Silicon Forms a Rich Diversity of Aliphatic Polyol Complexes in Aqueous Solution

Abstract

A detailed examination of aqueous Si complexation by alditols and aldonic acids was conducted using high-sensitivity 29Si NMR spectroscopy of isotopically enriched solutions combined with theoretical modeling. Contrary to previous thinking, we have established that aliphatic polyols do not require a threo pair of hydroxy groups to form hypercoordinated Si complexes, although formation constants may be orders of magnitude higher if they are present. Thirteen distinctly different molecular assemblages containing 4-, 5-, or 6-coordinate Si centers have been identified, with significant concentrations of 5-coordinate Si bis-ligand complex being detected even under biologically relevant solution conditions.

The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si–O Bond

“…This might explain the unique role of (biogenic) catechols in the (bio)­mineralization of silica or the poorly understood, high kinetics of catechols in quartz dissolution. It suggests pathways for the structural adaptation of silicates under mild geo- and biochemical equilibrium conditions. ,, Importantly, similar observations with sugars or with polyols in sol–gel chemistry indicate a generality of this phenomenon that is worth considerating The dynamic covalent chemistry of the Si–O bond calls for implementation in materials science.…”

The Lysosome Origin of Biosilica Machinery in the Demospongiae Model Petrosia ficiformis (Poiret, 1789)

“…The hypothesis of one organosilicon compound already emerged from the beginning of studies of silicatein (see Shimizu et al, 1998) but, at the same time no specific ideas have already been confirmed. Bio-organic chemistry works suggested the general possibility to have silica derivatives with organic molecules of biological relevance (Kinrade et al, 1999;Vis et al, 2020). The presence of many enzymes related to sugar metabolism could be suggestive of silicon-organic compounds specifically involved in this process, while cathepsins and silicateins can play a role both in the enzymatic control of biosilica precipitation and in the structural organisation of spicules.…”

Using Machine Learning Algorithms to Predict the Effects of Substituents on Molecular Properties and Structures

“…al. showed the many different structures silicate polyols can adapt in aqueous solutions [6]. The existence of these structures was proven using nuclear magnetic resonance spectra.…”

“…To begin building the algorithm a matrix and vectors need to be defined. For this research the matrix will be composed of the substituents and the properties determined by Lefrancois-Gagnon [6]. For investigating the isodesmic reactions acid dissociation energy the problem seems linear in nature.…”