Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase

Research output: Contribution to journalJournal articlepeer-review

Standard

Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase. / Singh, Raushan Kumar; Möllers Blossom, Benedikt; Russo, David A; Singh, Ranjitha; Weihe, Høgni; Andersen, Niels H.; Tiwari, Manish Kumar; Jensen, Poul Erik; Felby, Claus; Bjerrum, Morten Jannik.

In: Chemistry - A European Journal, Vol. 26, No. 2, 2020, p. 454-463.

Research output: Contribution to journalJournal articlepeer-review

Harvard

Singh, RK, Möllers Blossom, B, Russo, DA, Singh, R, Weihe, H, Andersen, NH, Tiwari, MK, Jensen, PE, Felby, C & Bjerrum, MJ 2020, 'Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase', Chemistry - A European Journal, vol. 26, no. 2, pp. 454-463. https://doi.org/10.1002/chem.201903562

APA

Singh, R. K., Möllers Blossom, B., Russo, D. A., Singh, R., Weihe, H., Andersen, N. H., Tiwari, M. K., Jensen, P. E., Felby, C., & Bjerrum, M. J. (2020). Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase. Chemistry - A European Journal, 26(2), 454-463. https://doi.org/10.1002/chem.201903562

Vancouver

Singh RK, Möllers Blossom B, Russo DA, Singh R, Weihe H, Andersen NH et al. Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase. Chemistry - A European Journal. 2020;26(2):454-463. https://doi.org/10.1002/chem.201903562

Author

Singh, Raushan Kumar ; Möllers Blossom, Benedikt ; Russo, David A ; Singh, Ranjitha ; Weihe, Høgni ; Andersen, Niels H. ; Tiwari, Manish Kumar ; Jensen, Poul Erik ; Felby, Claus ; Bjerrum, Morten Jannik. / Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase. In: Chemistry - A European Journal. 2020 ; Vol. 26, No. 2. pp. 454-463.

Bibtex

@article{3d66c4e8b8af47a7bfe4cfdcbdfa0af9,
title = "Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase",
abstract = "Lytic polysaccharide monooxygenases (LPMOs) are copper‐containing enzymes capable of oxidizing crystalline cellulose which have large practical application in the process of refining biomass. The catalytic mechanism of LPMOs still remains debated despite several proposed reaction mechanisms. Here, we report a long‐lived intermediate (t½ = 6 ‐ 8 minutes) observed in an LPMO from Thermoascus aurantiacus (TaLPMO9A). The intermediate with a strong absorption around 420 nm is formed when reduced LPMO‐Cu(I) reacts with sub‐equimolar amounts of H2O2. UV‐vis absorption spectroscopy, electron paramagnetic resonance, resonance Raman and stopped‐flow spectroscopy suggest that the observed long‐lived intermediate involves the copper center and a nearby tyrosine (Tyr175). Additionally, activity assays in the presence of sub‐equimolar amounts of H2O2 showed an increase in the LPMO oxidation of phosphoric acid swollen cellulose. Accordingly, this suggests that the long‐lived copper‐dependent intermediate could be part of the catalytic mechanism for LPMOs. The observed intermediate offers a new perspective into the oxidative reaction mechanism of TaLPMO9A and hence for the biomass oxidation and the reactivity of copper in biological systems.",
author = "Singh, {Raushan Kumar} and {M{\"o}llers Blossom}, Benedikt and Russo, {David A} and Ranjitha Singh and H{\o}gni Weihe and Andersen, {Niels H.} and Tiwari, {Manish Kumar} and Jensen, {Poul Erik} and Claus Felby and Bjerrum, {Morten Jannik}",
year = "2020",
doi = "10.1002/chem.201903562",
language = "English",
volume = "26",
pages = "454--463",
journal = "Chemistry: A European Journal",
issn = "0947-6539",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "2",

}

RIS

TY - JOUR

T1 - Detection and characterization of a novel copper-dependent intermediate in a lytic polysaccharide monooxygenase

AU - Singh, Raushan Kumar

AU - Möllers Blossom, Benedikt

AU - Russo, David A

AU - Singh, Ranjitha

AU - Weihe, Høgni

AU - Andersen, Niels H.

AU - Tiwari, Manish Kumar

AU - Jensen, Poul Erik

AU - Felby, Claus

AU - Bjerrum, Morten Jannik

PY - 2020

Y1 - 2020

N2 - Lytic polysaccharide monooxygenases (LPMOs) are copper‐containing enzymes capable of oxidizing crystalline cellulose which have large practical application in the process of refining biomass. The catalytic mechanism of LPMOs still remains debated despite several proposed reaction mechanisms. Here, we report a long‐lived intermediate (t½ = 6 ‐ 8 minutes) observed in an LPMO from Thermoascus aurantiacus (TaLPMO9A). The intermediate with a strong absorption around 420 nm is formed when reduced LPMO‐Cu(I) reacts with sub‐equimolar amounts of H2O2. UV‐vis absorption spectroscopy, electron paramagnetic resonance, resonance Raman and stopped‐flow spectroscopy suggest that the observed long‐lived intermediate involves the copper center and a nearby tyrosine (Tyr175). Additionally, activity assays in the presence of sub‐equimolar amounts of H2O2 showed an increase in the LPMO oxidation of phosphoric acid swollen cellulose. Accordingly, this suggests that the long‐lived copper‐dependent intermediate could be part of the catalytic mechanism for LPMOs. The observed intermediate offers a new perspective into the oxidative reaction mechanism of TaLPMO9A and hence for the biomass oxidation and the reactivity of copper in biological systems.

AB - Lytic polysaccharide monooxygenases (LPMOs) are copper‐containing enzymes capable of oxidizing crystalline cellulose which have large practical application in the process of refining biomass. The catalytic mechanism of LPMOs still remains debated despite several proposed reaction mechanisms. Here, we report a long‐lived intermediate (t½ = 6 ‐ 8 minutes) observed in an LPMO from Thermoascus aurantiacus (TaLPMO9A). The intermediate with a strong absorption around 420 nm is formed when reduced LPMO‐Cu(I) reacts with sub‐equimolar amounts of H2O2. UV‐vis absorption spectroscopy, electron paramagnetic resonance, resonance Raman and stopped‐flow spectroscopy suggest that the observed long‐lived intermediate involves the copper center and a nearby tyrosine (Tyr175). Additionally, activity assays in the presence of sub‐equimolar amounts of H2O2 showed an increase in the LPMO oxidation of phosphoric acid swollen cellulose. Accordingly, this suggests that the long‐lived copper‐dependent intermediate could be part of the catalytic mechanism for LPMOs. The observed intermediate offers a new perspective into the oxidative reaction mechanism of TaLPMO9A and hence for the biomass oxidation and the reactivity of copper in biological systems.

U2 - 10.1002/chem.201903562

DO - 10.1002/chem.201903562

M3 - Journal article

C2 - 31603264

VL - 26

SP - 454

EP - 463

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 2

ER -

ID: 229902496