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Poly-γ-glutamic acid (PGA) is a promising polymer that comprises d- and l-glutamic acid (Glu) connected via an amide bond. PGA is biosynthesized by a transmembrane enzyme complex composed of PgsB, PgsC, and PgsA. However, the detailed reaction, especially the mechanism for introducing d-Glu residues into PGA, remains elusive. We herein report isotope tracer experiments with deuterated l- and d-Glu and demonstrate that epimerization of a growing peptide is involved in PGA biosynthesis.

Crystals of charge-transfer (CT) complexes were synthesized using the polar molecule tetrachlorophthalonitrile (TCPN) as the electron acceptor and nonpolar aromatic hydrocarbons, such as perylene, coronene, chrysene, and pyrene, as the electron donors. Variable-temperature X-ray crystal structure analyses revealed that the TCPN molecules in all the CT crystals exhibit orientational disorder at room temperature. Some of the CT crystals undergo an order–disorder-type phase transition upon cooling, where the orientation of the TCPN molecules becomes ordered at low temperature. The CT crystals show large dielectric constants at room temperature arising from in-plane reorientation of the polar TCPN molecules. The order–disorder phase transition results in a drastic reduction of the dielectric constant of the CT crystals upon cooling. This study demonstrates that the formation of CT crystals from polar molecules represents a promising method for the development of dielectric crystalline materials, whose propert...

α-1,6-Glucosidase (isomaltase) belongs to glycoside hydrolase (GH) families 13 and 31. Genes encoding 3 isomaltases belonging to GH family 13 were cloned from filamentous fungi, Aspergillus oryzae (agl1), A. niger (agdC),and Fusarium oxysporum (foagl1), and expressed in Escherichia coli. The enzymes hydrolyzed isomaltose and α-glucosides preferentially at a neutral pH, but did not recognize maltose, trehalose, and dextran. The activity of AgdC and Agl1 was inhibited in the presence of 1 % glucose, while Foagl1 was more tolerant to glucose than the other two enzymes were. The three fungal isomaltases did not show transglycosylation when isomaltose was used as the substrate and a similar result was observed for AgdC and Agl1 when p-nitrophenyl-α-glucoside was used as the substrate.

Xyloglucan is a major hemicellulosic component in plant cell walls. Phytopathogenic fungi secrete cell wall-degrading enzymes on their infection to hosts, while the nature of the cell wall-lytic enzymes of such fungi are yet to be fully understood. Verticillium dahliae is a soil-borne fungus that causes vascular wilt diseases in a variety of commercially important crops worldwide. We purified two types of xyloglucanases, XEG12A and XEG74B, from the culture of naturally isolated Verticillium dahliae strain 2148. XEG12A showed a molecular size of 23 kDa with its maximal activity at pH 7.5. XEG12A specifically hydrolyzed xyloglucan with no activity on other β-glucans. XEG74B had a molecular size of 110 kDa with its optimum pH at 6.0. XEG74B primarily hydrolyzed xyloglucan, with a slight activity on β-1,3-1,4-glucan. Analysis of hydrolytic products of xyloglucanooligasaccharide (XXXGXXXG) by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) revealed that the both enzymes cleaved β-1,4-glucosidic linkage at the position of unbranched chain, while XEG74B showed a little fluctuation with the cleavage site. Both enzymes did not hydrolyzed xyloglucanoheptasaccharide (XXXG) at all. N-Terminal and internal amino acid sequencing of the enzymes revealed that XEG12A and XEG74B belonged to Glycoside Hydrolase (GH) Families 12 and 74, respectively. Based on these results we concluded that V. dahliae XEG12A and XEG74B were xyloglucan-specific endo-β-1,4-glucanases (EC 3.2.1.151).

A MoS2 layered thin film was grown by atmospheric-pressure solution-based mist CVD on a 30 mm2 large-area substrate at 400 °C, which is a significantly lower growth temperature than that of conventional CVD. The film formation was reliably confirmed by Raman spectroscopy, grazing incidence X-ray diffraction (GIXD), and transmission electron microscope (TEM). Possibly, film formation energy was decreased by dissolving (NH3)6Mo7O24 4H2O in methanol owing to formation of an intermediate product, whose decomposition temperature was lower than 760 °C — the decomposition temperature observed in thermogravimetric-differential thermal analysis (TG-DTA). Optical constants were derived by spectroscopic ellipsometry measurements, whose results indicate the reasonably good quality of MoS2 and the suitability of mist CVD in response to the large-area low-temperature growth request from industry.

Ammonium dichromate and chromium chloride were examined via thermogravimetric and differential thermal analyses and used to grow α-Cr2O3 via mist chemical vapor deposition. Only the former resulted in noticeable film formation. Using ammonium dichromate, α-Cr2O3 single crystals were grown in a wide growth-temperature range of 300–440 °C. The dependences of the lattice constants a and c on the growth temperature and precursor concentration were explained by combination of (i) lattice reconstruction and (ii) unit-cell volume variation. A maximum growth rate of 10 nm/min; a low (0006) rocking-curve full width at half maximum of 150 arcsec; and low a and c lattice mismatches (with α-Ga2O3) of 0.7 and 1.4%, respectively, were achieved.

β-1,4-Endoglucanase of glycosyl hydrolase family (GHF) 7 from a fungus Aspergillus oryzae catalyzed the condensation between lactose (Lac) and alkanols. With Lac as a glycosyl donor, methanol, ethanol, 1-butanol and 1-hexanol and 1,6-hexanediol (HD) could be aglycons. The maximal condensation was observed between 250 mM Lac and 1.5 M HD at 30°C, pH 5.0. Transglycosylation to HD occurred to a similar extent with Lac-β-pNP or with cellobiose-β-pNP as the sugar donors, while the condensation between N-acetyllactosamine and HD was negative. Lac-condensation activity was also observed with the cellulase from Fusarium oxysporum, which belongs to GHF7. These suggested that fungal cellulases belonging to GHF7 should possess an ability to perform the condensation using Lac as a glycosyl donor.

Yttrium iron garnet (YIG) thin films were deposited on c-plane sapphire substrates under atmospheric pressure by a mist CVD technique, and their chemical composition and optical properties were examined. The thin films deposited at 450 °C showed an [Y]/[Fe] ratio of 0.57, indicating the deposition of yttrium iron oxide, while the molar ratio of [Y]/[Fe] in the precursor solution was set at 1.5. A thermodynamic model was developed to explain the reaction paths of the YIG thin film fabrication process using thermogravimetric differential thermal analysis (TG-DTA) results. The model indicates that the decomposition rate of yttrium acetylacetonate [Y(acac)3 nH2O] was much lower than that of iron acetylacetonate [Fe(acac)3], providing a plausible explanation for the large difference between the composition ratio of the thin films and that of the precursor solutions.

The second generation total synthesis of the neo-clerodane diterpenoid, methyl barbascoate, was accomplished in seven or nine linear steps via double enol triflation and subsequent palladium catalyzed double carbonylation, followed by regioselective samarium diiodide mediated conjugate reduction.