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Is density functional theory accurate for lytic polysaccharide monooxygenase enzymes

Larsson, Ernst D. LU ; Dong, Geng LU ; Veryazov, Valera LU orcid ; Ryde, Ulf LU orcid and Hedegård, Erik D. LU (2020) In Dalton Transactions 49(5). p.1501-1512
Abstract

The lytic polysaccharide monooxygenase (LPMO) enzymes boost polysaccharide depolymerization through oxidative chemistry, which has fueled the hope for more energy-efficient production of biofuel. We have recently proposed a mechanism for the oxidation of the polysaccharide substrate (E. D. Hedegård and U. Ryde, Chem. Sci., 2018, 9, 3866-3880). In this mechanism, intermediates with superoxide, oxyl, as well as hydroxyl (i.e. [CuO2]+, [CuO]+ and [CuOH]2+) cores were involved. These complexes can have both singlet and triplet spin states, and both spin-states may be important for how LPMOs function during catalytic turnover. Previous calculations on LPMOs have exclusively been based on density... (More)

The lytic polysaccharide monooxygenase (LPMO) enzymes boost polysaccharide depolymerization through oxidative chemistry, which has fueled the hope for more energy-efficient production of biofuel. We have recently proposed a mechanism for the oxidation of the polysaccharide substrate (E. D. Hedegård and U. Ryde, Chem. Sci., 2018, 9, 3866-3880). In this mechanism, intermediates with superoxide, oxyl, as well as hydroxyl (i.e. [CuO2]+, [CuO]+ and [CuOH]2+) cores were involved. These complexes can have both singlet and triplet spin states, and both spin-states may be important for how LPMOs function during catalytic turnover. Previous calculations on LPMOs have exclusively been based on density functional theory (DFT). However, different DFT functionals are known to display large differences for spin-state splittings in transition-metal complexes, and this has also been an issue for LPMOs. In this paper, we study the accuracy of DFT for spin-state splittings in superoxide, oxyl, and hydroxyl intermediates involved in LPMO turnover. As reference we employ multiconfigurational perturbation theory (CASPT2).

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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
49
issue
5
pages
12 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:31922155
  • scopus:85079075133
ISSN
1477-9226
DOI
10.1039/c9dt04486h
language
English
LU publication?
yes
id
9933159b-b197-41a6-9dbf-8aac97fd987a
date added to LUP
2020-03-02 11:27:33
date last changed
2024-04-17 04:35:12
@article{9933159b-b197-41a6-9dbf-8aac97fd987a,
  abstract     = {{<p>The lytic polysaccharide monooxygenase (LPMO) enzymes boost polysaccharide depolymerization through oxidative chemistry, which has fueled the hope for more energy-efficient production of biofuel. We have recently proposed a mechanism for the oxidation of the polysaccharide substrate (E. D. Hedegård and U. Ryde, Chem. Sci., 2018, 9, 3866-3880). In this mechanism, intermediates with superoxide, oxyl, as well as hydroxyl (i.e. [CuO<sub>2</sub>]<sup>+</sup>, [CuO]<sup>+</sup> and [CuOH]<sup>2+</sup>) cores were involved. These complexes can have both singlet and triplet spin states, and both spin-states may be important for how LPMOs function during catalytic turnover. Previous calculations on LPMOs have exclusively been based on density functional theory (DFT). However, different DFT functionals are known to display large differences for spin-state splittings in transition-metal complexes, and this has also been an issue for LPMOs. In this paper, we study the accuracy of DFT for spin-state splittings in superoxide, oxyl, and hydroxyl intermediates involved in LPMO turnover. As reference we employ multiconfigurational perturbation theory (CASPT2).</p>}},
  author       = {{Larsson, Ernst D. and Dong, Geng and Veryazov, Valera and Ryde, Ulf and Hedegård, Erik D.}},
  issn         = {{1477-9226}},
  language     = {{eng}},
  month        = {{01}},
  number       = {{5}},
  pages        = {{1501--1512}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Is density functional theory accurate for lytic polysaccharide monooxygenase enzymes}},
  url          = {{http://dx.doi.org/10.1039/c9dt04486h}},
  doi          = {{10.1039/c9dt04486h}},
  volume       = {{49}},
  year         = {{2020}},
}