Simultaneous determination of major components of Huangqi–Honghua extract in rat plasma using LC–MS/MS and application to a pharmacokinetic study

A sensitive and reliable LC–MS/MS method was developed and validated for simultaneous quantification of the major components of Huangqi–Honghua extact in rat plasma, including hydroxysafflor yellow A (HSYA), astragaloside IV (ASIV), calycosin‐7‐O‐β‐d ‐glucoside (CAG), calycosin, calycosin‐3′‐O‐glucuronide (C‐3′‐G) and calycosin‐3′‐O‐sulfate (C‐3′‐S). After extraction by protein precipitation with acetonitrile and methanol from plasma, the analytes were separated on a Hypersil BDS C₁₈ column by gradient elution with acetonitrile and 5 mM ammonium acetate. The detection was carried out on a triple quadrupole tandem mass spectrometer equipped with electrospray ionization source switched between negative and positive modes. HSYA was monitored in negative ionization mode from 0 to 4.9 min, and ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S were determined in positive ionization mode from 4.9 to 10 min. The lower limits of quantification of the analytes were 6.25 ng/mL for HSYA, 0.781 ng/mL for CAG and 1.56 ng/mL for ASIV and calycosin. The intra‐ and inter‐assay precision (RSD) values were within 13.43%, and accuracy (RE) ranged from ?8.75 to 9.92%. The validated method was then applied to the pharmacokinetic study of HSYA, ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S in rat after an oral administration of Huangqi–Honghua extract.     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Facile fabrication of fast recyclable and multiple self‐healing epoxy materials through diels‐alder adduct cross‐linker

A reversibly cross‐linked epoxy resin with efficient reprocessing and intrinsic self‐healing was prepared from a diamine Diels‐Alder (DA) adduct cross‐linker and a commercial epoxy oligomer. The newly synthesized diamine cross‐linker, comprising a DA adduct of furan and maleimide moieties, can cure epoxy monomer/oligomer with thermal reversibility. The reversible transition between cross‐linked state and linear architecture endows the cured epoxy with rapid recyclability and repeated healability. The reversibly cross‐linked epoxy fundamentally behaves as typical thermosets at ambient conditions yet can be fast reprocessed at elevated temperature like thermoplastics. As a potential reversible adhesive, the epoxy polymer with adhesive strength values about 3 MPa showed full recovery after repeated fracture‐thermal healing processes. The methodology explored in this contribution provides new insights in modification of conventional engineering plastics as functional materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2094–2103     

Investigation of mononuclear,dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes

A new asymmetric Salamo‐based ligand H₂L was synthesized using 3‐tert‐butyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H₂L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}₂], and [{Ni(L)(CH₃COO)(CH₃CH₂OH)}₂Ni] with the ligand H₂L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H₂L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.     

Divergent Synthesis of Oxa-Cyclic Nitrones through Gold(I)-Catalyzed 1,3-Azaprotio Transfer of Propargylic α-Ketocarboxylate Oximes: Experimental and DFT Studies

1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally.     

Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Dimeric Manganese-Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling.     

海面油膜的偏振反射特性仿真实验

为了给海面溢油污染识别检测提供理论基础,根据菲涅尔反射公式的偏振反射系数,结合偏振双向反射率因子和粗糙海面的概率密度分布函数,建立了完善的pBRDF模型,仿真在不同太阳入射角度、不同探测器观测角度以及不同海面风速风向等条件下海水和油膜的偏振反射分布函数。结果表明:海水和油膜太阳天顶角为53°和56°时P偏振反射率分别为1.0×10^-5和2.5×10^-5,S偏振反射率随着太阳天顶角的增加而增加;海面风速越大偏振反射率峰值越小;海面风向只改变pBRDF的空间位置;海水和油膜线偏振度空间分布有明显差异。搭建实验平台相机以40°拍摄时,得出海水和油膜的线偏振度分别在0.2~0.4, 0.5~0.7之间,同时表明利用偏振探测获取目标场景的偏振度和偏振角图可提高图像质量。     

Single-Crystalline TiO2(B) Nanobelts with Unusual Large Exposed {100} Facets and Enhanced Li-Storage Capacity

The {100} facet of single-crystalline TiO₂(B) is an ideal platform for inserting Li ions, but it is hard to be obtained due to its high surface energy. Here, the single-crystalline TiO₂(B) nanobelts from H₂Ti₃O₇ with nearly 70% {100} facets exposed are synthesized, which significantly enhances Li-storage capacity. The first-principle calculations demonstrate an ab in-plane 2D diffusion through the exposed {100} facets. As a consequence, the nanobelts can significantly accommodate Li ions in LiTiO₂ formula with specific capacity up to 335 mAh g⁻¹, which is in good agreement with the electrochemical characterizations. Coating with conductive and protective poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), the cut-off discharge voltage is as low as 0.5 V, leading to a capacity of 160.7 mAh g⁻¹ after 1500 cycles with a retention rate of 66% at 1C. This work provides a practical strategy to increase the Li-ion capacity and cycle stability by tailoring the crystal orientation and nanostructures.     

Comparative study on Artemisia halodendron Turcz. and its two related plants by GC-MS analysis and protective effect against carbon tetrachloride-induced hepatotoxicity in mice

A rapid method had been used for comparative study on Artemisia halodendron Turcz. and its two related plants by gas phase-mass spectrometry (GC-MS). The comparison of the volatile oils obtained in three plants by GC-MS were similar in 20 compositions. However, n-Hexadecanoic acid (10.40%), Biphenyl (7.867%) and 9,12-Octadecadienoic acid (7.25%) were the predominant in the volatile oils of A. halodendron Turcz., whereas these constituents did not exist in the other two plants. And the study investigated the effect of three plants against CCl₄-induced hepatotoxicity in mice. 70% ethanol extracts of A. halodendron Turcz. showed weaker protective effect than the other two plants. It suggested that they provide a basis for the identification of the A. halodendron Turcz. from the other two plants and the ethanol extract from three plants exerted a protecting effect against hepatotoxicity.