Fe- and Cu-Complex Formation with Artificial Ligands Investigated by Ultra-High Resolution Fourier-Transform ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS): Implications for Natural Metal-Organic Complex Studies
Fe- and Cu-Complex Formation with Artificial Ligands Investigated by Ultra-High Resolution Fourier-Transform ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS): Implications for Natural Metal-Organic Complex Studies
复制标题
通过超高分辨率傅里叶变换离子回旋共振质谱 (FT-ICR-MS) 研究人工配体形成铁和铜络合物：对天然金属有机络合物研究的启示
DOI：
--
复制
发表时间：
2016
影响因子：
3.7
通讯作者：
T. Dittmar
中科院分区：
文献类型：
--
作者：
Hannelore Waska;A. Koschinsky;T. Dittmar
近年来，电喷雾电离质谱（ESI-MS）已越来越多地用于补充金属-配体平衡的批量测定，例如通过竞争性配体交换-吸附阴极溶出伏安法（CLE-ACSV）。然而，ESI-MS形态分析可能会受到仪器人为因素的影响，例如ESI源的还原反应、碎片化和加合物形成，检测到的物质相对于样品基质的电离效率的变化，以及响应于样品复杂性增加的峰重叠。在我们的研究中，已知的人工配体柠檬酸盐，乙二胺四乙酸（EDTA），1-亚硝基-2-萘酚（NN），水杨醛肟（SA）与铁（Fe）和铜（Cu）的平衡进行了研究的超高分辨率ESI-MS，傅立叶变换离子回旋共振质谱（FT-ICR-MS），在各种样品基质和电离设置。所获得的质谱进行了比较，从文献中的金属配体平衡数据，以及一个适应的形态模型。总体而言，质谱产生了先前报告中提到的代表性物质，并通过形态计算进行了预测，如Fe（Cit）、Cu（Cit）2、Fe（EDTA）、Cu（EDTA）、Fe（NN）3和Cu（SA）2。分析进一步揭示了新的物种，这些物种是假设的，但没有使用其他方法直接测量，例如柠檬酸盐与Fe和Cu的三元络合物、Cu（SA）单体和二聚体Fe（SA）2。最后，平行测量的Cu+SA校准系列和Cu+SA+EDTA竞争系列表明，FT-ICR-MS可以产生类似于ACSV的线性响应和低检测限。我们建议，超高分辨率FT-ICR-MS可以作为一个代表性的工具，研究痕量金属与人工以及天然的，未知的配体在分子水平上的相互作用。
In recent years, electrospray-ionization mass spectrometry (ESI-MS) has been increasingly used to complement the bulk determination of metal-ligand equilibria, for example via competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV). However, ESI-MS speciation analyses may be impacted by instrumental artefacts such as reduction reactions, fragmentation, and adduct formation at the ESI source, changes in the ionization efficiencies of the detected species in relation to sample matrix, and peak overlaps in response to increasing sample complexity. In our study, equilibria of the known artificial ligands citrate, ethylenediaminetetraacetic acid (EDTA), 1-nitroso-2-naphthol (NN), and salicylaldoxime (SA) with iron (Fe) and copper (Cu) were investigated by ultra-high resolution ESI-MS, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), under a variety of sample matrix and ionization settings. The acquired mass spectra were compared with metal-ligand equilibrium data from the literature as well as an adapted speciation model. Overall, the mass spectra produced representative species mentioned in previous reports and predicted by the speciation calculations, such as Fe(Cit), Cu(Cit)2, Fe(EDTA), Cu(EDTA), Fe(NN)3, and Cu(SA)2. The analyses furthermore revealed new species which had been hypothesized but not measured directly using other methods, for example ternary complexes of citrate with Fe and Cu, Cu(SA) monomers, and the dimer Fe(SA)2. Finally, parallel measurements of a Cu+SA calibration series and a Cu+SA+EDTA competition series indicated that FT-ICR-MS can produce linear responses and low detection limits analogous to those of ACSV. We propose that ultra-high resolution FT-ICR-MS can be used as a representative tool to study interactions of trace metals with artificial as well as natural, unknown ligands at the molecular level.
影响因子：
7.4
作者：
Riedel, Thomas;Dittmar, Thorsten
通讯作者：
Dittmar, Thorsten
影响因子：
6.2
作者：
Hawkes JA
通讯作者：
Hawkes JA