TY - JOUR
T1 - Key Intermediate Species Reveal the Copper(II)-Exchange Pathway in Biorelevant ATCUN/NTS Complexes
AU - Kotuniak, Radosław
AU - Strampraad, Marc J.F.
AU - Bossak-Ahmad, Karolina
AU - Wawrzyniak, Urszula E.
AU - Ufnalska, Iwona
AU - Hagedoorn, Peter Leon
AU - Bal, Wojciech
PY - 2020
Y1 - 2020
N2 - The amino-terminal copper and nickel/N-terminal site (ATCUN/NTS) present in proteins and bioactive peptides exhibits high affinity towards CuII ions and have been implicated in human copper physiology. Little is known, however, about the rate and exact mechanism of formation of such complexes. We used the stopped-flow and microsecond freeze-hyperquenching (MHQ) techniques supported by steady-state spectroscopic and electrochemical data to demonstrate the formation of partially coordinated intermediate CuII complexes formed by glycyl–glycyl–histidine (GGH) peptide, the simplest ATCUN/NTS model. One of these novel intermediates, characterized by two-nitrogen coordination, t1/2≈100 ms at pH 6.0 and the ability to maintain the CuII/CuI redox pair is the best candidate for the long-sought reactive species in extracellular copper transport.
AB - The amino-terminal copper and nickel/N-terminal site (ATCUN/NTS) present in proteins and bioactive peptides exhibits high affinity towards CuII ions and have been implicated in human copper physiology. Little is known, however, about the rate and exact mechanism of formation of such complexes. We used the stopped-flow and microsecond freeze-hyperquenching (MHQ) techniques supported by steady-state spectroscopic and electrochemical data to demonstrate the formation of partially coordinated intermediate CuII complexes formed by glycyl–glycyl–histidine (GGH) peptide, the simplest ATCUN/NTS model. One of these novel intermediates, characterized by two-nitrogen coordination, t1/2≈100 ms at pH 6.0 and the ability to maintain the CuII/CuI redox pair is the best candidate for the long-sought reactive species in extracellular copper transport.
KW - amino-terminal copper and nickel (ATCUN) motif
KW - copper
KW - electrochemistry
KW - EPR spectroscopy
KW - peptides
UR - http://www.scopus.com/inward/record.url?scp=85084420050&partnerID=8YFLogxK
U2 - 10.1002/anie.202004264
DO - 10.1002/anie.202004264
M3 - Article
SN - 1433-7851
VL - 59
SP - 11234
EP - 11239
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 28
ER -