Four Novel Eremophilanolides from Ligularia sagitta

Four new eremophilanolides, isolated from Ligularia sagitta, were identified as (1β,3β,6β,8β,10β)‐6‐acetoxy‐3‐(angeloyloxy)‐1,10‐epoxy‐8‐hydroxyeremophil‐7(11)‐en‐8,12α‐olide ( 1 ), (1β,3β,6β,8β,10β)‐3‐(angeloyloxy)‐1,10‐epoxy‐6,8‐dihydroxyeremophil‐7(11)‐en‐8,12α‐olide ( 2 ), (1β,3β,6β,8β,10β)‐3‐(angeloyloxy)‐1,10‐epoxy‐8‐ethoxy‐6‐hydroxyeremophil‐7(11)‐en‐8,12α‐olide ( 3 ), and (1β,3β,8β,10β)‐3‐(angeloyloxy)‐1,10‐epoxy‐8‐hydroxyeremophil‐7(11)‐en‐8,12α‐olide ( 4 ). Their structures were elucidated by spectroscopic methods, including 2D‐NMR techniques and chemical transformations.     

Xylan hydrolysis in zinc chloride solution

Xylan is the major component of hemicellulose, which consists of up to one-third of the lignocellulosic biomass. When the zinc chloride solution was used as a pretreatment agent to facilitate cellulose hydrolysis, hemicellulose was hydrolyzed during the pretreatment stage. In this study, xylan was used as a model to study the hydrolysis of hemicellulose in zinc chloride solution. The degradation of xylose that is released from xylan was reduced by the formation of zinc-xylose complex. The xylose yield was >90% (w/w) at 70°C. The yield and rate of hydrolysis were a function of temperature and the concentration of zinc chloride. The ratio of zinc chloride can be decreased from 9 to 1.3 (w/w). At this ratio, 76% of xylose yield was obtained. When wheat straw was pretreated with a concentrated zinc chloride solution, the hemicellulose hydrolysate contained only xylose and trace amounts of arabinose and oligosaccharides. With this approach, the hemicellulose hydrolysate can be separated from cellulose residue, which would be hydrolyzed subsequently to glucose by acid or enzymes to produce glucose. This production scheme provided a method to produce glucose and xylose in different streams, which can be fermented in separated fermenters.     

基质辅助激光解吸附飞行时间质谱分析缩合单宁的阳离子化问题

以单价金属离子Cs 和Na 作为离子化试剂,对3种缩合单宁进行基质辅助激光解吸附飞行时间(MALD I-TOF)质谱分析。加入Na 作为阳离子化试剂,能得到较高质量的质谱图。但由于实验通道中几乎不可能完全去除的K 的干扰而会高估棓儿茶酚/表棓儿茶酚单元的组成比例,从而影响对棓儿茶酚/表棓儿茶酚单元存在与否的判断;选择Cs 作为阳离子化试剂可以避免此问题,但在复杂的缩合单宁分析中,同样因为杂质离子Na 和K 的干扰而使得质谱图变得更复杂;未去离子处理直接对缩合单宁进行MALD I-TOF质谱分析与去离子并加入Cs 的处理比去离子并加入Na 能检测到更高聚合度的高聚物,检测到离子峰强度最高的聚合物随离子不同而不同。     

A Selective Cholesterol Biosensor Based on Composite Film Modified Electrode for Amperometric Detection

An amperometric cholesterol biosensor based on immobilization of cholesterol oxidase in a Prussian blue (PB)/polypyrrole (PPy) composite film on the surface of a glassy carbon electrode was fabricated. Hydrogen peroxide produced by the enzymatic reaction was catalytically reduced on the PB film electrode at 0 V with a sensitivity of 39 μA (mol/L)^?1. Cholesterol in the concentration range of 10^?5 ? 10^?4 mol/L was determined with a detection limit of 6 × 10^?7 mol/L by amperometric method. Normal coexisting compounds in the bio‐samples such as ascorbic acid and uric acid do not interfere with the determination. The excellent properties of the sensor in sensitivity and selectivity are attributed to the PB/PPy layer modified on the sensor.     

Quantitative determination of glutathione in single human erythrocytes by capillary zone electrophoresis with electrochemical detection

Glutathione (GSH) in single human erythrocytes is determined by capillary zone electrophoresis with end-column amperometric detection at a gold/mercury amalgam microelectrode. A capillary of 10 microm inner diameter is suitable for determination of GSH in an individual erythrocyte with a good signal-to-noise ratio. The limit of detection is 1 x 10(-7) mol/L or 26 amol and the linear dynamic range is 2 x 10(-7) to 2 X 10(-5) mol/L for the capillary. In this method, the calibration line is obtained with a capillary adsorbed before a certain amount of hemoglobin can be used for the quantification of GSH in the external standardization. The whole cell injection and the lack of necessity of a derivatization reaction lead to more accurate and precise results, which are closer to the macroscopic values of glutathione in human red blood cell (i.e., hemolysate) than those determined by indirect laser-induced fluorescence detection.     

Size-controlled preparation of Cu2O octahedron nanocrystals and studies on their optical absorption

We report herein the size-controlled preparation of monodispersed cuprous oxide octahedron nanocrystals smaller than 100 nm. The method is based on the reduction of copper nitrate in Triton X-100 water-in-oil (w/o) microemulsions by gamma-irradiation. The average edge length of the octahedron-shaped nanocrystals varies from 45 to 95 nm as a function of the dose rate. The quantum confinement effect was illustrated by the blueshift in the optical absorption. In addition, the growth process was also traced by absorption spectra.     

Synthesis and structures of 5-(pyridyl)tetrazole complexes of Mn(II)

New Mn(II) complexes containing 5-(2-pyridyl)tetrazole, 5-(3-cyano-4-pyridyl)tetrazole or 5-(4-pyridyl)tetrazole ligands are described. The complexes are prepared by reaction of the corresponding cyanopyridines with sodium azide in the presence of Mn(II) salts. All the complexes have been characterized by X-ray crystallography, which reveals that 5-(pyridyl)tetrazole ligands can coordinate to Mn through either type of nitrogen atom in the tetrazole residue or via the pyridyl group. In the solid state, extended 2D and 3D structures are produced through networks of hydrogen bonding (involving water molecules and the tetrazolate residue). Acidification of the complexes produces the corresponding free 5-(pyridyl)-1H-tetrazole.     

A Novel 3‐D Heterobimetallic Cyano‐bridged Coordination Polymer Incorporating Ag···Ag Interaction: [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2]

A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)₂]₂[Ag₂(CN)₃][Ag(CN)₂] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P2₁/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]²⁺ units bridged by [Ag(CN)₂]^— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)₂]^— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.     

Mesoporous amorphous MnO<Subscript>2</Subscript> as electrode material for supercapacitor

A kind of novel mesoporous, electrochemical active material, amorphous MnO₂ has been synthesized by an improved reduction reaction and using supramolecular as template. The synthesized sample was characterized physically by thermogravimetric analysis, X-ray diffraction, transmission electron microscope (TEM), and Brunauer–Emmett–Teller (BET) surface area measurement, respectively. Electrochemical characterization was performed using cyclic voltammetry and chronopotentiometry in 2 mol/l KOH aqueous solution electrolyte. The results of BET and TEM analysis indicated that supramolecular template plays an important role in the process of big specific surface area mesoporous material forming. After sintering at 200 °C, the sample still remained an amorphous structure, and its specific capacitance reached 298.7 F/g and presented a very stable capacitance after 500 cycles. In addition, the electrochemical process, such as ion transfer and electrical condition, was also investigated with electrochemical impedance spectroscopy.     

Hydrogenation of nitrobenzenes catalyzed by platinum nanoparticle core-polyaryl ether trisacetic acid ammonium chloride dendrimer shell nanocomposite

Platinum nanoparticle core-polyaryl ether trisacetic acid ammonium chloride dendrimer shell nanocomposites (Pt@G_n-NACl) were prepared and used as catalysts for hydrogenation of nitrobenzenes to anilines with molecular hydrogen under mild conditions. The as-prepared nanoparticles have mean particle size from 2.0 to 5.5 nm, depending on the molar ratio of the metal and the dendrimer. The Pt nanoparticles demonstrate near-monodisperse when the molar ratio of Pt and G₃-NACl is below 30. The interaction among three carboxyl groups terminated at the dendron and the metallic core keeps the Pt nanoparticles from agglomerating. The colloidal solution of Pt nanoparticles stabilized by the dendrimer, in which the molar ratio of Pt/G₃-NACl was less than 60, is stable without precipitation for several weeks. The dendrons attach to the metal core radially, and a substantial fraction of the surface of the metal nanoparticle is unpassivated and available for catalytic reactions. Turnover frequencies for the hydrogenation of nitrobenzenes to anilines change from 353 to 49 h⁻¹ depending on the dendrimer generation and substrates. The dendrimer catalysts are stable during the catalytic hydrogenation process and can be recovered by centrifugation and reused. The results suggest the effectiveness of polyaryl ether trisacetic acid ammonium chloride dendrimer as a stabilizer for the preparation of Pt nanoparticle catalysts.