A Combined Computational and Benchtop Chemistry Approach to a Model of the Formation, Growth and Precipitation of Hydroxyaluminosilicates.

羟基铝硅酸盐形成、生长和沉淀模型的计算和台式化学相结合的方法。

• 批准号: EP/J004146/1
• 负责人: Christopher Exley
• 金额: $ 37.16万
• 依托单位: Keele University
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2011
• 资助国家: 英国
• 起止时间: 2011 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ004146%2F1
• 关键词: Combined; Computational; Benchtop; Chemistry; Approach

The form of dissolved silicon which is found in natural waters such as lakes, rivers and the sea is called silicic acid. A molecule of silicic acid is composed of an atom of silicon surrounded by 4 hydroxyl (OH) groups in a tetrahedral arrangement. This molecule can almost be described as chemically inert as it has no known organic chemistry and almost no known inorganic chemistry. The latter is the subject of this proposal as we have identified the unique inorganic chemistry of silicic acid with aluminium in forming what we have called hydroxyaluminosilicates (HAS). We have been able to identify how the neutral silicic acid molecule reacts with a 'surface' composed of aluminium hydroxide to form two discrete HAS which we have called HAS'A' and HAS'B'. We have been able to confirm the structures of these solid phases and assign quantitative data to their composition and solubiblity. We have shown how they may also incorporate both fluoride and phosphate in their structures. All of our achievements in this field have now resulted in this chemistry being included in authoratative text books on inorganic chemistry. However, there is a great deal still to learn about HAS and in particular how their rate of formation will have profound influences upon their chemical and biological roles in specific environments. We have identified HAS as critical secondary minerals in the biogeochemical cycles of both aluminium and silicon. Thus we know that this chemistry plays an important role in the biological availability of silicon, for example, for biosilicification (organisms which build silica frameworks for structural roles) and aluminium, it keeps aluminium out of biota. The latter role of silicic acid as the natural antagonist to the potential toxicity of aluminium has been widely demonstrated by ourselves and, following us, many other groups and is probably the major role of silicon in living organisms. Thus gaining as much understanding as is possible about the formation of HAS will not only enable some new and exciting inorganic chemistry it will also inform us as to the role this chemistry plays and has played in biochemical evolution. In particular, in this project we wish to build a computational model of the kinetics of HAS formation as such a model should be invaluable to any application where it is important to be abe to predict the biological availability of aluminium. We will use state-of-the-art benchtop chemistry including particle-sizing and mass spectrometry to establish new and innovative data concerning how HAS form, aggregate and eventually precipitate as kinetcially inert secondary mineral-like solid phases. These data will be used in our new kinetic model of HAS formation to produce an effective and predictive computational model which will be readily accessible by many different interested parties including applications in fundamental chemistry but also in applied chemistry and in toxicology.

在湖泊、河流和海洋等天然水域中发现的溶解硅形式称为硅酸。硅酸分子由一个硅原子组成，周围有 4 个羟基 (OH)，呈四面体排列。这种分子几乎可以被描述为化学惰性的，因为它没有已知的有机化学，也几乎没有已知的无机化学。后者是本提案的主题，因为我们已经确定了硅酸与铝在形成羟基铝硅酸盐 (HAS) 时的独特无机化学性质。我们已经能够确定中性硅酸分子如何与氢氧化铝组成的“表面”反应，形成两个离散的 HAS，我们称之为 HAS'A' 和 HAS'B'。我们已经能够确认这些固相的结构，并为其成分和溶解度分配定量数据。我们已经展示了它们如何在其结构中结合氟化物和磷酸盐。我们在这一领域取得的所有成就现已使该化学被纳入无机化学的权威教科书中。然而，关于 HAS 还有很多东西需要了解，特别是它们的形成速度将如何对其在特定环境中的化学和生物作用产生深远的影响。我们已将 HAS 确定为铝和硅生物地球化学循环中关键的次生矿物。因此，我们知道这种化学在硅的生物利用度中发挥着重要作用，例如，对于生物硅化（为结构作用构建二氧化硅框架的生物体）和铝，它使铝远离生物群。硅酸作为铝潜在毒性的天然拮抗剂的后一种作用已被我们自己以及许多其他团体广泛证明，并且可能是硅在生物体中的主要作用。因此，尽可能多地了解 HAS 的形成不仅可以实现一些新的、令人兴奋的无机化学，还可以让我们了解这种化学在生化进化中所扮演的角色以及已经扮演的角色。特别是，在这个项目中，我们希望建立一个 HAS 形成动力学的计算模型，因为这样的模型对于任何需要预测铝的生物利用率的应用来说都是非常有价值的。我们将使用最先进的台式化学技术，包括粒度测定和质谱分析，建立有关 HAS 如何形成、聚集并最终沉淀为动力学惰性次生矿物状固相的新数据和创新数据。这些数据将用于我们新的 HAS 形成动力学模型，以生成有效的预测计算模型，许多不同的利益相关方都可以轻松访问该模型，包括基础化学、应用化学和毒理学中的应用。

项目成果

Pro-oxidant activity of aluminum: promoting the Fenton reaction by reducing Fe(III) to Fe(II).

铝的促氧化活性：通过将 Fe(III) 还原为 Fe(II) 来促进 Fenton 反应。

• DOI: 10.1016/j.jinorgbio.2012.09.008
• 发表时间: 2012-12-01
• 期刊: Journal of inorganic biochemistry
• 影响因子: 3.9
• 作者: F. Ruipérez;J. Mujika;J. Ugalde;C. Exley;X. López
• 通讯作者: X. López

The coordination chemistry of aluminium in neurodegenerative disease

铝在神经退行性疾病中的配位化学

• DOI: 10.1016/j.ccr.2012.02.020
• 发表时间: 2012-10-01
• 期刊: Coordination Chemistry Reviews
• 影响因子: 20.6
• 作者: C. Exley

What is the mechanism of formation of hydroxyaluminosilicates?

羟基铝硅酸盐的形成机理是什么？

• DOI: 10.1038/srep30913
• 发表时间: 2016-08-01
• 期刊: Scientific Reports
• 影响因子: 4.6
• 作者: Beardmore J;Lopez X;Mujika JI;Exley C
• 通讯作者: Exley C