Direct Electron Transfer between a Site-Specific Pyrene-Modified Laccase and Carbon Nanotube/Gold Nanoparticle Supramolecular Assemblies for Bioelectrocatalytic Dioxygen Reduction

Abstract

International audienc

Efficiency of Site‐Specific Clicked Laccase–Carbon Nanotubes Biocathodes towards O2 Reduction

“…Following our previous work on the orientation of pyrene‐laccase molecules at the MWCNT electrode surface, we initially compared in silico the pyrene‐UNIK 161 and (pyrene) 2 ‐LAC3 hybrid/MWCNT electrodes (Figure SI1, see Supporting Information for computational details). Modeling of the pyrene grafted K 40, K 71 and K 161 positions was performed as previously published .…”

“…Comparatively, reports targeting specific modifications of the surface of MCOs—that is, terminal tags, single surface exposed reactive variant or unnatural amino acid—are still few . Probably seen as complex because a modification of the DNA to encode a site‐selective anchor point is a prerequisite, this strategy has yet no equivalent to generate uniform enzyme–electrode interfaces where almost each enzyme molecule is bound through the same single point.…”

“…Moreover, in principle, for any given enzyme–electrode couple the interface can be as finely adjusted as moving the anchoring point (i.e., the reactive function) from one position to an adjacent surface exposed position. In a recent work, we have precisely introduced a pyrene moiety at the surface of a fungal laccase . This pyrene group has allowed us to immobilize the enzyme at the surface of CNTs (supra‐molecular interaction) with a predefined and DET favorable orientation.…”

Controlling Redox Enzyme Orientation at Planar Electrodes

“…Interestingly, a significant difference in current output was also observed between the two different grafting localizations, suggesting a control of the orientation of the enzyme. In the same way, a fungal laccase presenting a unique surface lysine residue close to the T1 Cu site was immobilized on planar electrodes [131]. This strategy can be applied in all the cases where a unique surface residue can be genetically engineered.…”

Metallvermittelte Funktionalisierung natürlicher Peptide und Proteine: Biokonjugation mit Übergangsmetallen

“…[45] 2015 berichteten Francis und Mitarbeiter von einer iridiumkatalysierten Va riante,w elche sich biokompatibler Formiate als stçchimetrischer Hydridquellen bedient (Abbildung 7a). [48] Die Struktur und das Konzept des biokompatiblen Iridiumhydrids wurden außerdem kürzlich zusammenhangslos auf ein Beispiel hydridbasierter Katalyse in lebenden Zellen ausgedehnt, was unter Beweis stellt, auf welchem Wege diese grundlegenden Untersuchungen zu Biokonjugationsreaktivitäten selbst die Forschung in anderen Bereichen der biologischen Chemie ankurbeln kann. Die Reaktion verläuft bei unter 37 8 8Cin einer Pufferlçsung mit neutralem pH-Wert.…”