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
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.