Light-responsive hydrophobic association of azobenzene-modified poly(acrylic acid) with neutral surfactants

Photoresponsive association between azobenzene-modified poly(acrylic acid)s (AMPs) and the nonionic surfactants tetraethylene glycol monododecyl ether and octadecyl ether (C12E4 and C18E4) has been achieved in dilute aqueous solution. The binding was investigated by (i) spectrophotometry that probes the polarity close to the azobenzene chromophore, (ii) capillary electrophoresis to obtain the amount of C12E4 bound per polymer chain, and (iii) pressure-area curves of Langmuir films to obtain information on the adsorption of AMP at the water-C18E4 interface. Increasing hydrophobicity of AMP (with increasing degree of modification with azobenzene side-groups) tightened the association with C12E4 in the dark. Exposure to UV light rapidly converted the azobenzene to their more polar cis isomer, which in turn weakened the association with surfactant. Almost complete photorelease of bound C12E4 was obtained with the optimal structure of AMP. Adsorption on large interfaces is much less sensitive to light. The possible origin of the photoresponse is analyzed in terms of AMP affinity for surfactant assemblies and azobenzene penetration in the hydrophobic core of micelles. We propose that the photoswing of polarity is amplified by the binding to small micelles because of the small number of anchors involved. A few azobenzene anchors afford tight binding in the dark, but also detach more easily than the whole AMP chain upon photoisomerization.     

Calorimetric investigation of poly(methacrylic acid) and poly(acrylic acid) in aqueous solution

The enthalpy of dissociation of poly(acrylic acid) and of poly(methacrylic acid) in water and in 0.5N NaCl at 25°C has been measured over a wide range of degrees of neutralization of the polyelectrolytes. In the case of poly(methacrylic acid) the calorimetric data permit the direct evaluation of the enthalpy of conformational transition of the polymer. For this transition, with the aid of standard free energy data derived from potentiometric titrations, the change in entropy was also estimated. The relative accuracy of the thermodynamic data, and the possibility of deriving therefrom information on the mechanism of transitions of the type, globular coils → expanded coils for partially hydrophobic synthetic polyelectrolytes in aqueous solution are discussed.     

Effect of urea on poly(methacrylic acid) and poly(acrylic acid) aqueous solutions

The effects of urea on aqueous solutions of both poly(methacrylic acid (PMA) and poly(acrylic acid) (PAA) have been investigated by using potentiometry, viscometry and study of the fluorescence of Auramine O, a cationic dye. The viscosity behaviour of unionized PMA obtained from direct dissolution of solid powder shows that the unneutralized macromolecules can be associated in water. The stability of such “aggregates” seems weak as indicated by their disappearance as soon as the charge density is very low. For PMA salt solution percolated through a cation (H⁺) exchange resin column, no association is observed. The pH-dependent conformational behaviour of PMA which, contrary to PAA, presents compact conformations in water at low charge density is discussed in terms of solvophobic/solvophilic interactions. It is shown that, even for urea concentration up to 8 M, the compact conformations of PMA are not completely destroyed. The formation of H⁺/urea complex is taken into account.     

Interpolymer complexes of poly(acrylic acid) with poly(2-hydroxyethyl acrylate) in aqueous solutions

Complexes formed from poly(acrylic acid) and poly(2-hydroxyethyl acrylate) were studied in aqueous solutions by viscometric, turbidimetric, FTIR spectroscopic, and thermogravimetric analysis methods. The formation of interpolymer complexes stabilized by hydrogen bonds was observed. It was found that the compositions of these interpolymer complexes are strongly dependent on the concentration of polymers, the order of mixing the solutions, and the pH. It was demonstrated that the complexation ability of poly(2-hydroxyethyl acrylate) is relatively low compared to other known nonionic water-soluble polymers. However, it can be significantly increased via hydrophobic modification of the poly(acrylic acid) using cetyl pyridinium bromide.     

Linear-dendritic nonionic poly(propylene oxide)-polyglycerol surfactants

A new type of linear-hyperbranched surfactant has been prepared by anionic ring-opening multibranching polymerization of glycidol onto an end-functional poly(propylene oxide) (PPO) macroinitiator. A hyperbranched, highly hydrophilic polyglycerol block is obtained as the polar segment of the structure. Molecular weights of the nonionic amphiphiles obtained were in the range of 390 to 8,600 g/mol. For comparison, initiators bearing a C16 alkyl chain have also been employed. Furthermore, hyperbranched polyglycerol homopolymers were investigated with respect to amphiphilic properties. All linear-dendritic amphiphiles have been characterized by SEC, DSC, ¹³C and ¹H NMR spectroscopy. A fluorescence-probe technique based on diphenyl hexatriene (DPH) as probe molecule was employed to determine the CMC (critical micelle concentration) of the samples in water. CMCs varied from 7.5×10⁻⁶ to 1.7×10⁻³ M and were found to depend on the copolymer architecture and the hydrophilic/hydrophobic balance. Measurements at pH 6.75 and 3.00 revealed an increase of the CMC by a factor of 10 for the amine containing copolymers upon lowering of the pH.     

The aggregation of nonionic surfactants in the presence of poly(methacrylic acid)

The solution properties of homogeneous hexaethylene and octaethylene glycol mono(n-dodecyl) ethers, C₁₂E₆ and C₁₂E₈, respectively, and octaethylene glycol mono(n-decyl) ether, C₁₀E₈, with poly(methacrylic acid) (PMA) were investigated by dye solubilization, surface tension, fluorescence, viscosity, and pH measurements. The data were discussed regarding non-cooperative and cooperative binding of surfactant to polymer. Whereas in the interaction with poly(acrylic acid) (PAA), the critical aggregation concentrations (cac or T ₁) of these surfactants were lower than the respective critical micelle concentration (cmc), in that with the more hydrophobic PMA, T ₁’s of C₁₂E₆ and C₁₂E₈ were higher than the respective cmc, but that of C₁₀E₈ was lower than its cmc. These may be ascribed to the hydrophobic microdomains (HMD) of the PMA coil in water, probably in its inside. It is considered that some surfactants are bound first to the HMD non-cooperatively and then they are abruptly bound cooperatively at T ₁. This raises T ₁ higher than cmc when the cmc is low, and the amount bound by the HMD is relatively large and vice versa. T ₁ of C₁₂E₆ or C₁₂E₈ is the former case, and that of C₁₀E₈ is the latter. Thus, different from PAA, T ₁ for PMA + nonionic surfactant system consists of the amount of non-cooperative binding and the cac of the cooperative binding in equilibrium. Therefore, this T ₁ has a different meaning from that for PAA and should be called apparent T ₁. As the binding to the HMD is dependent on PMA concentration and cac is not, which is like in the PAA system, separation of apparent T ₁ from the HMD binding was achieved by extrapolating T ₁’s to zero PMA concentration (denoted intrinsic T ₁). This value for C₁₂E₈ was found to be lower than the respective cmc and also lower than the respective T ₁ for PAA. With increase in surfactant concentration, the pH of PMA solution rose and demonstrated a peak. This pH rise and fall may be induced by loosening of the HMD coil due to binding increase and by rearrangement of PMA + surfactant complex in high surfactant concentrations region. By raising the initial pH, the HMD were loosened; consequently, T ₁ rose a little, and at higher pH, no surfactant binding took place.     

Interaction of nonionic surfactants with copolymer microgel particles of NIPAM and acrylic acid

Binding of the nonionic surfactants Triton X-100 and Triton X-405 onto linear copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid and to cross-linked microgel particles of similar composition but differing in their cross-link densities has been studied. The binding capacities vary for each of these polymeric systems, being smallest for the linear copolymer. The binding is also significantly less in all cases for the more hydrophilic surfactant, namely, Triton X-405. By comparing estimates of the pore or "cage" size within the microgel particles with the dimensions of the free micelles in solution, it is concluded that micelles of Triton X-100 form within the microgel particles more readily for the lower cross-linked microgel particles. However, micelles do not form as easily inside either microgel for Triton X-405. The swelling/deswelling behavior of each of the two microgels, in the presence of the surfactants, has been explained in terms of their relative binding behavior and how this contributes to the osmotic pressure difference inside and outside the microgel particles and also in terms of micelle "bridging" of the polymer network, causing shrinkage.     

Pulse radiolysis of poly(acrylic acid) in deoxygenated aqueous solution

Absorption spectra of macroradicals formed by irradiation of poly (acrylic acid) in aqueous solution are presented and the role of intermediates of water radiolysis in their formation is discussed. Both the rate constant of ·OH reaction with the polymer and the process of macroradicals decay are shown to be strongly dependent on pH. The macroradicals formed in dissociated polymer molecules have a lifetime of several minutes.     

The surface tension of poly(acrylic acid) in aqueous solution

Summary Surface tension has been measured of polyacrylic acidwater solutions with pH 3–11. Until approximately pH 4.6 corresponding to 10% neutralization, PAA-solutions are surface active and inactive at higher pH, time dependence of equlibrium surface tension is analysed. Non-ionized neutral chain segments are surface active, their diffusion to surface is rate determining.

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Zusammenfassung Es wurde die Oberflächenspannung von wäßrigen Polyacrylsäure-Lösungen der pH-Werte von 3–11 gemessen. Bis zu einem pH-Wert von etwa 4.6, d. h. 10% Neutralisation, sind die Lösungen oberflächenaktiv, bei höheren pH-Werten inaktiv. Es wird die Zeitabhängigkeit der Einstellung der Gleichgewichtsoberflächenspannung analysiert. Nicht ionisierte, neutrale Kettensegmente sind oberflächenaktiv. Diffusion zur Oberfläche ist der zeitbestimmende Faktor.

     

Electrokinetic characterization of poly(acrylic acid) and poly(ethylene oxide) brushes in aqueous electrolyte solutions

Surfaces carrying hydrophilic polymer brushes were prepared from poly(styrene)-poly(acrylic acid) and poly(styrene)-poly(ethylene oxide) diblock copolymers, respectively, using a Langmuir-Blodgett technique and employing poly(styrene)-coated planar glass as substrates. The electrical properties of these surfaces in aqueous electrolyte were analyzed as a function of pH and KCl concentration using streaming potential/streaming current measurements. From these data, both the zeta potential and the surface conductivity could be obtained. The poly(acrylic acid) brushes are charged due to the dissociation of carboxylic acid groups and give theoretical surface potentials of -160 mV at full dissociation in 10(-)(3) M solutions. The surface conductivity of these brushes is enormous under these conditions, accounting for more than 93% of the total measured surface conductivity. However, the mobility of the ions within the brush was estimated from the density of the carboxylic acid groups and the surface conductivity data to be only about 14% of that of free ions. The poly(ethylene oxide) (PEO) brushes effectively screen the charge of the underlying substrate, giving a very low zeta potential except when the ionic strength is very low. From the data, a hydrodynamic layer thickness of the PEO brushes could be estimated which is in good agreement with independent experiments (neutron reflectivity) and theoretical estimates. The surface conductivity in this system was slightly lower than that of the polystyren substrate. This also indicates that no significant amount of preferentially, i.e., nonelectrostatically attracted, ions taken up in the brush.     

Conformational analysis of poly(oxyethylene) chain in aqueous solution as a hydrophilic moiety of nonionic surfactants

Conformational states of poly(oxyethylene) chain in aqueous solution are examined in connection with hydrophilic property of nonionic surfactants. The Raman spectra in various states are analyzed on the basis of comprehensive normal coordinate treatment. The poly(oxyethylene) chain is more ordered in more dilute aqueous solution. This conformational ordering is further promoted by lowering temperature. The ordered structure, which is similar, at least in part, to that in the solid state, is substantiated by the hydrogen bonds making the gauche conformation of the OCH₂-CH₂O group more favorable. The hydration has no significant effect on the conformation of the CH₂O-CH₂CH₂ group.     

Influence of nonionic surfactants on the chromatographic behaviour of proteins in hydrophobic interaction chromatography

The chromatographic characteristics of proteins in the presence of additives of nonionic surfactants Brij-35 and Tween-80 in the conditions of descending gradient of ammonium sulfate and phenyl-coated polymeric stationary phase were investigated. It was revealed that retention factors of proteins may be regulated by use of mentioned additives. The improvement of resolution is achieved for some hardly separated pairs of proteins, viz. albumin egg/albumin bovine, aldolase/tripsin. A reversion of the elution order is observed for tripsin/chymotrypsinogen A.     

Doxorubicin-poly(acrylic acid) complexes: interaction with liposomes

Complexation of antitumor drug, doxorubicin (DOX), with poly(acrylic acid) (PAA) in buffer solutions was examined. The DOX-to-PAA binding was governed by electrostatic and stacking interactions resulting in a complex of characteristic composition with a PAA/DOX = 1.6 molar ratio. Sizes of the complex particles were found to lie in 600-900-nm range. However, the particles were able to interact with small neutral egg yolk lecithin liposomes (80-100 nm in diameter), a ternary DOX/PAA/liposome complex being formed. The observations and conclusions we made may be useful for interpreting biological effects of polymer-based bioactive constructs.     

Photoresponsive viscosity and host-guest association in aqueous mixtures of poly-cyclodextrin with azobenzene-modified poly(acrylic)acid

In aqueous solutions, beta-cyclodextrin (CD) and cyclodextrin-containing polymers (PolCD) associate with azobenzene-modified polyacrylate (AMP). Inclusion complexes in solution of CD (or PolCD) and AMP, and the viscosity of these mixtures, have been studied as a function of the composition of AMP and concentrations of samples. AMPs are random copolymers containing a low fraction of a light-responsive hydrophobic moieties (<10 mol % of 6-[4-alkylamido]phenylazobenzene acrylamide), and a charged hydrophilic unit, sodium acrylate. PolCDs are beta-cyclodextrin randomly conjugated with epichlorohydrin and fractionated to yield copolymers of average number of CD per chain equal to 50. In dilute solutions, the composition of complexes has been investigated by capillary electrophoresis and UV-vis spectrometry. Association between PolCD and AMP appears more complex than the conventional Benesi-Hildebrand scheme. We identified a tight (quantitative) binding regime followed by a gradual increase of the density of AMP-bound PolCD upon increasing the concentration of PolCD. At higher concentrations, the formation of large clusters has been characterized by the increase of viscosity by several decades. Light-triggered trans-conformation of the azobenzene moieties of AMPs leads to a marked photoswitch of viscosity. Reversible viscosity swings by up to 6-fold were achieved by alternative exposure to UV and visible lights. In contrast, the composition of PolCD/AMP complexes in dilute regime does not respond to light, though subtle modifications of the structures of complexes are reflected by variation of electrophoretic mobilities and UV spectra. The properties of interpolymer clusters and photoviscosity are accordingly the result of modification of the dynamics of association. In practice, the low concentration of photochrome makes it possible to obtain rapid responses in samples having a thickness of the order of cm. The data reported provide guidelines for the formulations of CD/polymer systems, specifically, viscosity enhancers, which should show promising developments in pharmaceuticals or cosmetics.     

The interaction between triton X series surfactants and poly (ethylene glycol) in aqueous solutions

 A series of Triton X surfactants with different ethylene oxide chain length and poly(ethylene glycols) with different molecular weight were used, to find the effects of polymer chain length and size of the micelles on the cloud point of the surfactants. Two possible models are considered on the basis of cloud point changes of the solutions, to describe the polymer–surfactant interactions. One model considers that intra-chain micelles of polysoap are formed among the surfactant monomers and long polymer chains. The bridging attraction between two intra-chain micelles in such structures can enhance the collisions among the micelles, due to the exchange of amphiphilic monomers among the neighboring micelles. The other model suggests that flocculation depletion for the polymer chains exists between two regular micelles. This provides the driving force for the neighboring micelles to approach each other and destabilize the colloidal system. The flocculation effect is more significant for polymer with a long chain. Polymers with a shorter chain block the approach of the micelles, since there is no typical polymer–surfactant association formed but just simple small molecule associations in which the steric and solvation effects of the polymer chains make the inter-micelle interactions repulsive. Received: 19 August 1997 Accepted: 11 December 1997     

Novel amphiphilic graft copolymers bearing hydrophilic poly(acrylic acid) backbones and hydrophobic poly(butyl methacrylate) side chains

A novel amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbones and hydrophobic poly(butyl methacrylate) side chains was synthesized by successive atom transfer radical polymerization followed by hydrolysis of poly‐(methoxymethyl acrylate) backbone. A grafting‐from strategy was employed for the synthesis of graft copolymers with narrow molecular weight distributions (polydispersity index < 1.40). Hydrophobic side chains were connected to the backbone through stable C? C bonds instead of ester connections. Poly(methoxymethyl acrylate) backbone was easily hydrolyzed to poly(acrylic acid) backbone with HCl without affecting the hydrophobic side chains. The amphiphilic graft copolymer could form stable micelles in water. The critical micelle concentration in water was determined by a fluorescence probe technique. The morphology of the micelles was preliminarily explored with transmission electron microscopy and was found to be spheres. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6857–6868, 2006     

Molecular mobility in micellar complexes of a nonionic surfactant and the poly(acrylic acid)-based hydrogel

The interaction between the polyelectrolyte gel of crosslinked poly(acrylic acid) (PAA) and nonionic surfactant Brij 58 based on poly(ethylene glycol) (C₁₆H₃₃(CH₂CH₂O)₂₀OH) is studied. It is established that poly(acrylic acid)-surfactant complexes are formed. Nondissociated carboxyl groups of poly(acrylic acid) and oxygen atoms of the surfactant are involved in the complexation. Surfactant micelles are a kind of bridge that connects polymer chains. The presence of the surfactant decreases the equilibrium swelling of the hydrogel. The spin probe method is employed to determine the local mobility of the hydrocarbon core of a micelle in the complex. It was shown that the local mobility is independent of the hydrogel crosslink density and is much lower in acidic than in alkaline media. In acidic media, much more surfactant molecules of micelles are involved in the complexation than in alkaline media. However, even in alkaline media, surfactant micelles cannot leave the hydrogel, while the spin probes located in micelles are at equilibrium with the spin probes present in the external aqueous medium. The prospects for applying the considered systems as carriers for controlled release drugs are discussed.     

Competition between poly(methyl methacrylate) and poly(ethylene glycol) during their interaction with poly(silicic acid) in an organic solvent

It is shown that the interpolymer complex of poly(silicic acid) and poly(ethylene glycol) formed in the organic solvent benzene is thermodynamically more stable than the corresponding complex with PMMA. Therefore, poly(silicic acid) prepared via template polycondensation conducted in the presence of poly(ethylene glycol) contains a smaller amount of defects (branches and crosslinks) than the same polymer obtained in the presence of PMMA. To provide evidence for the interaction between poly(silicic acid) and PMMA, the dynamic light-scattering method with the use of “invisible” macromolecules has been applied for the first time.     

Controlled synthesis of oligomeric poly(acrylic acid) and its behavior in aqueous solutions

The controlled synthesis of oligomeric poly(acrylic acid) via the pseudoliving radical reversible addition-fragmentation chain-transfer polymerization of acrylic acid in bulk is developed. It is shown that, at high concentrations of reversible addition-fragmentation chain-transfer agents, the polymerization of acrylic acid in bulk occurs via the pseudoliving mechanism, as evidenced by a linear increase in the numberaverage molecular mass of oligomers with conversion and a narrow molecular-mass distribution of the reaction products. The surfactant properties and behavior of the oligomers in aqueous solutions are studied.     

A starlike amphiphilic graft copolymer with hydrophilic poly(acrylic acid) backbones and hydrophobic polystyrene side chains

A well‐defined starlike amphiphilic graft copolymer bearing hydrophilic poly(acrylic acid) backbones and hydrophobic polystyrene side chains was synthesized by successive atom transfer radical polymerization followed by the hydrolysis of poly‐(methoxymethyl acrylate) backbone. A grafting‐from strategy was employed for the synthesis of a graft copolymer with narrow molecular weight distribution. Hydrophobic polystyrene side chains were connected to the backbones through stable C? C bonds. The poly(methoxymethyl acrylate) backbones can be easily hydrolyzed with HCl without affecting the hydrophobic polystyrene side chains. This kind of amphiphilic graft copolymer can form stable sphere micelles in water. The sizes of the micelles were dependent on the ionic strength and pH value. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3687–3697, 2007