Dynamics in DHFR. (a) Crystal structures of E. coli DHFR show the Met20 loop in the occluded (1rx4, blue) and closed
(1rx2, red)
conformations. During the catalytic cycle of DHFR, this loop fluctuates
between these conformations on the millisecond time scale. The ligands
NADPH (left ligand) and folate (right ligand) are shown in orange
and yellow, respectively. (b) Mutation of Asn23 to two proline residues
(N23PP) shown as sticks in red and Ser148 to alanine (S148A) shown
in pink reduce activity of ecDHFR. Mutation of Gly51 to the sequence
PEKN (shown in blue) partially recovers the catalytic activity. The
activity is increased further by the Leu28Phe (L28F, green) mutation.
The structure of N23PP/PEKN (4gh8) is shown with NADPH shown in orange, with substrate
mimic methotrexate in tan. (c) pH independent hydride transfer rates
of different mutants show the quantitative effects of mutations that
alter the dynamics of the Met20 loop and packing around the substrate.