NMR shifts of silicate complexes with carbohydrates, amino acids, and MuHicarboxylic acids: Potential role in biological silica utilization

The existence of ether or ester-like complexes of silicate with organic compounds has long been debated in the literature on biological utilization of silicon. Comparison of theoretically calculated Si NMR chemical shifts for such complexes with experimentally measured values in biological systems could provide a diagnostic tool for identifying which, if any of these molecules exist under physiological conditions. Results are presented here for ab initio molecular orbital calculations of Si NMR shifts and formation energies of silicate complexes with polyalcohols, sugar-acids, pyranose sugars, amino acids and multicarboxylic acids. The effects of functional group and molecular structure including ligand size, denticity, ring size, silicon polymerization and coordination number on calculated Si shifts were considered. The potential role of such compounds in biological silica utilization pathways is discussed. Si NMR shifts and energies were calculated at the HF/6-311 G(2d,p)//HF/6-31G* level. The main result is that only five-membered rings containing pentaand hexa-coordinated Si can explain experimentally observed resonances at 101 and 141 ppm. Further, the heptet observed in H-Si coupled spectra can only be explained by structures where Si bonds to oxygens atoms in H-C-O-Si linkages with six symmetrically equivalent H atoms. While compounds containing quadra-coordinated silicon may exist in intracellular silicon storage pools within diatoms, calculated reaction energies suggest that the organism has no thermodynamic advantage in taking up extracellular organ-silicate compounds, instead of silicic acid, from the ambient aqueous environment. Hyper-coordinated complexes are deemed unlikely for transport and storage, though they may exist as transient reactive intermediates or activated complexes during enzymaticallycatalyzed silica polymerization, as known previously from sol-gel silica synthesis studies. Copyright © 2004 Elsevier Ltd