卡尔曼滤波分光光度法用于铝、镓和铁的同时测定——铬天青 S-溴化十六烷基三甲胺法

本文运用卡尔曼滤波(KF)递推算法,通过三元络合物显色体系:CAS-CTMAB-Me,实现了Al(Ⅲ)、Ga(Ⅲ)和Fe(Ⅲ)三元素的同时测定,合成样分析结果良好。     

New developments in the chemistry of organoaluminum and organogallium hydrides

A survey of our recent work on organoaluminum and organogallium hydrides is presented. Three types of ligand system have been employed for the stabilization of monomeric aluminum and gallium mono- and dihydrides. The “two-armed” 2,6-bis (dimethylaminomethyl) phenyl ligand is effective when intramolecular bis(base) stabilization is necessary; its use has permitted the isolation of the first examples of monomeric aluminum and gallium dihydrates. The use of the corresponding “one-armed” 2-(dimethylaminomethyl) phenyl ligand resulted in the formation of gallium mono- and dihydride monomers and an aluminum dihydride dimer. The first base-free aluminum and gallium monohydrides and gallium dihydride have been stabilized by employing the bulky 2, 4, 6, -tris(t-butyl) phenyl ligand.     

Synthesis and characterization of two novel organocation containing group 13 metal ethylenediphosphonates

Two novel group 13 metal diphosphonates: (H₃NC₃H₆NH₃)₂[Al₂F₆(O₃PC₂H₄PO₃)]·H₂O (1) (monoclinic, C2/c, a=16.9697(7) Å, b=8.0273(4) Å, c=16.3797(8) Å, β=117.762(2)°, Z=4, R₁=4.66%, wR₂=11.82%), and (H₃NC₃H₆NH₃)[Ga₂F₄(O₃PC₂H₄PO₃)] (2) (triclinic, P-1, a=5.398(7) Å, b=8.122(6) Å, c=15.839(18) Å, α=78.89(4)°, β=89.60(7)°, γ=79.35(6)°, Z=2, R₁=2.90%, wR₂=3.17%) have been synthesized by solvothermal methods in the presence of the propyldiammonium cations and their structures determined using single and micro-crystal X-ray diffraction data, respectively. The structures of 1 and 2 are closely related and contain dimers of edge-sharing trivalent metal centered octahedra that are linked together by the ethylenediphosphonate groups to form chains and aperture-containing layers, respectively. The propyldiammonium cations surround the aluminum diphosphonate chains in 1 and separate the gallium diphosphonate layers in 2. Both compounds 1 and 2 are examples of metal phosphonate materials containing only one type of octahedral-tetrahedral secondary building unit (SBU-4).     

CL-P204萃淋树脂吸萃镓的性能和机理

本文采用静态法研究了CL-P204萃淋巴脂在硫酸介质中吸萃镓的性能。结果表明，在pH2.8时，镓在树脂上的分配系数最大，其吸附反应的热效应为43.2KJ/mol，树脂对镓的饱和吸附容量为42.4mg/g；吸萃过程为离子交换过程。     

A comparative study of aluminum(III), gallium(III), indium(III), and thallium(III) binding to human serum transferrin

Group 13 cations exhibit an essentially similar chemical behavior in aqueous solution. Under physiological conditions these cations exist as metal complexes. They are known to bind tightly to human serum transferrin in the blood. Here, the numerous published studies on the interactions of Group 13 metals with transferrin are reviewed, particular attention being given to the comparative analysis of the binding constants and to the kinetics and mechanisms of metal ion uptake and release. The structural and functional information obtained on these metallotransferrins by advanced physicochemical methods, such as NMR spectroscopy, is presented in light of the recent crystal structures of ferric- and apotransferrin. The biological consequences of binding of aluminum(III), gallium(III) and indium(III) to transferrin are discussed in relation to the relevant roles played by these metal ions in pharmacology and toxicology.     

Reactions of 1,2-catechol with Bu3M (M = Ga, In). Structures of intermediate products

Reactions of 1,2-catechol with ^tBu₃M (M = Ga, In) have been studied. Trinuclear compounds [^tBu₅M₃(OC₆H₄O)₂] [M = Ga (1), M = In (2)] were synthesised in the reaction of 2 equiv. of C₆H₄(OH)₂ with 3 equiv. of ^tBu₃M in refluxing solvents. At room temperature the reaction of 1,2-catechol with ^tBu₃In in Et₂O leads to the formation of a binuclear complex [^tBu₄In₂(OC₆H₄OH)₂ · 2Et₂O] (3) possessing a four-membered In₂O₂ core and two unreacted hydroxyl groups. The same reaction carried out in a non-coordinating solvent (CH₂Cl₂) results in formation a compound [^tBu₃In₂(OC₆H₄O)(OC₆H₄OH)] (4), which undergoes a reaction with ^tBu₃In to yield the product 2. Moreover two intermediate isomeric products 5 and 6 of formula [^tBu₃Ga₂(OC₆H₄O)(OC₆H₄OH)] were isolated from the post-reaction mixture of 1,2-catechol with ^tBu₃Ga. The compound 6 possessing a different coordination of gallium atoms than 5 is a result of the intramolecular rearrangement of the compound 5 to decrease the steric repultion between ligands. Compounds 3 and 6 were structurally characterised. According to the structure of intermediate products 3-6 a reaction pathway of 1,2-catechols with group 13 metal trialkyls was proposed.     

镓(Ⅲ)-向红菲咯啉络合物极谱吸附波的研究及应用

在 ＰＨ＝４．２的 ０．０７ ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ介质中，Ｇａ（Ⅲ）－向红菲咯啉络合物在单扫描极谱仪上于－０．９８ Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的吸附还原波，其二阶导数波灵敏度高，波形好，峰电流 Ｉｐ与 Ｇａ（Ⅲ）在 ８．０×１０－８～３．０× １０－６ｍｏｌ／Ｌ的浓度范围内呈现良好线性关系，检出限为７．０×１０－８ｍｏｌ／ＬＧａ（Ⅲ）。用该法对粮食中的镓进行了测定，并对电极过程进行了研究。     

Reaktionen des Gallium‐haltigen Heterocyclus [Me2Ga{HNC(Me)}2CCN]

Reactions of the Gallium‐containing Heterocycle [Me₂Ga{HNC(Me)}₂CCN] The reaction of [Me₂Ga{HNC(Me)}₂CCN] ( 1 ) with fac‐[Mo(CO)₃(MeCN)₃] leads after addition of TMEDA to the molybdenum complex fac‐[Mo(CO)₃( 1 )(TMEDA)] ( 2 ). Under identical reaction conditions with fac‐[W(CO)₃(MeCN)₃] only the tetracarbonyle complex [W(CO)₄(TMEDA)] ( 3 ) could be isolated. Treatment of dilithiated 1 with Me₂SiCl₂ or InCl₃ initiate a fragmentation of the skeleton in 1 . Obtained were the salt [Me₂Ga(TMEDA)][Me₂GaCl₂] ( 4 ) and the indium complex [Me₂InCl(TMEDA)] ( 5 ), respectively. 2 — 5 were investigated by spectroscopical and spectrometrical methods as well as by X‐ray structure determinations. According to these 1 occupies a facial site in 2 by donation of the N‐Atom from the NC group in 1 . The molecules 2 are forming a network of hydrogen bonds. In 3 , the TMEDA ligand acts as an intramolecular chelate ligand. In the salt 4 , the cation as well as the anion are coordinated in a distorted tetrahedral environment, while in 5 a distorded trigonal‐bipyramidal coordination‐sphere is present, leading to a elongated In1‐Cl1 distance of 261.74(9) pm.     

Synthesis and characterization of a new layered gallium phosphate [Co(en)3][Ga3(H2PO4)6(HPO4)3] templated by cobalt complex

A new layered gallium phosphate [Co(en)₃][Ga₃(H₂PO₄)₆(HPO₄)₃], denoted as GaPO-CJ14, has been synthesized solvothermally by using a racemic mix of chiral metal complex Co(en)₃Cl₃ as a template. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The compound crystallizes in the monoclinic space group P2₁/m (No. 11) with a=9.2103(3), b=22.0936(8), c=9.5458(4) Å, β=108.278(2)°, Z=2, R₁=0.0497 and wR₂=0.1122 for all data. The inorganic layer is built up by alternation of Ga-centered octahedra (GaO₆) and P-centered tetrahedra (PO₃(OH), PO₂(OH)₂ , PO₂(O)(OH) and PO(O)(OH)₂) forming a 4.12-net. The sheet structure is featured by a series of structural units composed of two centrosymmetrically related [3.3.3] propellane-like chiral motifs. The metal complex cations locate in the interlayer region and interact with the host network through H-bonds.     

镓,铟与酸性铬深蓝络合物吸附波的研究及其应用

在醋酸盐缓冲溶液中，用单扫示波极谱法分别获得了镓（Ⅲ）、铟（Ⅲ）与酸性铬深蓝灵敏的络合物吸附波。两个波的峰电位分别为－０５１Ｖ和－０６３Ｖ（ｖｓＳＣＥ），镓（Ⅲ）的线性范围为７２０×１０－７～７４６×１０－６ｍｏｌ／Ｌ；铟（Ⅲ）为１７４×１０－７～４８８×１０－６ｍｏｌ／Ｌ。作者研究了该电极反应机理。该法用于矿石中镓、铟的测定，结果满意。