Characterization of a NiIII species during reductive catalysis by [Ni(cyclam)]2+ implicates an ECCE mechanism for hydrogen production in aqueous solution.
Degradation of saccharides
is relevant to the design of catalytic therapeutics, the production
of biofuels, inhibition of biofilms, as well as other applications
in chemical biology. Herein, we report the design of multinuclear
Cu complexes that enable cleavage of saccharides under physiological
conditions. Reactivity studies with para-nitrophenyl
(pNP)-conjugated carbohydrates show that dinuclear
Cu complexes exhibit a synergistic effect and promote faster and more
robust cleavage of saccharide substrates, relative to the mononuclear
Cu complex, while no further enhancement is observed for the tetranuclear
Cu complex. The use of scavengers for reactive oxygen species confirms
that saccharide cleavage is promoted by the formation of superoxide
and hydroxyl radicals through CuII/I redox chemistry, similar
to that observed for native copper-containing lytic polysaccharide
monooxygenases (LMPOs). Differences in selectivity for di- and tetranuclear
Cu complexes are modest. However, these are the first reported small
multinuclear Cu complexes that show selectivity and reactivity against
mono- and disaccharide substrates and form a basis for further development
of metalloglycosidases for applications in chemical biology.
Page 11221. Some recent reports also provide additional details of the current mechanistic understanding of LPMO activity 1−3 and an example of a model complex with catalytic activity around physiological pH. 4
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