Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

A microspectroscopic study of the electronic homogeneity of ordered and disordered Sr2FeMoO6

Disordered Sr₂FeMoO₆ shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that e_xtensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr₂Fe_1+x Mo_1-x O₆ with Fe-rich (x > 0) and Mo-rich (x < 0) regions. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.     

The role of variable surface charge and surface complexation in the adsorption of humic acid on magnetite

The ionic strength dependence of humic acid (HA) adsorption on magnetite (Fe₃O₄) was investigated at pH 5, 8 and 9, where variable charged magnetite is positive, neutral and negative, respectively. The adsorption studies revealed that HA has high affinity to magnetite surface especially at lower pH, where interacting partners have opposite charges. However, in spite of electrostatic repulsion at pH 9 notable amounts of humate are adsorbed. Increasing ionic strength enhances HA adsorption at each pH due to charge screening. The dominant interaction is probably a ligand-exchange reaction, nevertheless the Coulombic contribution to the organic matter accumulation on oxide surface is also significant under acidic condition. The results from size exclusion chromatography demonstrate that the smaller size HA fractions enriched with functional groups are adsorbed preferentially on the surface of magnetite at pH 8 in dilute NaCl solution.     

Molecular electric field mapping of some anions and cations of 2- aminopurine and 6- thioguanine

Electric fields of the anions, cations and neutral forms of 2-aminopurine and 6-thioguanine have been mapped. Certain important features of the maps are similar to those found earlier in the neutral and ionic forms of adenine and guanine. The computed electric field patterns satisfactorily explain reactive sites and biological activity of the molecules.     

Gas solubility of carbon dioxide in poly(lactic acid) at high pressures: Thermal treatment effect

The sorption of carbon dioxide in glassy Poly(lactic acid) (PLA) films was studied by quartz crystal microbalance (QCM) at high pressures. Two thermal treatments, melted and quenched, were performed in PLA with two different L:D contents, 80:20 and 98:2, films and compared with a third thermal protocol, annealed, and used in a previous work. The results obtained show that for pressures higher than 2 MPa, the carbon dioxide solubility is larger in PLA 80:20 than in PLA 98:2, indicating that the L:D plays a dominant role on this property. The thermal treatments only affect the gas solubility in PLA 98:2. Sorption isotherms at temperatures 303, 313, and 323 K, below the glass transition temperature of the polymer, and pressures up to 5 MPa were measured and analyzed with three different models, the dual‐mode sorption model, the Flory–Huggins equation, and a modified dual‐mode sorption model where the Henry's law term was substituted by the Flory–Huggins equation. This last model performs especially well for CO₂ in PLA 80:20, due to the convex upward curvature of the solubility isotherms for that system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 616–625, 2007     

Interpretation of inorganic arsenic metabolism in humans in the light of observations made in vitro and in vivo in the rat

The toxicity of inorganic trivalent arsenic for living organisms is reduced by in vivo methylation of the element. In man, this biotransformation leads to the synthesis of monomethylarsonic (MMA) and dimethylarsinic (DMA) acids, which are efficiently eliminated in urine along with the unchanged form (As_i). In order to document the methylation process in humans, the kinetics of As_i, MMA and DMA elimination were studied in volunteers given a single dose of one of these three arsenicals or repeated doses of As_i. The arsenic methylation efficiency was also assessed in subjects acutely intoxicated with arsenic trioxide (As₂O₃) and in patients with liver diseases. Several observations in humans can be explained by the properties of the enzymic systems involved in the methylation process which we have characterized in vitro and in vivo in rats as follows: (1) production of As_i metabolites is catalyzed by an enzymic system whose activity is highest in liver cytosol; (2) different enzymic activities, using the same methyl group donor (S-adenosylmethionine), lead to the production of mono- and di-methylated derivatives which are excreted in urine as MMA and DMA; (3) dimethylating activity is highly sensitive to inhibition by excess of inorganic arsenic; (4) reduced glutathione concentration in liver moderates the arsenic methylation process through several mechanisms, e.g. stimulation of the first methylation reaction leading to MMA, facilitation of As_i uptake by hepatocytes, stimulation of the biliary excretion of the element, reduction of pentavalent forms before methylation, and protection of a reducing environment in the cells necessary to maintain the activity of the enzymic systems.     

Synthesis and characterization of novel thermoresponsive‐co‐biodegradable hydrogels composed of N‐isopropylacrylamide,poly(L‐lactic acid), and dextran

A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004