芴2,7位取代的9,9’-二芳基螺芴类化合物的合成及性能

设计并合成了一系列以三苯胺为核,芴衍生物为外围基团的有机蓝光小分子,该合成通过Suzuki反应在9-芳基芴的2位和(或)7位引入相同或不同取代基作为模块,并利用Friedel-Crafts反应将4-甲基三苯胺与这一系列模块结合.用NMR,MS和元素分析进行结构表征.荧光测试结果表明该类化合物溶液的荧光发射波长范围在442～466 nm之间,属蓝光发射.电化学测试显示该类材料的HOMO能级位于-5.15～-5.19 eV之间.差示扫描量热仪与热重分析得出化合物的玻璃化转变温度在166℃以上,热分解温度高于398℃,表明该类材料具有良好的热稳定性.     

Synthesis,characterization, and fluorescence of pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer with pentaerythritol core

Novel and well‐defined pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymers were successfully achieved by combination of esterification, atom transfer radical polymerization (ATRP), divergent reaction, ring‐opening polymerization (ROP), and coupling reaction on the basis of pentaerythritol. The reaction of pentaerythritol with 2‐bromopropionyl bromide permitted ATRP of styrene (St) to form four‐arm star‐shaped polymer (PSt‐Br)₄. The molecular weights of these polymers could be adjusted by the variation of monomer conversion. Eight‐hydroxyl star‐shaped polymer (PSt‐(OH)₂)₄ was produced by the divergent reaction of (PSt‐Br)₄ with diethanolamine. (PSt‐(OH)₂)₄ was used as the initiator for ROP of ε‐caprolactone (CL) to produce eight‐arm star‐shaped dendrimer‐like copolymer (PSt‐b‐(PCL)₂)₄. The molecular weights of (PSt‐b‐(PCL)₂)₄ increased linearly with the increase of monomer. After the coupling reaction of hydroxyl‐terminated (PSt‐b‐(PCL)₂)₄ with 1‐pyrenebutyric acid, pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer (PSt‐b‐(PCL‐pyrene)₂)₄ was obtained. The eight‐arm star‐shaped dendrimer‐like copolymers presented unique thermal properties and crystalline morphologies, which were different from those of linear poly(ε‐caprolactone) (PCL). Fluorescence analysis indicated that (PSt‐b‐(PCL‐pyrene)₂)₄ presented slightly stronger fluorescence intensity than 1‐pyrenebutyric acid when the pyrene concentration of them was the same. The obtained pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer has potential applications in biological fluorescent probe, photodynamic therapy, and optoelectronic devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2788–2798, 2008     

New Quantum Effect for Vaidya-Bonner-de Sitter Black Holes

The field equations of spin s = 0, 1/2, 1, and2 in the Vaidya–Bonner–de Sitter space-timeare investigated. The results show that the radiativemechanism of massive spin fields depends on the spinstate. We have sufficient reasons to conjecture thatthe effect originates from the quantumergosphere.     

Elemental Analysis of Stone Fruits by Inductively Coupled Plasma Mass Spectrometry and Direct Mercury Analysis

This study reports the concentrations of eight trace essential (Zn, Mn, Cu, Ni, Cr, Co, V, and Se) and four toxic elements (Pb, As, Cd, and Hg) in commonly consumed stone fruits from South Korea. The samples were digested by microwave-induced combustion and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The concentrations of mercury were analyzed by direct mercury analysis (DMA). The analytical techniques were validated by linearity, limits of detection and quantification, precision, recovery, and for accuracy by analyzing a spinach leave-certified reference material; satisfactory results were obtained in all cases. The concentrations of essential trace elements varied considerably among the stone fruits. Generally stone fruits contained comparatively high concentrations of Zn (0.946 to 7.86?µg/g) and Mn (below the limit of detection to 1.66?µg/g), while lower contents of Cu (0.214 to 1.24?µg/g), Cr (0.032 to 0.114?µg/g), Ni (0.006 to 0.091?µg/g), Co (0.004 to 0.016?µg/g), V (below the limit of detection to 0.023?µg/g), and Se (0.0002 to 0.005?µg/g) were obtained. The concentrations (µg/g) of toxic metals were 0.007 (peach) to 0.016 (cherry) for Pb, 0.001 (plum) to 0.007 (cherry) for As, 0.002 (apricot and cherry) to 0.003 (peach) for Cd, and 0.0003 (peach) to 0.0016 (jujube) for Hg. The values for the estimated dietary intakes, target hazard quotients, and hazard indices were lower than the recommended safety limits by World Health Organization. Therefore, the analyzed stone fruits were deemed to be safe for human consumption.     

Determination of Immunosuppressive Pharmaceuticals in Whole Blood Following Kidney Transplantation by High-performance Liquid Chromatography–Tandem Mass Spectrometry

Cyclosporine, tacrolimus, sirolimus, and everolimus are commonly used immunosuppressants following organ transplantation. Their monitoring is used to determine the optimal dose for therapeutic effectiveness and minimize toxicity. High-performance liquid chromatographic–tandem mass spectrometry with positive electrospray ionization and multiple reaction monitoring mode was validated for the determination of cyclosporine A, tacrolimus, sirolimus, and everolimus in whole blood. A C18 analytical column was employed with a gradient elution of pH 4.0 aqueous 10?mmol/L ammonium acetate and acetonitrile. For the pretreatment of whole blood, simple protein precipitation was used with methanol:zinc sulfate. The calibration curves were linear from 20.0 to 1000?ng/mL for cyclosporine A, 1.0 to 50?ng/mL for tacrolimus and sirolimus, and 1.0 to 30?ng/mL for everolimus. The intra-assay precision and inter-assay precision were less than 15%. The method provides reliable and reproducible results according to the linearity, precision, accuracy, recovery, and matrix effects. The method has been introduced to routine clinical practice in Slovakia for the determination of immunosuppressants in patients after kidney transplantation.     

The Cu-catalyzed asymmetric conjugate addition with chiral diphosphite ligands derived from D-(-)-tartaric acid

A series of diphosphite ligands, which were derived from D-(-)-tartaric acid, have been synthesized and successfully applied in the Cu-catalyzed asymmetric conjugate addition of organozincs to enones. There was a synergic effect between the stereogenic centers of the D-(-)-tartaric acid skeleton and the axially H₈-binaphthyl moieties of ligand 2c. And ligand 2c shows a comparative catalytic performance to ligand 1-N-benzylpyrrolidine-3,4-bis[(S)-1,1′-H₈-binaphthyl-2,2′-diyl]phosphite-L-tartaric acid1d derived from L-(+)-tartaric acid. Therefore, for cyclic enones, both enantiomers of the addition products can be obtained in high enantioselectivity (ees up to 96%) by simply selecting ligands 1d or 2c derived from D-(-)-tartaric acid or L-(+)-tartaric acid. Moreover, the sense of enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl phosphite moieties.     

C_2H_2分解爆轰的实验研究

在长30m,公称直径(Dg)分别为50、65、80和100mm的管道内,进行了C_2H_2分解爆轰实验。用O_2—C_2H_2爆轰波引爆C_2H_2,测量了管道内的爆轰压力,及在管道端面上的反射压力。与以前认为在管径500mm管道内不会出现自持的C_2H_2分解爆轰的意见相反,在这样的管道内也发生了C_2H_2分解炸轰。在管端测到了1700kg/cm~2的异常高压,并对数次异常高压的破坏威力作了记录。     

Vorticity characteristics of the turbulent intermediate wake

Measurements of the lateral components _j (j=2 and 3) of the vorticity fluctuation vector have been made, using a vorticity probe consisting of two X-wires, in the intermediate wake of a circular cylinder. The effect of the spatial resolution of the probe on the measurement of _j has been studied. As the spatial resolution impairs, the variance and flatness factor of _j decrease whereas the skewness of _j increases. Reasonably accurate values of _j ² can be obtained by applying spectral corrections for the spatial resolution effect.Near the beginning of the intermediate wake, the variance of ₂ is larger than that of ₃ due to the significant contribution from ribs which connect consecutive spanwise roll vortices. This difference decreases with downstream distance. Also, the presence of the rolls is reflected by a local extremum in the skewness of ₃ on each side of the wake centerline. The magnitude of the extremum decreases with downstream distance.The support of the Australian Research Council is gratefully acknowledged.     

Rheological behaviour of two-phase flow of solid particles in a gas

The present investigation was concerned with the rheological behaviour of dilute suspensions of solid particles in a gas in a vertical cocurrent flow moving upwards. Starting from the experimentally determined dependence of the pressure drop on the concentration of solid particles and the Reynolds number of the carrier medium in the steady flow region, the rheological parameters were estimated using pseudo-shear diagrams. Air was the carrier medium and the dispersed phase was one of six fractions of polypropylene powder and five fractions of glass ballotini. The results show that the investigated two-phase systems have pseudoplastic character which becomes more pronounced with increases in concentration, equivalent diameter and density of solid particles in the flowing suspension. C _d coefficient of particle resistance - d _e equivalent diameter of particles - D column diameter - Fr Froude number - g gravitational acceleration - K rheological parameter - L length - n rheological parameter - p _t pressure drop due to friction - p _m total pressure drop - p _ag pressure drop due to acceleration of the gas phase - p _as pressure drop due to acceleration of the solid phase - p _g hydrostatic pressure of the gas phase - p _s specific effective weight of the dispersed phase - r radius - Re Reynolds number - Re _p Reynolds number of a particle - Re _G generalized Reynolds number - Re _G1 generalized Reynolds number relating to the end of the laminar flow region - Re _G2 generalized Reynolds number relating to the beginning of the turbulent flow region - w _z axial component of velocity - u _t steady free-fall velocity of a single particle - w average velocity - w _g average velocity of the gas phase - w _s average velocity of the dispersed phase of solid particles - relative mass fraction of solid particles - x _s volume fraction of solid particles - _g coefficient of pressure drop due to friction - µ dynamic viscosity - _g density of the gas phase - _m density of the suspension - _s density of solid particles - _ds density of the dispersed phase - _w shear stress at the wall