Evidence for
covalent modification of WRN by H3B-859. (A) Chemical
structure for starting lead H3B-859. The pyrimidine ring is numbered
according to convention. (B) Real-time DNA unwinding progress curves
with 0.6 nM WRN helicase domain, 0.5 μM Hel-10bp, 5 μM
Trap-10bp, 120 μM ATP, and the indicated concentrations of H3B-859.
(C) Intact mass analysis of WRN helicase domain (expected MW = 51026.6
Da) with DMSO. (D) Intact mass analysis after overnight treatment
with a 10-fold excess of H3B-859. Alkylation by H3B-859 is expected
to shift the mass by 253 Da. Masses corresponding to unmodified, monoalkylated,
and dialkylated proteins are indicated in the spectrum as 0×,
1×, and 2×, respectively. (E) Proposed mechanism
of inhibition by 2-sulfonylpyrimidine. A cysteine from WRN undergoes
nucleophilic aromatic substitution to form the indicated adduct with
departure of the sulfinic acid leaving group.