Binding principles of silicic acid by carbohydrates

碳水化合物是硅建立稳定的水解性硅氧碳键的合适的配位体。在这一领域中，高价硅配合物(配位数为5和6)在强碱性溶液中是稳定的，但在生理pH值条件下是不稳定的，因此它们在硅的生化中不应该具有相关性。因此，本项目的目标是合成(水解性稳定的)四配位碳水化合物-硅化合物，Si(OR)4，它代表了仿生生产二氧化硅衍生物的新的Si1构建块，作为生物化学中可能的传输形式。第一部分涉及对合成这类物种的规则和概念的认识，以深入了解它们的结构和成键原理，包括建立适当的光谱方法来检测它们(特别是通过核磁共振方法)。第二部分应该证明在硅的生物化学中获得的知识的实用性，也就是说，每个新识别的基序都应该在真正的生物分子上进行测试。我们合成感兴趣物种的策略是提供基于碳水化合物的O-原子图案，以确保硅在没有任何应变的情况下被螯合。根据DFT的计算，有足够的证据表明这种结构应该是可以获得的。

Carbohydrates are suitable chelating ligands for silicon to establish hydrolytically stable Si¿O¿C bonds. In this field ¿hypervalent¿ silicon complexes (coordination number five and six) are stable in strongly alkaline solution but unstable under the conditions of a physiological pH value and therefore they should possess no relevance in the biochemistry of silicon. Thus it is the aim of this project to synthesise (hydrolytically stable) tetracoordinate carbohydrate-silicon compounds, Si(OR)4, representing novel Si1 building blocks for biomimetic production of silica derivatives as possible transport forms in biochemistry. One part deals with the recognition of rules and concepts for synthesising such species in order to gain insight into the principles of their structure and bonding, including the establishment of suitable spectroscopic methods for their detection (in particular by NMR methods). A second part should prove the usefulness of the knowledge gained in the biochemistry of silicon, that is, each newly recognised motif shall be tested on real biomolecules. Our strategy to synthesise the species of interest is to provide carbohydrate-based O-atom patterns that ensure chelation of silicon without any strain. According to DFT calculations, there is enough evidence that such structures should be obtainable.