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@ARTICLE{Cohen:306285,
author = {I. Cohen and M. Coban and A. Shahar and B. Sankaran and A.
Hockla and S. Lacham and T. R. Caulfield and E. S. Radisky
and N. Papo},
title = {{D}isulfide engineering of human {K}unitz-type serine
protease inhibitors enhances proteolytic stability and
target affinity toward mesotrypsin.},
journal = {The journal of biological chemistry},
volume = {294},
number = {13},
issn = {0021-9258},
address = {Bethesda, Md.},
publisher = {Soc.},
reportid = {DKFZ-2025-02511},
pages = {5105 - 5120},
year = {2019},
note = {#DKFZ-MOST-GR-2495#},
abstract = {Serine protease inhibitors of the Kunitz-bovine pancreatic
trypsin inhibitor (BPTI) family are ubiquitous biological
regulators of proteolysis. These small proteins are
resistant to proteolysis, but can be slowly cleaved within
the protease-binding loop by target proteases, thereby
compromising their activity. For the human protease
mesotrypsin, this cleavage is especially rapid. Here, we
aimed to stabilize the Kunitz domain structure against
proteolysis through disulfide engineering. Substitution
within the Kunitz inhibitor domain of the amyloid precursor
protein (APPI) that incorporated a new disulfide bond
between residues 17 and 34 reduced proteolysis by
mesotrypsin 74-fold. Similar disulfide engineering of tissue
factor pathway inhibitor-1 Kunitz domain 1 (KD1TFPI1) and
bikunin Kunitz domain 2 (KD2bikunin) likewise stabilized
these inhibitors against mesotrypsin proteolysis 17- and
6.6-fold, respectively. Crystal structures of
disulfide-engineered APPI and KD1TFPI1 variants in a complex
with mesotrypsin at 1.5 and 2.0 Å resolution, respectively,
confirmed the formation of well-ordered disulfide bonds
positioned to stabilize the binding loop. Long all-atom
molecular dynamics simulations of disulfide-engineered
Kunitz domains and their complexes with mesotrypsin revealed
conformational stabilization of the primed side of the
inhibitor-binding loop by the engineered disulfide, along
with global suppression of conformational dynamics in the
Kunitz domain. Our findings suggest that the Cys-17-Cys-34
disulfide slows proteolysis by dampening conformational
fluctuations in the binding loop and minimizing motion at
the enzyme-inhibitor interface. The generalizable approach
developed here for the stabilization against proteolysis of
Kunitz domains, which can serve as important scaffolds for
therapeutics, may thus find applications in drug
development.},
keywords = {Amyloid beta-Protein Precursor: chemistry / Amyloid
beta-Protein Precursor: genetics / Amyloid beta-Protein
Precursor: metabolism / Animals / Aprotinin: chemistry /
Aprotinin: genetics / Aprotinin: metabolism /
Crystallography, X-Ray / Disulfides: chemistry / Disulfides:
metabolism / Humans / Models, Molecular / Protein
Conformation / Protein Domains / Protein Engineering /
Proteolysis / Trypsin: chemistry / Trypsin: metabolism /
crystal structure (Other) / disulfide (Other) / molecular
dynamics (Other) / protease inhibitor (Other) / protein
engineering (Other) / protein structure (Other) /
proteolysis (Other) / serine protease (Other) / APP protein,
human (NLM Chemicals) / Amyloid beta-Protein Precursor (NLM
Chemicals) / Disulfides (NLM Chemicals) / Aprotinin (NLM
Chemicals) / PRSS3 protein, human (NLM Chemicals) / Trypsin
(NLM Chemicals)},
ddc = {540},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:30700553},
pmc = {pmc:PMC6442025},
doi = {10.1074/jbc.RA118.007292},
url = {https://inrepo02.dkfz.de/record/306285},
}