SOLUBLE SILICA WITH HIGH-AFFINITY FOR ALUMINUM UNDER PHYSIOLOGICAL AND NATURAL CONDITIONS

Citation
Pd. Taylor et al., SOLUBLE SILICA WITH HIGH-AFFINITY FOR ALUMINUM UNDER PHYSIOLOGICAL AND NATURAL CONDITIONS, Journal of the American Chemical Society, 119(38), 1997, pp. 8852-8856
Citations number
35
Categorie Soggetti
Chemistry
ISSN journal
00027863
Volume
119
Issue
38
Year of publication
1997
Pages
8852 - 8856
Database
ISI
SICI code
0002-7863(1997)119:38<8852:SSWHFA>2.0.ZU;2-C
Abstract
Soluble silica reduces aluminum availability and ameliorates toxicity in several biological systems. It has therefore been suggested that th ese two species strongly interact in solution. However, there is only weak affinity between monomeric silicic acid and aluminum with reporte d log K-eff of between 4 and 6 at pH 7.2. We now show the existence of a soluble low molecular weight form of silica that is nonmonomeric bu t has an affinity for aluminum at least 1 000 000 times greater than t he monomeric form (log K-eff = 11.70 +/- 0.30 at pH 7.2). This was est ablished by competition, for binding of aluminum, between different pr eparations of soluble silica and the powerful M3+ chelator, 1,2-dimeth yl-3-hydroxy-4-pyridinone (DMHP). At pH 7.2, this nonmonomeric silica quantitatively displaced one equiv of DMHP for every 34.42 +/- 0.77 eq uiv of total silica, suggesting that the soluble silica that so avidly binds aluminum is an oligomer containing fewer than 35 silicon atoms. The presence of oligomeric or monomeric silica in solution depends on how the solution is prepared. The oligomer is formed when alkali stoc k solutions of silica (42 mM in this work) are pH neutralized prior to dilution, to physiological and natural levels of soluble silica (<2.5 mM). The diluted oligomeric silica is at least transiently stable (<1 day or >17 days; absence or presence of aluminum) and would compete e ffectively with endogenous physiological chelators for aluminum, such as citrate (log K-eff aluminum citrate = 7.15 at pH 7.2). Oligomeric s ilica is probably responsible for the many experimental observations o n the amelioration of aluminum availability and toxicity, but whether this silica species occurs naturally in the environment or is formed i n vivo, remains to be established.