Biocatalytic synthesis of polymers. III. Formation of a high molecular weight polyester through limitation of hydrolysis by enzyme-bound water and through equilibrium control

Enzyme-catalyzed preparation of polymers offers several potentially valuable advantages over the usual polymerization procedures and has been studied for several years. A significant limitation on the polyesters prepared to date has been the low molecular weights achieved. The present studies have established that, in the polycondensation of bis(2,2,2-trifluoroethyl) glutarate with 1,4-butanediol using porcine pancreatic lipase as the catalyst, this limitation arises from at least two sources: hydrolysis of activated ester end groups by water introduced along with the enzyme and the polymerization's reaching equilibrium despite using the poorly nucleophilic 2,2,2-trifluoroethanol as the leaving group. Evidence is also developed that the presence of trifluoroethanol accelerates the release of the enzyme-bound water which hydrolyzes the activated ester end groups. The hydrolysis could be avoided by choosing a relatively high-boiling solvent, such as bis(2-ethoxyethyl) ether, then removing the trifluoroethanol by placing the reaction mixture under vacuum periodically or by drying the enzyme rigorously. The vacuum method also removed the limitation on molecular weight resulting from the reaction's reaching equilibrium. A further improvement in the molecular weight to nearly 40,000 daltons, well within the range that is technically interesting, was achieved by using 1,2-dimethoxybenzene or 1,3-dimethoxybenzene as the polymerization solvent. © 1995 John Wiley & Sons, Inc.     

A Titration Microcalorimetric Study of the Effects of Halide Counterions on Vesicle-Forming Aggregation in Aqueous Solution of Branched-Chain Alkylpyridinium Surfactants

Titration microcalorimetry is used to study the influences of iodide, bromide, and chloride counterions on the aggregation of vesicle-forming 1-methyl-4-(2-pentylheptyl)pyridinium halide surfactants. Formation of vesicles by these surfactants was characterised using transmission electron microscopy. When the counterion is changed at 303 K through the series iodide, bromide, to chloride, the critical vesicular concentration (cvc) increases and the enthalpy of vesicle formation changes from exo- to endothermic. With increase in temperature to 333 K, vesicle formation becomes strongly exothermic. Increasing the temperature leads to a decrease in enthalpy and entropy of vesicle formation for all three surfactants. However the standard Gibbs energy for vesicle formation is, perhaps surprisingly, largely unaffected by an increase in temperature, as a consequence of a compensating change in both standard entropy and standard enthalpy of vesicle formation. Interestingly, standard isobaric heat capacities of vesicle formation are negative, large in magnitude but not strikingly dependent on the counterion. We conclude that the driving force for vesicle formation can be understood in terms of overlap of the thermally labile hydrophobic hydration shells of the alkyl chains. Copyright 2000 Academic Press.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Relativistic electronic structures of the Ag2 and Au2 molecules

The relativistic electronic structures of the Ag₂ and Au₂ molecules have been calculated using the recently developed self-consistent-field Xα Dirac-scattered-wave programs. Calculations have been carried out for transition energies and ionization potentials for selected molecular orbitals. The results indicate a large degree of s-d hybridization in the ground state of the Au₂ molecule. The calculations are in good agreement with other theoretical work and with existing experimental results.     

Stable and efficient algorithms for Xα multiple scattering calculations

Solutions to some practical problems that arise in multiple scattering calculations on large molecules are discussed. (1) Numerical instabilities near the zero of energy can be removed by rescaling the secular matrix. (2) The calculation of structure factors can be made much more efficient by the application of symmetry projection operators. (3) An energy search procedure is described that ensures that no states are inadvertently neglected. Test calculations incorporating these changes illustrate the improved numerical stability, and show decreases in computation time of 30–60%, when compared to previous codes. The procedures suggested here are applicable to both relativistic and nonrelatitistic calculations.     

Absorption coefficient measurements of particle-laden filters using laser heating: Validation with nigrosin

A laser-heating technique, referred as the laser-driven thermal reactor, was used in conjunction with laser transmissivity measurements to determine the absorption coefficient of particle-laden substrates (e.g., quartz-fiber filters). The novelty of this approach is that it analyzes a wide variety of specific samples (not just filtered samples) and overcomes measurement issues (e.g., absorption enhancement) associated with other filter-based particle absorption techniques. The absorption coefficient was determined for nigrosin-laden, quartz-fiber filters and the effect of the filter on the absorption measurements was estimated when compared to the isolated nigrosin results. The isolated nigrosin absorption coefficient compared favorably with Lorenz–Mie calculations for an idealized polydispersion of spherical particles (based on a measured nigronsin/de-ionized water suspension size distribution) dispersed throughout a volume equivalent to that of the nigrosin-laden filter. To validate the approach, the absorption coefficient of a nigrosin/de-ionized water suspension was in good agreement with results obtained from an ultraviolet/visible spectrometer. In addition, the estimated imaginary part of the refractive index from the Lorenz–Mie calculations compared well with literature values and was used to estimate the absorption coefficient of optically opaque packed nigrosin.