Structural and kinetic characterization of spiro-benzoxazole
inhibitors
of GALK1. (A) Chemical structures of the two spiro-benzoxazole inhibitors
characterized in this work. The spiro-ring, differing between the
two compounds, is highlighted in red. (B) Superimposed structures
of GALK1-galactose-AMPPNP (PDB 1WUU; light/dark gray), GALK1-galactose-T1 (light/dark blue), and GALK1-galactose-T2 (yellow/orange)
structures. The N-terminal domain is shaded lighter than the C-terminal
domain. Galactose and magnesium are shown as spacefill; AMPPNP, T1, and T2 are shown as gray, blue, and yellow
sticks, respectively. (C) Close-up view of the boxed area shown in
panel B. The four ATP binding loops (L1, Ser79–Pro85; L2, Ser98–Arg105;
L3, Val133–Ser140; and L4; Arg228–Glu235) are shown
as ribbons. Galactose and magnesium ions are shown as spacefill, and
AMPPNP, T1, and T2 are shown as gray, blue,
and yellow sticks, respectively. (D) Close-up view of the GALK1 active
site illustrating the binding mode of AMPPNP, T1, and T2. Nearby protein residues of the GALK1–galactose–AMPPNP,
GALK1–galactose–T1, and GALK1–galactose–T2 structures are shown as gray, blue, and orange lines, respectively.
(E) Least-squares nonlinear fit of GALK1 reaction rate (total galactose
consumed after 1 h reaction, μM) against increasing ATP concentrations
(0–250 μM) in the presence of different concentrations
of the inhibitor T2 (0–1 mM). Curves were fitted
to the competitive inhibition model, the best fitting enzyme kinetics–inhibition
equation, using the GraphPad Prism software. Inset: Close-up view
of plot showing GALK1 reaction rate (total galactose consumed after
1 h reaction, μM) against increasing ATP concentrations (0–10
μM) in the presence of different concentrations of the inhibitor T2 (0–1 mM).