Cu(phen)22+与6-巯基嘌呤及DNA间的相互作用

在Tris-NaCl（pH=7.2）缓冲溶液中,应用伏安法、电子吸收光谱分析、溴化乙锭荧光分析、粘度测量和琼脂糖凝胶电泳等技术研究了Cu（phen）2^2＋（phen=1,10-邻菲咯啉）与6-巯基嘌呤（6-MP）及DNA间的相互作用。结果表明,Cu（phen）2^2＋与6-MP发生了明显的相互作用,其作用产物不仅与小牛胸腺DNA具有更强的相互作用,并且在H2O2和抗坏血酸存在下对质粒pBR322 DNA具有更强的断裂能力,与DNA的作用模式可能为部分插入模式。     

Triangular halogen trimers. A DFT study of the structure, cooperativity, and vibrational properties

Triangular halogen trimers (RX)3, where X = Br, I and R represents H, H3C, H2FC, HF2C, F3C, CH2=CH, CH[triple bond]C, and Ph, have been investigated using the density functional theory in the Perdew, Burke, and Ernzerhof method. We report herein the optimized geometries of the stable structures, their vibrational frequencies, and binding energies with the two- and three-body terms. All trimer structures possess a cyclic array of halogen atoms in the type II approach by virtue of the nonspherical atomic charge distribution around the halogens. The Br...Br interactions in trimers are very weak, whereas the I...I interactions in trimers are relatively stronger. While all bromine trimers and most of iodine trimers are predicted to be noncooperative, three of iodine trimers show weak cooperativity. The analysis of vibration modes reveals that all halogen trimers exhibit no especially remarkable frequency shifts. It is also shown that the electrostatic contribution plays a major role in the halogen...halogen interactions in halogen trimers. In contrast to bromine trimers, the relative contribution of charge-transfer component to the halogen...halogen interactions becomes more important for iodine trimers.     

SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl toquinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M_w ca. 750) as flexible segments, were synhesized. Thechemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by ~1H-NMR and MALDI-TOF mass spectromeny. The diblock oligomers showed good solubility in common organic solvents and aggregated in wateras characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescenceand formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant thatthis effort might lead to commercial important highly organized functional materials.     

Separation and determination of carnosine-related peptides using capillary electrophoresis with laser-induced fluorescence detection

A capillary electrophoresis (CE) method with laser-induced fluorescence (LIF) detection was developed for the separation and detection of carnosine-related peptides (carnosine, anserine, and homocarnosine). A sensitive and fluorogenic regent, 3-(4-carboxybenzoyl) quinoline-2-carboxaldehyde (CBQCA) was selected as a precapillary labeling reagent for imidazole dipeptides to form isoindole derivatives. The optimized molar ratio between CBQCA and peptide was found to be 75:1, and 50 mmol/L borate buffer (pH 9.2) was used for the derivatization in order to achieve good efficiency. Three imidazole dipeptides were baseline-separated within 20 min by using 112 mmol/L sodium borate (pH 10.4-10.8) as running buffer. Concentration detection limits (signal-to-noise ratios) for carnosine, anserine, and homocarnosine were 4.73, 4.37, and 3.94 nmol/L, respectively. This method has been applied to the analysis of human cerebrospinal fluid (CSF) and meat dry powder of pig and sheep. Recoveries were in the range of 82.9-104.8% for homocarnosine in CSF. For carnosine and anserine, the recoveries are 98.3% and 80.2% in meat dry powder of pig and 111.2% and 112.8% in meat dry powder of sheep, respectively.     

Direct dynamics study of the hydrogen abstraction reaction of CF3CH2Cl + Cl → CF3CHCl + HCl

The hydrogen abstraction reaction of Cl atoms with CF₃CH₂Cl (HCFC‐133a) is investigated by using density function theory and ab initio approach, and the rate constants are calculated by using the dual‐level direct dynamics method. Optimized geometries and frequencies of reactants, transition state, and products are computed at the B3LYP/6‐311+G(2d,2p) level. To refine the energetic information along the minimum energy path, single‐point energy calculations are carried out at the G3(MP2) level of theory. The interpolated single‐point energy method is employed to correct the energy profiles for the title reaction. The rate constants are evaluated by using the canonical variational transition state theory with a small‐curvature tunneling correction over a wide range of temperature, 200–2000 K. The variational effect for the reaction is moderate at low temperatures and very small at high temperatures. However, the tunneling correction has an important contribution in the lower temperature range. The agreement between calculated rate constants and available experimental values is good at lower temperatures but diverges significantly at higher temperatures. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 661–667, 2012     

一个2+1维可积方程的代数几何解

该文从1+1维的孤子方程出发,构造出一个2+1维在Lax意义下可积的方程.接着这个2+1维可积方程被分解为可解的常微分方程.随后引入超椭圆Riemann曲面和Abel-Jacobi坐标把流进行了拉直.再利用Riemannθ函数给出了这个2+1维方程的代数几何解.     

Explicit exact solutions for a new generalized Hamiltonian amplitude equation with nonlinear terms of any order

Making use of a proper transformation and a generalized ansatz, we consider a new generalized Hamiltonian amplitude equation with nonlinear terms of any order, iu_x + u_tt + (|u|^p + |u|^2p)u + u_xt = 0. As a result, many explicit exact solutions, which include kink-shaped soliton solutions, bell-shaped soliton solutions, periodic wave solutions, the combined formal solitary wave solutions and rational solutions, are obtained.Received: April 4, 2002     

焦酚对蓝藻和绿藻生长、光合色素及微量元素的作用

研究了焦酚对4种常见蓝藻和绿藻的生长影响.结果表明,焦酚对几种藻的生长具有抑制作用.相同的处理浓度,4种藻生长率从小到大依次是:铜绿微囊藻(Microcystic aeruginosa )、羊角月牙藻(Selenastrum capricornutum)、蛋白核小球藻(Chlorella pyrenoidosa)、水华鱼腥藻(Anabaena flos-aquae).焦酚作用后铜绿微囊藻和羊角月牙藻的叶绿素a和胡萝卜素的含量有显著的变化,随着焦酚浓度的升高,铜绿微囊藻和羊角月牙藻叶绿素a和胡萝卜素含量减少,并且变化的趋势与生长率相一致.其中铜绿微囊藻的类胡萝卜素含量的减少比叶绿素a快.焦酚作用72 h,铜绿微囊藻和羊角月牙藻体内的铁、锰、铜及锌等元素的含量都表现出下降的趋势,其中焦酚对铜绿微囊藻体内微量元素的减少影响更大.焦酚抑制藻的光合作用、减少藻类对微量元素的吸收是其抑制藻类生长的机制之一.     

A Biomass-Ligand-Based Ru(III) Complex as a Catalyst for Cycloaddition of CO2 and Epoxides to Cyclic Carbonates and a Study of the Mechanism

Aiming highly efficient conversion of greenhouse gas CO₂ to cyclic carbonates, a biomass Ru(III) Schiff base complex catalyst ( SalRu ) was constructed by employing a derivative of Lignin degradation (5-aldehyde vanillin). The SalRu catalyst had a remarkable conversion for epoxides into corresponding cyclic carbonates even at atmospheric pressure of CO₂ without the presence of co-catalyst. As the condition at 120 °C and 2 MPa CO₂ the conversion reached to 94 % with selectivity at 99 % after 8 h. 32 % cyclic carbonate production was obtained even under 0.2 MPa CO₂ pressure. The epoxide activation and ring opening, CO₂ insertion and cyclic carbonate formation were illuminated explicitly through the of characteristic absorption peaks changing, which further providing direct and visual evidence for the mechanism proposing. This study has important theoretical significance for the comprehensive utilization of environmental pollutants and energy.