>-butylcalix[8]arene in solution

The synthesis of luminescent-labeled copolymers of octa-tert-butylcalix[8]arene with 8 poly-2-isopropyl-2-oxazoline arms is carried out. Each macromolecule involves one luminescent label of the anthracene structure located at the end of one of the arms. The luminescent properties of the copolymers in water and methanol are studied. It is shown that, in aqueous solutions, the formation of intermolecular aggregates with a hydrophobic core and a hydrophilic shell results in a new photophysical process of migration of electron excitation energy accompanied by a decrease in the solution luminescence polarization. The interaction of oxazoline arms with poly(methacrylic acid) via the mechanism of interpolymer complex formation implies a weakening of the efficiency of energy migration.     

Aggregation properties of oligo(methacrylic acid)-shelled dendrimer and its microenvironment in aqueous solutions

A third-generation poly(amido amine) dendrimer having poly(methacrylic acid) segments on the periphery (G3-PMAA) was newly synthesized. A xanthate-modified dendrimer (G3-X) was first prepared by condensation of the terminal amino groups of the poly(amido amine) dendrimer with an activated-ester xanthate. G3-PMAA was then synthesized by polymerization of methacrylic acid initiated with G3-X. The number-average degree of polymerization of PMAA segment was estimated to be 10. The pK_a value for G3-PMAA was evaluated to be 7.3 that is somewhat higher than that (6.8) of the corresponding linear PMAA with the same segment length, indicating the interaction of PMAA segments caused by assembling them at the dendrimer surface. When the diameter of G3-PMAA in aqueous solution at various pHs was measured by a dynamic light scattering, G3-PMAA was found to self-aggregate in a pH region, where the PMAA segment took a hydrophobic, compact coil conformation. Subsequently, the interaction of a fluorescent probe (1-anilino-8-naphthalenesulfonic acid ammonium salt (ANS)) with G3-PMAA was examined by means of fluorescence spectroscopy. As a result, ANS was found to bind to the hydrophobic site of G3-PMAA aggregates at lower pH, and to be released into water phase at higher pH.     

The Solubilization of Isophorone in Ionic Surfactant Solutions

Solubilization of isophorone was studied in an anionic and a cationic surfactant solution of SDS and BKC respectively. Solubility of isophorone increases with increase in the surfactant concentrations due to solubilization in micelles. FT NMR spectroscopy was used to understand the location and orientation of isophorone at the micellar interface.     

Adsorption of octadecyltrimethylammonium chloride and adsolubilization on to cellulosic fibers

The coadsorption of different organic solutes on cellulosic fibers treated with octadecyltrimethylammonium chloride (ODTMA) has been studied. In the absence of ODTMA cellulosic fibers had little tendency to retain organic compounds. The enhanced solute incorporation was ascribed to the adsolubilization of these compounds on the aggregated domains of the adsorbed surfactant molecules at the solid/liquid interface. The specific shape of solute coadsorption isotherms indicated that the adsolubilization process may be regarded as a partition phenomenon between the aqueous bulk phase and the adsorbed surfactant aggregates. The decrease in solute uptake at the cellulose/water interface above the CMC of ODTMA was ascribed to micelle formation in the bulk solution and to the ensuing micellar solubilization of organic solutes. Preliminary experiments performed using vertical fixed bed columns showed that modified cellulosic fibers can be conveniently used as substrate for treating organic pollutants.     

Interfacial solubilization of model amphiphilic molecules in block copolymer micelles

We investigate the solubilization of 2-nitrodiphenylamine, a hydrophobic but polar dye molecule, in aqueous solutions of polystyrene(310)-b-poly(acrylic acid)(47) micelles. The solubilization capacity of the micelles, which consist of a polystyrene core and poly(acrylic acid) corona, and the micelle-water partition coefficient are evaluated as a function of the solubilizate concentration. The solubilization isotherm shows a nonlinear behavior, and the partition coefficient, instead of being constant, is strongly dependent on the dye concentration. These results are explained by treating solubilization as a binding process, and by fitting the data to a Langmuir adsorption model. In addition, we examine the locus of solubilization of 2-nitrodiphenylamine using its solvatochromic properties and solubility in model solvents, and we identify the micellar interface as the solubilization site. Confirmatory studies, including the dependence of solubilization on the interfacial area of the aggregates, the role of the poly(acrylic acid) corona chains in stabilizing the solubilized molecules, and the effect of the solubilizate structure on the extent of incorporation, were also conducted. The results, consistent with surface localization, show that solubilization is dependent on the interfacial area of the aggregates, and on the affinity of the solubilizate for the micellar interface.     

Polymerisation radiochimique de l''acide methacrylique en solution

The polymerization of methacrylic acid was investigated in various solvents under the action of gamma-rays. It was found that, as in the case of acrylic acid, solvents could be divided into groups according to the observed effects. The addition of methanol or dioxane up to 50 per cent does not significantly alter the polymerization rate. These two solvents do not dissociate the plurimolecular aggregates of methacrylic acid, the presence of which is demonstrated by the high viscosity of the medium. In the presence of either toluene or n-hexane, the rate gradually decreases and the aggregates are dissociated. Chloroform and CCl₄ also dissociate the aggregates but lead to acceleration of the reaction. This effect which was not observed with acrylic acid presumably results from an energy transfer process. The polymerization of methacrylic acid in bulk and in solution has a very small overall activation energy, 1·0–1·5 kcal/mole between 16 and 60°. All conversion curves are linear in contrast to the case of acrylic acid where auto-accelerated conversion curves were observed in most mixtures. A comparison of these results shows that the initial rates of polymerization of acrylic acid follow relationships similar to those observed for methacrylic acid except for the chlorinated solvents. It is concluded that the molecular aggregates produce the same influence on the polymerization of methacrylic acid as on the initial stages of the reaction for acrylic acid, but the “matrix effect” of poly(acrylic acid) does not appear in the case of poly(methacrylic acid).     

Physical properties of aqueous solutions of a thermo-responsive neutral copolymer and an anionic surfactant: turbidity and small-angle neutron scattering studies

Aqueous mixtures of the anionic sodium dodecyl sulfate (SDS) surfactant and thermo-responsive poly(N-vinylcaprolactam) chains grafted with omega-methoxy poly(ethylene oxide) undecyl alpha-methacrylate (PVCL-g-C11EO42) have been characterized using turbidimetry and small-angle neutron scattering (SANS). Turbidity measurements show that the addition of SDS to a dilute aqueous copolymer solution (1.0 wt %) induces an increase of the cloud point (CP) value and a decrease of the turbidity at high temperatures. In parallel, SANS results show a decrease of both the average distance between chains and the global size of the objects in solution at high temperatures as the SDS concentration is increased. Combination of these findings reveals that the presence of SDS in the PVCL-g-C11EO42 solutions (1.0 wt %) promotes the formation of smaller aggregates and, consequently, leads to a more homogeneous distribution of the chains in solution upon heating of the mixtures. Moreover, the SANS data results show that the internal structure of the formed aggregates becomes more swollen as the SDS concentration increases. On the other hand, the addition of moderate amounts of SDS (up to 4 mm) to a semidilute copolymer solution (5.0 wt %) gives rise to a more pronounced aggregation as the temperature rises; turbidity and SANS studies reveal in this case a decrease of the CP value and an increase of the scattered intensity at low q. The overall picture that emerges from this study is that the degree of aggregation can be accurately tuned by varying parameters such as the temperature, level of surfactant addition, and polymer concentration.     

On the Behavior of Nonionic Surfactants at the N-Heptane/Silica Gel Interface: Influence of the Presence of Interfacial Water Inferred from Adsorption Isotherms and Calorimetric Data

The behavior of two polydisperse nonionic surfactants, poly (oxyethylene) glycol alkylphenyl ether TX-35 and TX-100, at the prewetted silica gel/n-heptane and dried silica gel/n-heptane interfaces has been compared by the determination of the average adsorption isotherms of the polydisperse surfactants and of displacement enthalpies. From HPLC experiments, we could also separately quantify the adsorption of each ethyleneoxide (EO) fractions for silica gel from the polydisperse surfactant solution. The adsorption isotherms clearly indicate an incomplete preferential adsorption of the large (EO) chains over the small ones, as well on dried silica gel as on a prehydrated sample. This preferential adsorption and its driving force follow the solubility rules of the poly(oxyethylene) glycol alkylphenyl ether in an apolar solvent and support the idea of a solubility-limited adsorption: solubility in organic solvents of the smaller (EO) chains is much more significant than that of the longer ones and hence prevents adsorption of the smaller species. Consequently, it is observed that the presence of interfacial water decreases the affinity of TX-35 molecules for the hydrophilic silica surface due to the hydration of (EO) chains. In contrast, for TX-100 adsorption after the prewetting treatment the clearest trend is a drastic increase of the adsorption ascribed to the additional solubilization (and micellization) of the TX-100 molecules in the interfacial aqueous phase. The differential molar enthalpies of displacement show a change in the adsorption mechanism, depending on the presence of molecular water on the surface. In the initial part of the adsorption isotherm, a prevailing exothermic process is obtained with prehydrated silica and suggests that hydration of the polar heads of TX-35 and the solubilization of the TX-35 in interfacial water are occurring. For higher equilibrium concentrations, the enthalpies of displacement observed with the prehydrated adsorbent become slightly lower than those obtained with dry silica gel. It may be that this difference is due to the micellization phenomenon of the surfactant species with longer EO chains in interfacial water. These features emphasize the influence of interfacial water on the adsorption of EO fractions from organic solvent. Copyright 2000 Academic Press.     

Spectrophotometric study of anionic azo-dye light yellow (X6G) interaction with surfactants and its micellar solubilization in cationic surfactant micelles

Solubilization and interaction of azo-dye light yellow (X6G) at/with cationic surfactants cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC) was investigated spectrophotometricaly. The effect of cationic micelles on solubilization of anionic azo dye in aqueous micellar solutions of cationic surfactants was studied at pH 7 and 25 degrees C. The binding of dye to micelles implied a bathochromic shift in dye absorption spectra that indicates dye-surfactant interaction. The results showed that the solubility of dye increased with increasing surfactant concentration, as a consequence of the association between the dye and the micelles. The binding constants, K(b), were obtained from experimental absorption spectra. By using pseudo-phase model, the partition coefficients between the bulk water and surfactant micelles, K(x), were calculated. Gibbs energies of binding and distribution of dye between the bulk water and surfactant micelles were estimated. The results show favorable solubilization of dye in CTAB micelles.     

Silicon-mediated synthesis of new amphiphilic oligomers

A series of amphiphilic oligomers have been synthesized in which the hydrophobic component was polyisobutylene, polystyrene, poly(methyl methacrylate) or dodecane, and the hydrophilic component was poly(vinyl alcohol) or poly(methacrylic acid). These syntheses exploited the chain extension chemistry of aldehyde-functionalized materials using silyl aldol polymerization or the group transfer polymerization of methacrylates. The interfacial character of these new amphiphilic oligomers was examined using water/toluene emulsification tests. © 1997 John Wiley & Sons, Inc.