Speciation analysis of aluminium(III) in natural waters and biological fluids by complexing with various catechols followed by differential pulse voltammetry detection

The biological effects of aluminium have received much attention in recent years. Speciation of Al is of basic relevance as it concerns its reactivity and bioavailability. A differential pulse voltammetry (DPV) procedure is proposed for speciation analysis of Al(III) in natural waters and biological fluids using six catechols (L-dopa, dopamine, epinephrine, norepinephrine, caffeic acid and o-benzenediol) as electroactive ligands. The decrease of the DPV anodic peak current for each catechol ligand is linear with the increase of Al concentration. This speciation analysis idea is based on the measurement of the complexation capacity, namely, different affinities of Al(III) for catechols and organic ligands under two pH conditions. The labile monomeric Al fraction (mainly inorganic aluminium) is determined at pH 4.6, while the total monomeric Al fraction is determined at pH 8.5. The principle for Al(III) speciation analysis by an electrochemical method is discussed. This sensitive and simple fractionation method is successfully applied to the speciation analysis of Al in natural waters and the results agree well with those of Driscoll's method. The speciation analysis of Al in biological fluids is also explored and the results are compared with those obtained by ultrafiltration and dialysis. Compared with other speciation protocols the electrochemical method possesses some remarkable advantages: rapidity, high sensitivity, cheap instrumentation and a simple operation procedure.     

原位沉析法制备磁性氧化铁羟基磷灰石/壳聚糖棒材

首先通过化学沉淀法制备磁性氧化铁羟基磷灰石(Fe3O4/HA),然后以壳聚糖(CS)为基体,利用原位沉析法将Fe3O4/HA与CS复合,制得磁性Fe3O4/HA/CS复合材料.经XRD、粒径分布和PPMS测试,结果表明了Fe3O4/HA复合物的生成.系统研究了磁性Fe3O4/HA/CS棒材力学性能的影响因素,最终确定Fe3O4与HA质量比为3∶17,磁性Fe3O4/HA与CS质量比为9∶91时,棒材的力学性能最优,弯曲强度可达到87.0 MPa,弯曲模量1.57 GPa.     

Analysis of the Thermal Decomposition Path of SF6 on the Surface of Cu and its Oxides

Plasma Chemistry and Plasma Processing - Accurately grasping the decomposition path of SF6 on the surface of typical metals and metal oxides is the key to reveal the decomposition mechanism of...     

Hydrothermal synthesis and characterization of a new organically templated three-dimensional open-framework gallium phosphate–phosphite (C6N2H18)2(C6N2H17)Ga15(OH)8(PO4)2(HPO4)12(HPO3)6·2H2O

Using H₃PO₃ as a phosphorus source and oxalic acid as a reducing agent, the first three-dimensional open-framework gallium phosphate–phosphite formula as (C₆N₂H₁₈)₂(C₆N₂H₁₇)Ga₁₅(OH)₈(PO₄)₂(HPO₄)₁₂(HPO₃)₆·2H₂O (1), has been hydrothermally synthesized in the presence of N,N,N′,N′-tetramethylenediamine (TMEDA) as a structure-directing agent. Compound 1 crystallizes in trigonal system with space group P ? 3, a = b = 19.046(3) Å, c = 8.3306(17) Å, γ = 120°, V = 2617.1(7) Å³, and Z = 1. Its 3-D network is based on alternated Ga-centered (GaO₄ tetrahedra, GaO₅ trigonal bipyramids, and GaO₆ octahedra) and P-centered (PO₄^3?, HPO₄^2?, and HPO₃^2?) units. Protonated organic amines and water molecules are located in the 12-membered ring channels.     

抗肿瘤缺氧诱导因子-1的小分子抑制剂

肿瘤的缺氧微环境与其增殖、分化、血管生成、能量代谢、耐药性的发生以及患者预后状况密切相关。缺氧诱导因子1(Hypoxia-inducible factor 1, HIF-1)是细胞适应缺氧环境的重要转录因子和调控蛋白,通过调控下游靶基因如EPO、VEGF、GLUT等的表达,促进血管新生及有氧糖酵解以适应缺氧的环境,进而影响肿瘤细胞代谢、血管生成和肿瘤转移等。因此,开发以HIF-1为靶标的小分子抑制剂药物有望成为一种有效的肿瘤治疗方法。本文就HIF-1小分子抑制剂在肿瘤学研究中的进展进行综述,旨在为靶向HIF-1抗肿瘤药物的研发提供新思路。     

Copolymerization of norbornene and 5‐norbornene‐2‐yl acetate using novel bis(β‐ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3 catalytic system

Vinyl‐type copolymerization of norbornene (NBE) and 5‐NBE‐2‐yl‐acetate (NBE‐OCOMe) in toluene were investigated using a novel homogeneous catalyst system based on bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃/AlEt₃. The copolymerization behavior as well as the copolymerization conditions, such as the levels of B(C₆F₅)₃ and AlEt₃, temperature, and monomer feed ratios, which influence on the copolymerization were examined. Without combination of AlEt₃, the catalytic bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃ exhibited very high catalyst activity for polymerization of NBE. Combination of AlEt₃ in catalyst system resulted in low conversion for polymerization of NBE. For copolymerization of NBE and NBE‐OCOMe, involvement of AlEt₃ in catalyst is necessary. Slight addition of NBE‐OCOMe in copolymerization of NBE and NBE‐OCOMe gives rise to significant increase of catalyst activity for catalytic system bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃/AlEt₃. Nevertheless, excess increase of the NBE‐OCOMe content in the comonomer feed ratios results in decrease of conversion as well as activity of catalyst. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of FTIR, ¹H NMR, and ¹³C NMR spectra. ¹³C NMR studies further revealed the composition of the copolymer and the incorporation rate was 7.6–54.1 mol % ester units at a content of 30–90 mol % of the NBE‐OCOMe in the monomer feeds ratios. TGA analysis results showed that the copolymer exhibited good thermal stability (T_d > 410 °C) and failed to observe the glass transitions temperature over 300 °C. The copolymers are confirmed to be noncrystalline by WAXD analysis results and show good solubility in common organic solvents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3990–4000, 2009     

双相高强钢FeNiAlC的动态剪切行为及微结构机理

绝热剪切带是金属材料在高应变率载荷下常见的一种失效模式。利用霍普金森压杆装置,对双相钢Fe-24.86Ni-5.8Al-0.38C不同微结构的帽形样品施加冲击载荷,研究它的动态剪切变形行为及微结构机理。先通过对固熔处理得到的粗晶态样品进行大应变冷轧获得冷轧态样品,再使用透射电子显微镜和扫描电子显微镜表征两种样品冲击前后微结构的变化差异。结果表明,双相钢FeNiAlC拥有较优异的动态剪切性能,剪切强度达1.3 GPa,均匀剪切应变达1.5。变形前,材料由奥氏体相和马氏体相构成,马氏体体积分数约为20%。变形过程由位错滑移和孪生变形主导,但因应变速率较高致使马氏体相变被抑制。不同微结构样品内均形成绝热剪切带,带内发生动态再结晶,形成超细晶粒,平均晶粒尺寸约300 nm,且剪切带内不发生相变;冷轧态剪切带宽度的实验值（14.6 μm）与理论计算值(12.3 μm)较好吻合,而粗晶态剪切带宽度的实验值（14.6 μm）与理论计算值（30 μm）相差甚远,初步分析可能是因为粗晶态样品应变较大基本不满足完全绝热的理论条件。在变形过程中,粗晶态因塑性变形做功产生的绝热温升高达720 K,而冷轧态的只有190 K。通过实验结果与热塑模型分析,得出绝热温升不是形成绝热剪切带的唯一因素,而应考虑材料的微观结构和局部化变形等的共同影响。     

边界元素法中有关积分的计算方法(Ⅱ)柱状边界条件下对曲面积分及椭圆积分的计算

在柱状边界条件下将对柱侧面的曲面积分表示成一维积分,同时还给出了椭圆积分的计算方法,由对空间立体角积分的算例可知,其计算的速度有了显着的提高。     

Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines

The kinetics of the acid dissociation of copper(II) complexes of novel C-functionalized macrocyclic dioxotetraamines has been studied by means of a stopped-flow spectrophotometer. The acid dissociation rate follows the law V_d = C_comkK₁K₂H ²/(1+K₁H+K₁K₂H ²). From the experimental facts we have obtained, the dissociation kinetics are interpreted by a mechanism involving the negatively charged carbonyl oxygen of the complex being rapidly protonated in a pre-equilibrium step, the rate-determining step being intramolecular hydrogen (enolic tautomer) migration (to imine nitrogen). The dissociation rate reached a plateau in the strongly acidic solution. By means of temperature coefficient method, ΔH ^φ, ΔS ^φ of the pre-equilibrium step and ΔH ^≠, ΔS^≠ of the rate-determining step were obtained. The results of 13-membered macrocyclic dioxotetraamines have been discussed. The influence of the substituents to the acid dissociation rates has also been discussed. The Bronsted type linear free energy relationships do also exist in these C-functionalized dioxotetraamine copper(II) complexes.