Syntheses,Crystal Structures and Magnetic Properties of Two New Low-dimensional Manganese (Ⅱ) Coordination Compounds

Two new low-dimensional Mn(Ⅱ) coordination compounds of Mn(H_2pimdc)_2(phen)(compound 1) and [Mn(Hpimdc)(phen)]n·nH_2O(compound 2) were synthesized, where H_3pimdc is a 2-propyl-imidazole-4,5-dicarboxylic acid and phen is 1,10-phenanthroline. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, element analysis, IR spectra, PXRD and thermal analysis. X-ray single-crystal diffraction analyses indicate that the phen ligands terminate metal ions on two sides to prevent the linkage between the neighboring metal ions into a higher dimensional structure in compounds 1 and 2. Compound 1 is constructed from mononuclear molecules which form the 1D helical supramolecular chain by N–H···O hydrogen bonds. In compound 2, Hpimdc is a tetradentate bridging ligand, which binds Mn(Ⅱ) ions to generate a single-stranded right helical chain parallel to the b axis. These 1D chains are additionally coupled by H-bonds as well as π···π stacking interactions, which formed a 3D supramolecular structure. Additionally, compound 2 demonstrated temperature-dependent magnetic susceptibility and negative value of θ(equal to –9.09 K), which is indicative of weak antiferromagnetic interactions between Mn(Ⅱ) ions.     

氧化石墨烯调控钼酸铋在可见光下选择性光催化降解环境水中的抗生素

以氧化石墨烯(GO)作为增强光催化剂活性的调节剂, 采用一步水热法制备钼酸铋/氧化石墨烯(Bi₂MoO₆/GO)异质结光催化剂, 其可见光响应拓展至570 nm, 带隙能降至2.56 eV. 当m_Bi2MoO6/m_GO=100∶1时, Bi₂MoO₆/GO(100∶1)光催化剂在可见光的辐射下, 对水溶液中四环素和喹诺酮类抗生素选择性的高效催化降解去除能力为Bi₂MoO₆的2.1倍. Bi₂MoO₆/GO(100∶1)光催化剂活性的提高依赖于范德华力作用下的二维Bi₂MoO₆纳米片-二维GO纳米片界面的紧密接触. 有效的界面接触改善了光生电子的转移和光生载流子的分离. 自由基清除实验结果表明, ?OH起主要作用. 结合高效液相色谱-质谱(HPLC-MS)法对降解产物的分析, 提出了不同光催化剂催化降解恩诺沙星具有相似的降解途径和降解产物.     

Co_2Si@C催化剂的合成及其加氢脱硫性能

采用微波法制备了Co_2Si@C催化剂并对其在加氢脱硫反应中的催化性能进行了研究.通过XRD、 XPS、 TEM和N_2-物理吸附表征分析Co_2Si@C催化剂的组成和结构. Co_2Si@C催化剂具有一致的介孔结构,高钴含量(21%)、高比表面积(116.6 m~2·g~(-1))和均匀分布的纳米粒子.由于硅原子对钴原子结构和参数的修饰、纳米粒子效应和高金属含量等因素, Co_2Si@C催化剂在温和的反应条件下(340℃和3.0 MPa)具有良好的加氢脱硫活性和对直接脱硫(DDS)反应途径的高选择性,产物联苯的选择性超过了60%.     

同结构GdIIIMII(M=Cu，Ni，Co，Fe，Mn)配合物磁性理论研究

基于DFT-BS方法,在不同泛函方法和基组下计算[CuIIGdIII{pyCO(OEt)py C(OH)(OEt)py}3]2+及3d-Gd异金属配合物的磁耦合常数,结果表明,PBE0/TZVP(Gd为SARC-DKH-TZVP)水平可用于描述其磁学性质。顺磁中心CuII、GdIII与桥联配位氧原子间存在较强的轨道相互作用,其磁轨道主要由GdIII的4fz3、4fz(x2-y2)轨道、CuII的3dx2-y2轨道和桥联配位原子O的p轨道组成。顺磁中心CuII离子以自旋离域作用为主,GdIII离子以自旋极化作用为主,顺磁中心CuII自旋离域作用对桥联氧原子的影响大于顺磁中心GdIII的自旋极化作用。在同结构3d-Gd配合物中,随着MII离子未成对电子的增加,顺磁中心间自旋密度平方差越大,顺磁中心MII和GdIII之间的反铁磁性贡献越大,其磁耦合常数越小。     

神经元的形态分类和识别

对神经元特性的认识,最基本问题是神经元的分类.神经元的形态复杂多样,神经元的识别分类问题有相当的困难.对提供的参考数据进行统计分析,将其转化成对应每类神经元的空间形态的指标参数,然后对每个指标进行定性分析和对比分析,确定对各类型神经元细胞识别起关键作用的指标,利用层次分析法、图形截面、几何相似性等分析方法建立神经元的分类模型.分类模型能够将附录提供的神经元进行准确的分类.数据分析采用开源科学计算软件Scilab进行处理,运行环境为Scilab5.2,部分代码采用C#基于VS2008开发.     

Banach空间中带Poisson跳的随机种群方程的数值分析

本文研究Banach空间中带Poisson跳的随机种群方程,通过离散使之成为随机微分方程,进而运用显式Euler公式来分析其数值解与解析解的误差.     

Preparation, characterization and MRI application of carboxymethyl dextran coated magnetic nanoparticles

Superparamagnetic nanoparticles functionalized with carboxymethyl dextran (CM-dextran) were synthesized by a two-step method. First, the magnetic nanoparticles (MNPs) coated with dextran (M_w ≈ 20000) were prepared by co-precipitation of Fe²⁺ and Fe³⁺ ions. Then, dextran on the surface of MNPs reacted with monochloroacetic acid (MCA) in alkaline condition. The influences of temperature and reactant concentration on the amount of -COOH on the surface of nanoparticles were systematically studied. The obtained MNPs coated with CM-dextran were stable over the entire range of pH and NaCl concentration. The MRI experiment indicated that the CM-dextran MNPs could potentially be used as MRI contrast agents for magnetic resonance molecular imaging.     

Single-molecule conductance measurement of self-assembled organic monolayers using scanning tunneling spectroscopy in combination with statistics analysis

Based on ambient atmosphere scanning tunneling microscope (STM) technique, scanning tunneling spectroscopy (STS) combined with statistics analysis was developed to investigate the single-molecule conductance of various kinds of molecules which were self-assembled on the Au (1 1 1). Conductance histograms obtained from current-voltage curves revealed well-defined peaks at integer multiples of a fundamental conductance and were used to identify the conductance of a single molecule. The conductances of saturated molecules like 1,8-octanedithol and hexanethiocyanate were found to be 0.072 × 10⁻⁴G₀ and 0.06 × 10⁻⁴G₀ respectively and 0.23 × 10⁻⁴G₀ and 0.13 × 10⁻⁴G₀ for unsaturated molecules like 5,5′-dithiol- 2,2′,5′,2″-terthiophene and 4,4′-dithio-tert(phenylene ethylene).     

Direct α-alkylation of ketones with primary alcohols catalyzed by iridium–CNP complex

The α-alkylation of ketones with primary alcohols was realized by CC cross-coupling with iridium–CNP complexes as catalyst. This reaction proceeds via dehydrogenation reactions, aldol condensation, and hydrogenation using the borrowed hydrogen atoms from alcohols. The pyridyl methanols and other heterocyclic substituted methanols, especially alkyl alcohols, were also suitable for this transformation.     

Total synthesis of (±)-antofine

An efficient preparation of (±)-antofine is described. The main steps involved in this synthesis are the Horner–Wadsworth–Emmons reaction, the intramolecular Schmidt reaction of an azido aldehyde, and the one-pot deprotection of the N-formyl group, followed by Pictet–Spengler cyclization. The asymmetric hydrogenation of the trisubstituted α,β-unsaturated ester is also explored, however only moderate enantio-control (55% ee) is obtained. Finally, (±)-antofine is prepared in six steps from the phenanthryl aldehyde 5 with an overall yield of 35%.