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2019-06-20

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Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/166522

Oxidative Cleavage of Cellobiose by Lytic Polysaccharide Monooxygenase (LPMO)-Inspired Copper Complexes

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Recurs relacionat

https://doi.org/10.1021/acsomega.9b00785
 https://doi.org/10.1021/acsomega.0c04910

Resum

The potentially tridentate ligand bis[(1-methyl-2-benzimidazolyl)ethyl]amine (2BB) was employed to prepare copper complexes [(2BB)CuI]OTf and [(2BB)CuII(H2O)2](OTf)2 as bioinspired models of lytic polysaccharide copper-dependent monooxygenase (LPMO) enzymes. Solid-state characterization of [(2BB)CuI]OTf revealed a Cu(I) center with a T-shaped coordination environment and metric parameters in the range of those observed in reduced LPMOs. Solution characterization of [(2BB)CuII(H2O)2](OTf)2 indicates that [(2BB)CuII(H2O)2]2+ is the main species from pH 4 to 7.5; above pH 7.5, the hydroxo-bridged species [{(2BB)CuII(H2O)x}2(μ-OH)2]2+ is also present, on the basis of cyclic voltammetry and mass spectrometry. These observations imply that deprotonation of the central amine of Cu(II)-coordinated 2BB is precluded, and by extension, amine deprotonation in the histidine brace of LPMOs appears unlikely at neutral pH. The complexes [(2BB)CuI]OTf and [(2BB)CuII(H2O)2](OTf)2 act as precursors for the oxidative degradation of cellobiose as a cellulose model substrate. Spectroscopic and reactivity studies indicate that a dicopper(II) side-on peroxide complex generated from [(2BB)CuI]OTf/O2 or [(2BB)CuII(H2O)2](OTf)2/H2O2/NEt3 oxidizes cellobiose both in acetonitrile and aqueous phosphate buffer solutions, as evidenced from product analysis by high-performance liquid chromatography-mass spectrometry. The mixture of [(2BB)CuII(H2O)2](OTf)2/H2O2/NEt3 results in more extensive cellobiose degradation. Likewise, the use of both [(2BB)CuI]OTf and [(2BB)CuII(H2O)2](OTf)2 with KO2 afforded cellobiose oxidation products. In all cases, a common Cu(II) complex formulated as [(2BB)CuII(OH)(H2O)]+ was detected by mass spectrometry as the final form of the complex.

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Correction published on October 23, 2020 https://doi.org/10.1021/acsomega.0c04910

Matèries

Coure, Enzims, Polisacàrids, Amines

Matèries (anglès)

Copper, Enzymes, Polysaccharides, Amines

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Articles publicats en revistes (Química Inorgànica i Orgànica)

Citació

NEIRA, Andrea. c., MARTÍNEZ-ALANIS, Paulina r., AULLÓN LÓPEZ, Gabriel, FLORES ALAMO, Marcos, ZERÓN, Paulino, COMPANY, Anna, CHEN, Juan, KASPER, Johann b., BROWNE, Wesley r., NORDLANDER, Ebbe, CASTILLO, Ivan. Oxidative Cleavage of Cellobiose by Lytic Polysaccharide Monooxygenase (LPMO)-Inspired Copper Complexes. _ACS Omega _. 2019. Vol. 4, núm. 10729-10740. [consulta: 21 de gener de 2026]. ISSN: 2470-1343. [Disponible a: https://hdl.handle.net/2445/166522]

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