流动注射在线共沉淀预富集火焰原子吸收法测定痕量铜

研究了以Ｎｉ＾２＋－ＤＤＴＣ为共沉淀载体，流动注射在线共沉淀预富集－火焰原子吸收光谱法测定痕量铜的体系，在０．３ｍｏｌ．Ｌ＾－１的硝酸介质中，铜离子在编织反应器中与Ｎｉ＾２＋－ＤＤＴＣ（产生共沉淀，并被收集在编织器内壁上，用甲基异丁基酮（ＭＩＢＫ）在线洗脱沉积物并引入火争原子化器中测定。当富集时间为４０ｓ时，４０μｇ．Ｌ＾－１的铜１０次测定的相对标准偏差为３．０％，灵敏度提高６０倍，检出限（３σ）     

Electronic structure of the Fe3S4 cluster and its quasi-aromaticity

The localized molecular orbitals and their energy levels for the clusters [Fe₃S₄(SH)₃]^2–, [(HS)₃Fe₃S₄·Ni(PH₃)]^2–, [Mo₃S₄(OH₂)₉]⁴⁺, and [Mo₃S₄·Ni]⁴⁺ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe₃S₄]⁺ and [Mo₃S₄]⁴⁺ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M ₃(₃-S)(-S)₃} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M₃S₃} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo₃S₄]⁴⁺ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe₃S₄]⁺ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo₃S₄]⁴⁺ cluster.     

Microstructure and Viscosity of Aggregating Colloids under Strong Shearing Force

Disaggregation under strong shearing force is simulated for an aggregating colloid based on a sticky particle model which can describe the disaggregating and aggregating kinetics, the deformation, and the rupture of clusters with a minimum number of parameters. For a 2-dimensional system, the viscosity and coordination number of the model colloid are calculated at each time step, and the changes of microstructure with shear flow are observed directly by displaying the configuration of particles onto a monitor. The viscosity depends on both area fraction and shear rate, but coordination number depends only on shear rate. Furthermore, the viscosity and coordination number at steady state are independent of the initial state of particles, which indicates that the disaggregation and aggregation are mutually reversible. Copyright 1999 Academic Press.     

Formation of α-Mn2O3 nanorods via a hydrothermal-assisted cleavage-decomposition mechanism

A hydrothermal cleavage-decomposition mechanism was used to synthesize single-crystal α-Mn₂O₃ nanorods at 160 °C for 16 h using KMnO₄ as manganese source and CTAB as reducing regent. The as-synthesized products were characterized by powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and infrared spectrum. The results indicate that the reaction temperature is a crucial factor for the formation of α-Mn₂O₃ nanorods. These nanorods exhibit single-crystal nature, and have an average diameter of 36 nm and lengths of up to 1 μm. Based on our experimental results, a hydrothermal cleavage-decomposition mechanism has been proposed on the formation of α-Mn₂O₃ nanorods.     

Carboxylic Acids from <Emphasis Type="Italic">Phyllanthus urinaria</Emphasis>

Five compounds, terephthalic acid mono-[2-(4-carboxy-phenoxycarbonyl)-vinyl] ester (1), (E)-3-(5′-hydroperoxy-2,2′-dihydroxy[1,1′-biphenyl]-4-yl)-2-propenoic acid (2), 3,4,5-trihydroxybenzoic acid (3), succinic acid (or butanedioic acid) (4), and 2,3,4,5,6-pentahydroxybenzoic acid (5), were isolated from Phyllanthus urinaria. The structures of these compounds were elucidated by means of spectral techniques including IR, MS, and 1D/2D NMR. 1 and 2 are new compounds.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2005.     

Preparation and Characterization of Mixed‐Valent Nickel Oxide/Nickel Hexacyanoferrate Hybrid Films and Their Electrocatalytic Properties

Polynuclear mixed‐valent nickel oxide and nickel hexacyanoferrate hybrid film was prepared on glassy carbon electrode by multiple scan cyclic voltammetry. The film growth was monitored using electrochemical quartz crystal microbalance (EQCM). The cyclic voltammogram of the nickel hexacyanoferrate film is characterized by single redox couple whereas nickel oxide/nickel hexacyanoferrate hybrid film exhibits two redox couples. Cyclic voltammetric features suggest that the charge transfer process in both films resembles that of surface‐confined redox species. In stronger basic solution (pH ≥9), nickel hexacyanoferrate film was gradually converted into nickel oxide film during potentiodynamic cycling. The peak potential of nickel oxide redox couple moved into more negative side with increasing pH of contacting solution whereas the peak potential of nickel hexacyanoferrate redox couple remains the same. Electrocatalytic behavior of hybrid film coated electrodes toward ascorbic acid, hydrazine and hydroxylamine was investigated using cyclic voltammetry technique. Analytical application of nickel oxide/nickel hexacyanoferrate hybrid film electrode was tested in amperometry and flow injection analysis.     

血卟啉及其金属衍生物的化学电离质谱

本研究采用直接曝热技术，分别以氢气和甲烷为反应气，测定了１０个血卟啉衍生物和１３个金属血卟啉衍生物的正、负离子解吸化学电离质谱，探讨了各种化学电离质谱法在结构测定中的应用。     

Antineoplastic anthraquinones. II. Design and synthesis of 1,2-Heteroannelated anthraquinones

Based on the “2-phenyinaphthalene-type” structural pattern hypothesis, a number of heterocycle-fused anthraquinones were designed by taking morindaparvin-A ( 2a ) as the lead structure. The compounds we synthesized and tested for antineoplastic activity include 1,2-alkylenedioxyanthraquinone, naphtho [2,3-f]-quinoxaline-7,12-dione, anthra[1,2-d]imidazole-6,11-dione and naphtho[2,3-f]quinoxaline-7,12-dione derivatives. Most of the synthesized anthraquinones possessed various degrees of anticancer activity. One of these compounds, 2-chloromethyl-1H-anthra[1,2-d]imidazole-6,11-dione ( 4b ), exhibited cytotoxic activity against all tested human carcinoma cell lines.     

探究Cu/ZnO相互作用对CO2加氢制甲醇反应性能的影响

Using renewable green hydrogen and carbon dioxide (CO₂) to produce methanol is one of the fundamental ways to reduce CO₂ emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO₂ catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO₂ (Nor-CZS), co-precipitation Cu/ZnO-SiO₂ (Co-CZS), and reverse precipitation Cu/ZnO-SiO₂ (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO₂ to methanol. The results of temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO₂ interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO₂ conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO₂ conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO₂ conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts.     

Catalytic Adsorptive Stripping Voltammetry of Germanium(IV) in the Presence of Gallic Acid and Vanadium(IV)‐EDTA

A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO₄ (pH1.6), 6.0×10^?3 mol/L GA, 3.0×10^?3 mol/L V(IV), 4.0×10^?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10^?11 to 1.0×10^?8 mol/L and the detection limit is 2×10^?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10^?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results.