Palladium（ Ⅱ ） and Platinum（ Ⅱ ） Compounds Derived From Potentially Terdentate Ligands

Transition metal complexes derived from potentially terdentate ligands have attracted great interest in the late years. Among all the examples described so far, those containing palladium（ Ⅱ ） or platinum（ Ⅱ ） and ligands holding three heteroatoms with different donor abilities are particularly relevant. In compounds of this kind, the potential hemilability of one of the terminal σ（M-donor atom） bonds, plays an important role in the view of their applications in homogeneous catalysis. On the other hand, it is well-known that in dimetallic complexes the presence of two different metals in a close vicinity may influence their mutual cooperation in a wide variety of processes. Besides that, some examples of the utility of chiral palladium（ Ⅱ ） as well as platinum（ Ⅱ ） complexes as precursors for organic and/or organometallic synthesis, as chiral recognitors or discriminators, or even in Bio-Medicine have also been reported. However, chiral heterodimetallic compounds holding ferrocenyl units and potentially terdentate ligands are scarce.     

Highly Efficient Asymmetric Synthesis Usomg Organocatalyst Derived From(S)-proline

1 Results Much effort has been focused on organocatalytic asymmetric synthesis in these several years. We have already documented highly efficient organocatalytic asymmetric acylation of a wide variety of racemic alcohols and meso-diols catalyzed bya chiral 1,2-diamine derived from (S)-proline[1]. (S)-Homoproline seems to be a potentially interesting organocatalyst, but no examples using (S)-homoproline itself in asymmetric synthesis has been reported. We have accomplished an efficient and practical synthesis of (S)-homoproline, which is a one-carbon homologated proline, starting from (S)-proline in 7 steps. And then we have developed a novel asymmetric Michael additionreaction of ketones to β-nitrostyrene and its derivatives using (S)-homoproline as a chiral organocatalyst. The reaction was performed in a highly diastereoselective and enantioselective manner over 90% ee[2].     

瑞香素与锌(Ⅱ)、镉(Ⅱ)、镁(Ⅱ)、钙(Ⅱ)、锶(Ⅱ)、钡(Ⅱ)相互作用的研究

用ｐＨ电位法及计算机平衡模拟研究了瑞香素（ｄａｐｈｎｅｔｉｎ,Ｈ２Ｄ）与锌（Ⅱ）、镉（Ⅱ）、镁（Ⅱ）、钙、（Ⅱ）、锶（Ⅱ）、钡（Ⅱ）在０．１５ｍｏｌ／ＬＮａＣｌ溶液中的配位反应．建立了各体系的最佳化学平衡模型,测定了Ｍ（Ⅱ）－Ｈ２Ｄ体系中有关配离子的稳定常数,绘制了Ｚｎ（Ⅱ）－Ｈ２Ｄ及Ｃｄ（Ⅱ）－Ｈ２Ｄ体系的物种分布图．在ｐＨ滴定条件下,分离出组成为ＣｄＤ·２Ｈ２Ｏ的固体配合物．     

Cu(Ⅱ)、Cd(Ⅱ)、Co(Ⅱ)、Pb(Ⅱ)的薄层色谱分离

本文研究了无机阳离子 Cu(Ⅱ)、Cd(Ⅱ)、Co(Ⅱ)、Pb(Ⅱ)的薄层色谱特性,提出了分离和测定它们的薄层分析方法。以0.2mol/L HAC—0.2mol/LNaAc 为展开剂,在硅胶 H 板上分离 Cu(Ⅱ)、Cd(Ⅱ)、Co(Ⅱ)、Pb(Ⅱ)的混合物,用双硫腙喷雾显色,它们的 R_f 值分别为0.39,0.54,0.69,0.19;检测下限可达10~(-9)g;对这四种离子的混合水溶液进行五次平行测定,其变动系数依次为2.7%、4.5%、3.8%、2.4%,回收率均在96%～104%之间。用本法对地面水及电镀废水进行了定性、定量测定,得到了满意的结果。     

铁(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)和锌(Ⅱ)水扬醛肟配位化合物的合成

本文报导了水扬醛肪与第一过渡系金属铁(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)和锌(Ⅱ)配位化合物的合成。它们的组成已由红外光谱和元素分析所证实.     

Improved hemimorphite flotation using xanthate as a collector with S(Ⅱ) and Pb(Ⅱ) activation

The flotation of hemimorphite using the S(Ⅱ)–Pb(Ⅱ)–xanthate process, which includes sulfidization with sodium sulfide, activation by lead cations, and subsequent flotation with xanthate, was investigated. The flotation results indicated that hemimorphite floats when the S(Ⅱ)–Pb(Ⅱ)–xanthate process is used; a maximum recovery of approximately 90% was obtained. Zeta-potential, contact-angle, scanning electron microscopy–energy-dispersive spectrometry (SEM–EDS), and diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements were used to characterize the activation products on the hemimorphite surface and their subsequent interaction with sodium butyl xanthate (SBX). The results showed that a ZnS coating formed on the hemimorphite surface after the sample was conditioned in an Na₂S solution. However, the formation of a ZnS coating on the hemimorphite surface did not improve hemimorphite flotation. With the subsequent addition of lead cations, PbS species formed on the mineral surface. The formation of the PbS species on the surface of hemimorphite significantly increased the adsorption capacity of SBX, forming lead xanthate (referred to as chemical adsorption) and leading to a substantial improvement in hemimorphite flotation. Our results indicate that the addition of lead cations is a critical step in the successful flotation of hemimorphite using the sulfidization–lead ion activation–xanthate process.     

Improved hemimorphite flotation using xanthate as a collector with S(Ⅱ) and Pb(Ⅱ) activation

The flotation of hemimorphite using the S(Ⅱ)–Pb(Ⅱ)–xanthate process,which includes sulfidization with sodium sulfide,activation by lead cations,and subsequent flotation with xanthate,was investigated.The flotation results indicated that hemimorphite floats when the S(Ⅱ)–Pb(Ⅱ)–xanthate process is used; a maximum recovery of approximately 90% was obtained.Zeta-potential,contact-angle,scanning electron microscopy–energy-dispersive spectrometry(SEM–EDS),and diffuse-reflectance infrared Fourier transform spectroscopy(DRIFTS) measurements were used to characterize the activation products on the hemimorphite surface and their subsequent interaction with sodium butyl xanthate(SBX).The results showed that a Zn S coating formed on the hemimorphite surface after the sample was conditioned in an Na2 S solution.However,the formation of a Zn S coating on the hemimorphite surface did not improve hemimorphite flotation.With the subsequent addition of lead cations,Pb S species formed on the mineral surface.The formation of the Pb S species on the surface of hemimorphite significantly increased the adsorption capacity of SBX,forming lead xanthate(referred to as chemical adsorption) and leading to a substantial improvement in hemimorphite flotation.Our results indicate that the addition of lead cations is a critical step in the successful flotation of hemimorphite using the sulfidization–lead ion activation–xanthate process.     

熵(Ⅱ)

介绍了解决遍历理论经典问题的Kolmogorov熵,以及为研究拓扑动力系统而产生的拓扑熵等概念,进而引导读者对这一引人入胜的领域去进行研究.     

正辛烷基亚氨二乙酸与Mn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)络合平衡的研究

本文在温度25±0.1℃,离子强度μ=0.1(KNO_3)的条件下,用pH电位法测定了正辛烷基亚氨二乙酸与Mn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)络合物的稳定常数分别为: Mn(Ⅱ) Fe(Ⅱ) Co(Ⅱ) Ni(Ⅱ) Cu(Ⅱ) Zn(Ⅱ)1gK_(ML) 5.79 7.05 8.07 8.72 10.94 7.731gK_(ML_2) 4.84 6.01 6.04 5.78 6.01 5.981gK_(MHL)~(HL) — 1.02 1.92 1.26 — 1.41 采用过量金属离子中和曲线法和过量配体中和曲线法以及它们联合求解的数据处理方法处理数据井对处理方法作了适当的改进。     

HEH[EHP]从硫酸介质中萃取锰(Ⅱ)铁(Ⅲ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)和锌(Ⅱ)

考察了水相酸度、萃取剂浓度、温度和水相介质浓度对HEH[EHP]煤油从硫酸介质中萃取Mn(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)等元素的影响;确定了萃取反应式、萃合物组成和萃取平衡常数;计算出萃取反应的△H°、△G°及△S°;对HEH[EHP]萃取金属的顺序和Co(Ⅱ)、Ni(Ⅱ)的萃取分离中的某些问题作了简单讨论。     

Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)非有机溶剂液—液萃取行为的研究

本文研究了PEG—EBT—(NH_4)_2SO_4体系对Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)的非有机溶剂萃取行为。指出在pH7～10(NH_3H_2O～NH_3Cl)的水溶液中,有(NH_4)_2SO_4存在下,Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)可被PEG相几乎完全萃取,而Cd(Ⅱ)基本上不被萃取。从而获得了(d(Ⅱ)与Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)混合离子的定量分离。     

PH电位法研究瑞香素与锰(Ⅱ)钴(Ⅱ)镍(Ⅱ)及镉(Ⅱ)的相互作用

本文对瑞香素与锰(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)及镉(Ⅱ)的相互作用进行了PH电位法研究。采用SCOGSZ计算机程序处理实验数据,确定了各二元体系的最佳化学模型,求得了有关参数。本文还提出了各配合物的可能结构和形成机制。     

Synthesis of Calix[4] arene Thia Derivative and Extraction Effect of Substituents on Mercury( Ⅱ) and Lead( Ⅱ)

Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg~(2+)and Pb~(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg~(2+)and Pb~(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg~(2+)by promoting the formation of the negative oxygen ions that could bind with Hg~(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb~(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb~(2+)with higher charge-to-radius ratio than Hg~(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg~(2+)and Pb~(2+))increased with the increase of pH value in acidic aqueous system(pH7).     

Latice Deformation and Meso-Phase Structure in Poly(Ethylene Terephthalate)From Solid State Coextrusion

The development of crystalline and Meso-phase structure by solid state extrusion from50℃ to 90℃ is studied for PET. The unit cell parameters of stress-induced crystallites inextrudates are determined as a function of extrusion draw ratio (EDR), and ext