高效液相色谱检测Zn（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Pb（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Hg（Ⅱ）

用双-(2-羟乙基)二硫代甲酸铵(HEDC)在反相液相色谱中作检测某些金属离子的衍生化试剂，HEDC的金属螯合物微溶于水，可直接水样注射于C18柱中进行检测，范围为0．006～10mg／L相对偏差1％～2％，检测波长254nm，金属汞的整合物在HPLC分析前进行浓缩富集检测限可低至0．06～25μg／L，相对偏差小于2％。     

Pre-Column Derivatization of Amines with 1,2-Benzo-3,4-Dihydrocarbazole-9-Isopropyl Chloroformate Followed by LC-Fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCI-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH]⁺ under APCI in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH₂-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0–10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of I_BCIC/I_CEOC and I_BCIC/I_FMOC are, respectively, 1.23–3.14 and 1.25–3.08 for fluorescent (FL) responses (here, I is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C₈ column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6–37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV<7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997. Revised: 12 December 2005 and 13 Febrauary 2006     

Theoretical study of the local structure and Raman spectra of CaO-SiO2 binary melts

A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature.     

Fabrication of lead titanate single crystalline nanowires by hydrothermal method and their characterization

Single crystalline nanowires of lead titanate (PbTiO₃) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure and optical properties of PbTiO₃ nanowires were investigated. The PbTiO₃ nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO₃ with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies are responsible for the light emission of PbTiO₃ nanowires.     

Unusual magnetic properties of one-dimensional molecule-based magnets associated with a structural phase transition

Three ion-pair complexes, [RbzPy](+)[Ni(mnt)(2)](-) (mnt(2)(-) = maleonitriledithiolate; [RbzPy](+) = 4-R-benzylpyridinium; R = Br (1), Cl (2), and NO(2) (3)), with unusual magnetic properties have been synthesized and characterized. The crystal structures of 1 and 2 have been solved. The two complexes belong to the P2(1)/c space group with Z = 4 and C(20)H(11)BrN(5)NiS(4), a = 12.0744(17) A, b = 26.369(4) A, c = 7.440(3) A, and beta = 102.63(3) degrees for 1 and C(20)H(11)ClN(5)NiS(4), a = 12.105(2) A, b = 26.218(4) A, c = 7.374(2) A, and beta = 102.55(2) degrees for 2, respectively. The [Ni(mnt)(2)](-) anions in 1-3 form uniformly spaced one-dimensional (1-D) magnetic chains of s = 1/2 at room temperature. The temperature dependences of the susceptibility for 1-3 show that they undergo phase transitions. All three complexes are paramagnetic in their high-temperature (abbreviation HT) phase and diamagnetic in the low-temperature (abbreviation LT) phase because of strong dimerization along the stacking direction. The results of thermal analysis (DSC) further confirm that the phase transition for 1 and 2 is first-order but maybe second-order for 3. The phenomena observed in this study are similar to those of the 1-D radical systems.     

Composite Electrode SnO2／TiO2 for Dye-Sensitized Solar Cells

Composite nanoporous electrode SnO2/TiO2 was fabricated for the dye sensitized solar cell (DSSC) with N3 (Cis-Ru). After introducing of TiO2, the open-circuit photovoltage (Voc) was higher than that of the pure SnO2 electrode, while short-circuit photocurrent (Isc) was varied with the ratio of the TiO2. Appropriate content of the TiO2 can be beneficial to the efficiency of the solar cell, and it gives negative impact on the composite electrode when the content of TiO2 is higher.     

Characterization and electrochemical investigation of boron-doped mesocarbon microbead anode materials for lithium ion batteries

The structure and anodic performance of boron-doped and undoped mesocarbon microbeads (MCMBs) have been comparatively studied and the results obtained by XPS, XRD, SEM, Raman spectroscopy and electrochemical measurements are discussed. It is found that boron doping introduces a depressed d ₀₀₂ spacing and the larger amount of "unorganized carbon", which induces vacancy formation in the graphite planes and leads to a quite different morphology from that of the undoped material. Electrochemical charge/discharge cycle tests indicated that after boron doping the lithium intercalation was carried through at a somewhat higher potential, being attended by greater irreversible capacity loss. Electronic Publication     

Synthesis of a Photolabeling Probe for the Study of Antiviral Mechanism of Ribavirin

Ribavirin has been used in urgency to treat SARS patients recently. In order to study its antiviral mechanism by photolabeling approach, we have synthesized and characterized 5-azido-1-β-D-ribofuranosyl-1,2,4-triazole-3-carboxiamide 1 as a photolabeling probe of ribavirin. The azidotriazole nucleoside showed rapid and clean photochemical reaction, suggesting that 1 is a promising probe to study the antiviral mechanism ofribarivin by photolabeling.     

双8-羟基喹啉端开链冠醚金属络合物的光物理性质

设计合成了双8-羟基喹啉端的开链冠醚QP3Q,研究了金属离子铝或锌与其形成络合物的组成和发光性质,并测定了络合物的激发态寿命.这些络合物在溶液中有较高的荧光量子产率,所得到的络合物固体具有较强的蓝光发光性能.结果表明,有可能通过QP3Q与不同离子形成的络合物得到不同发光波长的发光材料.     

流动分析法同时测定铬（Ⅵ）及铬（Ⅲ）过程中铈（Ⅳ）氧化剂的影响

以Ｃｅ（Ⅳ）为氧化剂，采用流动分析在线氧化技术，实现了对Ｃｒ（Ⅵ）和Ｃｒ（Ⅲ）的同时在线分析，发现Ｃｅ（Ⅳ）氧化剂在测定过程中产生负干扰，在而Ｃｒ（Ⅲ）存在时会使Ｃｒ（Ⅵ）的测定结果偏高，本文提出了一个校正模型，通过数学方法消除上述干扰，所建立的分析方法对Ｃｒ（Ⅵ）和Ｃｒ（Ⅲ）分析的平均相对误差不大于６．５％。