Spontaneous adsorption of ferrocenes on highly ordered pyrolytic graphite edges

The spontaneous adsorption of ferrocene and eight derivatives have been examined electrochemically on highly ordered pyrolytic graphite edges. All compounds give surface coverages of ca. 2×10^?8 mol/cm². Three of the adsorbed compounds give oxidation waves significantly more negative than their solution counterparts, in contrast with the other six derivatives.     

Process improvement in acetone-butanol production from hardwood by simultaneous saccharification and extractive fermentation

The acetone-butanol production by simultaneous saccharification and extractive fermentation (SSEF) was investigated. In the SSEF employing cellulase enzymes andClostridium acetobutylicum, both glucan and xylan fractions of pretreated aspen are concurrently converted into acetone and butanol. Continuous removal of the fermentation products from the bioreactor by extraction was an important factor that allowed long-term fed-batch operation. The use of membrane extraction prevented the problems of phase separation and extractant loss. Increase in substrate feeding as well as reduction of nutrient supply was found to be beneficial in suppressing the acid production, thereby improving the solvent yield. Because of prolonged low growth conditions prevalent in the fed-batch operation, the butanol-to-acetone ratio in the product was significantly higher at 2.6–2.8 compared to the typical value of two.     

Semistable measures and limit theorems on real andp-adic groups

For any locally compact groupG, we show that any locally tight homomorphism from a real directed semigroup intoM ¹ (G) (semigroup of probability measures onG) has a shift which extends to a continuous one-parameter semigroup. IfG is ap-adic algebraic group then the above holds even iff is not locally tight. These results are applied to give sufficient conditions for embeddability of some translate of limits of sequences of the form {v _n ^kn } and M ¹ (G) such that ()= ^M , for somek>1 and AutG (cf. Theorems 2.1, 2.4, 3.7).     

Enantioselective transacetylation of (R,S)-β-citronellol by propanol rinsed immobilized Rhizomucor miehei lipase

Background  

Use of enzymes in low water media is now widely used for synthesis and kinetic resolution of organic compounds. The frequently used enzyme form is the freeze-dried powders. It has been shown earlier that removal of water molecules from enzyme by rinsing with n-propanol gives preparation (PREP) which show higher activity in low water media. The present work evaluates PREP of the lipase (from Rhizomucor miehei) for kinetic resolution of (R,S)-β-citronellol. The acylating agent was vinyl acetate and the reaction was carried out in solvent free media.     

Validation of LC/MS electrospray ionisation method for the estimation of ursodiol in human plasma and its application in bioequivalence study

A novel High Performance Liquid Chromatography-electrospray mass spectrometric method has been developed for the estimation of Ursodiol (Ursodeoxycholic acid)--a bile acid, in human plasma using Ornidazole as internal standard. The methodology involved solid phase extraction of the analyte from human plasma matrix. The chromatographic separation was achieved within seven minutes by an isocratic mobile phase containing 1.0 mM ammonium acetate and Acetonitrile (65:35, v/v), flowing through XTerra MS C18, 100 x 2.1, 3.5 microm analytical column, at a flow rate of 0.2 ml/min. Ion signals were measured in negative mode for Ursodiol and internal standard at m/z 391.3 and 278.1, respectively. A detailed validation of the method was performed as per USFDA guidelines and the standard curves were found to be linear in the range 50.0 ng/ml to 3000.0 ng/ml with the mean correlation coefficient more than 0.99. The absolute recovery was more than 54.90% for Ursodiol and 76.51% for internal standard. Ursodiol was stable for sixty-nine days at -70 degrees C and for eight hours at ambient temperature. After extraction from plasma, the reconstituted samples of Ursodiol were stable in autosampler at 10 degrees C for forty-eight hours. Upon subjecting to three freeze thaw cycles, there was no change in the recovery of the analyte. The integrity of the plasma samples remained unaffected even upon four-fold dilution with drug free human plasma. The method was simple, specific, sensitive, precise, accurate and suitable for bioequivalence and pharmacokinetic studies. It was successfully applied to the pilot bioequivalence study of Ursodiol in male human subjects.     

Preprocessing of rotamers for protein design calculations

We have developed a process that significantly reduces the number of rotamers in computational protein design calculations. This process, which we call Vegas, results in dramatic computational performance increases when used with algorithms based on the dead-end elimination (DEE) theorem. Vegas estimates the energy of each rotamer at each position by fixing each rotamer in turn and utilizing various search algorithms to optimize the remaining positions. Algorithms used for this context specific optimization can include Monte Carlo, self-consistent mean field, and the evaluation of an expression that generates a lower bound energy for the fixed rotamer. Rotamers with energies above a user-defined cutoff value are eliminated. We found that using Vegas to preprocess rotamers significantly reduced the calculation time of subsequent DEE-based algorithms while retaining the global minimum energy conformation. For a full boundary design of a 51 amino acid fragment of engrailed homeodomain, the total calculation time was reduced by 12-fold.     

Copolymers and two-layered composites of poly(<Emphasis Type="Italic">o</Emphasis>-aminophenol) and polyaniline

Electroactive conducting copolymers of aniline (ANI) and o-aminophenol (OAP) and two-layered poly(o-aminophenol) (POAP)/polyaniline (PANI) composites were prepared in aqueous acidic solution by electrode potential cycling. Copolymerization was carried out at different feed concentrations of OAP and ANI on a gold electrode. A strong inhibition of electropolymerization was found at a high molar fraction of OAP in the feed. The copolymers showed good adherence on the electrode surface and gave a redox response up to pH=10.0. Two transitions were observed in the in situ conductivities of the copolymers (as with PANI), but the conductivities were lower by 2.5–3 orders of magnitude as compared to PANI. Electrosynthesis of PANI on POAP modified electrodes showed copolymer formation after reaction initiation and finally formation of a PANI layer at the copolymer/solution interface. The ‘memory effect’ of the bilayer structures of both polymers was discussed in terms of protonation/deprotonation and anion consumption taking place during redox processes of both polymers.     

Steric Stabilization of Colloids by Poly(dimethylsiloxane) in Carbon Dioxide: Effect of Cosolvents

Steric stabilization and flocculation of colloids with surface-grafted poly(dimethylsiloxane) (PDMS) chains are examined in liquid and supercritical carbon dioxide with and without hexane as a cosolvent. Neither poly(methyl methacrylate) (PMMA) nor silica particles with grafted 10,000 g/mol PDMS could be stabilized in pure CO(2) at pressures up to 345 bar at 25 degrees C and 517 bar at 65 degrees C without stirring. The addition of 15 wt% hexane to CO(2) led to stable dispersions with sedimentation velocities of 0.2 mm/min for 1-2 μm PMMA particles. The critical flocculation pressure of the colloids in the hexane/CO(2) mixture, determined from turbidity versus time measurements, was found to be the same for silica and PMMA particles and was well above the upper critical solution pressure for the PDMS-CO(2) system. The addition of a nonreactive cosolvent, hexane, eliminates flocculation of PMMA particles synthesized through dispersion polymerization in CO(2) with PDMS-based surfactants. Copyright 2000 Academic Press.