A Cu(Ⅱ) Complex with IM-MeImz-к2 N,O Mode in [Cu(IM-MeImz)2]·(SCN)2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.     

Scanning force microscopy based rapid force curve acquisition on supported lipid bilayers: experiments and simulations using pulsed force mode.

In situ pulsed force mode scanning force microscopy (PFM-SFM) images of phase separated solid-supported lipid bilayers are discussed with the help of computer simulations. Simultaneous imaging of material properties and topography in a liquid environment by means of PFM-SFM is severely hampered by hydrodynamic damping of the cantilever. Stiffness and adhesion images of solid-supported membranes consisting of cholesterol, sphingomyelin, and 1,2-dioleyl-phosphatidylcholine obtained in aqueous solution exhibit contrast inversion of adhesion and stiff. ness images depending on parameters such as driving frequency, amplitude, and trigger setting. Simulations using a simple harmonic oscillator model explain experimental findings and give a deeper insight into the way PFM-SFM experiments have to be performed in order to obtain interpretable results and hence pave the way for reliable material contrast imaging at high speed.     

“双一流”背景下高等农业院校有机化学基础课程教学新模式的构建及实践

The crop science of Sichuan Agricultural University is an authorized first-class discipline. As the strategic supporting department for innovative talent cultivation in agriculture and forestry major, we are facing a long-term challenge in reforming the teaching mode for basic course-organic chemistry and cultivating talented students with solid basic knowledge and strong sense of innovation. Herein a thorough survey was performing to establish the executable teaching programs for this course during the "Double-First Class Universities Plan" period. A multidimensional teaching resource library for organic chemistry course was also constructed. The new classroom teaching mode "Interest cultivation-Creative thought development-Autonomous and Cooperative learning", along with a stepwise practice teaching mode "Foundation skills-Integrated application-Innovative trial" was proposed and practiced among thirty-five majors including agriculture, forestry and veterinary, to improve the quality for innovative talent cultivation and support our first-class discipline construction. This research could probably serve as a reference for congeneric agricultural university.     

喜树碱类抗肿瘤药物作用模式的柔性分子对接研究

研究采用柔性分子对接技术，将15个喜树碱类化合物对接到拓扑异构酶I (Topo I)-DNA切割复合物中，从原子水平和分子力场角度阐明了喜树碱类抗肿瘤药 物与DNA，Topo I的相互作用机制。研究发现，喜树碱分子插入Topp I-DNA复合物 的切割位点，并与Asn722，Asp533，Lys532和Lys720形成氢键作用网络。定量构效 关系研究进一步表明喜树碱分子可以与Topo I-DNA切割复合物形成电荷迁移作用。 该对接模型系统解释了喜树碱类化合物的构效关系、定点突变等诸多实验事实，为 下一步设计、合成新型高效的喜树碱类衍生物打下了坚实基础。     

Voltammetric study of the interaction of lomefloxacin (LMF)–Mg(II) complex with DNA and its analytical application

The voltammetric behavior of the LMF-Mg(II) complex with DNA at a mercury electrode is reported for the first time. In NH₃–NH₄Cl buffer (pH=9.10), the adsorption phenomena of the LMF–Mg(II) complex were observed by linear sweep voltammetry. The mechanism of the electrode reaction was found to be a reduction of LMF in the complex, and the composition of the LMF–Mg(II) complex is 2:1. In the presence of calf thymus DNA (ctDNA), the peak current of LMF–Mg(II) complex decreased considerably, and a new well-defined adsorptive reduction peak appeared at −1.63 V (vs. SCE). The electrochemical kinetic parameters and the binding number of LMF–Mg(II) with ctDNA were also obtained. Moreover, the new peak currents of LMF–Mg(II)–DNA system increased linearly correlated to the concentration of DNA in the 4.00×10⁻⁷–2.60×10⁻⁶ g ml⁻¹ range when the concentrations of LMF–Mg(II) complex was fixed at 5.00×10⁻⁶ mol l⁻¹, with the detection limits of 2.33×10⁻⁷ g ml⁻¹. An electrostatic interaction was suggested by electrochemical method.     

Theoretical Study of Reaction Mechanism of 1-Propenyl Radical with NO

The reaction system of 1-propenyl radical with NO is an ideal model for studying the intermolecular and intramolecular reactions of complex organic free radicals containing C=C double bonds. On the basis of the full optimization of all species with the Gaussian 98 package at the B3LYP/6-311++G** level, the reaction mechanism was elucidated extensively using the vibrational mode analysis. There are seven reaction pathways and five sets of small molecule end products: CH2O+CH3CN, CH2CHCN+H2O, CH3CHO+HCN, CH3CHO+HNC, and CH3CCH+HNO. The channel of C3H5￠+NO→ IM1→TS1→IM2→TS2→IM3→TS3→CH3CHO+HCN is thermodynamically most favorable.     

四角点简支双稳态层合板振动特性研究

双稳态层合板作为一种柔性可变体结构,为实现振动状态下的构型调控,将对其开展固有振动特性的研究.本文以四角点简支约束的矩形非对称铺设双稳态板作为研究对象,运用最小势能原理、一阶剪切变形理论、以及冯卡门几何非线性位移应变关系,得到双稳态板的两种稳态构型.首次给出了适合于四点简支的6参数构型函数与17参数构型函数,研究对比发现对于稳态构型采用17参数的构型函数结果相对更精确;对于应用线性位移应变关系的基于任一稳态构型下振动固有特性而言,这两种构型函数得到的结果基频相差2%,其它阶次频率相差也不大.随后采用6参数构型函数得到的稳态构型研究了几何尺寸、铺层数分别对两种稳态构型固有振动特性的影响.本研究对于进一步研究该类结构动态跳变机理具有重要意义.     

变质砂板岩Ⅰ型断裂韧度各向异性初探

Ⅰ型断裂韧度是岩石的主要特征力学参数,且影响因素很多。目前,国内可查的细观层理对岩石Ⅰ型断裂韧度影响的相关研究较少。试验利用隧道开挖中的变质砂板岩,测试了横向、纵向和无细观层理砂板岩纵波波速,并采用三点弯曲圆梁方法研究了相应砂板岩试件的Ⅰ型断裂力学性质。试验表明KIC、断裂破坏挠度、细观层理和纵波波速间存在相关关系,根据试验成果提出各向异性系数Y的概念,利用各向异性系数Y计算的K’IC值与实测的相应试件KIC符合较好。     

Ⅰ型裂纹中低速冲击荷载下起裂韧度测试新方法

为了探寻更加合理的构型试件来研究纯Ⅰ型裂纹在冲击荷载下的起裂及扩展行为, 提出一种新构型试件, 即双倾斜底边中心裂纹试件(double inclined bottom central cracked, DIBCC)。借助于中低速落锤式冲击实验装置进行冲击实验, 通过应力波来使试件内预制裂纹起裂并扩展, 同时利用应变片测试系统监测裂纹起裂时刻, 并采用AUTODYN有限差分软件对实验过程进行数值模拟, 最后计算裂纹的动态应力强度因子, 利用实验测得的起裂时刻, 确定试件的起裂韧度。结果表明:(1)在反射拉伸波作用下, 预制裂纹两侧会产生垂直于裂纹面向外的位移, 使预制裂纹扩张, 从而使裂纹起裂。(2)数值模拟结果与实验结果在裂纹扩展路径上具有一致性, 说明本文中提出的DIBCC构型试件有效, 可以用来测试裂纹在冲击载荷下的断裂韧度。

     

原子力显微镜轻敲模式下由液桥引起的能量耗散

轻敲模式下的相位像反映的是探针样品间接触分离过程的能量耗散, 大气环境下的能量耗散主要由液桥引起. 因此为理解成像机理, 本文分析轻敲模式下液桥的形成和破碎的动力学过程, 得到此种模式下的耗散能.