Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers

Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10^?3 mol L^?1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation‐binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4964–4975, 2004     

Novel liquid crystals based on [1]benzothieno[3,2- b ][1]benzothiophene

Four series of new [1]benzothieno[3,2- b ][1]benzothiophene derivatives have been synthesized. In the non-chiral series a SmA phase occurs, while the chiral series exhibits a rather wide antiferroelectric SmC * A phase just below the SmA phase. The SmA-SmC * A phase transition has been studied using DSC and dielectric spectroscopy. In the SmC * A phase the spontaneous quantities have been measured. The tilt angle shows a typical temperature dependence and the values of spontaneous polarization are rather moderate. The length of the helical pitch increases on increasing the length of the non-chiral alkyl chain.     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007     

On the retrograde condensation of one or two liquids

This contribution discusses the phenomena of retrograde condensation of one or two liquids. It w1 be shown that both phenomena can be well understood. Also the relation of retrograde condensation of one liquid phase with the condensation behavior of natural gas will be discussed. Similarly that of two liquid phases with multiple phase behavior occurring in low temperature reservoir fluids will be pointed out.     

Recycling in telomerization of butadiene with D‐xylose: Pd(TPPTS)n‐KF/Al2O3 as an active catalyst

A palladium‐TPPTS catalyst heterogenized on KF/alumina has been shown to be effective and recyclable for the selective formation of monooctadienylxylopyranosides via the telomerization of butadiene with D ‐xylose. Copyright © 2007 John Wiley & Sons, Ltd.     

Specific high performance liquid chromatographic determination of the molecular weight and concentration of hyaluronic acid in complex mixtures by labelled hyaluronate binding proteins.

A simple High performance liquid chromatographic (HPLC) method for the specific determination of the molecular weight and concentration of hyaluronic acid (HA) in complex mixtures has been developed. Hyaluronate-binding proteins isolated from bovine cartilage labelled by 125I or fluoresceinisothiocyanate were used as specific markers. The specific binding affinities of the markers were compared and were found to have association constants of 1.6 x 10(7) M-1 and 1.2 x 10(7) M-1 respectively. The HA levels and molecular weight distributions can be easily determined in the range 10-500 ng/mL in complex mixtures by the use of markers, molecular sieving HPLC columns and appropriate detectors. It has been demonstrated clearly that the method is useful for the highly specific determination of the parameters in complex biological samples such as serum and synovial fluids and is recommended for clinical applications.