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. 2017 May 12;2(5):964-968.
doi: 10.1021/acsenergylett.7b00167. Epub 2017 Apr 3.

Protection and Reactivation of the [NiFeSe] Hydrogenase from Desulfovibrio vulgaris Hildenborough under Oxidative Conditions

Adrian Ruff  1 , Julian Szczesny  1 , Sónia Zacarias  2 , Inês A C Pereira  2 , Nicolas Plumeré  3 , Wolfgang Schuhmann  1
Affiliations

Protection and Reactivation of the [NiFeSe] Hydrogenase from Desulfovibrio vulgaris Hildenborough under Oxidative Conditions

Adrian Ruff et al. ACS Energy Lett. .

Abstract

We report on the fabrication of bioanodes for H2 oxidation based on [NiFeSe] hydrogenase. The enzyme was electrically wired by means of a specifically designed low-potential viologen-modified polymer, which delivers benchmark H2 oxidizing currents even under deactivating conditions owing to efficient protection against O2 combined with a viologen-induced reactivation of the O2 inhibited enzyme. Moreover, the viologen-modified polymer allows for electrochemical co-deposition of polymer and biocatalyst and, by this, for control of the film thickness. Protection and reactivation of the enzyme was demonstrated in thick and thin reaction layers.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis and Electrochemical Induced Cross-linking Process of the Viologen-Modified Redox Hydrogel P(N3MA-BA-GMA)-vio
(a) The polymer backbone P(N3MA-BA-GMA) was synthesized in a free radical polymerization reaction with the co-monomers N3MA (azidopropyl methacrylate), BA (butyl acrylate), and GMA (glycidyl methacrylate); Mn(P(N3MA-BA-GMA)) = 15 kDa, PDI = 2.1 (determined from size exclusion chromatography); composition determined by NMR: k = 71 mol %, l = 20 and 9 mol %. (b) Proposed mechanism for the electrochemical-induced cross-linking process.
Figure 1
Figure 1
Cyclic voltammograms (a) and chronoamperogram (b) of a thick P(N3MA-BA-GMA)-vio/DvH-[NiFeSe] film drop cast onto a GC electrode under H2/O2/Ar mixtures; working electrolyte: PB (0.1 M, pH 7.4); nominal polymer loading: 69 μg cm–2; nominal enzyme loading: 21 μg cm–2. (a) Scan rate: 10 mV s–1; black line: 100% argon bubbling through the cell; red solid line: 100% H2; red dashed line: 5% H2/95% Ar. (b) Applied potential: + 160 mV vs SHE.
Figure 2
Figure 2
Cyclic voltammograms (a) and chronoamperogram (b) of thin P(N3MA-BA-GMA)/DvH-[NiFeSe] films prepared by electrochemical induced deposition applying the pulse sequence n(+1.71 V/0.2 s; +0.21 V/2 s), with n = number of repetitions; working electrolyte: PB (0.1 M, pH 7.4). (a) n = 20; scan rate: 10 mV s–1; black line: 100% Ar; red solid line: 100% H2; red dashed line: 5% H2/95% Ar. (b) Applied potential: +0.16 or −0.39 V vs SHE (see graph); H2/O2 ratios were adjusted by varying the argon content in the gas flow; black trace: n = 2; blue trace: n = 10.
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