Complete replacement of H2 by D2 via Pd/C-catalyzed H/D exchange reaction

[reaction: see text] A general and in situ D2 gas generation method using 10% Pd/C-catalyzed H2-D2 exchange reaction in a H2-D2O system has been developed. H2 gas sealed in a reaction flask was efficiently converted into nearly pure D2 gas, which can be used for the reductive deuteration of substrates possessing reducible functionalities within the molecule.     

Removal of fine powders from film surface. I. Effect of electrostatic force on the removal efficiency

A novel fine particle removal system composed of a corona-discharge neutralizer, a pulse-jet air unit and an image processing system has been developed. First of all, adhesion force between particle and film was directly measured and effect of electrostatic force on the adhesion force was calculated experimentally and theoretically. The electrostatic force was found to be significant, leading to the suggestion that the countermeasure for the electrostatic force was required to effectively remove fine particles. This system was then applied to the removal of fine particles from surface of a gelatin film used for conventional capsule material. The number of particles removed by the system was calculated by an image processing system and number base removal efficiency was computed with and without the elimination of electrostatic charge by the neutralizer. It was found that the difference between the removal efficiency of particles with elimination of electrostatic charge and that of without the elimination showed linear relationship with the electrostatic adhesion force. The data confirmed the necessity of electrostatic charge elimination for the effective removal of fine particles.     

Synthesis of large macrocyclic tetraaza compounds with a methylene backbone: Cyclo[-NH- (CH2)n-]4, (n = 6, 7, 8, 9 and 10). The formation of 28-, 32-, 36-, 40- and 44-membered rings

A series of macrocyclic tetraamines with 28-, 32-, 36-, 40- and 44-membered rings have been efficiently prepared from the corresponding ditosylamide and monobromoalcohol derivatives in 6 steps via a double condensation reaction. Overall yields were: 41, 41, 46, 29, and 33%, respectively, for 1,8,15,22-tetraazacyclooctacontane ( 11a ), 1,9,17,25-tetraazacyclodotriacontane ( 11b ), 1,10,19,28-tetraazacyclohexatriacontane ( 11c ), 1,11,21,31-tetraazacyclotetracontane ( 11d ) and 1,12,23,34-tetraazacyclotetratetracontane ( 11e ).     

Stereochemistry and mechanism of catalytic hydrogenation of substituted cyclohexanones

Substituted alkylcyclohexanones were hydrogenated over several transition metal catalysts. The hydrogenation with freshly prepared Raney Ni gave predominantly the axial alcohols but catalyst to which sodium hydroxide was added or aged catalyst increased the stereoselectivity. In contrast to the PtO₂ hydrogenation in which the equatorial alcohols were favoured, more axial alcohols were obtained than the equatorial counterparts on Pt-black. On Pd catalyst the isomeric ratios of the cyclohexanols changed as the reaction progressed. This may be due to a decrease in the amount of hydrogen available caused by the strong adsorption of ketones on the catalyst. Rh catalyst gave more of the axial alcohols than any other catalyst used in the present study.     

Effects of electron beam preirradiation on the γ radiolysis of polyethylene

The γ radiolysis of polyethylene preirradiated with electron beams to 3 Mrad was carried out at 30–100°C in vacuo with a dose rate of 6.35 × 10⁵ rad/hr. The hydrogen formation in the γ radiolysis was little affected by the preirradiation of electron beams, whereas the formation of trans-vinylene unsaturation and gel was somewhat retarded. The rates of the formation of hydrogen and trans-vinylene unsaturation were described by the zero-order formation kinetics with respect to each concentration combined with the first-order disappearance. The apparent rate constants and activation energies for the formation and disappearance of hydrogen and trans-vinylene unsaturation were almost independent of the preirradiation. The gel fraction was analyzed by using the Charlesby–Pinner equation. The G values of crosslinking and main chain scission were increased by the preirradiation, whereas their activation energies remained unaltered. On the basis of these results the effects of preirradiation on the reactions induced by γ rays in polyethylene were discussed.     

Thermodynamically stable vesicle formation from glycolipid biosurfactant sponge phase

Thermodynamically stable vesicle (L(alpha1)) formation from glycolipid biosurfactant sponge phase (L(3)) and its mechanism were investigated using a "natural" biocompatible mannosyl-erythritol lipid-A (MEL-A)/L-alpha-dilauroylphosphatidylcholine (DLPC) mixture by varying the composition. The trapping efficiency for calcein and turbidity measurements clearly indicated the existence of three regions: while the trapping efficiencies of the mixed MEL-A/DLPC assemblies at the compositions with X(DLPC)< or =0.1 or X(DLPC)> or =0.8 were almost zero, the mixed assemblies at the compositions with 0.1 or =0.8 were multilamellar vesicles (L(alpha)) with diameter from 2 to 10 microm. Meanwhile, dynamic light scattering (DLS) measurement revealed that the average size of the vesicles at the composition of X(DLPC)=0.3 was 633.2 nm, which is remarkably small compared to other compositions. Moreover, the mixed vesicle solution at the composition of X(DLPC)=0.3 was slightly bluish and turbid and kept its dispersion stability at 25 degrees C for more than 3 months, indicating the formation of a thermodynamically stable vesicle (L(alpha1)). These results exhibited the formation of a thermodynamically stable vesicle (L(alpha1)) with a high dispersibility from the MEL-A/DLPC mixture. The asymmetric distribution of MEL-A and DLPC in the two vesicle monolayers caused by the difference in geometrical structures is very likely to have changed their self-assembled structure from a sponge phase (L(3)) to a thermodynamically stable vesicle (L(alpha1)).     

Contracted polarization functions for B to Ar

Using optimal exponents for B through Ne given by Dunning and those for Al through Ar by Woon and Dunning, d-type contracted polarization functions (2d/1d), (3d/1d), and (3d/2d) are generated from natural orbitals of atomic single and double excitation configuration interaction (SDCI) calculations, where the numbers before and after the slash are those of the primitive and contracted Gaussian type functions. The resulting contracted functions are tested on N₂ and P₂ molecules by self-consistent field and SDCI calculations, which clarify characteristics of the present polarization functions. Received: 5 June 1997 / Accepted: 20 August 1997     

Cross-linking chemistry and biology: development of multifunctional photoaffinity probes

An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions.     

The catalytic hydrogenolysis of 1-phenylbicyclo[4.1.0]heptane and the corresponding azidirine and epoxide

The hydrogenolysisof 1-phenylbicyclo[4.1.0]heptane (1a), cis-1-phenyl-2-methylbicyclo[4.1.0]heptane (1b), 1-phenyl-7-azabicyclo[4.1.0]heptane (2) and 1-phenyl-7-oxabicyclo[4.1.0]heptane (3) was studied using Ni, Pd, Rh and Pt as catalysts. The hydrogenolysis of the C₁C₇ bond of 1a and 1b led to the selective formation of trans-1-phenyl-2-methylcyclohexane (4a) with retention of configuration. Compound 1a gave not only 4a but also phenylcycloheptane (6a), which is the product of C₁C₆ bond fission, and the ratio of 6a to 4a increased in the sequence: Ni ? Pd, Rh < Pt. No C₁C₆ bond fission was observed in the hydrogenolysis of 1b. These results can be explained by a mechanism involving the formation of the π-benzyl complex.trans-2-Phenylcyclohexylamine (8) was obtained stereoselectively in the hydrogenolysis of 2 over Raney Ni. This selective formation can be ascribed to the competition of “SN i” and “radical” processes. The Pd catalysed hydrogenolysis gave cis-2-phenylcyclohexylamine (9) as the main product, while the presence of sodium hydroxide promoted the formation of 8.Raney Ni catalysed hydrogenolysis of 3 yielded a mixture of phenylcyclohexane (13) and 2-phenylcyclohexanols (10 and 11). trans-2-Phenylcyclohexanol (10) was the dominant isomer; the hydrogenolysis resulted in the predominant configurational retention. Compound 13 was confirmed to be produced via 1-phenylcyclohexene (12). This deoxygenation may be explained by a mechanism involving the radical cleavage reaction of 3. The presence of sodium hydroxide led to the formation of cis-2-phenylcyclohexanol (11). The Pd catalysed hydrogenolysis also gave mainly 11.The difference in behaviour of cyclopropane, azidirine and epoxide we ascribe to the differences in the affinity for the catalyst and differences in the electronegativity between C, N and O atoms.     

Determination of threo and erythro configurations of 3-fluorophenylalanine for verifying stereochemical aspects of recently reported syntheses

Determination of threo and erythro configurations of both diastereoisomers of 3-fluorophenylalanine on the basis of chemical transformation and X-ray analysis has confirmed that the aziridine ring opening reaction gives the threo isomer stereoselectively, whereas the fluorodehydroxylation reaction affords both isomers nonselectively.