Influence of drying method on morphology and properties of asymmetric cellulose hollow fiber membrane

Using a dry/wet spinning process, asymmetric cellulose hollow fiber membranes (CHFM) were prepared from a dope composed of cellulose/N-methylmorpholine-N-oxide/water. The formation mechanism for the finger-like macrovoids at the inner portion of as-spun fibers was explained. Naturally drying and three solvent exchange drying methods were tried to investigate their influence on morphology and properties of CHFM. It was found that the ethanol-hexane exchange drying was an appropriate method to minimize morphology change of the as-spun CHFM, whereas the naturally drying caused the greatest shrinkage of the fibers that made the porous membrane become dense. The result, CHFM from ethanol-hexane exchange drying performed the highest gas permeation rate but gas permeation of the naturally dried membrane could not be detectable. The resultant CHFM from the ethanol-hexane exchange drying also showed acceptable, mechanical properties, thus it was proposed to be an appropriate method for gas separation purpose. The experimental results supported the proposed drying mechanism of CHFM. The free water would evaporate or be replaced by a solvent that subsequently would evaporate but the bonded water would remain in the membrane. What dominated the changes of membrane morphology during drying should be. the molecular affinities of cellulose-water, water-solvent and solvent-solvent. (C) 2004 Elsevier B.V. All rights reserved.

N-arylamides from selenium-catalyzed reactions of nitroaromatics and amides in the presence of carbon monoxide and mixed organic bases

N-Arylamides were exclusively obtained in moderate to good yields from selenium-catalyzed reactions of nitroaromatics with amides in the presence of CO and mixed organic bases Et3N and DBU.

New chiral ferrocenyldiphosphine ligand for catalytic asymmetric transfer hydrogenation

New chiral ferrocenyldiphosphine ligands (R)-(S)-3 and (R)-(S)-4 were prepared. The ligands were employed in Ru(II) catalyzed asymmetric transfer hydrogenation of ketones to give corresponding secondary alcohols. Up to 99% conversion with 90% e.e. was obtained on Ru(DMSO)(4)Cl-2/4 in transfer hydrogenation of acetophenones with propan-2-ol. (C) 2003 Elsevier B.V. All rights reserved.

Chiral ferrocene-based phosphine-imine and sulfur-imine ligands for palladium-catalyzed asymmetric allylic alkylation of cycloalkenyl esters

Chiral ferrocene-based phosphine-imine ligands 1-3 and sulfur-imine ligand 4 were applied in the palladium-catalyzed asymmetric allylic alkylation of cycloalkenyl esters. The results revealed that the substitutents in aryl ring, ferrocenylmethyl and benzyliene position strongly affected the enantioselective induction of phosphine-imine ligands, and the most stereoselective ligand was ferrocenylphosphine-imine 1b with a nitro group in the meta-position of phenyl ring. Under the optimized condition, up to 91% (enantiomeric excesses) e.e. of cyclic alkylation product was obtained by the use of 1b. (C) 2004 Elsevier B.V. All rights reserved.

State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(D-1) + H-2 --> OH+H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H-3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H+HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H+D-2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.