Mimicking the Electron Transport Chain and Active Site of [FeFe] Hydrogenases in One Metal-Organic Framework: Factors That Influence Charge Transport

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Castner, Ashleigh T.Uppsala universitet,Syntetisk molekylär kemi (författare)

Mimicking the Electron Transport Chain and Active Site of [FeFe] Hydrogenases in One Metal-Organic Framework : Factors That Influence Charge Transport

Artikel/kapitelEngelska2021

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2021-05-24
American Chemical Society (ACS),2021
electronicrdacarrier

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LIBRIS-ID:oai:DiVA.org:uu-448926
https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-448926URI
https://doi.org/10.1021/jacs.1c01361DOI

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Språk:engelska
Sammanfattning på:engelska

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[FeFe] hydrogenase (H2ase) enzymes are effective proton reduction catalysts capable of forming molecular dihydrogen with a high turnover frequency at low overpotential. The active sites of these enzymes are buried within the protein structures, and substrates required for hydrogen evolution (both protons and electrons) are shuttled to the active sites through channels from the protein surface. Metal–organic frameworks (MOFs) provide a unique platform for mimicking such enzymes due to their inherent porosity which permits substrate diffusion and their structural tunability which allows for the incorporation of multiple functional linkers. Herein, we describe the preparation and characterization of a redox-active PCN-700-based MOF (PCN = porous coordination network) that features both a biomimetic model of the [FeFe] H2ase active site as well as a redox-active linker that acts as an electron mediator, thereby mimicking the function of [4Fe4S] clusters in the enzyme. Rigorous studies on the dual-functionalized MOF by cyclic voltammetry (CV) reveal similarities to the natural system but also important limitations in the MOF-enzyme analogy. Most importantly, and in contrast to the enzyme, restrictions apply to the total concentration of reduced linkers and charge-balancing counter cations that can be accommodated within the MOF. Successive charging of the MOF results in nonideal interactions between linkers and restricted mobility of charge-compensating redox-inactive counterions. Consequently, apparent diffusion coefficients are no longer constant, and expected redox features in the CVs of the materials are absent. Such nonlinear effects may play an important role in MOFs for (electro)catalytic applications.

Ämnesord och genrebeteckningar

NATURVETENSKAP Kemi Organisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Organic Chemistry hsv//eng
NATURVETENSKAP Biologi Biokemi och molekylärbiologi hsv//swe
NATURAL SCIENCES Biological Sciences Biochemistry and Molecular Biology hsv//eng

Biuppslag (personer, institutioner, konferenser, titlar ...)

Johnson, Ben A.Uppsala universitet,Syntetisk molekylär kemi(Swepub:uu)benjo679 (författare)
Cohen, Seth M.Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92023 USA (författare)
Ott, SaschaUppsala universitet,Syntetisk molekylär kemi(Swepub:uu)saott499 (författare)
Uppsala universitetSyntetisk molekylär kemi (creator_code:org_t)

Sammanhörande titlar

Ingår i:Journal of the American Chemical Society: American Chemical Society (ACS)143:21, s. 7991-79990002-78631520-5126

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Av författaren/redakt...: Castner, Ashleig ...; Johnson, Ben A.; Cohen, Seth M.; Ott, Sascha

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NATURVETENSKAP: NATURVETENSKAP; och Kemi; och Organisk kemi

NATURVETENSKAP: NATURVETENSKAP; och Biologi; och Biokemi och mole ...

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Av lärosätet: Uppsala universitet

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