Complexation by small
organic ligands controls the bioavailability
of contaminants and influences their mobility in the geosphere. We
have studied the interactions of Cm3+, as a representative
of the trivalent actinides, and Eu3+, as an inactive homologue,
with glucuronic acid (GlcA) a simple sugar acid. Time-resolved laser-induced
luminescence spectroscopy (TRLFS) shows that complexation at pH 5.0
occurs only at high ligand to metal ratios in the form of 1:1 complexes
with standard formation constants log β0 = 1.84 ± 0.22 for Eu3+ and log β0 = 2.39 ± 0.19
for Cm3+. A combination of
NMR, QMMM, and TRLFS reveals the structure of the complex to be a
half-sandwich structure wherein the ligand binds through its carboxylic
group, the ring oxygen, and a hydroxyl group in addition to five to
six water molecules. Surprisingly, Y3+, which was used
as a diamagnetic reference in NMR, prefers a different coordination
geometry with bonding through at least two hydroxyl groups on the
opposite side of a distorted GlcA molecule. QMMM simulations indicate
that the differences in stability among Cm, Eu, and Y are related
to ring strain induced by smaller cations. At higher pH a stronger
complex was detected, most likely due to deprotonation of a coordinating
OH group.