Eenheid Algemene Chemie, Vrije Universiteit Brussel (VUB), Faculteit Wetenschappen, 1050, Brussels, Belgium.
J Am Soc Mass Spectrom. 2013 Jun;24(6):926-31. doi: 10.1007/s13361-013-0617-x. Epub 2013 Apr 18.
We present results showing that our recently developed density functional theory (DFT)-based speciation model of the aqueous Al(3+) system has the potential to improve the interpretations of ESI-MS studies of aqueous metal cation hydrolytic speciation. The main advantages of our method are that (1) it allows for the calculation of the relative abundance of a given species which may be directly assigned to the signal intensity in a mass spectrum; (2) in cases where species with identical m⁄z ratios may coexist, the assignment can be unambiguously assigned based on their theoretical relative abundances. As a demonstration of its application, we study four pairs of monomer and dimer aqueous Al(3+) species, each with identical m/z ratio. For some of these pairs our method predicts that the dominant species changes from the monomer to the dimer species under varying pH conditions.
我们展示了研究结果，表明我们最近开发的基于密度泛函理论（DFT）的水合 Al(3+)体系形态分布模型有可能改进对 ESI-MS 研究水合金属阳离子水解形态分布的解释。我们方法的主要优点是：(1) 它允许计算给定形态的相对丰度，该丰度可直接分配给质谱中的信号强度；(2) 在存在具有相同 m⁄z 比值的形态共存的情况下，可以根据它们的理论相对丰度来明确地进行归属。作为其应用的一个示例，我们研究了四对具有相同 m/z 比值的单体和二聚体水合 Al(3+)形态。对于其中一些对，我们的方法预测在不同 pH 条件下，主要形态从单体变为二聚体。
