EAST快速极紫外光谱仪绝对强度的原位标定

磁约束等离子体中杂质(特别是高Z杂质)的存在将大大增强等离子体辐射功率损失，破坏等离子体的约束性能。杂质行为的定量研究首先要求对杂质测量的光谱诊断系统进行绝对强度标定，获得灵敏度响应曲线。介绍了EAST托卡马克上的快速极紫外光谱仪系统绝对强度的原位标定方法。在波长范围20～150Å内，通过对比极紫外(EUV)波段连续轫致辐射强度的计算值和测量值得到光谱仪的绝对强度标定。在此过程中，首先由(523±1) nm范围内可见连续轫致辐射强度的绝对测量值计算出有效电荷数Z_eff，进而结合电子温度和密度分布计算EUV波段连续轫致辐射强度；EUV波段连续轫致辐射强度的测量值即为不同波长处探测器的连续本底计数扣除背景噪声计数值。对于较长波段范围130～280Å，通过对比等离子体中类锂杂质离子(Fe23+，Cr21+，Ar15+)和类钠杂质离子(Mo31+，Fe15+)发出的共振谱线对(跃迁分别为1s22s 2S_1/2-1s22p 2P_{1/2, 3/2}及2p63s 2S_1/2-2p63p 2P_{1/2, 3/2})强度比的理论和实验值进行相对强度标定。其中共振谱线对强度比的理论值由辐射碰撞模型计算得到，模型中处在各个能级的离子数主要由电子碰撞激发，去激发以及辐射衰变三个过程决定。两种方法相结合，实现了光谱仪20～280Å范围的绝对强度标定。考虑轫致辐射、电子温度及电子密度的测量误差，绝对标定误差约为30%。在绝对标定的基础上，我们对杂质特征谱线强度进行绝对测量，并将测量结果与杂质输运程序结合ADAS(Atomic Data and Analysis Structure)原子数据库计算得到的模拟值进行比较，进而估算等离子体中的杂质浓度。     

Thermosensitive t‐PLA‐b‐PNIPAAm tri‐armed star block copolymer nanoscale micelles for camptothecin drug release

Thermosensitive polylactide‐block‐poly(N‐isopropylacrylamide) (t‐PLA‐b‐PNIPAAm) tri‐armed star block copolymers were synthesized by atom transfer radical polymerization (ATRP) of monomer NIPAAm using t‐PLA‐Cl as macroinitiator. The synthesis of t‐PLA‐Cl was accomplished by esterification of star polylactides (t‐PLA) with 2‐chloropropionyl chloride using trimethylolpropane as a center molecule. FT‐IR, ¹H NMR, and GPC analyses confirmed that the t‐PLA‐b‐PNIPAAm star block copolymers had well‐defined structure and controlled molecular weights. The block copolymers could form core‐shell micelle nanoparticles due to their hydrophilic‐hydrophobic trait in aqueous media, and the critical micelle concentrations (CMC) were from 6.7 to 32.9 mg L^?1, depending on the system composition. The as‐prepared micelle nanoparticles showed reversible phase changes in transmittance with temperature: transparent below low critical solution temperature (LCST) and opaque above the LCST. Transmission electron microscopy (TEM) observations revealed that the micelle nanoparticles were spherical in shape with core‐shell structure. The hydrodynamic diameters of the micelle nanoparticles depended on copolymer compositions, micelle concentrations and media. MTT assays were conducted to evaluate cytotoxicity of the camptothecin‐loaded copolymer micelles. Camptothecin drug release studies showed that the copolymer micelles exhibited thermo‐triggered targeting drug release behavior, and thus had potential application values in drug controlled delivery. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4429–4439     

Solvatochromic Behavior of Chiral Mesoporous Metal–Organic Frameworks and Their Applications for Sensing Small Molecules and Separating Cationic Dyes

Two anionic metal–organic frameworks (MOFs) with 1D mesoporous tubes ( 1 ) and chiral mesoporous cages ( 2 ) have been rationally constructed by means of a predesigned size‐extended hexatopic ligand, namely, 5,5′,5′′‐(1,3,5‐triazine‐2,4,6‐triyl)tris‐ (azanediyl)triisophthalate (TATAT). Charge neutrality is achieved by protonated dimethylamine cations. Notably, the two MOFs can be used to separate large molecules based on ionic selectivity rather than the size‐exclusion effect so far reported in the literature. Owing to the imino triazine backbone and carboxyl groups of the hexatopic ligand, which provide important host–guest interactions, rare solvatochromic phenomena of 1 and 2 are observed on incorporating acetone and ethanol guests. Furthermore, guest‐dependent luminescence properties of compound 2 were investigated, and the results show that luminescence intensity is significantly enhanced in toluene and benzene, while quenching effects are observed in acetone and ethanol. Thus, compound 2 may be a potential material for luminescent probes.     

氮杂环卡宾催化的不对称安息香缩合反应

N-Heterocyclic carbene (NHC) plays an important role in catalytic processes, as the catalyst it has shown high activities in organic reactions. Synthesis of chiral triazole carbene, the structure and the application of NHCs in asymmetric catalytic benzoin reactions are described. The aims are to broad students' vision and make students feel the charm of organic chemistry through extension of undergraduate curriculum content. Meanwhile, their ability of finding, analyzing and solving problems on the basis of generalizing and thinking about the knowledge will be improved.     

Blue‐light‐emitting polyfluorene functionalized with triphenylamine and cyanophenylfluorene bipolar side chains

A new bipolar conjugated polyfluorene copolymer with triphenylamine and cyanophenylfluorene as side chains, poly{[9,9‐di(triphenylamine)fluorene]‐[9,9‐dihexyl‐fluorene]‐[2,7‐bis(4′‐cyanophenyl)‐9,9′‐spirobifluorene]} ( PTHCF ), was synthesized for studying the polymer backbone emission. Its absolute weight‐average molecular weight was determined as 4.85 × 10⁴ by using gel permeation chromatography with a multiangle light scattering detector. In contrast to the electronic absorption spectrum in dilute solution, the absorbance of PTHCF in thin film was slightly blue shifted. By comparison of the solution and thin‐film photoluminescence (PL) spectra, a red shift of Δλ = 8–9 nm was observed in the thin‐film PL spectrum. The HOMO and LUMO energy levels of the resulting polymer were electrochemically estimated as ?5.68 and ?2.80 eV, respectively. Under the electric‐field intensity of 4.8 × 10⁵ V cm^?1, the obtained hole and electron mobilities were 2.41 × 10^?4 and 1.40 × 10^?4 cm² V^?1 s^?1, respectively. An electroluminescence device with configuration of ITO/PEDOT:PSS/ PTHCF _70%+PBD_30%/CsF/Ca/Al exhibited a deep‐blue emission as a result of excitons formed by the charges migrating along the full‐fluorene main chain. The incorporation of the bipolar side chains into the polymer structure prevented the intermolecular interaction of the fluorene moieties, balance charge injection/transport, and thereby improve the polymer backbone emission. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Analysis of Synthetic Drugs in Chinese Medicine by High Performance Liquid Chromatography/Mass Spectrometry with In‐Source Collision Induced Dissociation

Sixteen chemical drugs, often found in adulterated Chinese medicine, were studied by high performance liquid chromatography/atmospheric ionization mass spectrometry. Under optimal conditions, three pairs of compounds were either coeluted or unresolved. The lack of chromatographic resolution and the lack of specificity in UV detection were overcome by a method based on high performance liquid chromatography/electrospray mass spectrometry. This method was capable of detecting the adulterants based on their retention times, molecular ions, and characteristic fragments resulting from in‐source collision induced dissociation.     

2000 Vol.11 No.8 P.Preparation of AChE Inhibitors From Jujubogenin

A dammarane derivative dihydrojujubogenin-2-en-1-one, which possesses a skeleton and pharmacophore partially similar to those of Territrem B, a potent AChE inhibitor, was synthesized via three different paths. The anti-AChE activity of this compound and related analogue was measured.     

Catalytic pyrolysis of Pubescens to phenols over Ni/C catalyst

The pyrolysis of Pubescens over Ni/C catalyst was studied at 350 °C in H₂ flow. The presence of Ni/C catalyst efficiently improved the degradation of raw materials, and produced bio-oil with high content of phenols but low contents of acetic acid, furfural and water. In the reaction, Ni/C catalyst plays the role of catalytic decomposition and catalytic hydrogenation. The existence of the carbon carrier favors the formation of active Ni in small sizes with more defects, which results in high catalytic activity of Ni in biomass decomposition and selective production of phenols.     

Screening and analysis of the multiple absorbed bioactive components and metabolites in rat plasma after oral administration of Jitai tablets by high‐performance liquid chromatography/diode‐array detection coupled with electrospray ionization tandem mass spectrometry

Based on the serum pharmacochemistry technique and high‐performance liquid chromatography/diode‐array detection (HPLC/DAD) coupled with electrospray tandem mass spectrometry (HPLC/ESI‐MS/MS), a method for screening and analysis of the multiple absorbed bioactive components and metabolites of Jitai tablets (JTT) in orally dosed rat plasma was developed. Plasma was treated by methanol precipitation prior to liquid chromatography, and the separation was carried out on a Symmetry C₁₈ column, with a linear gradient (0.1% formic acid/water/acetonitrile). Mass spectra were acquired in negative and positive ion modes, respectively. As a result, 26 bioactive components originated from JTT and 5 metabolites were tentatively identified in orally dosed rat plasma by comparing their retention times and MS spectra with those of authentic standards and literature data. It is concluded that an effective and reliable analytical method was set up for screening the bioactive components of Chinese herbal medicine, which provided a meaningful basis for further pharmacology and active mechanism research of JTT. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of cross‐linkable ruthenium complex dye and its application on dye‐sensitized solar cells

A new crosslinkable light sensitizer, Ru(2,2′‐bipyridine‐4,4′‐bicarboxylic acid)(4,4′‐bis(11‐dodecenyl)‐2,2′‐bipyridine)(NCS)₂, denoted as Ru‐C for titanium oxide nanocrystalline‐based solar cells was synthesized with its crosslinking properties invesitigated by Fourier‐transform infrared and UV‐vis absorption spectroscopies. After crosslinking by itself or copolymerizing with methyacrylic acid, their sensitized solar cells with poly(methylacrylate)‐gelled electrolyte system not only attained more than 5% of power conversion efficiency at AM 1.5 illumination (100 mW/cm²), but also gave rise to long storage life. To the best our knowledge, this is the first crosslinkable dye ever applied to the DSSC in the literature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 366–372, 2010