(A) Competitive patterns of mesotrypsin inhibition by
APPIM17G. Mesotrypsin cleavage of peptide substrate Z-GPR-pNA is
competitively inhibited by APPIM17G. (B) The
Lineweaver-Burk double reciprocal transform of the data used in panel
A. The APPI (inhibitor) concentration is given at the top
of each plot; the mesotrypsin concentration was 0.25 nM. Data was fitted
globally to the competitive inhibition equation using Prism, GraphPad Software.
(C, E) Slow, tight binding inhibition of mesotrypsin by APPI
variants. Steady-state equilibrium for the reactions of APPIM17G
(C) and APPIM17G/I18F/F34V (E)
with various concentrations of APPI and 145 μM of
peptide substrate Z-GPR-pNA. (D, F) A re-plot of slopes
(V0 and Vi) calculated from the binding curves shown
in panels C and E, respectively, where
V0 is the uninhibited rate and Vi is the rate in the
presence of inhibitor, which allows calculation of
Ki using eq. 2 (as described in SI
Materials and Methods under “ Inhibition studies”).
(G) Kinetics of APPIM17G/I18F/F34V hydrolysis by
mesotrypsin. Representative HPLC chromatograms are shown from a time course of
APPIM17G/I18F/F34V hydrolysis by mesotrypsin. Green and red peaks
represent intact and cleaved inhibitor, respectively. (H) Initial
rate of hydrolysis, from which kcat is calculated.
Disappearance of intact APPIM17G/I18F/F34V was quantified by
integration of the HPLC peak in a time course that is illustrated in panel
G. Hydrolysis reaction contained 50
μM of APPIM17G/I18F/F34V and 2.5
μM of enzyme.