偶氮苯自组装单分子膜中长程电子转移机理

利用自组装技术在金电极表面构造了具有不同前端健长度偶氮苯功能化的单分子膜体系：Au／S（CH2）nNHCO-N＝N-OCH2CH3（n＝2，3，4，6）．研究结果表明，仍氮苯到金电极的表现电子转移速率随它们之间的距离长度的增加而呈指数性的下降趋势．基于Marcus电子隧穿理论，得到了此自组装膜体系的长程电子隧穿系数ρ＝（1．35±0．2）／CH2在和可逆电活性分子自组装膜体系及理论计算相比较的基础上，从偶氮苯分子自组装膜结构与电子转移过程的关系角度对这一结果进行了分析和说明．     

Electrochemical and spectroelectrochemical characterization of Ru(2)(4+) and Ru(2)(3+) complexes under a CO atmosphere

Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available.     

Optical properties of ZnO and ZnO:In nanorods assembled by sol-gel method

Self-assembled zinc oxide (ZnO) and indium-doping zinc oxide (ZnO:In) nanorod thin films were synthesized on quartz substrates without catalyst in aqueous solution by sol-gel method. The samples were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM), Raman-scattering spectroscopy, room-temperature photoluminescence (PL) spectra, and temperature-dependent PL spectra measurements. XRD and Raman spectra illustrated that there were no single In2O3 phase in ZnO lattice after indium doping. The PL spectra of ZnO showed a strong UV emission band located at 394 nm and a very weak visible emission associated with deep-level defects. Indium incorporation induced the shift of optical band gap, quenching of the near-band-edge photoluminescence and enhanced LO mode multiphonon resonant Raman scattering in ZnO crystals at different temperatures. Abnormal temperature dependence of UV emission integrated intensity of ZnO and ZnO:In samples is observed. The local state emission peak of ZnO:In samples at 3.37 eV is observed in low-temperature PL spectra. The near-band-edge emission peak at room temperature was a mixture of excitons and impurity-related transitions for both of two samples.     

On-line Separation and Detection of Peptides by Capillary Electrophoresis / Electrospray FT-ICR-MS

Recently, capillary electrophoresis/electrospray ionization mass spectrometry (CE/ESI- MS) has been rapidly developed as a powerful analytical tool for charged species ranged from small molecules such as carboxylic acids1, phenolic compounds2, metal species3, tetramines4, herbicides5, drugs and drug metabolites6 to peptides and proteins7, 8. The ESI mode has proven to be sensitive, versatile and relatively easy to use in combination with CE. CE confers rapid analysis and efficient separ…     

甲烷在Ni表面及La薄膜上激活解离化学吸附

利用分子束技术改变甲烷的平动能E_k来研究E_k及其法向分量E_n对甲烷在Ni表面及La薄膜上激活解离吸附的影响。对CH_4/Ni及CH_4/La系统, 当甲烷的平动能E_k分别低于58.5 kJ·mol~(-1)及52.3 kJ·mol~(-1)时, 没观察到甲烷的解离吸附。当甲烷的平动能超过此阈值时, 即对CH_4/Ni系统, 当Ek=58.5增至63.8 kJ·mol~(-1)时, 初始沾着几率s_0由0至0.54线性增加; 对CH_4/La系统, 当E_k=52.3增至63.8 kJ·mol~(-1)时, S_0由0至0.49线性增加。这些结果表明, 两个系统的化学吸附是不经过前趋态的直接化学吸附。最后求出CH_4/Ni, CH_4/La系统的表观活化能分别为46.8 kJ·mol~(-1)和38.1 kJ·mol~(-1)。     

Theoretical Studies on the Abstraction Reaction of Atomic O（^3p） with Si2H6

The hydrogen abstraction reaction of O(^3P) with Si2H6 has been studied theoretially. Two transition states of ^3A″ and ^3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G (d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value.     

On a lemma of Butzer and Kirschfink

In [1], Butzer and Kirschfink discussed the convergence rates for C[0,1]-valued dependent random functions on Donsker's weak invariance principle and introduced the concept of dependency from below to deal with the martingale difference sequence. They asserted in their Lemma 8 that Lemma A. A martingale difference sequence (X_n,F_n,n≥1) with is dependent from below, i.e., for each 1≤i≤n and each n≥1 . The purpose of this note is to prove that Lemma A is not always true and to improve the conditions of Butzer and Kirschfink. We shall apply the notations in [1].     

Cu(ii)/SPDO complex catalyzed asymmetric Baeyer–Villiger oxidation of 2-arylcyclobutanones and its application for the total synthesis of eupomatilones 5 and 6

A novel classical kinetic resolution of 2-aryl-substituted or 2,3-disubstituted cyclobutanones of Baeyer–Villiger oxidation catalyzed by a Cu(ii)/SPDO complex is reported for the first time, producing normal lactones in excellent enantioselectivities (up to 96% ee) and regioselectivities (up to >20/1), along with unreacted ketones in excellent enantioselectivities (up to 99% ee). The current transformation features a wide substrate scope. Moreover, catalytic asymmetric total syntheses of natural eupomatilones 5 and 6 are achieved in nine steps from commercially available 3-methylcyclobutan-1-one.

A novel classical kinetic resolution of Baeyer–Villiger oxidation catalyzed by a Cu(ii)/SPDO complex with excellent enantioselectivity, regioselectivity and wide substrate scope is reported for the first time and explore the synthetic application.     

Antibacterial Activity of Aureonuclemycin Produced by Streptomyces aureus Strain SPRI-371

Actinomycetes play a vital role as one of the most important natural resources for both pharmaceutical and agricultural applications. The actinomycete strain SPRI-371, isolated from soil collected in Jiangsu province, China, was classified as Streptomyces aureus based on its morphological, physiological, biochemical and molecular biological characteristics. Its bacterial activity metabolites were identified as aureonuclemycin (ANM), belonging to adenosine derivatives with the molecular formula C₁₆H₁₉N₅O₉ for ANM A and C₁₀H₁₃N₅O₃ for ANM B. Simultaneously, the industrial fermentation process of a mutated S. aureus strain SPRI-371 was optimized in a 20 m³ fermentation tank, featuring a rotation speed of 170 rpm, a pressure of 0.05 MPa, an inoculum age of 36–40 h and a dissolved oxygen level maintained at 1–30% within 40–80 h and at >60% in the later period, resulting in an ANM yield of >3700 mg/L. In the industrial separation of fermentation broth, the sulfuric acid solution was selected to adjust pH and 4# resin was used for adsorption. Then, it was resolved with 20% ethanol solution and concentrated in a vacuum (60–65 °C), with excellent results. Antibacterial experiments showed that ANM was less active or inactive against Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri and Xanthomonas oryzae pv. oryzicola and most bacteria, yeast and fungi in vitro. However, in vivo experiments showed that ANM exhibited extremely significant protective and therapeutic activity against diseases caused by X. oryzae pv. oryzae and X. oryzae pv. oryzicola in rice and X. citri in oranges and lemons. In field trials, ANM A 150 gai/ha + ANM B 75 gai/ha exhibited excellent therapeutic activity against rice bacterial leaf blight, citrus canker and rice bacterial leaf streak. Furthermore, as the dosage and production cost of ANM are lower than those of commercial drugs, it has good application prospects.     

Unravelling the essential difference between TiOx and AlOx interface layers on Ta3N5 photoanode for photoelectrochemical water oxidation

Tantalum nitride(Ta₃N₅) is a very promising photoanode material due to its narrow band gap(2.1 eV)and suitable band alignment for solar water splitting.However,it suffers from severe photocorrosion during water oxidation.In this work,it was found that surface passivation by AlO_x and TiO_x layers results in dramatically different PEC performance of Ta₃N₅ photoanode for water oxidation.The mechanism study indicates that the negative ...