Simultaneous Determination of Clopidogrel and Its Carboxylic Acid Metabolite (SR26334) in Human Plasma by LC–ESI–MS–MS: Application to the Therapeutic Drug Monitoring of Clopidogrel

A sensitive and specific liquid chromatography-tandem-mass spectrometry method was developed and validated for the simultaneous determination of clopidogrel and its carboxylic acid metabolite (SR26334) in human plasma using nateglinide and pioglitazone as internal standards. Analytes were extracted from 0.50 mL of plasma using diethyl ether–n-hexane (4:1, v/v). Chromatographic separation was performed on a Teknokroma C₁₈ column with a mobile phase of methanol–water (containing 0.1% formic acid) (80:20, v/v) at a flow rate of 0.20 mL min^?1 within 5.6 min. Linearity was established over the concentration range of 0.005–5 ng mL^?1 for clopidogrel and 20–2,500 ng mL^?1 for SR26334. Intra- and inter-batch standard deviations were less than 9.2% and the accuracy of this assay was found to fall within an acceptable range ≤10.0%. The method was successfully applied to the therapeutic drug monitoring of clopidogrel.     

Realizing fast photoinduced recovery with polyfluorene-block-poly(vinylphenyl oxadiazole) block copolymers as electret in photonic transistor memory devices

Photonic field-effect transistor (FET) memory devices offer unique advantages owing to their solution processability, low cost production, and their lightweight and structural flexibility. Despite the plethora of research demonstrated the photon based programming process, limited reports are available for photoinduced recovery mechanism in such devices. To investigate the influence of polymer electret design on photonic memory performance, poly(9,9-dioctylfluorene) (PFO)–block–poly (vinylphenyl oxadiazole) (POXD) conjugated block copolymers were employed to a photonic FET memory with n-type semiconducting channel. The studied device exhibited bistable ON/OFF current states after electrical programming and photoinduced recovery (erasing) processes. The device operating mechanism was elaborated by comparing the device performance with respective electrets of PFO-b-POXD and PFO-b-polystyrene (PS) and PFO homopolymer. We found that PFO-b-POXD can efficiently generate photoexciton under UV illumination to neutralize the trapped hole, and assuage the hole trapping propensity of PFO segment, simultaneously. By optimizing the POXD content in the block copolymer, a decent memory ratio (I_ON/I_OFF) of ~10⁵ was achieved after 10⁴ s, indicating its superior long-term stability and data discernibility. This research shows the judicious strategy to design polymer electret for photonic memory, and it opens up the possibility of developing photonic memory, human perception and futuristic communication systems using simple, convenient and reliable optoelectronic technique.     

Theoretical studies on the mechanism and stereoselectivity of Rh(Phebox)-catalyzed asymmetric reductive aldol reaction

Density functional theory calculations (B3LYP) have been carried out to understand the mechanism and stereochemistry of an asymmetric reductive aldol reaction of benzaldehyde and tert-butyl acrylate with hydrosilanes catalyzed by Rh(Phebox-ip)(OAc)(2)(OH(2)). According to the calculations, the reaction proceeds via five steps: (1) oxidative addition of hydrosilane, (2) hydride migration to carbon-carbon double bond of tert-butyl acrylate, which determines the chirality at C2, (3) tautomerization from rhodium bound C-enolate to rhodium bound O-enolate, (4) intramolecular aldol reaction, which determines the chirality at C3 and consequently the anti/syn-selectivity, and (5) reductive elimination to release aldol product. The hydride migration is the rate-determining step with a calculated activation energy of 23.3 kcal mol(-1). In good agreement with experimental results, the formation of anti-aldolates is found to be the most favorable pathway. The observed Si-facial selectivity in both hydride migration and aldol reaction are well-rationalized by analyzing crucial transition structures. The Re-facial attack transition state is disfavored because of steric hindrance between the isopropyl group of the catalyst and the tert-butyl acrylate.     

三次采油用疏水缔合型AM/DBA共聚物的研究

微乳液;耐温耐盐聚合物;三次采油用疏水缔合型AM/DBA共聚物的研究     

Silicon-containing formal 4π-electron four-membered ring systems: antiaromatic, aromatic, or nonaromatic?

Density functional theory calculations (B3LYP) have been carried out to investigate the 4π-electron systems of 2,4-disila-1,3-diphosphacyclobutadiene (compound 1) and the tetrasilacyclobutadiene dication (compound 2). The calculated nucleus-independent chemical shift (NICS) values for these two compounds are negative, which indicates that the core rings of compounds 1 and 2 have a certain amount of aromaticity. However, deep electronic analysis reveals that neither of these two formal 4π-electron four-membered ring systems is aromatic. Compound 1 has very weak, almost negligible antiaromaticity, and the amidinate ligands attached to the Si atoms play an important role in stabilizing this conjugated 4π-electron system. The monoanionic bidentate ligand interacts with the conjugated π?system to cause π-orbital splitting. This ligand-induced π-orbital splitting effect provides an opportunity to manipulate the gap between occupied and unoccupied π?orbitals in conjugated systems. Conversely, compound 2 is nonaromatic because its core ring does not have a conjugated π?ring system and does not fulfill the requirements of a Hückel system.     

基于金刚石氮-空位色心自旋系综与超导量子电路混合系统的量子节点纠缠

量子纠缠是实现量子计算和量子通信的核心基础,本文提出了在金刚石氮-空位色心(NV centers)自旋系综与超导量子电路耦合的混合系统中实现两个分离量子节点之间纠缠的理论方案.在该混合系统中,把金刚石NV centers自旋系综和与之耦合的超导共面谐振器视为一个量子节点,两个量子节点之间通过一个空的超导共面谐振器连接.具有较长相干时间的NV centers自旋系综作为一个量子存储器,用于制备、存储和发送量子信息;易于外部操控的超导量子电路可执行量子逻辑门操作,快速调控量子信息.为了实现两个分离量子节点之间的纠缠,首先对系统的哈密顿量进行正则变换,将其等价为两个NV centers自旋系综与同一个超导共面谐振器之间的JC耦合;然后采用NV centers自旋-光子混合比特编码的方式,通过调节超导共面谐振器的谐振频率,精确控制体系演化时间,高保真度地实现了两个分离量子节点之间的量子纠缠.本方案还可以进一步扩展和集成,用于构建多节点纠缠的分布式量子网络.     

Ag/Ag_3PO_4/g-C_3N_4复合光催化剂的合成与再生及其可见光下的光催化性能(英文)

研究了用离子交换沉淀法制备的Ag/Ag3PO4/g-C3N4的可见光光催化性能及再生方法.通过X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、紫外-可见(UV-Vis)吸收光谱及X射线光电子能谱(XPS)对其进行了结构特性分析.XRD结果显示再生后催化剂的结构未发生改变.FESEM及UV-Vis分析结果说明催化剂由Ag3PO4与g-C3N4复合而成.XPS分析结果表明催化剂表面出现少量的银单质.利用可见光(λ420nm)照射下的苯酚降解实验评价了样品的光催化活性,并通过活性物种及能带结构的分析对催化剂的光催化机理进行了推测.研究表明,Ag/Ag3PO4/g-C3N4的光催化活性明显高于纯Ag3PO4及纯g-C3N4,主要原因归结为单质银、Ag3PO4及g-C3N4的协同效应.经过氧化氢和磷酸氢铵钠(NaNH4HPO4)的再生可完全恢复催化剂的活性,这表明该绿色环保的再生方法可实现Ag/Ag3PO4/g-C3N4催化剂在环境中的实际应用.     

Syntheses, crystal structures and properties of two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers

Two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers, {[Ln₂Cu₅Br₄(IN)₇(H₂O)₆]·H₂O}_n (Ln=Eu (1) and Gd (2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. The structure determination reveals that 1 and 2 are isostructural and feature a novel three-dimensional pillared-layer hetrometallic structure built upon the linkages of one-dimensional (1D) linear Ln-carboxylate chains, zero-dimensional (0D) Ln-carboxylate Ln₂(IN)₈ dimers, rare 1D zigzag [Cu₅Br₄]_n inorganic chains and IN⁻ pillars. In both 3D structures, there are Ln-carboxylate layers resulted from the connections of 1D Ln-carboxylate chains and 0D Ln₂(IN)₈ dimers through O-H?O hydrogen bondings. The luminescent properties of 1 have been investigated. The magnetic properties of 1 and 2 have also been studied.     

Synthesis,Crystal Structure and Characterization of a New Coordination Polymer from the Self-assembly of CoCl_2 Salt and Flexible Ligand 1,3-Bis（4-pyridyl）propane

A new 1D coordination polymer [Co(bpp)3Cl2(H2O)2]n 1 (bpp = 1,3-bis(4-pyridyl)-propane) was synthesized and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system,space group Ibca with a = 16.569(9),b = 17.240(10),c = 27.087(16) ,V = 7738(8) 3,Z = 8,Dc = 1.306 g/cm3,Mr = 760.65,λ(MoKa) = 0.71073 ,μ = 0.623 mm1,F(000) = 3192,the final R = 0.0678 and wR = 0.2011. The Co(II) atom is coordinated in a slightly distorted octahedral CoN4Cl2 geometry by two Cl atoms in the axial positions,four N atoms from the two bridging bpp ligands and two pendant bpp ligands. The CoN4Cl2 octahedra are connected by the bridging bpp ligands to form a 1D neutral coordination polymer chain. The chains are linked by face-to-face π-π interactions between adjacent pendant bpp ligands to give rise to a 3D supramolecular architecture. The photoluminescent investigation indicates that the emission of 1 is attributed to ligand-centered emission. The variable-temperature magnetic susceptibility measurement shows weak antiferromagnetic behavior in the complex.     

吹扫捕集气相色谱法分析化妆品中挥发性化合物

建立了同时测定化妆品中7种挥发性化合物的吹扫捕集气相色谱法（PT-GC）,该方法最大的优点就是不用任何有机溶剂对样品萃取和浓缩,减少了对环境的污染,具有灵敏度高、检出限低、定量准确、操作简便等特点。结果表明：此方法有较好的重复性,相对标准偏差在6%以下;检出限为0.3056-7.1373ng/mL;7种物质的回收率在80.87%—107.15%之间。