pH effects on the complexation, miscibility and radiation-induced crosslinking in poly(acrylic acid)-poly(vinyl alcohol) blends

The effect of pH on the complexation of poly(acrylic acid) with poly(vinyl alcohol) in aqueous solution, the miscibility of these polymers in the solid state and the possibility for crosslinking the blends using gamma radiation has been studied. It is demonstrated that the complexation ability of poly(vinyl alcohol) with respect to poly(acrylic acid) is relatively low in comparison with some other synthetic non-ionic polymers. The precipitation of interpolymer complexes was observed below the critical pH of complexation (pH(crit1)), which characterizes the transition between a compact hydrophobic polycomplex and an extended hydrophilic interpolymer associate. Films prepared by casting from aqueous solutions at different pH values exhibited a transition from miscibility to immiscibility at a certain critical pH, pH(crit2), above which hydrogen bonding is prevented. It is shown here that gamma radiation crosslinking of solid blends is efficient and only results in the formation of hydrogel films for blends prepared between pH(crit1) and pH(crit2). The yield of the gel fraction and the swelling properties of the films depended on the absorbed radiation dose and the polymer ratio. [Diagram: see text] SEM image of an equimolar PAA-PVA blend cast from a pH 4.6 solution.     

Spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene)

Direct spectroscopic evidence for radiation-induced crosslinking of poly(tetrafluoroethylene) (PTFE) is presented for all x-ray and electron dose levels above which it is possible to distinguish between deliberately introduced radiation damage and the x-ray damage inherent in obtaining an x-ray photoelectron spectrum (XPS). The C (1s) spectrum obtained after irradiation with 2 keV electrons for all doses greater than 1 μA-min/cm² consists of a four-peak spectrum identical to that previously obtained for plasma-polymerized tetrafluoroethylene and assigned to carbon atoms with variable numbers of bound F atoms (CF₃, CF₂, CF₁, and CF₀). X-ray irradiated PTFE can be fitted with the same four-peak spectrum. At or below an electron dose level of 1 μA-min/cm², the radiation damage is comparable to that produced by the x-ray dose necessary to obtain an XPS spectrum. The CF₁ and CF₀ components increase with increasing electron dose, and at high electron doses dominate the spectrum. With increasing dose the CF₃ component approaches a constant value while both the CF₂ component and the total F : C ratio decreases. These four components are those expected to result from radiation-induced crosslinking reactions of the polymer and are consistent with previous suggestions that crosslinking is the basis of radiation patterned adhesion to PTFE. © 1993 John Wiley & Sons, Inc.     

Preparation of poly(ε-caprolactone)-co-poly(acrylic acid) by radiation-induced grafting

Acrylic acid was grafted onto poly(ε-caprolactone) (PCL) films by using electron beam (EB) preirradiation technique. The effect of reaction time, monomer concentration, radiation dose, time between irradiation and grafting, radiation atmosphere, and polymer crystallinity on the extent of grafting were studied. Silver and tin ions were attached to the grafted chains in order to study the grafting process. The irradiation in air was initially more rapid, but the final extent of grafting was the same when irradiated in nitrogen atmosphere. Maximum grafting extents exceeding 400% could be obtained. The optimal grafting was obtained at an acrylic acid to water ratio of 30 : 70. The grafting process could be initiated at a dose as low as 12 kGy. The grafting process proved to start at the surface and was extended into the bulk with time. The ability to form crystals was reduced as the grafting extent increased. The water uptake of the poly(ε-caprolactone)-graft-poly(acrylic acid) was increasing with increasing grafting extent, but reached a maximum of ca 100% for all grafting extents above 85%. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1805–1812, 1998     

Cloning of poly(aspartic acid) (PAA) hydrolase-1 gene from Pedobacter sp. KP-2 and hydrolysis of thermally synthesized PAA by its gene product

Pedobacter sp. KP-2 can degrade and metabolize thermally synthesized alpha,beta-poly(D,L-aspartic acid) (tPAA), which contains 70% of unnatural beta-amide units, with high-molecular-weight. In this study, gene cloning and molecular characterization of PAA hydrolase-1 from KP-2 was carried out. Gene analysis reveals that deduced amino acid sequence of the enzyme shows a similarity to only that of PAA hydrolase-1 from Sphingomonas sp. KT-1. GPC and NMR analyses of the hydrolyzed products of tPAA by PAA hydrolase-1 of KP-2 indicate that this enzyme cleaves the beta-beta amide linkage via endo-mode to yield oligo(aspartic acid) from tPAA. Taking the composition of tPAA and the substrate specificity of PAA hydrolase-1 into consideration, the enzyme possibly plays a crucial role in tPAA biodegradation by KP-2.     

A study on the swelling behavior of poly(acrylic acid) hydrogels obtained by electron beam crosslinking

Poly(acrylic acid) (PAA) hydrogels were prepared by using electron beam (EB) crosslinking of PAA homopolymer from its aqueous solutions. The swelling behavior of the hydrogels was studied as a function of the concentration of PAA solution, radiation dose, pH of the swelling medium and swelling time. Also the environmental pH effect on the water diffusion mode into hydrogels was investigated. These hydrogels clearly showed pH-sensitive swelling behavior with Fickian type of diffusion in the stomach-like pH medium (pH 1.3) and non-Fickian type in the intestine-like pH medium (pH 6.8).     

Structure and swelling-release behaviour of poly(vinyl pyrrolidone) (PVP) and acrylic acid (AAc) copolymer hydrogels prepared by gamma irradiation

Copolymer network hydrogels were prepared by gamma irradiation of aqueous solutions of poly(vinyl pyrrolidone) (PVP) and acrylic acid monomer (AAc). The composition of the final hydrogels compared to the composition of the initial preparation solutions of hydrogels was determined. The chemical structure and nature of bonding was characterized by IR spectroscopy analysis, while the thermal durability of the prepared hydrogels was assessed by thermogravimetric analysis (TGA). The kinetic swelling in water and the pH-sensitivity of PVP/AAc copolymer hydrogels was studied. The drug release properties of PVP/AAc hydrogels taking methyl orange indicator as a drug model was investigated. The IR spectra indicate the formation of copolymer networks, whereas the TGA study showed that the PVP/AAc hydrogels possess higher thermal stability than pure PAAc and lower than PVP hydrogels. The kinetic swelling in water showed that all the hydrogels reached equilibrium after 24 h and that the degree of swelling increases with increasing the ratio of AAc in the initial feeding solutions. It was found that the degree of swelling of PVP/AAc hydrogels increases greatly within the pH range 4-7 depending on composition.     

Synthesis of poly(acrylic acid) (PAA) modified Pluronic P123 copolymers for pH-stimulated release of doxorubicin

Pluronic P123 was chain-extended at their terminal groups using atom transfer radical polymerization to form poly(acrylic acid) (PAA) tails and obtain the PAA-b-P123-b-PAA (P123-PAA) copolymer. The incorporation of PAA had the effect of increasing the carrier's drug loading capacity of an anti-cancer drug, Doxorubicin (DOX), and also allowed for pH-controlled release of the drug. Drug release assays showed that up to 60% of DOX cargo could be retained in the DOX/P123-PAA complex for 3 days at normal physiological pH (7.4). This was then followed by a secondary burst release of DOX when the environment became more acidic (pH 5). Therefore, it was possible that the more acidic physiological environment of tumor sites could be used to trigger an accelerated release of DOX from the drug carriers. The material was demonstrated for potential application in the delivery of cationic drugs for cancer treatment.     

The synthesis and characterization of monodisperse poly(acrylic acid) and poly(methacrylic acid)

A number of polyacrylic (PAA) and polymethacrylic (PMAA) acids have been synthesized by living anionic polymerization of the monomeric tert-butyl esters followed by subsequent hydrolysis of the corresponding polyesters. The necessary precautions were taken in order to assure good molecular weight control, as well as high yields in the polymerization reactions. The intermediate and final polymers were characterized by gel permeation chromatography and NMR-H¹ spectrometry.     

羧甲基纤维素与丙烯酸接枝共聚凝胶的溶胀动力学及过溶胀平衡特性的研究

采用接枝共聚合成了羧甲基纤维素钠、丙烯酸与N,N′-亚甲基双丙烯酰胺的交联凝胶, 研究了这类凝胶在不同pH值的缓冲溶液中的溶胀行为, 发现在酸性介质中凝胶的溶胀动力学行为表现出过溶胀平衡特性(overshooting effect), 即凝胶先发生溶胀到最大值, 然后再逐渐消溶胀到平衡. 这种现象可归因于凝胶溶胀过程中羧基之间通过氢键所产生的协同物理交联. 较之凝胶的组成, 缓冲溶液的pH值对过溶胀平衡现象的影响更为显著. 前者是因为凝胶羧基的总摩尔分数并不随两组分结构单元摩尔数的改变而改变, 羧基之间通过氢键形成的物理交联程度在交联剂摩尔分数接近的条件下变化不大; 后者是由于溶液的pH值显著影响凝胶羧基的质子化程度, 进而影响羧基之间通过氢键形成的物理交联程度. 凝胶在酸性介质中的溶胀过程符合E. Díez-Peña等提出的溶胀动力学定量模型, 理论曲线与实验数据有较好的相关性. 凝胶在pH≥5.0的缓冲溶液中的溶胀不产生过溶胀平衡现象, 这一现象归因于完全离子化的羧基之间不能形成物理交联. 凝胶的溶胀过程遵循Schott二级溶胀动力学.     

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.     

Anomalous crosslinking in acrylic acid and acrylic acid-polyethylene systems by γ-irradiation

Studies have been carried out on irradiated systems of acrylic acid in aqueous solution and acrylic acid-polyethylene systems in order to discover the cause of the enhanced crosslinking mentioned in previous literature from this laboratory. Theories which have been investigated include: free radical mechanisms, anhydride mechanisms, ionic mechanism, entanglements, hydrogen bonding. It seems that hydrogen bonding is the most plausible.     

Polyelectrolyte complex nanoparticles from chitosan and poly(acrylic acid) and Polystyrene‐block‐poly(acrylic acid)

Interpolymer polyelectrolyte complexes of chitosan (CS) with poly(acrylic acid) homopolymers and polystyrene‐block‐poly(acrylic acid) diblock copolymers were prepared and characterized. The influence of the positive/negative charge balance (charge ratio), pH, and ionic strength were thoroughly studied by dynamic light scattering. The existence of a strong polyelectrolyte effect was also highlighted in this study. Domains of stability, in which nanoparticle sizes are smaller than 100 and 200 nm for complexes of CS with the homopolymer and copolymer, respectively, were identified and confirmed by scanning electron microscopy and atomic force microscopy. The charged nature of the surface of the nanoparticles was evidenced by Zeta potential measurements. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

壳聚糖-聚丙烯酸复合水凝胶的药物控制释放行为

以壳聚糖(Cs)和丙烯酸(AA)为原料,利用自由基聚合法制备了具有孔洞结构的复合水凝胶Cs-PAA,并研究了AA的量、交联剂的量、聚合温度和AA的中和度对水凝胶溶胀度的影响以及复合水凝胶对烟酸的控制释放。 结果表明,Cs-PAA复合水凝胶具有良好的pH值、离子强度敏感性,且溶胀度最高达1228 g/g,其在pH=686的缓冲溶液中的烟酸累积释放率明显大于其在pH=1.80的缓冲溶液,因此Cs-PAA水凝胶可作为肠口服药物的载体。     

Oxidative and photooxidative degradation of poly(acrylic acid)

The oxidative degradation of poly(acrylic acid) (PAA), a water soluble polymer, was studied at various temperatures with different concentrations of persulfates, potassium persulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS). The photodegradation of PAA was also examined with APS as oxidizer. The degraded samples were analyzed for the time evolution of molecular weight distribution by gel permeation chromatography. A theoretical model based on the continuous distribution kinetics was developed that accounted for the polymer degradation and the dissociation of persulfate. The rate coefficients for the oxidative and photooxidative degradation of PAA were determined from the parametric fit of the model with experimental data. The rate of degradation increased with increasing amount of persulfate in both oxidative and photooxidative degradation. The rate of degradation also increased with increasing temperature in the case of oxidative degradation.     

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     

Synthesis of poly(acrylic acid) nanogels by preparative pulse radiolysis

Nanogels are sub-micron size, water-swellable crosslinked structures of hydrophilic polymers. In this work a radiation-based synthesis method that has been previously tested for neutral polymers is applied for production of nanogels of a synthetic polyelectrolyte—poly(acrylic acid) (PAA). In this technique dilute, deoxygenated PAA solution (pH 2) circulating in a closed loop is subjected to pulse irradiation with fast electrons. In each pulse many tens of radicals are instantaneously formed on every macromolecule. One of the major reaction paths of these radicals is intramolecular recombination leading to the formation of nanogels. It is demonstrated that radiation-induced reactions in our system show a typical feature of intramolecular crosslinking, i.e. a strong decrease in dimensions of a polymer coil without an accompanying decrease in molecular weight. In accordance with expectations based on earlier observations on non-polar polymers, intramolecular recombination of PAA-derived radicals proceeds according to non-classical kinetics. A model of non-homogeneous kinetics with time-dependent rate constant has been applied to describe this behaviour and the relationship between kinetic parameters and initial average number of radicals per chain is briefly discussed. The weight-average molecular weight of the products is influenced by side reactions, mainly degradation (chain breakage) and intermolecular crosslinking.     

Molecular structure and dynamics of poly(methacrylic acid) and poly(acrylic acid) complexes with dodecyl-substituted poly(ethylene glycol)

The molecular dynamics and the structure of molecular complexes formed by micelles of dodecyl-substituted poly(ethylene glycol) with poly(methacrylic acid) and poly(acrylic acid) in aqueous solutions were studied by viscosimetry, pH measurement, and electron spin resonance spin-probe techniques. At low surfactant concentrations, the conformation of the complex is a compact globule. The local mobility of surfactant molecules in such a complex is much slower than that in the free micelle. At high surfactant concentration, the nonionic micelles and polyacids form hydrophilic associates. The associates have the conformation of extended coils. In an associate, a major part of the micellar poly(ethylene glycol) groups is free. The local mobility of the micellar phase depends on the number of micelles involved in an associate. The mobility of surfactant molecules is slower in the complexes of poly(methacrylic acid) than in the complexes of poly(acrylic acid).