First principles investigations of hydrazine adsorption conformations on Ni(111) surface

Theoretical investigation on hydrazine (N₂H₄) adsorption on Ni(111) was done by using density functional theory. Stability and mechanism of hydrazine adsorption in anti, gauche and cis conformation on nickel surface were studied. Charge transfer between lone-pair orbital and d-band was found to stabilize the anti-conformation as the most stable conformation, in contrast with hydrazine in the gas-phase where gauche conformation is more favored. However, the derived anti-bonding state between adsorbate and substrate is partially occupied due to the spin-polarization in the local states near the Fermi level and thus contributes in weakening the bonding. The stable adsorption structure was further verified by comparing the calculated vibrational frequencies with HREELS measurement results. The results were found to be in agreement with experimental results. It was also found that the adsorption in cis-conformation is a transition state as evident from the existence of imaginary frequency on its lowest vibrational mode which belongs to NH₂ torsional movement around N–N axis.     

Decreased l-tryptophan concentration in distinctive brain regions of mice treated repeatedly with phencyclidine

It has been reported that repeated phencyclidine (PCP) treatment induces schizophrenia-like behavior in mice. l-Tryptophan (Trp) concentrations in brain tissues of control (n?=?8) and PCP-treated mice (10 mg/kg/day, s.c., 14 days, n?=?10) were determined using high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC method involved pre-column fluorescence derivatization with (R)-(?)-4-(N,N-dimethylaminosulfonyl)-7-(3-isothiocyanatopyrrolidin-1-yl)-2,1,3-benzoxadiazole (DBD-PyNCS). Eight different parts of the brain, namely, the frontal cortex, nucleus accumbens, striatum, hippocampus, amygdala, thalamus, hypothalamus, and cerebellum, of both groups were investigated. A significant decrease in the l-Trp concentration in the nucleus accumbens (p?=?0.024) and hippocampus (p?=?0.027) was observed in PCP-treated mice, suggesting that alteration of the l-Trp metabolism might occur in these brain parts.     

Synthesis of chiral 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine and their application to enantioselective borane reduction of prochiral ketones as chiral catalysts

Chiral diamines, 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine, were prepared from N-(tert-butoxycarbonyl)pyrrolidine or (S)-proline as a starting material, respectively. These chiral diamines were efficient for the catalytic enantioselective borane reduction of acetophenone. Using (S)-2-(anilinodiphenylmethyl)pyrrolidine, chiral secondary alcohols were obtained from prochiral ketones with good to excellent enantiomeric excesses (up to 98% ee).     

Conformation and Atropisomeric Properties of Indometacin Derivatives

The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the N? C7′ and/or C7′? C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations.     

Application of ZnO nanoparticles to enhance the antimicrobial activity and ultraviolet protective property of bamboo pulp fabric

Hyperbranched polymer HSDA was synthesized from methyl acrylate, tetraethylenepentamine, and dodecanoic acid by melt polycondensation. ZnO nanoparticle colloidal solution was prepared in one step by mixing Zn(NO₃)₂ and HSDA aqueous solution under hydrothermal condition. The results of transmission electron microscopy and ultraviolet–visible (UV–Vis) spectroscopy indicated that ZnO nanoparticles were formed in colloidal solution. Bamboo pulp fabric was treated with ZnO nanoparticle colloidal solution by an impregnation method to provide the bamboo pulp fabric with antibacterial and UV protective properties. The whiteness, antibacterial activity, UV protective property, and washing durability of the ZnO nanoparticle-treated fabrics were determined. The results indicated that the bamboo pulp fabric treated with ZnO nanoparticles showed good UV protective properties and its ultraviolet protection factor (UPF) can reach 90.38. The UPF value of treated fabric drops to 70.42 after washing for 20 times, but it retains good UV protective properties. The ZnO nanoparticle-treated fabric showed 99.91 % bacterial reduction of Staphylococcus aureus and 99.97 % bacterial reduction of Escherichia coli. The fabric retained over 98.93 % reduction level even after being exposed to 20 consecutive home-laundering conditions. In addition, the results of scanning electron microscopy and X-ray spectroscopy confirmed that ZnO nanoparticles were fixed and well dispersed on bamboo pulp fabric.     

Oxidative Bond Cleavage of the Silicon–Silicon Bond of a Pentacoordinated Disilicate

The Si Si bond of a pentacoordinated disilicate was readily cleaved by treatment with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone in the presence of sodium carbonate under mild conditions. The bond cleavage did not proceed under the same conditions after conversion of the disilicate into the corresponding monoanionic silylsilicate and neutral disilane by protonation. The difference in the charges of the Si Si bond compounds affects the reactivity toward an oxidant, resulting in the Si Si bond cleavage, considering that all of these compounds have a bond between pentacoordinated silicon atoms.     

Biosynthesis of Indole Diterpene Lolitrems: Radical‐Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.