Dinuclear Cu(II) complexes based on p‐xylylene‐bridged bis(1,4,7‐triazacyclononane) ligands: Synthesis,characterization, DNA cleavage abilities and evaluation of superoxide dismutase‐ and catalase‐like activities

Three new dinuclear Cu(II) complexes with the formulas [Cu₂(pxdmbtacn)Cl₄] ( 1 ), [Cu₂(pxdmbtacn)Cl_0.7(NO₃)_1.3(OH)₂(H₂O)_1.3]?6H₂O ( 2 ) and [Cu₂(pxdiprbtacn)Cl₄] ( 3 ) together with one previously reported complex, [Cu₂(pxbtacn)Cl₄] ( 4 ), were obtained from Cu(II) salts with three p‐xylylene‐bridged bis‐tacn ligands bearing pendant alkyl substituents or without pendant group. Complex 2 was structurally characterized as a centrosymmetric dinuclear molecule with each metal center being coordinated to some labile ligands in addition to one tacn ring. Based on the results of mass spectrometry and UV–visible spectroscopy, complexes 1 and 3 are capable of existing in aqueous solution as dinuclear species but 4 can partially form a dimer of the original dinuclear motif. Complexes 1 , 3 and 4 can all effectively cleave supercoiled DNA oxidatively in the presence of hydrogen peroxide. The superoxide dismutase (SOD) activities of 1 and 3 measured under physiological conditions are comparable to that of the native CuZnSOD enzyme but the enzymatic activity of 4 is about three‐ to fourfold lower. Furthermore, complexes 1 , 3 and 4 demonstrate moderate scavenging effect on hydrogen peroxide and their catalase activities are in the decreasing order of 3 > 1 > 4 .     

Chemoselective hydrogenation of α,β-unsaturated aldehydes with modified Pd/C catalyst

Selective hydrogenation of α, β-unsaturated aldehydes with modified Pd/C catalyst was developed.The reduction of C=O bond could be efficiently inhibited by the addition of carbonates,and high selectivity to the corresponding saturated aldehydes was achieved under mild conditions.This protocol provides an alternative for efficient preparation of saturated aldehydes.     

Development and validation of a UPLC‐MS/MS method for the determination of cucurbitacin B in rat plasma and application to a pharmacokinetic study

Cucurbitacin B (CuB), one of the most abundant forms of cucurbitacins, is a promising natural anticancer drug candidate. Although the anticancer activity of CuB has been well demonstrated, information regarding the pharmacokinetics is limited. A rapid, selective and sensitive UPLC‐MS/MS for CuB was developed and validated using hemslecin A (HeA) as internal standard (IS). Plasma samples were pre‐treated by liquid–liquid extraction with dichloromethane. Separation was achieved on a reversed‐phase C₁₈ column (50 × 4.6 mm, 5 µm) at 35°C using isocratic elution with water–methanol (25:75, v/v) at a flow rate of 0.3 mL/min. The analytes were monitored by a triple quadrupole tandem mass spectrometer with positive electrospray ionization mode. The calibration curve was linear (r > 0.995) in a concentration range of 0.3–100 ng/mL with a limit of quantification of 0.3 ng/mL. Intra‐ and inter‐day accuracy and precision were validated by percentage relative error and relative standard deviation, respectively, which were both lower than the limit of 15%. This assay was successfully applied to a pharmacokinetic study of CuB in Wistar rats. Copyright © 2015 John Wiley & Sons, Ltd.     

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3− and SO32− in Aqueous Solution

The kinetics and mechanism of the reaction of S^IV (SO₃^2?+HSO₃^?) with a ruthenium(VI) nitrido complex, [(L)Ru^VI(N)(OH₂)]⁺ (Ru^VIN, L=N,N′‐bis(salicylidene)‐o‐cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO₃^? and SO₃^2? by Ru^VIN. A deuterium isotope effect of 4.7 is observed in the HSO₃^? pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N?S bond formation (partial N‐atom transfer) between Ru^VIN and HSO₃^? and H⁺ transfer from HSO₃^? to a H₂O molecule.     

Improvement of multistep WENO scheme and its extension to higher orders of accuracy

This paper presents an efficient procedure for overcoming the deficiency of weighted essentially non‐oscillatory schemes near discontinuities. Through a thorough incorporation of smoothness indicators into the weights definition, up to ninth‐order accurate multistep methods are devised, providing weighted essentially non‐oscillatory schemes with enhanced order of convergence at transition points from smooth regions to a discontinuity, while maintaining stability and the essentially non‐oscillatory behavior. We also provide a detailed analysis of the resolution power and show that the solution enhancements of the new method at smooth regions come from their ability to render smoothness indicators closer to uniformity. The new scheme exhibits similar fidelity as other multistep schemes; however, with superior characteristics in terms of robustness and efficiency, as no logical statements or mapping function is needed. Extensions to higher orders of accuracy present no extra complexity. Numerical solutions of linear advection problems and nonlinear hyperbolic conservation laws are used to demonstrate the scheme's improved behavior for shock‐capturing problems. Copyright © 2016 John Wiley & Sons, Ltd.     

Terpenoids from Loxocalyx urticifolius

Two new diterpenoids, loxocalyxin A ( 1 ) and 13‐epiloxocalyxin A ( 2 ), and two new sesquiterpenoids, loxocalyxins B and C ( 3 and 4 , resp.), together with three known compounds, were isolated from the MeOH extract of the whole plant of Loxocalyx urticifolius Hemsl . The structures of the new compounds were established by means of spectroscopic analysis including one‐ and two‐dimensional NMR spectroscopy. All new structures were confirmed by X‐ray crystallographic analysis. Their absolute configurations were established.     

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides

We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F-K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition, while the binding energy difference of the O-1s core electrons leads to a small shift of the O-K leading edges between trivalent and quadrivalent manganese oxides, a significant edge shift, with an order of magnitude larger in energy, was found between divalent and trivalent compounds, which is attributed to the spin exchange stabilization of half-filled 3d system. This shift is much enhanced in the ionic fluoride system. This work provides the spectroscopic foundation for further studies of complicated Mn compounds.     

Studies toward the Synthesis of (R)‐(+)‐Harmicine

The study toward the total synthesis of (R)‐(+)‐harmicine is reported in this paper. The enantioselective synthesis of pyrrolidinone, the main backbone of of (R)‐(+)‐harmicine, has been completed by the methodology based on photo‐induced Wolff rearrangement of α‐diazo‐β‐carbonyl compounds.