流动注射区域采样法测定镀锌钝化液中高浓度锌

本文建立了流动注射二甲酚橙光度法测定镀锌纯化液中Ｚｎ￣２＋的自动分析方法。利用区域采样技术和调整管路参数自动完成对样品的上千倍稀释，确定了最佳分析条件并研究了干扰离子的影响及消除办法。所建方法仪器简单，分析速度为８４次／小时，变异系数（Ｚｎ￣２＋１６．０ｇ／Ｌ，ｎ＝２０）为１．Ｏ％，用于实际钝化液分析，相对误差小于±１０％。     

Random copolymerization of macromonomers as a versatile strategy to synthesize mixed-graft block copolymers

The random copolymerization of norbornene-functionalized macromonomers was explored as a method of synthesizing mixed-graft block copolymers (mGBCPs). The copolymerization kinetics of a model system of polystyrene (PS) and poly(lactic acid) (PLA) macromonomers was first analyzed, revealing a gradient composition of side chains along the mGBCP backbone. The phase separation behavior of mGBCPs with PS and PLA side chains of various backbone lengths and side chain molar ratios was investigated, and increasing the backbone length was found to stabilize the phase-separated nanostructures. The graft architecture was also demonstrated to improve the processability of the mGBCP, compared to a linear counterpart. Investigations of mGBCPs comprised of polydimethylsiloxane and poly(ethylene oxide) side chains exemplified the diverse self-assembled morphologies, including a Frank-Kasper A15 phase, that can be obtained with mGBCPs synthesized by random copolymerization of macromonomers. Lastly, a ternary mGBCP was synthesized by the copolymerization of three macromonomers.     

基于响应面法的直拉硅单晶生长工艺参数优化方法

在直拉法制备硅单晶的过程中,要得到优质的晶体必须建立合理的温度分布,而单晶炉内热场的分布与工艺参数的设定密切相关.其中以晶体转速、坩埚转速和拉速等三个工艺参数对热场分布的影响尤为显著.为了确定最佳热场分布下晶转、埚转及拉速的设定值,本文采用响应面算法通过方程拟合、回归分析等步骤求解这三个工艺参量与温度梯度之间的最佳函数模型,并在该模型下同时对这三个工艺参量进行优化分析,且通过仿真实验和拉晶实验表明该方法的有效性.     

Structural characterization of two lanthanide complexes attached to [H<Subscript>2</Subscript>W<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>6−</Superscript>

In this article, two compounds [H₂bpy][Ln(DMF)₄(H₂O)₃(Hbpy)][H₂W₁₂O₄₀] (Ln = La,Ce; DMF = N,N-dimethylformamide, bpy = 4,4′-bipyridine) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectra, and TG analysis. X-Ray analysis showed that the [Ln(DMF)₄(H₂O)₃(Hbpy)]⁴⁺ unit is supported on the α-Keggin polyoxoanion [H₂W₁₂O₄₀]⁶⁻ via the surface bridging oxygen atom. The [H₂bpy][Ln(DMF)₄(H₂O)₃(Hbpy)][H₂W₁₂O₄₀] entity is further extended into 2D supramolecular networks with 1-D channels by hydrogen-bonding interactions, in which 4,4′-bipy ligands reside. To the best of our knowledge, these complexes represent the first examples of rare earth metal-organic complex-decorated α-metatungstate clusters. Furthermore, the electrochemical properties of these compounds have been studied via the method of bulk-modified carbon paste electrodes.     

稀土元素对人肝癌细胞SMMC-7721增殖的影响

用MTT法研究了14种稀土元素(La，Ce，Pr，Nd，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb和Lu)对人肝癌细胞SMMC-7721增殖的影响。他们对肝癌细胞的生长作用可分为3类。其中La^3 、Ce^3 和Eu^3 对肝癌细胞的增殖有剂量依赖性正效应，能够在一定浓度范围内刺激细胞生长；Sm^3 ，Gd^3 ，Ho^3 ，Er^3 ，Yb^3 对肝癌细胞生长的刺激作用没有剂量依赖性特征；而Pr^3 ，Nd^3 ，Tb^3 ，Dy^3 ，Tm^3 和Lu^3 则表现出对肝癌细胞的增殖具有不用程度的抑制。推测14种稀土元素作用方式的不同与他们的原子结构有一定的关系，它们对肝癌细胞的相对增殖率随着原子序数的增加呈现出一定的规律性。     

中药土鳖虫溶栓成分的分离纯化研究

对土鳖虫水浸醇沉提取物2号样品进行了离子交换柱层析，得组分Ⅰ、Ⅱ、Ⅲ。实验结果表明，组分Ⅲ的溶栓活性明显高于组分Ⅰ和组分Ⅱ，其蛋白质占量为88．9％，分子量约为38，018，效价为313UK／mg，比活力为352UK／mg蛋白。将组分Ⅲ再进行凝胶过滤柱层析，得组分Ⅳ、Ⅴ、Ⅵ。组分Ⅵ的生物活性高于组分Ⅳ和组分Ⅴ，蛋白质含量为89．3％，电泳呈现两条带，分子量约为34，623和39，811，效价为77UK／mg，比活力为86UK／mg蛋白。将组分Ⅵ进行反相高效液相色谱柱层析，收集保留时间为17min的洗脱峰，得到土鳖虫纯蛋白质，呈白色絮状，极易溶于水。再一次用反相高效液相色谱检查其纯度，保留时间为17．073min．无杂质峰。纤溶活性实验结果表明，组分Ⅵ既有直接降解纤维蛋白的作用，同时也有纤溶酶原激活剂样作用。     

Synthesis and Crystal Structures of Antimony(III) Complexes With a Bis(amino)silane Ligand

Bis(amino)silane bearing bulky substituents on nitrogen, LH₂ [L = Me₂Si(NDipp)₂, Dipp = 2, 6‐diisopropylphenyl] was reacted with nBuLi (ratio 1:1 and 1:2) in toluene. The Me₂Si(LiNDipp)₂ was treated with SbCl₃ in a 1:1 ratio to yield the four‐membered SiN₂Sb ring compound of composition [η²(N,N)‐Me₂Si(NDipp)₂SbCl] ( 1 ). The mono lithiated bis(amino)silane was used to synthesize the monodentate heterotetraatomic complex [(η¹‐Me₂SiNDipp)NHDippSbCl₂] ( 2 ) by the reaction with SbCl₃. The complexes were characterized by ¹H and ¹³C NMR, elemental analysis, IR, and single‐crystal X‐ray structural analysis.     

Design and synthesis of a novel protected mixed ligand siderophore

A novel siderophore analog (4) has been designed to facilitate iron transport-mediated drug delivery and drug release. This mixed ligand siderophore analog includes three bidentate ligands intended to octahedrally coordinate iron (III). The ligands include a 2,3-dihydroxy benzoic acid moiety, N⁵-acetyl-N⁵-hydroxy-l-ornithine, and a β-N-hydroxy-α,β-diaminopropionic acid derivative. The total synthesis of 15, a form of 4 that is suitably protected, yet contains a free carboxylic acid for subsequent drug conjugation, is described.     

Non‐Isothermal Decomposition Kinetics,Specific Heat Capacity and Adiabatic Time‐to‐explosion of a Novel High Energy Material: 1‐Amino‐1‐Methylamino‐2,2‐Dinitroethylene (AMFOX‐7)

A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) $. The critical temperature of thermal explosion of AMFOX‐7 is 244.89°C. The specific heat capacity of AMFOX‐7 was determined with micro‐DSC method and theoretical calculation method, and the standard molar specific heat capacity is 199.39 J·mol^?1·K^?1 at 298.15 K. Adiabatic time‐to‐explosion of AMFOX‐7 was also calculated to be 215.41 s. AMFOX‐7 has higher thermal stability than FOX‐7.     

Synthesis and DNA Cleavage Activity of Piperazine Containing Guanidinoethyl and Hydroxyethyl Side Arms

According to active groups synergetic catalysis principle, a novel phosphodiester receptor 1‐(N‐guanidinoethyl)‐4‐(N‐hydroxyethyl)‐piperazidine hydrochloride was firstly synthesized and the preliminary studies of its DNA cleavage activity. It is characterized and confirmed by methods as ¹H NMR and ^13C NMR. A “couple hardness with softness” piperazidine is designed to connect guanidinium group and hydroxyl group; The reserch was showed that the best cleaving conditions was 7.2 in pH; Cleaving DNA by the compound reaction was oxidation process that were proved through the free radicals quenches experiments; The compound can cleaved the pUC 19 DNA by phospholipid transferance was proved by BDNPP.