Two New Syntheses of the Pyranojuglone Pigment α-Caryopterone

By a simple process, 3-methoxyjuglone (= 8-hydroxy-2-methoxy-1,4-naphthoquinone; 9 ) has been synthesized from 1,2,4-trimethoxybenzene ( 5 ) and converted, after prenylation, to α-caryopterone ( 1 ; Scheme 1), a pyranojuglone pigment from Caryopteris clandonensis. On the other hand, juglone (= 5-hydroxy-1,4-naphthoquinone; 12 ) was regioselectively prenylated at C(2) via its 1-methoxy-cyclohexa-1,3-diene adduct 15 (Scheme 2). The 2-prenyljuglone ( 4 ) thus formed led to 1 after oxidation and other reactions.     

Hydrogenase-based nanomaterials as anode electrode catalyst in polymer electrolyte fuel cells

We consider hydrogenase-based nanomaterials for possible use as anode electrode catalysts in polymer electrolyte fuel cells (PEFCs). We choose Fe-only hydrogenase component of Desulfovibrio desulfuricans (DdHase) as a hydrogenase complex, and investigate its catalytic activity for H₂ dissociation using ab initio calculations based on density functional theory (DFT). We found two possible H-H bond cleavage pathways, which are heterolytic and possess low activation barriers. Moreover, the H₂ dissociation can be promoted by inducing spin polarization of the H₂ adduct. We report that hydrogenase or hydrogenase-based nanomaterials can manipulate to exhibit the catalytic activity equivalent to the well-known platinum catalyst.     

Analysis of a discrete-time queueing system with time-limited service

We analyze a discrete-time, single-server queueing system in which the length of each service period is limited. The server takes a vacation when the limit expires or the queue empties, whichever occurs first. In the former case, the preempted service is resumed after the vacation without loss or creation of any work. This system models the transmission of message frames from a station on timed-token local-area networks (for example, FDDI and IEEE 802.4 token bus). We study the process of the unfinished work and the joint process of the queue size and the remaining service time. By using the technique of discrete Fourier transforms to determine some unknown functions in the governing equations, we numerically obtain exact mean waiting times.A part of the work of H. Takagi was done while he was with IBM Research, Tokyo Research Laboratory.     

Microlocal energy methods and pseudo-differential operators

A functionk(x, u) of the(n+n)-variables is said to be a positive Hermite kernel if , and the matrix(k(x _i, x_j))_i,j is positive semi-definite for every integerN and everyx ₁, ..., x_N. In this paper, we prove that this positive structure can be microlocalized in the category of microfunctions. Further we obtain a useful theorem concerning the positivity of pseudo-differential operators. This theory will play important roles in the study of analytic singularities of solutions of boundary value problems.     

Identification of novel sesterterpenes by genome mining of phytopathogenic fungi Phoma and Colletotrichum sp.

Two homologous gene clusters for the biosynthesis of sesterterpenes betaestacins were identified from two phytopathogens, Phoma betae and Colletotrichum orbiculare. Heterologous expression of identified oxidation enzymes with previously-characterized PbTS1 (BtcA_Pb) resulted in the production of seven novel sesterterpenes. Although both strains possessed homologous enzymes, oxidation state of corresponding products were different from each other, suggesting that structural diversification of sesterterpene skeletons might be achieved by these homologous enzymes with different functions.     

Synthesis and structure revision of litseaone A

Litseaone A, isolated from the stem barks of Litsea rubescens and Litsea pedunculata, is a chalcone derivative with a novel spiro-epoxide moiety. The structural revision of litseaone A was achieved by the racemic synthesis of the proposed structure and the asymmetric synthesis of the revised structure. The major tautomeric structure of litseaone A and the relative stereochemistry at the epoxide carbon center were also clarified.     

Photochemistry of poly(vinyl cinnamylideneacetate) and related compounds

The photochemistry of the cinnamylideneacetyl group was investigated with respect to a photosensitive polymer, poly(vinyl cinnamylideneacetate). The photochemical reaction of 1,4-butanediol dicinnamylideneacetate was intramolecular cyclobutane formation. The photosensitive polymer underwent dimerization of the cinnamylideneacetyl moiety to form a cyclobutane ring. The reactivity of the double bond adjacent to the carbonyl group was larger than that of the double bond adjacent to the phenyl group in the chromophore. The quantum yield of the reaction was larger in the solid state than in solution: ? > 1.2 in crystalline state, ? = 0.5 in polymer film, ? = 0.1 in solution. The reaction was sensitized by triplet sensitizers (E_T > 42 kcal/mole). The thermal reaction of the polymer was completely different from the photochemical reaction. A radical initiator was very ineffective for reaction of the polymer.     

Anomalous binding profile of phenylboronic acid with N-acetylneuraminic acid (Neu5Ac) in aqueous solution with varying pH

Borates are known to interact with carbohydrate moieties expressed on the surface of biological membranes of a variety of cells, viruses, bacteria, and fungi. This study revealed the anomalous binding profile of borate in aqueous solution with N-acetylneuraminic acid (Neu5Ac, sialic acid) as a potential receptor site on the surfaces of biological membranes using (11)B, (1)H, (13)C, and (15)N nuclear magnetic resonance spectroscopies. 3-(Propionamido)phenylboronic acid (PAPBA) was chosen as the model borate compound. The equilibrium constant (K) for Neu5Ac binding to PAPBA was compared with those for glucose, mannose, and galactose, which are the major carbohydrate constituents of glycoproteins and glycolipids expressed on biological membranes. In the Neu5Ac/PAPBA system, the unusual pH dependency of the K values, a decrease in K with increasing pH, was observed, suggesting the formation of a trigonal-formed complex stabilized by the coordination of an amide group of Neu5Ac at the C-5 position to the boron atom, forming intramolecular B-N or B-O bonding. Furthermore, the anomalously high complexing ability at physiological pH 7.4 was confirmed for this system, with the K value 37.6 which is approximately 7 times higher than that for glucose. This exceptionally high value of K at physiological pH, compared to those of other sugars, strongly suggests that the boronic acid selectively recognizes the Neu5Ac residues of the glycosylated components including glycoproteins and gangliosides existing on the surface of the biological membranes.     

Asymmetric synthesis of alanine by hydrogenolytic asymmetric transamination

Hydrogenolytic asymmetric transamination between alkyl (R)-phenylglycinate and ethyl pyruvate was studied. The effect of the asymmetric moieties and of the solvents used in the asymmetric synthesis were explained by the substrate-catalyst complex.