Chiral cobalt(II)-salen-catalyzed Michael addition of amines to β-substituted nitroalkenes

Optically active cobalt(II) salen complexes were found to be effective Lewis acid catalysts for the enantioselective Michael addition of O-alkylhydroxylamines to nitroalkenes to afford the corresponding N-alkylhydroxyl-1,2-nitroamines in high yields and with good to high enantioselectivities. This study represents the first example of a transition-metal-catalyzed asymmetric Michael addition of amines to nitroalkenes.     

Comparison of the Catalytic Activities of Three Isozymes of Carnitine Palmitoyltransferase 1 Expressed in COS7 Cells

The enzyme carnitine palmitoyltransferase 1 (CPT1) catalyzes the transfer of an acyl group from acyl-CoA to carnitine to form acylcarnitine, and three isozymes of it, 1a, 1b, and 1c, have been identified. Interestingly, the 1c isozyme was reported to show no enzymatic activity, but it was not clearly demonstrated whether this inactivity was due to its dysfunction or due to its poor expression. In the present study, we (a) expressed individual CPT1 isozymes in COS7 cells, (b) evaluated quantitatively their expression levels by Western blotting using the three bacterially expressed CPT1 isozymes as standards, and (c) evaluated their catalytic activities. With these experiments, we successfully demonstrated that the absence of the enzymatic activity of the 1c isozyme was due to its dysfunction. In addition, experiments on the preparation of standard CPT1 isozymes revealed that the 1c isozyme did not show the standard relationship between migration in an SDS–PAGE gel and molecular size. We further tried to determine why the 1c isozyme was inert by preparing chimeric CPT1 between 1a and 1c, but no clear conclusion could be drawn because one of the chimeric CPT1s was not sufficiently expressed.     

Precise operation-frequency control of monolithic mode-locked laser diodes for high-speed optical communication and all-optical signal processing

We describe a method for pulse-repetition-frequency tuning of mode-locked laser diodes (MLLDs) monolithically integrated with a distributed Bragg reflector (DBR). The pulse-repetition frequency, i.e., the cavity-roundtrip time, is tuned through loss-induced change in the effective length of the DBR. The frequency-tuning range as large as the chip-to-chip frequency deviation caused by cavity-length fabrication variation of 10 μm has been confirmed experimentally, and the MLLDs operate at SDH (synchronous digital hierarchy) frequencies of 9.953, 19.906 and 39.813 GHz. Synchronization with an external system-clock through the hybrid mode-locking operation reduces the timing jitter of the optical pulses to less than 0.3 ps. As an optical pulse source for optical communication, error-free 20-Gbps transmission over 3000 km has been demonstrated, confirming that the MLLD properties satisfy the requirements for use in real systems. The novel application of MLLDs to all-optical clock extraction, one of the essential functions required in all-optical signal processing, has been demonstrated at the 40-GHz SDH frequency.     

Partial Protection of Carbohydrate Derivatives. Part 13.1 Chemical Conversion of Kanamycin A Into 2′-Deoxykanamycin A, 2′-Epi-Kanamycin A,and 2′-Epi-Kanamycin B

Abstract

Hydrazinolyses of hexa-0-benzoyl-tetra-N-benzyloxycarbonyl-and N-ethoxycarbonylkanamycin A were performed and found to be sufficiently regioselective to give the corresponding 2′-hydroxyl derivatives in good yields under controlled conditions. The products were converted into the corresponding 2′-triflates, which were then subjected to nucleophilic substitution reactions with sodium benzenethioxide, sodium benzoate, and sodium azide to give the corresponding d-mannopyranosyl derivatives in good yields. Deprotection of the phenylthio (10) and azido (12) derivatives, and hydrogenolysis, gave 2′-deoxykankmycin A and 2′-epi-kanamycin B, respectively. Moreover, deprotection of the benzoyl compound 11 gave 2′-epi-kanamycin A.     

Enzymatic Syntheses of N-Acetyllactosamine and N-Acetylallolactosamine by the Use of β-D-Galactosidases

Abstract

A β-D-galactosidase from Bacillus circulans induced β-D-galactopyranosyl transfer from lactose predominantly to a secondary (OH-4) rather than the primary hydroxyl group (OH-6) of 2-acetamido-2-deoxy-D-glucopyranose. 4-O-β-D-Galacto-pyranosyl-2-acetamido-2-deoxy-D-glucopyranose (N-acetyl-lactosamine) was thus readily synthesized on a gram scale and conveniently isolated by chromatography on a column of charcoal-Celite. On the other hand, the glycosyl transfer to the 6-position predominantly was efficiently induced to give 6-O-β-D-galactopyranosyl-2-acetamido-2-deoxy-D-glucopyranose (N-acetyl-allolactosamine) by consecutive use of β-D-galactosidases from Kluyveromyces lactis and B. circulans. These enzyme reactions were efficient enough to allow the one-pot preparation of the desired disaccharides.     

Experimental and computational study of intermolecular migration of N,N-dimethylcarbamoyl group from N(7) to N(1) on a 7-azaindoline derivative

N,N-Dimethylcarbamoylation of the anilinic nitrogen atom N(1) on the spiro 7-azaindoline consists of two steps. The first step is N,N-dimethylcarbamoylation of the pyridyl nitrogen atom N(7), leading to the formation of an isolable intermediate. The second step is intermolecular migration of the N,N-dimethylcarbamoyl group from the pyridyl nitrogen atom N(7) to the anilinic nitrogen atom N(1). We accomplished optimization of the reaction conditions based on the revealed reaction mechanism and a large scale synthesis of compound 3 in quantitative yield.     

Thermo‐Responsive Hydrogels with Nanodomains: Rapid Shrinking of a Nanogel‐Crosslinking Hydrogel of Poly(N‐isopropyl acrylamide)

Rapidly shrinking poly(N‐isopropyl acrylamide) (PNIPAM) hydrogels are prepared by crosslinking with self‐assembled nanogels that consist of cholesteryl‐ and methacryloyl‐substituted pullulan (CHPMA). The CHPMA nanogel (R_h = 26.4 nm) was used as a crosslinker for a hydrophilic nanodomain. Transmission electron microscopy images of the nanogel‐crosslinked PNIPAM hydrogel reveal a well‐defined nanoporous structure. The nanogel‐crosslinked PNIPAM hydrogel shows rapid shrinking based on its structure. The shrinking half‐time was ≈2 min, which is about 3 400 times faster than that of a PNIPAM hydrogel crosslinked by methylene(bisacrylamide).

     

In operando quantitation of Li concentration for a commercial Li‐ion rechargeable battery using high‐energy X‐ray Compton scattering

Compton scattering is one of the most promising probes for quantitating Li under in operando conditions, since high‐energy X‐rays, which have high penetration power, are used as the incident beam and the Compton‐scattered energy spectrum has specific line‐shapes for each element. An in operando quantitation method to determine the Li composition in electrodes has been developed by using line‐shape (S‐parameter) analysis of the Compton‐scattered energy spectrum. In this study, S‐parameter analysis has been applied to a commercial coin cell Li‐ion rechargeable battery and the variation of the S‐parameters during the charge/discharge cycle at the positive and negative electrodes has been obtained. By using calibration curves for Li composition in the electrodes, the change in Li composition of the positive and negative electrodes has been determined using the S‐parameters simultaneously.     

Mechanical Properties of Uniaxially Cold-Drawn Films of Poly[(R)-3-hydroxybutyrate] and Its Copolymers

Uniaxially oriented films of poly[(R)-3-hydroxybutyrate] (P(3HB)) and two kind of copolymers, poly[(R)-3-hydroxybutyrate-co-8%-[R]-3-hydroxyvalerate] (P(3HB-co-8%-3HV)), and poly[(R)-3-hydroxybutyrate-co-[R]-5%-3-hydroxyhexanoate] (P(3HB-co-5%-3HH)), were prepared by cold-drawing from amorphous preforms at temperatures near to the respective glass transition temperatures. Melt-quenched films in a rubber state could be stretched reproducibly to a draw ratio of 500%∼1800%, and subsequent annealing under tension led to improvement of the tensile strength and Young's modulus. Two-step drawing resulted in further improvement of the mechanical properties. The mechanical properties remained unchanged after storing for 6 months at room temperature, suggesting that high orientation and crystallinity suppress the secondary crystallization.