Chelation properties of polymer complexes of poly(acrylic acid) with poly(acrylamide), and poly(acrylic acid) with poly(N,N-dimethylacrylamide)

The metal-complexing properties of intermolecular complexes of poly(acrylic acid) with poly(acrylamide), and poly(acrylic acid) with poly(N,N-dimethylacrylamide) were studied by means of the liquid-phase polymer based retention (LPR) technique. The metal ion retention ability at pH 5 for 400 μg of Cu(II), Cd(II), Co(II), Cr(III), Hg(II), Ni(II), Pb(II), and Zn(II) was investigated due to their environmental and analytical interest in the presence of 1.1 M of carboxylic acid units and variable amounts of amide groups. The retention profiles of the intermolecular complexes were compared with those of the correspondent homopolymers and copolymers. The retention capacity of poly(acrylic acid) is 100% for all metal ions except for Co(II), Ni(II), and Zn(II) whose values were about 90%, while poly(acrylamide) does not retain any of the metal ion studied. The presence of poly(acrylamide) decreases the retention capacity down to 60% for Co(II) and Ni(II) and to 70% for Zn(II). The decrease on the retention values is dependent on the polymer ratio. A smaller effect is observed by the addition of poly(N,N-dimethylacrylamide) which also decreases the retention capacity down to 80% for Co(II) and Ni(II) for a ratio poly(acrylic acid)/poly(N,N-dimethylacrylamide) = 1/2. The metal ion binding behavior of the interpolymer complexes is very close to that of the copolymers.     

The behaviour of poly(methacrylic acid) and poly(2-hydroxyethyl methacrylate) in water/2-chloroethanol mixtures

The viscosimetric behaviour and the preferential solvation of poly(methacrylic acid), (PMA, poly(1-carboxy-1-methylethylene)) and poly(2-hydroxyethyl methacrylate), (PHEMA, poly[1-(2-hydroxyethoxycarbonyl)-1-methylethylene]) in water/2-chloroethanol mixtures were studied. The system PHEMA/water/2-chloroethanol is a typical polymer/solvent/precipitant system in which 2-chloroethanol is preferentially solvated in the whole range of solubility. On the contrary, the system PMA/water/2-chloroethanol is a typical cosolvent system which exhibits the so-called inverse adsorption. This difference is attributed to the more hydrophilic character of the carbonyl group in PMA.     

Behaviour of permeation and separation for aqueous organic acid solutions through poly(vinyl chloride) and poly[(vinyl chloride)-co-(vinyl acetate)] membranes

The permeation and separation characteristics of poly(vinyl chloride) (PVC) and poly[(vinyl chloride)-co-(vinyl acetate)] (poly(VC-co-VAc)) membranes were investigated for aqueous organic acid solutions by pervaporation and evapomeation. The PVC membrane preferentially incorporates organic acids and predominantly permeates water from aqueous organic acid solutions. Water permselectivities of these aqueous solutions through the PVC membrane are significantly dependent on high diffusivity of water across the membrane. It was found that the permeation rate increases and the separation factor for the water permselectivity decreases with increasing vinyl acetate (VAc) content in the poly(VC-co-VAc) membrane. Preferential solubility of acetic acid into the poly(VC-co-VAc) membrane increases with the VAc content. This result was explained by a strong affinity between acetic acid and the VAc unit in the poly(VC-co-VAc) membrane.     

The phase behaviour of a poly(ether sulfone) with poly(ethylene oxide)

Blends of poly(ethylene oxide) with a poly(ether sulfone) were prepared by casting from a common solvent and were found to be miscible and show a single, composition dependent, glass transition temperature. Mixtures in both cyclohexanone and N,N-dimethylformamide phase, separated on heating and thus conditions need to be carefully chosen to obtain homogeneous blends. At higher PEO contents, PEO crystallised from the blends at lower temperatures. The melting point depression, as determined by trubidity measurements, was used to calculate an interaction parameter which was negative, as expected for miscible polymers. The blends also phase separated on heating, and the cloud point curve could be measured by turbidity measurements and confirmed by both visible and electron microscopy. The cloud point curve was very skew with a minimum at around 10 wt.-% PES content. This was not a strong function of the molecular weight and the skew nature was thus presumably due to differences in the state parameters of the pure components. The blends showed a very high mobility with sharp and reproducible could points which might make them ideal for future miscibility studies.     

Synthesis and pharmacokinetic behaviour of ester derivatives of 4-isobutylphenyl-2-propionic acid (Ibuprofen) with end-hydroxylated poly(N-vinyl pyrrolidinone) and poly(N-acryloyl morpholine) oligomers

Four derivatives of 4-isobutylphenyl-2-propionic acid (Ibuprofen), in which the drug was bound by ester linkages to poly(ethylene glycols) (PEG 2000-I), monomethoxy poly(ethylene glycols) (PEG 1900-I), poly(N-vinyl pyrrolidinone) (PVP-I) and poly(N-acryloyl morpholine) (PACM-I), all having approximatively the same number average molecular weight (M_n? 2000), were prepared and tested for their pharmacokinetic properties after oral administration. It was found that the two end-hydroxylated amphiphilic oligomers of polyvinylic structure, PACM and PVP, whose physico-chemical properties are comparable to those of PEGs especially as regards solvent affinity, have in principle a similar potential as promoieties for preparing oligomeric prodrugs.     

Swelling behaviour of a non-ionic poly(N-vinyl-2-pyrrolidone) gel in a linear poly(acrylic acid) solution

The swelling behaviour of a non-ionic poly(N-vinyl-2-pyrrolidone) hydrogel in a linear poly-(acrylic acid) solution upon the influence of chain length, pH, ionic strength, and water/dimethyl sulfoxide composition was studied. The sharp shrinkage of the gel volume within a narrow range of polyacid concentration takes place as a result of the formation of an intermacromolecular gel-polymer complex on the base of hydrogen bonding. According to X-ray diffraction this complex is amorphous. The formation of the gel-polymer complex is a long term process and the system reaches equilibrium within 48 h. The swelling behaviour strongly depends on the chain length of the polyacid whereas it does not depend on the ionic strength. With increasing pH value and changing water/dimethyl sulfoxide composition the gel reswelling is induced. The complex formation with poly(acrylic acid) occurs in the same way for linear and crosslinked poly(N-vinyl-2-pyrrolidone).     

Crystallization behaviour of poly(ethylene terephthalate) and poly(tetramethylene terephthalate) blends

The isothermal and non-isothermal crystallization behaviour of blends of poly(ethylene terephthalate) (PET) and poly(tetramethylene terephthalate) (PBT) is investigated at low percentage of the second component. The melting behaviour of the isothermally crystallized sample shows that the crystallization behaviour in the blend is governed by the mobility of PBT. Below 200°C the crystallization process is hindered, whereas above 200°C the PET crystals are larger in case of added PBT. The non-isothermal crystallization behaviour shows that the crystallization process is hindered when the PBT content in the blend is less or higher than 6 wt.-%.     

Interaction of poly(diallyldimethylammonium chloride) with ferro- and ferricyanide anions

The interaction of poly(1,1-dimethylpyrrolidinium-3,4-diylethylene chloride) [poly(diallyldimethylammonium chloride)] ( 1 ) with ferro- and ferricyanide anions was investigated by conductometric titration, viscometry, IR and Raman spectroscopy. It could be shown that the binding of ferro- and ferricyanide anions with 1 proceeds by means of an ionic mechanism and is accompanied by a spectral shift of the cyanide bands.     

Stereoregularity of poly(methacryloyl chloride) and poly(methacrylic salts) prepared by photopolymerization

Poly(methacryloyl chloride) (PMACl) and poly(methacrylic tetramethylammonium salts) and poly(methacrylic tetraethyl ammonium salts) (PMAAN⁺) have been prepared by radical photopolymerization at different temperatures. The obtained molecular weights are independent of the polymerization temperature in the range studied (+24 to ?30°C) which is in agreement with a purely photochemical process. The dependence of the tacticity upon temperature was examined by means of NMR spectroscopy. Deviations from Bernoullian statistics were confirmed. PMAAN⁺ salts prepared in water are highly syndiotactic and a nearly pure syndiotactic structure is obtained at +5°C. This behavior is explained by the repulsive interactions between the carboxylate anions promoting the racemic placement. The tacticity of PMACl is comparable with that of poly(methacryloyl fluoride). The structure is less syndiotactic and much more isotactic than that of poly(methyl methacrylate). This result is interpreted by considering the electron-withdrawing character of chlorine and fluorine atoms which affects the electronic structure and polarity of the carbonyl group near to the macroradical and competes with the preferential syndiotactic placement observed with α-substituted acrylates.     

Stereospecific functionalization of poly(vinyl chloride)

The substitution reaction of PVC with sodium dimethyldithiocarbamate (NaDC) and sodium azide (NaN₃) was performed in cyclohexanone and dimethylformamide at various temperatures. The degree of compositional heterogeneity was estimated and found to be important up to conversions of about 0,5%, but to vanish afterwards. The evolution of unreacted iso, hetero and syndiotactic triads was measured by ¹³C NMR spectroscopy. For conversions of at least up to 12%, the content of both the isotactic and heterotactic triads was found to decrease, relative to the syndiotactic ones, but at different relative rates depending on the nucleophile. From these results, together with the kinetic ones, it is concluded that the reaction proceeds by a stereoselective mechanism. The results are discussed on the basis of a hypothesis concerning the role of the local triad conformations in PVC that contain the TT isotactic diad conformation. The results enable the selective substitution of PVC with NaDC and NaN₃, which may be used as a useful tool to prepare specific graft copolymers based on PVC.     

Preparation and ESCA characterization of poly(vinyl chloride) surf ace-grafted with heparin-complexing poly(amido amine) chains

By a simple process poly(amido-amine) chains have been grafted on the surface of poly(vinyl chloride). Grafted poly(vinyl chloride) is able to adsorb heparin, thus providing potentially non-thrombogenic surfaces. The grafting of poly(amido-amine), and the heparin adsorption have been studied by ESCA. It has been found that the total amount of grafted poly(amido-amine) depends on the molecular weight of the poly(amido-amine) used in the grafting reaction, but the amount of heparin adsorbed on the grafted material is relatively independent of the length of the poly(amido-amine) grafted chains.     

Effects of complexation between liposome and poly(malic acid) on aggregation and leakage behaviour

The design and development of novel pH-sensitive liposomes were investigated to improve the release of liposome-encapsulated chemicals. Stable liposomes comprising of L-alpha-dipalmitoylphosphatidylcholine (DPPC) and poly(carboxylic acid) were prepared and characterized. Poly(malic acid) (PMLA) was chosen as a fusogen, because of its excellent biodegradability in physiological regions. Octyl groups introduced in the poly(malic acid) worked as anchors at the surface of the liposomes and made a remarkable contribution to complexing. The interaction between the liposomes and the polyacids was studied in terms of the change in size of the liposomes. The influences of molecular weight and amounts of polymer upon their characteristics, especially fusion, were discussed. The influences of pH change with respect to the association behavior of the liposomes such as aggregation and fusion were estimated by the particle size of the liposomes, turbidimetry of the solution and resonance energy transfer assay. From the results of these studies, it was shown that more tightly complexed liposomes aggregated and fused more positively with increasing acidity of the solution. The leakage of calcein entrapped in the inner aqueous phase of the liposomes increased with decreasing pH. The effect of pH on the liposome aggregation in a solution qualitatively paralleled that found in the leakage behavior.     

Improvement of the functions of osteoblasts seeded on modified poly(D,L-lactic acid) with poly(aspartic acid)

Microelectromechanical systems (MEMS) create an opportunity for the development of smaller, cheaper, and more precise biomedical instrumentation and devices. Little is known, however, about the hemocompatibility of the materials used to fabricate these devices. Because of the potentially harmful consequences of thrombus formation, a better understanding of blood interactions with bioMEMS materials is desirable. This study is an in vitro assessment of the hemocompatibility of silicon (Si), silicon dioxide (SiO2), silicon nitride (Si3N4), low-stress silicon nitride (Si(1.0)N(1.1)), SU-8 photoresist, and parylene thin films. A polycarbonate-based polyurethane, was used as a reference material. Experiments were carried out to detect differences in platelet adhesion or morphology after contact with these materials under static conditions. Platelet adhesion on Si, Si3N4, Si(1.0)N(1.1,) and SU-8 photoresist was significantly greater (P < 0.05) than platelet adhesion on polyurethane. Adhesion on parylene and SiO(2) was not significantly different from on polyurethane (P < 0.05). The median platelet area and circularity were higher on polyurethane than all other materials. Materials that showed higher levels of platelet adhesion tended to have platelets that showed less spreading, except for SiO2, where platelets exhibited relatively low adhesion and spreading. This data suggests that Si, Si3N4, Si(1.0)N(1.1), and SU-8 photoresist may be more reactive to platelets and therefore more thrombogenic than parylene, SiO2, and polyurethane. These results may be helpful in guiding the selection of materials for use in the development of blood-contacting microelectromechanical systems.     

Characterization of dehydrochlorinated poly(vinylidene chloride) and the shock-compressed material

Dehydrochlorinated poly(vinylidene chloride) proved to be a conjugated polyene-polyene polymer. Shock compression of the polymer formed a large portion of graphite and trace amounts of diamond and of an unknown carbon. The unknown carbon belongs to the hexagonal crystal system and possesses the cell dimension α₀ = 0.338 nm. A comparison with known carbynes was made in terms of the crystalline parameters.