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首页> 外文期刊>Chemistry: A European journal >Minerals as Molecules-Use of Aqueous Oxide and Hydroxide Clusters to Understand Geochemical Reactions
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Minerals as Molecules-Use of Aqueous Oxide and Hydroxide Clusters to Understand Geochemical Reactions

机译：矿物作为分子-使用氧化水和氢氧化物簇理解地球化学反应

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摘要

Geochemists and environmental chemists make predictions about the fate of chemicals in the shallow earth over enormously long times. Key to these predictions is an understanding of the hydrolytic and complexation reactions at oxide mineral surfaces that are difficult to probe spectroscopically. These minerals are usually oxides with repeated structural motifs, like silicate or aluminosilicate polymers, and they expose a relatively simple set of functional groups to solution. The geochemical community is at the forefront of efforts to describe the surface reactivities of these interfacial functional groups and some insights are being acquired by using small oligomeric oxide molecules as experimental models. These small nanometer-size clusters are not minerals, but their Solution structures and properties are better resolved than for minerals and calculations are relatively well constrained. The primary experimental data are simple rates of steady oxygen-isotope exchanges into the structures as a function of solution composition that can be related to theoretical results. There are only a few classes of large oxide ions for which data have been acquired and here we review examples and illustrate the general approach, which also derives directly from the use of model clusters to understand for the active core of metalloenzymes in biochemistry.
机译：地球化学家和环境化学家对很长一段时间内浅层地球化学物质的命运做出了预测。这些预测的关键是对氧化物矿物表面难以进行光谱探测的水解和络合反应的理解。这些矿物通常是具有重复结构图案的氧化物，例如硅酸盐或铝硅酸盐聚合物，并且它们使相对简单的一组官能团暴露于溶液中。地球化学界在描述这些界面官能团的表面反应性方面处于最前沿，通过使用小的低聚氧化物分子作为实验模型，正在获得一些见识。这些小的纳米级簇不是矿物质，但是它们的溶液结构和性质比矿物质更好地解析，并且计算受到相对较好的约束。主要的实验数据是稳定的氧-同位素交换到结构中的简单速率，其与溶液组成的函数关系可以与理论结果相关。只有少数几类大型氧化物离子已获取了数据，在这里我们回顾了示例并举例说明了一般方法，该方法也直接来源于使用模型簇来了解生物化学中金属酶的活性核心。

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