金属离子与氨羧类螯合配体的键合特性研究

利用前沿色谱法,通过Cu2＋、Ni2＋和Co2＋与螯合配体IDA键合的准确度（R2〉0.98）与精密度（RSD〈5%）实验,研究了前沿色谱法同时测定络合稳定常数KML与总键合位点数Λ0值的可行性。为了进一步证明前沿色谱法的普适性,以Cu2＋、Ni2＋和Co2＋为代表,在3种键合缓冲体系（Na Ac-HAc、Na-PB、Tris-HCl）中,考察了金属离子在3种氨羧类螯合配体（IDA、Asp、Glu）上络合稳定常数KML的变化规律。结果表明,螯合配体对金属离子键合强度遵循IDA〉Asp〉Glu;金属离子对螯合配体键合强度遵循Cu2＋〉Ni2＋〉Co2＋;3种键合缓冲体系中,Na Ac-HAc键合...

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Bibliographic Details
Published in分析化学 Vol. 45; no. 9; pp. 1303 - 1308
Main Author 陈斌 王石慧 李蓉 樊安
Format Journal Article
LanguageChinese
Published 西北大学化工学院,西安,710069 2017
Subjects
前沿色谱法
总键合位点数
氨羧类螯合配体
络合稳定常数
量子计算
氨羧类螯合配体
Complexation stability constant
Frontal chromatography
Quantum computing
Aminocarboxyl chelating ligand
络合稳定常数
总键合位点数
量子计算
前沿色谱法
Total mole of binding site
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ISSN0253-3820
DOI10.11895/j.issn.0253-3820.170154

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Summary:利用前沿色谱法,通过Cu2＋、Ni2＋和Co2＋与螯合配体IDA键合的准确度（R2〉0.98）与精密度（RSD〈5%）实验,研究了前沿色谱法同时测定络合稳定常数KML与总键合位点数Λ0值的可行性。为了进一步证明前沿色谱法的普适性,以Cu2＋、Ni2＋和Co2＋为代表,在3种键合缓冲体系（Na Ac-HAc、Na-PB、Tris-HCl）中,考察了金属离子在3种氨羧类螯合配体（IDA、Asp、Glu）上络合稳定常数KML的变化规律。结果表明,螯合配体对金属离子键合强度遵循IDA〉Asp〉Glu;金属离子对螯合配体键合强度遵循Cu2＋〉Ni2＋〉Co2＋;3种键合缓冲体系中,Na Ac-HAc键合效果最好。按照M06/6-311＋＋G（d,p）方法对螯合配体与金属离子的结合能（ΔE）与吉布斯自由能（ΔG）进行相关的量子计算。根据ΔE与ΔG的大小,从理论上推测出螯合配体与金属离子的键合规律,此规律与上述实验结果基本相符。本研究为金属离子与螯合配体间键合参数的求取提供了有效的方法和手段,从而为今后提高IMAC柱的稳定性,解决固定金属亲和柱在应用过程中尤其是竞争洗脱过程中金属离子的流失问题奠定了良好的基础。
Bibliography:CHEN Bin, WANG Shi-Hui, LI Rong, FAN An （ School of Chemical Engineering, Northwest University, Xi＇an 710069, China）
22-1125/O6
The feasibility of frontal chromatography for determining the complexation stability constant KMLand total mole of binding site Λowas demonstrated by the accuracy and precision binding experiments between metal ions（ Cu2＋,Ni2＋and Co2＋） and chelating ligand（ IDA）,in which R2〉0. 98 and RSD 〈5%. To further prove the universality of the frontal chromatography,the changing rules of KMLvalues between Cu2＋,Ni2＋,Co2＋and IDA,Asp,L-Glu were examined under Na Ac-HAc,Na-PB and Tris-HCl buffer systems. The results showed that the binding strength of chelating ligands for metal ions followed IDA 〉Asp 〉Glu; binding strength of metal ions for chelate ligands followed Cu2＋〉Ni2＋〉Co2＋; and the binding effect with Na Ac-HAc buffer was the best. In aqueous solution,quantum computing of binding energy（ ΔE） and gibbs free energy（ ΔG）between chelating ligand and metal ion was performed at the M06/6-311 ＋＋G（ d
ISSN:0253-3820
DOI:10.11895/j.issn.0253-3820.170154