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，河流和海洋等自然水域中发现的溶解硅的形式称为硅酸。硅酸分子由四面体排列中的4个羟基（OH）基团组成。该分子几乎可以被描述为化学惰性，因为它没有已知的有机化学，几乎没有已知的无机化学。后者是该提案的主题，因为我们已经确定了硅酸的独特无机化学，并在形成我们所谓的羟基氧硅酸盐时（HAS）。我们已经能够确定中性硅酸分子如何与由氢氧化铝组成的“表面”反应，形成我们称为“ has a and'b''and'b'的两个离散化。我们已经能够确认这些实体相的结构，并将定量数据分配给其组成和溶解度。我们已经展示了它们也可以在其结构中同时掺入氟化物和磷酸盐。现在，我们在该领域的所有成就都导致该化学被包括在有关无机化学的作者教科书中。但是，仍然有很多值得了解的人，尤其是它们的形成速率将如何对它们在特定环境中的化学和生物学作用产生深远的影响。我们已经确定在铝和硅的生物地球化学周期中具有关键的二级矿物质。因此，我们知道，这种化学在硅的生物利用率中起着重要作用，例如，在生物硅化（建立用于结构角色的二氧化硅框架的生物体）和铝中，它使铝不在生物群体之外。硅酸作为对铝潜在毒性的自然拮抗剂的后一种作用已被我们自己广泛证明，跟随我们，许多其他群体，可能是硅在生物体中的主要作用。因此，对形成的理解尽可能多，不仅可以使一些新的令人兴奋的无机化学能够告知我们这种化学的作用，并且在生化进化中发挥了作用。特别是，在这个项目中，我们希望构建一个构造动力学的计算模型，因为这种模型对于预测铝的生物学可用性至关重要的任何应用都应该是无价的。我们将使用最先进的台式化学性质，包括粒度和质谱，以建立有关如何形成，聚集并最终作为动力学惰性二级矿物样固相的新的创新数据。这些数据将在我们的新动力学模型中使用，以产生有效且预测的计算模型，该模型将很容易被许多不同的兴趣方面访问，包括基本化学中的应用以及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).

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

What is the mechanism of formation of hydroxyaluminosilicates?

• 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

The coordination chemistry of aluminium in neurodegenerative disease

• 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: Exley, Christopher