Aggregate manganese Schiff base moieties by terephthalate or acetate: dinuclear manganese and trinuclear mixed metal Mn2/Na complexes

A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn(2)(mu-phth)(CH(3)OH)(H(2)O) (3), and (salen)(2)Mn(2)(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH(3)OH)(NO(3)) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H[Mn(2)Na(salpn)(2)(mu-OAc)(2)(H(2)O)(2)](OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. (1)H NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/-0.12V has been assigned to the redox of Mn(2)(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.     

A novel definition of the overall hyper-wiener index for unsaturated hydrocarbons

By replacing the distances between pairs of vertices with the relative distances, we define a novel overall hyper-Wiener index (NOR); the novel overall hyper-Wiener index extends the usefulness of the hyper-Wiener index and the overall hyper-Wiener index to unsaturated hydrocarbons.     

Syntheses and structural characterizations of Fe4S4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl₂, tetrathiometallate and cycloalkylthiolate, two Fe₄S₄ cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH₂NMe₃)₂ [ Fe₄S₄ (SC₅H₉)₄] (I), monoclinic space groupP2₁/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et₄N)₂[F₄S4(SC₆H_lI)₄] (II), tetragod space group ,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, D_obs = 1. 28 g/cm³, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe₄S₄ core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe₄S₄ cluster dianion is also discussed. Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China.     

Application of artificial neural networks in multivariable optimization of an on-line microwave FIA system for catalytic kinetic determination of iridium(III)

A new rapid, selective and sensitive on-line microwave flow injection-kinetic method was developed for spectrophotometric determination of micro amounts of Ir(III), based on its catalytic effect on the m-acetylchlorophosphonazo (CPA-mA) and KIO(4) reaction in NaOH media. An on-line microwave oven was employed to accelerate the reaction. The reaction was followed spectrophotometrically by measuring the decrease of the absorbance of CPA-mA at 580 nm. The effect of five variables for the determination of Ir(III) was optimized by means of a multilayer artificial neural network using extended delta-bar-delta (EDBD) algorithms. Under the optimum experimental conditions, Ir(III) could be determined in the range 0.060-0.60 micro gZZZ;mL(-1) with detection limit of 0.02 micro gZZZ;mL(-1) and the sampling frequency of 34 h(-1). The proposed method was applied to the determination of micro amounts of Ir(III) in refined ore and secondary alloy with the recoveries from 91.4% to 109%.     

锗元素测定方法综述

锗在国防工业、航空航天和通信等领域中的战略性,锗含量的测定对于保证材料质量和满足国际标准至关重要。本文综述了锗含量测定方法的多种技术,包括分光光度法、原子荧光光谱法、原子吸收光谱法、电感耦合等离子体原子发射光谱法、电感耦合等离子体质谱法以及滴定法。在每个检测方法的介绍中,详细探讨了方法的原理、前处理步骤以及应用范围,并分别总结了各个方法的优势和不足。最后,强调了锗含量测定方法的意义,特别是在满足出口监管和促进科学研究方面的作用。同时对锗元素的测定方法进行了展望,为未来的发展提供了参考方向。     

HIGH-FREQUENCY VIBRATIONS OF CORRUGATED CYLINDRICAL PIEZOELECTRIC SHELLS

Coupled extensional and flexural cylindrical vibrations of a corrugated cylindrical piezoelectric shell consisting of multiple pieces of circular cylindrical surfaces smoothly connected along their generatrix are studied. To validate the results for the case of relatively thick shells or equivalently high-frequency modes with short wavelengths, existing analysis is extended by considering shear deformation and rotatory inertia. An analytical solution is obtained. Based on the solution, resonant frequencies and mode shapes are calculated.     

杜氏盐藻多糖的高效体积排阻色谱的保留特性及其分析方法的研究

通过对从杜氏盐藻中提取出的不同多糖级分在高效体积排阻色谱柱(Waters Ultrahydragel Linear,7.8 mm i.d.×300 mm,2根串联)上的保留特性的考察及其分离分析条件的优化,建立了高效体积排阻色谱分析盐藻多糖平均相对分子质量及其分布的方法。结果表明:流动相中盐的种类及其浓度、pH值对3种酸性多糖级分(特别是硫酸化多糖级分PD4a)的保留行为有显著影响;在柱温为45 ℃,流速为0.9 mL/min条件下,使用0.1 mol/L的NaAc水溶液作流动相基本上能消除非特异性吸附作用及分子间缔合等因素的干扰,使各多糖级分基本以非缔合状态按立体排除机制保留和分离。在优化的色谱条件下,测得的盐藻多糖5个级分的重均相对分子质量(Mw)分别为1548000,33000,67000,424000,10000;测得的硫酸化多糖级分PD4a的Mw和峰面积的相对标准偏差分别为1.7%和 0.88%(n=5)。     

Metal‐Organic Gels Based on Carboxyl‐Functionalized Benzimidazole and Their Stimuli Responsivenesses

Three multi‐responsiveness supramolecular metal‐organic gels (MOGs) have been prepared upon Ba(OAc)₂, CdSO₄·8H₂O and Pb(NO₃)₂ with a simple ligand (G17) based on a carboxyl‐functionalized benzimidazole derivative in alcoholic‐water solutions. The MOGs display the formation of well‐developed nanofibrillar networks composed of intertwined fibers which provide stability to gels structures through coordination, hydrogen bonding and π‐ π interactions characterized by using field emission scanning electron microscopy (FESEM), the fourier transform infrared (FT‐IR) spectroscopy and powder X‐ray diffraction (XRD) techniques. MOG‐1 shows good stimuli responsiveness toward the changes in K₂CrO₄, both MOG‐2 and MOG‐3 do good job toward the changes in Na₂S. Moreover, because these MOGs were formed easily by gelator with some heavy metal ion, such as Cd(II) and Pb(II), it might provide the basis for heavy metal ion capture and removal.     

In situ scanning FTIR microscopy and IR imaging of Pt electrode surface towards CO adsorption

In situ scanning FTIR microscopy was built up for the first time in the present work, which consists of an FTIR apparatus, an IR microscope, an X-Y mapping stage, and the specially designed electrochemical IR cell and computer software. It has been demonstrated that this new space-resolvd in situ IR technique can be used to study vibration properties of micro-area, and to perform IR imaging of electrode surface. The chemical image obtained using this technique fur CO adsorption on Pt electrode illustrated, at a space-resolution of 10~(-2) cm, the inhomogeneity and the distribution of reactivity of micro-area of electrode surface.