基于XPS对硫铁矿去除SeO2-3的机理研究

硒是动植物及人体生长必需的十五种微量元素之一，具有清除体内自由基、抗氧化、增强免疫力等功能，但其安全剂量的范围却很窄。利用扫描电子显微镜（SEM）和X射线衍射仪（XRD）对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体，粒径范围在17～200 nm之间，平均粒径138 nm。XRD衍射图谱中的特征峰与FeS₂衍射图谱中各峰位置基本一致，因此判定硫铁矿中主要化学组分为FeS₂，且图谱中基本没有杂峰，表明制备过程中并未混入杂质，样品纯度较高。实验结果表明，该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪（XPS）对硫铁矿去除水体中SeO2-₃的机理进行了研究。研究结果表明, （1）在较为广泛的实验pH范围（pH 2.2～11.5），硫铁矿均能有效去除水体中SeO2-₃，去除效率（除pH值7.8以外）均达到90%以上；（2）硫铁矿与SeO2-₃发生反应后，其主要组成元素的XPS特征峰结合能有所减小，表明硫铁矿表面发生了一定化学变化；（3）酸碱环境下硫铁矿去除SeO2-₃的机理不完全相同，酸性环境下，硫铁矿对SeO2-₃的去除是单纯的氧化还原过程，即硫铁矿中被酸活化的S2-₂将SeO2-₃还原为单质Se(0)，并且酸性越强，SeO2-₃去除效果越好；碱性环境下，SeO2-₃的去除过程中氧化还原与络合反应并存，硫铁矿表面有络合态Fe(OH)SeO₃和单质Se(0)两种存在形态，且碱性越强，络合态Fe(OH)SeO₃含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-₃为代表的可变价金属阴离子提供重要理论依据和应用基础。     

Syntheses,crystal structures and properties of Cd(II) and Ag(I) complexes based on 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole

Abstract

Complexes of [CdL₂(NO₃)₂]·1.5H₂O and [Ag₂(μ-L)₂(NO₃)₂] were synthesized by the reactions of 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole (L) with Cd(NO₃)₂·4H₂O and AgNO₃, respectively. Their structures were determined by single crystal X-ray diffraction. The photophysical property and thermal stability were characterized by FT???IR, UV???Vis absorption, fluorescence, and thermogravimetric analysis (TGA). Both complexes belong to the triclinic system with space group p???1. The central metal of [CdL₂(NO₃)₂]·1.5H₂O has a distorted octahedral geometry [CdN₄O₂], while two central Ag(I) atoms of [Ag₂(μ-L)₂(NO₃)₂] exhibit distorted tetrahedral geometries [AgN₃O].     

Theoretical study of (e,2e) triple differential cross sections of pyrimidine and tetrahydrofurfuryl alcohol molecules using multi-center distorted-wave method

We report theoretical studies of electron impact triple differential cross sections of two bio-molecules,pyrimidine and tetrahydrofurfuryl alcohol,in the coplanar asymmetric kinematic conditions with the impact energy of 250 eV and ejected electron energy of 20 eV at three scattering angles of-5°,-10°,and-15°.Present multi-center distorted-wave method well describes the experimental data,which was obtained by performing(e,2e)experiment.The calculations show that the secondary electron produced by the primary impact electron is strongly influenced by the molecular ionic multi-center potential,which must be considered when the low energy electron interacts with DNA analogues.     

Thermal gradient induced sidebranching in directional solidification

The polycrystalline perovskitelike manganese oxides La_1-xA_xMnO (A = Na, and K, ) have been fabricated by sol-gel technique. For all the compositions explored in this work, the average manganese oxidation state is practically constant, at for A = Na, and for A = K, respectively. A close relationship is confirmed to hold between the Curie temperature (T_c) and the bond distance of Mn-O. Results of magnetic measurements show that these materials can be utilized as suitable candidates for magnetic refrigerants with wide applied temperature span, for their significant entropy change and the easily tuned Curie temperature. Received: 12 September 1997 / Revised: 18 December 1997 / Accepted: 21 January 1998     

First excitations of the spin 1/2 Heisenberg antiferromagnet on the kagomé lattice

We study the exact low energy spectra of the spin 1/2 Heisenberg antiferromagnet on small samples of the kagomé lattice of up to N=36 sites. In agreement with the conclusions of previous authors, we find that these low energy spectra contradict the hypothesis of Néel type long range order. Certainly, the ground state of this system is a spin liquid, but its properties are rather unusual. The magnetic () excitations are separated from the ground state by a gap. However, this gap is filled with nonmagnetic () excitations. In the thermodynamic limit the spectrum of these nonmagnetic excitations will presumably develop into a gapless continuum adjacent to the ground state. Surprisingly, the eigenstates of samples with an odd number of sites, i.e. samples with an unsaturated spin, exhibit symmetries which could support long range chiral order. We do not know if these states will be true thermodynamic states or only metastable ones. In any case, the low energy properties of the spin 1/2 Heisenberg antiferromagnet on the kagomé lattice clearly distinguish this system from either a short range RVB spin liquid or a standard chiral spin liquid. Presumably they are facets of a generically new state of frustrated two-dimensional quantum antiferromagnets. Received: 27 November 1997 / Accepted: 29 January 1998     

二维位置灵敏探测器输出图像畸变的修正

高分辨(e,2e)谱仪采用二维位置灵敏探测器同时对能量和角度进行多道测量.二维位置灵敏探测器由级联使用的微通道板和电阻阳极板组成,由于电阻阳极板的边缘效应和制造工艺的缺陷,测量得到的位置图像与实际图像总会有一定的形变,存在一定的非线性.本文针对高分辨(e,2e)谱仪二维位置灵敏探测器输出图像的“桶形”畸变及位置非线性,采用一种简易的冷刻法(用脉冲信号来模拟真实电子束团),检验了二维位置灵敏探测器的Gear型电阻阳极板的线性好坏,并用分割成小三角形的方法找出测量得到的畸变图像与原始真实图像的映射关系,再用此关系对其它测量得到的畸变图像进行修正,并对修正的结果进行了评估.通过修正,由“桶形”畸变所造成的图像扭曲得到明显改善.修正后的x方向非线性由修正前的2.1%变为0.59%.这种检验和修正方法对其它领域类似探测器输出图像的修正也有一定的指导意义.     

基于小波变换和数学形态学的运动物体检测

提出了一种基于帧差法和小波变换相结合的运动目标检测方法，充分利用帧差法计算简单和小波变换的多尺度特性。实验表明，这种方法可以有效地从复杂自然场景的图像序列中检测出完整的运动目标。而且能够有效的抑制噪声。同时减少计算时间，满足检测的实时性要求。     

2-(2-喹啉偶氮)-5-二甲氨基苯胺光度法测定铜

在pH=4.0的磷酸盐缓冲介质中,CTMAB存在下,2-(2-喹啉偶氮)-5-二甲氨基苯胺(QADMAA)与铜反应生成2:1稳定络合物,络合物λmax=580nm,ε=1.14×105L·mol-1·cm-1.铜含量在0.01-0.6μg/mL内符合比耳定律,方法用于环境样品中铜的测定,结果令人满意.     

Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.