β‐Diketiminatoytterbium aryloxides: synthesis,structural characterization,and catalytic activity for addition of amines to carbodiimides

The steric effect of an aryloxido group on the synthesis and molecular structures of ytterbium aryloxides supported by β‐diketiminato ligand L (L = [N(2,6‐Me₂C₆H₃)C(Me)]₂CH^?) is reported. Reactions of β‐diketiminatoytterbium dichloride, LYbCl₂(THF)₂, with NaOAr¹ in THF (Ar¹ = [2,6‐^tBu₂‐4‐MeC₆H₂], THF = tetrahydrofuran) at 60°C gave the corresponding ytterbium complexes LYb(OAr¹)Cl(THF) ( 1 ) and LYb(OAr¹)₂ (1), depending on the molar ratio of dichloride to sodium aryloxide, respectively, while the same reactions with NaOAr² and NaOAr³ (Ar² = [2,6‐ⁱPr₂C₆H₃], Ar³ = [2,6‐Me₂C₆H₃]) in 1:1 or 1:2 molar ratio in THF afforded only bisaryloxide complexes LYb(OAr²)₂(THF) (1) and LYb(OAr³)₂(THF) ( 4 ) in good yields, respectively. Complexes 1 , 2 , 3 , 4 were fully characterized, including X‐ray crystal structure analyses. All the complexes are efficient pre‐catalysts for the catalytic addition of amines to carbodiimides giving guanidines. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of chikusetsusaponin V and chikusetsusaponin IV in rat plasma by liquid chromatography–mass spectrometry and its application to a preliminary pharmacokinetic study

A sensitive liquid chromatography–electrospray ionization–mass spectrometry method has been developed and validated for determination of two major bioactive saponins in rat plasma after oral administration of saponins extracted from Rhizoma Panacis Japonici, including chikusetsusaponin V and chikusetsusaponin IV for the first time. Akebia saponin D was used as the internal standard (IS). Plasma samples were prepared by protein precipitation with methanol. A Phenomenex C₁₈ column (150 × 4.6 mm, 4 µm) was used as the analytical column with a mobile phase of acetonitrile and 0.05% aqueous formic acid. Mass spectrometric detection was achieved by single quadrupole mass spectrometer equipped with an electrospray ionization interface operating in negative ionization mode. Calibration curves showed good linearity over the concentration range of 5–500 ng/mL for the two analytes in rat plasma. The lower limit of quantification was 5 ng/mL. The intra‐ and inter‐batch precisions were within 10.3% and accuracy ranged from ?3.9 to 5.4%. The method was validated and successfully applied to the preliminary pharmacokinetic study of chikusetsusaponin V and chikusetsusaponin IV in rat plasma after oral administration of saponins extracted from Rhizoma Panacis Japonici. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of Divert-Thrusters on Homing Performance of Endo-atmospheric Interceptors

A new guidance law is proposed for interceptor missiles by using a differential game formulation with bounded controls. The interceptor is steered by the aerodynamic-lift control system and the divert-thrusters control system. By using game space decomposition, the parameter effects of divert-thrusters control system on homing performance are investigated. Under propellant limits and given the time constant of the divert-thrusters control system, the hit-to-kill performance requires the following conditions. Firstly, the maximum acceleration generated by the divert-thrusters control system is greater than a critical value. Secondly, the thrusters close after interception terminates. Thirdly, the operation time of the divert-thrusters control system is sufficient long to cancel the miss distance. These results are also demonstrated by a realistic ballistic missile-defense simulation program.     

Synthesis, structure, and luminescent properties of three silver(I) complexes with organic carboxylic acid and 4,4′-bipyridine-like ligands

The reactions of AgNO₃ with combinations of 1,2-bis(4-pyridyl)ethane(bpa)/4,4′-bipyridine (bpy), 4,4′-stilbenedicarboxylic acid (H₂sda)/2,2′-diphenylaminedicarboxylic acid (H₂dpadc)/2,6-naphthalenedicarboxylic acid (H₂ndc) in aqueous alcohol/ammonia at room temperature produce block-like crystals of [Ag₂(bpa)_1.5(sda)_0.5](sda)_0.5·7H₂O, [Ag₂(bpa)₂(H₂O)₃](dpadc), [Ag₂(bpy)₂](ndc)·4H₂O. All three complexes consist of 1D infinite silver–ligand cationic chains, interspersed with organic carboxylate anions that provide charge compensation in the crystal structures. The lattice water molecules are situated among the framework of the crystal structure and show rich hydrogen-bonding interactions, which help to orientate the organic carboxylate anions in the crystal packing, and the presence of Ag···N and Ag···Ag contacts contributes to strengthen the frameworks. The luminescent properties and thermogravimetric analyses of the three complexes are also presented.     

Identification of metabolites in WZS‐miniature pig urine after oral administration of Danshen decoction by HPLC coupled with diode array detection with electrospray ionization tandem ion trap and time‐of‐flight mass spectrometry

Danshen (DS) is a widely used traditional Chinese medicine for treating cardiovascular and cerebrovascular diseases. A simple, rapid and sensitive method was developed for identification of the in vivo metabolites in urine of WZS‐miniature pigs after oral administration of DS decoction by HPLC coupled with diode array detection with electrospray ionization tandem ion trap and time‐of‐flight mass spectrometry. This method has been successfully applied to simultaneous identification of 50 compounds (including 11 new ones) in pig urine. In addition, one new compound, (3‐hydroxyphenyl) crylic acid glycine methyl ester (C1), along with eight known ones were first isolated by column chromatography and identified by spectroscopic means, including 1D/2DNMR and mass spectrometry, as reference substances. Ten phenolic compounds (protocatechuic aldehyde, protocatechuic acid, caffeic acid, danshensu, ferulic acid, isoferulic acid, rosmarinic acid and salvianolic acid A/B/D) were found to be the main absorbed original constituents of DS decoction, which underwent the metabolic reactions of glucuronidation, sulfation, methylation, hydrogenation and glycine conjugation in vivo. In conclusion, the developed method is applicable to the analysis and identification of constituents in biological matrices after administration of DS decoction. Copyright © 2012 John Wiley & Sons, Ltd.     

Mo2C/Reduced Graphene Oxide Composites with Enhanced Electrocatalytic Activity and Biocompatibility for Microbial Fuel Cells

A simple, cost-effective strategy was developed to effectively improve the electron transfer efficiency as well as the power output of microbial fuel cells (MFCs) by decorating the commercial carbon paper (CP) anode with an advanced Mo₂C/reduced graphene oxide (Mo₂C/RGO) composite. Benefiting from the synergistic effects of the superior electrocatalytic activity of Mo₂C, the high surface area, and prominent conductivity of RGO, the MFC equipped with this Mo₂C/RGO composite yielded a remarkable output power density of 1747±37.6 mW m⁻², which was considerably higher than that of CP-MFC (926.8±6.3 mW m⁻²). Importantly, the composite also facilitated the formation of 3D hybrid biofilm and could effectively improve the bacteria–electrode interaction. These features resulted in an enhanced coulombic efficiency up 13.2 %, nearly one order of magnitude higher than that of the CP (1.2 %).     

Chiral separation and molecular simulation study of six antihistamine agents on a coated cellulose tri-(3,5-dimethylphenycarbamate) column (Chiralcel OD-RH) and its recognition mechanisms

Enantiomeric separation of six antihistamine agents was first systematically investigated on a cellulose-based chiral stationary phase (CSP), that is, cellulose tris-(3,5-dimethyl phenyl carbamate) (Chiralcel OD-RH), under the reversed-phase mode. Orphenadrine, meclizine, terfenadine, dioxopromethazine, and carbinoxamine enantiomers were completely separated under the optimized mobile phase conditions with resolutions of 5.02, 1.93, 1.68, 1.67, and 1.54, respectively. Mequitazine was partially separated with a resolution of 0.77. The influences of type and concentration of buffer salt, the pH of buffer solution, and the type and ratio of organic modifier on the chiral separation were evaluated and optimized. For a better insight into the enantiorecognition mechanisms, molecular docking was carried out via the Autodock software. The lowest binding energy and the optimal conformations of the analytes/CSP complexes were supplied, and the mechanisms of chiral recognition were determined. According to the results, the key interactions for the chiral recognition of these six analytes on CDMPC were π–π interactions, hydrophobic interactions, hydrogen bond interactions, and some special interactions.     

Controlled release of acetochlor from poly (butyl methacrylate-diacetone acrylamide) based formulation prepared by nanoemulsion polymerisation method and evaluation of the efficacy

Acetochlor is an important herbicide for gramineous weeds and some small seed broadleaf weeds. Controlled-release formulations of herbicide are highly desirable not only for attaining the most effective utilisation of the weed control, but also for reducing environmental pollution. Acetochlor was incorporated in poly (butyl methacrylate-diacetone acrylamide) based formulation to obtain controlled release properties. The acetochlor nanocapsules were characterised by size distribution, infrared spectroscopy (IR) and field emission scanning electron microscopy (FESEM), and factors related to loading efficiency, swelling behaviour of the formulation were investigated. For this controlled-release formulation, the loading efficiency could reach about 50% (w/w). n, the diffusion parameter was indicative of the transport mechanism, and the values for ‘n’ were in the range of 0.28–0.61, which indicated that the release of acetochlor was diffusion-controlled. The time taken for 50% of the active ingredient to be released into water, t₅₀, was also calculated for the comparison of formulations in different conditions. The formulation with higher temperature and more diacetone acrylamide had lower value of t₅₀, which means a quicker release of the active ingredient. This study highlighted some pieces of evidence that improved herbicide incorporation and slower release were linked to potential interactions between the herbicide and the polymer.