Isolation,Structure Determination,and Synthesis of Allo‐RA‐V and Neo‐RA‐V,RA‐Series Bicyclic Peptides from Rubia cordifolia L.

Two bicyclic hexapeptides, allo‐RA‐V ( 4 ) and neo‐RA‐V ( 5 ), and one cyclic hexapeptide, O‐seco‐RA‐V ( 6 ), were isolated from the roots of Rubia cordifolia L. Their gross structures were elucidated on the basis of spectroscopic analysis and X‐ray crystallography of compound 5 . The absolute stereochemistry of compounds 4 and 5 were established by their total syntheses, and the absolute stereochemistry of compound 6 by chemical correlation with deoxybouvardin ( 3 ). Comparison of the 3D structures of highly active RA‐VII ( 1 ) with less‐active compounds 4 and 5 suggests that the orientation of the Tyr‐5 and/or Tyr‐6 phenyl rings plays a significant role in their biological activity. The isolation of peptides 4 – 6 , along with compound 3 , and the comparison of their structures seem to indicate that peptide 6 may be the common precursor to bicyclic peptides 3 – 5 in the plant.     

Micropore-free surface-activated carbon for the analysis of polychlorinated dibenzo-p-dioxins-dibenzofurans and non-ortho-substituted polychlorinated biphenyls in environmental samples

2,3,7,8-Substituted polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and non-ortho-substituted polychlorinated biphenyls (PCBs) account for almost all of the total toxic equivalents (TEQ) in environmental samples. Activated carbon columns are used to fractionate the samples for GC-MS analysis or bioassay. Micropore-free surface-activated carbon is highly selective for PCDD/Fs and non-ortho-PCBs and can improve the conventional activated carbon column clean-up. Along with sulfuric acid-coated diatomaceous earth columns, micropore-free surface-activated carbon provides a rapid, robust, and high-throughput sample preparation method for PCDD/Fs and non-ortho-PCBs analysis.     

Magnetic and Crystallographic Properties of LnCrO4 (Ln=Nd, Sm, and Dy)

Zircon-type compounds LnCrO₄ (Ln=Nd, Sm, and Dy) were prepared. Their precise crystal structures at room temperature were determined from X-ray diffraction measurements. These compounds have a tetragonal system with space group I4₁/amd. Magnetic susceptibility and specific heat measurements have been performed for all the compounds in the temperature range between 1.8 and 300 K. For NdCrO₄, an antiferromagnetic transition was found at 25.2 K. SmCrO₄ and DyCrO₄ show magnetic transitions at 15.0 and 22.8 K, respectively. In addition, structural phase transitions were observed at 58.5 and 31.2 K, respectively. For DyCrO₄, the crystal structure below the transition temperature was determined by low-temperature powder X-ray diffraction measurements to be orthorhombic with space group Imma.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Ruthenium-catalyzed hydrosilylation of 1-alkynes with novel regioselectivity

[reaction: see text] A ruthenium catalyst precursor bearing a bulky and electron-donating pentamethylcyclopentadienyl (Cp) ligand, typically CpRuH3(PPh3), mediates hydrosilylation of several 1-alkynes with novel regioselectivity to give preferentially 2-silyl-1-alkenes.     

Synthesis of MoVNbTe(Sb)O(x) composite oxide catalysts via reduction of polyoxometalates in an aqueous medium

The synthesis of MoVNbTe(Sb)O(x)() composite oxide catalysts based on the self-organization of polyoxometalates (POMs) was investigated. The catalysts which were synthesized via reduction of POMs by using reducing agents under mild conditions and/followed by calcination in an O(2)-excluded atmosphere which superior performance for propane (amm)oxidation. It was suggested that the metastable phase formed at an elevated temperature with a specific oxidation state corresponds to the catalytic activity.     

Effects of triphenylsulfonium hexafluorophosphate in the radiation-induced cationic polymerization of styrene

Radiation-induced cationic polymerization of styrene was studied in methylene chloride in the presence of triphenylsulfonium hexafluorophosphate. Acceleration in polymerization and an increase in molecular weight at a low temperature (?78°C) were observed in the presence of triphenylsulfonium salt. A study of pulse radiolysis revealed that both effects are due mainly to PF^?6, which forms ion pairs with the cationic species involved in the polymerization.     

Isolation and structure elucidation of genuine oat phytoalexin,avenalumin I

The major phytoalexin from oat leaves has been identified as 2-[2-(4-hydroxyphenyDethenyl] -6-hydroxy-4H-3,1-benzoxazin-4-one ($\text{A}$).