Reductive electrochemical formation of 6H-dibenzo[b,d]pyran-6-one and 2-benzopyran-1(1H)-one

In the present Letter several carbolactones (oxidative products) are obtained under aprotic cathodic conditions in the preparative scaled electrolysis of 1,2-quinones in a divided electrochemical cell and in the presence of oxygen. When 9,10-phenanthrenequinone is reduced 6H-dibenzo[b,d]pyran-6-one and [1,1′-biphenyl]-2,2′-dicarboxylic acid are obtained as major products. In the reduction of 1,2-naphthoquinone, 2-benzopyran-1(1H)-one, and 2-(2-carboxyethenyl)-benzoic acid were formed as main products. The proposed mechanism to explain the formation of these and other products, that involves an electron-transfer reaction to the oxygen in air, is now discussed.     

模糊判断矩阵一致性的调整方法

给出了模糊判断矩阵一致性调整的新方法 .该方法是在模糊判断矩阵一致性定义及判定方法的基础上 ,通过构造和分析模糊判断矩阵的调和矩阵 ,进一步给出了将模糊判断矩阵改进为满意一致性矩阵的计算步骤 .最后给出了一个算例 .     

N‐Linked Glycosyl Auxiliary‐Mediated Native Chemical Ligation on Aspartic Acid: Application towards N‐Glycopeptide Synthesis

A practical approach towards N‐glycopeptide synthesis using an auxiliary‐mediated dual native chemical ligation (NCL) has been developed. The first NCL connects an N‐linked glycosyl auxiliary to the thioester side chain of an N‐terminal aspartate oligopeptide. This intermediate undergoes a second NCL with a C‐terminal thioester oligopeptide. Mild cleavage provides the desired N‐glycopeptide.     

Carbon black nanoparticles film electrode prepared by using substrate-induced deposition approach

A new type of carbon film electrode, composed of a thin layer of tightly packed carbon black (CB) nanoparticles deposited onto a gelatin-covered indium tin oxide/glass support using the surface-induced deposition (SID) approach, is presented. Some parameters of the novel SID method were optimized and the surface image and functionalization of the investigated carbon black film electrode (CBFE) was inspected by employing scanning electron microscopy and infrared spectroscopy. A cyclic voltammetry (CV) study was conducted in which the electron-transfer kinetics and CBFE interfacial characteristics were evaluated employing several selected reference redox systems, such as [Ru(NH₃)₆]^3+/2+, [Fe(CN)₆]^3−/4− and Fe^3+/2+ in aqueous, and ferrocene/ferrocenium in acetonitrile media. CV recordings were also performed in order to compare the electrochemical behavior of the CBFE with that of some well-known and established bare carbon-based electrodes. In order to confirm the validity of the CB film preparation method, the electroanalytical performance of the proposed CBFE was examined by carrying out linear sweep voltammetry of ascorbic acid (AA), anodic stripping square-wave voltammetry of Cu(II) in acidic medium, and amperometric measurements of hydrogen peroxide under flow injection conditions. The sensing characteristics of the novel carbon film electrode, demonstrated in this preliminary study, comprise: (i) a wide working potential window ranging from +1.0 to −1.3 V (depending on the solution pH), (ii) a wide applicable pH range (at least from 2 to 12), (iii) low voltammetric background (<5 μA cm⁻²), (iv) a satisfactory linear voltammetric and amperometric response (r² > 0.99) to various analytes, (v) good reproducibility (for example, r.s.d. of 2% in amperometric detection of H₂O₂ and r.s.d. of 8.5% for electrode-to-electrode CV runs), and (vi) stable and fast current response (at least 100 CV runs with negligible change in CV response). The main advantages of the proposed CBFE originate from the unique CB film formation procedure that enables fast, simple, inexpensive and non-toxic CBFE preparation, which can find application in advanced electrochemical devices and is suitable for mass production.     

Voltammetric Sensing of Soybean Agglutinin Using an Electrode Modified with Electron-transfer,Carbohydrate-mimetic/Cross-linker-peptide-collagen Film

We constructed an electrochemical sensor based on an electrode modified with electron-transfer, carbohydrate-mimetic peptides on collagen film. The peptide consisted of Ac-Y₄C combined with soybean agglutinin (SBA). To evaluate the binding between SBA and the peptide, we prepared Ac-Y₄CA_n (3-6) containing oligoalanine as a cross-linker. When SBA and Y₄C on the electrode were incubated, the peak was decreased by the SBA uptake of the peptide. The change in the peak current using Ac-Y₄CA₆ was the greatest of the four peptides. The calibration curve was linear and ranged from 4.0×10⁻¹⁴ to 1.2×10⁻¹² M with a detection limit of 1.3×10⁻¹⁴ M.     

管理层业绩预告会影响定增价格吗？——基于中介效应的视角

本文研究上市公司是否以及如何利用业绩预告根据定增对象的不同操纵新股发行价格。实证结果表明,管理层会根据定增对象的不同,策略性地发布信息含量不一样的业绩预告以影响定增新股发行价,业绩预告在定增对象与发行价格之间发挥了显著的中介效应。具体来说,若大股东参与认购新股,则倾向于发布坏消息的业绩预告,以压低新股发行价,若大股东不参与认购新股,则倾向于发布好消息的业绩预告,以抬高新股发行价;进一步分类分析发现,非国有上市公司比国有上市公司、主动披露业绩预告的上市公司比强制披露业绩的上市公司这种行为表现更为强烈,业绩预告的中介效应也更为显著。研究结论为投资者的投资决策和监管部门的监管活动提供了一定的参考价值。     

Ultrasonic irradiation in a single-stage synthesis of chloroiodomethane from iodoalkanes and dichloromethane under aluminum mediation

In the presence of iodine, a mixture of dichloromethane, iodoalkanes (alkyl = Me, Et, Pr, iso-Pr, Bu, iso-Bu, pentyl) and aluminum powder was irradiated at room temperature with ultrasound to give readily chloroiodomethane ICH₂Cl. The preferred reactant to give the best yield of ICH₂Cl was PrI. Alkylaluminum sesqui-iodides were postulated as intermediates.     

利用荧光探针技术研究氧鎓盐光引发丁基乙烯基醚的阳离子聚合

本工作合成了一组带不同取代基的氧鎓盐化合物,并对它们的荧光寿命、荧光量子产率以及用丁基乙烯基醚(BVE)进行猝灭的荧光猝灭常数进行了测定,发现带拉电子基的氧鎓盐化合物和BVE间存在着较强的相互作用,相反,推电子基的引入则减弱了这种影响,表明反应具有电子转移性质.由于在BVE的聚合过程中,被猝灭的氧鎓盐荧光会因BVE聚合、双键减少而使氧鎓盐荧光逐步恢复.因此利用这一现象作为荧光探针,考察了氧鎓盐光引发BVE的阳离子聚合过程.文中还对氧鎓盐光引发BVE聚合的机理进行了初步讨论.     

Dipole–reaction field interaction model for the solvent reorganization energy and its application to the benzoquinone–benzoquinone anion radical system

 Based on the spherical cavity approximation and the Onsager model, a dipole–reaction field interaction model has been proposed to elucidate the solvent reorganization energy of electron transfer (ET). This treatment only needs the cavity radius and the solute dipole moment in the evaluation of the solvent reorganization energy, and fits spherelike systems well. As an application, the ET reaction between p-benzoquinone and its anion radical has been investigated. The inner reorganization energy has been calculated at the level of MP2/6–31+G, and the solvent reorganization energies of different conformations have been evaluated by using the self-consistent reaction field approach at the HF/6–31+G level. Discussions have been made on the cavity radii and the values are found to be reasonable when compared with the experimental ones of some analogous intramolecular ET reactions. The ET matrix element has been determined on the basis of the two-state model. The fact that the value of the ET matrix element is about 10 times larger than RT indicates that this ET reaction can be treated as an adiabatic one. By invoking the classical Marcus ET model, a value of 4.9 × 10⁷M⁻¹s⁻¹ was obtained for the second-order rate constant, and it agrees quite well with the experimental one. Received: 19 October 2001 / Accepted: 17 January 2002 / Published online: 3 May 2002     

Photon emission from clean and oxygenated Si and SiO2 surfaces bombarded by 5 keV krypton ions

The effect of oxygen on the light emission from a Si (1 0 0) semiconductor bombarded by energetic Kr⁺ ions has been studied in the 200–300 nm wavelength range. The influence of oxygen was verified by studying the optical spectra of SiO₂ bombarded under similar experimental conditions. It has been found that the measured intensities of the emitted photons are always higher in the presence of oxygen, even higher than those obtained for SiO₂. The electron-transfer model can explain our experimental observations. We do believe that in the presence of oxygen, an intermediate structure of silicon sub-oxide SiO_X<2 is formed on silicon surface, which is responsible for the increase of photon emission. In addition, the radiative dissociation process and breaking of chemical bond seems contribute to the enhancement of emitted photons intensity.