title: Reversible Electrochemical Modulation of a Catalytic Nanosystem.
abstract: A catalytic system based on monolayer-functionalized gold nanoparticles (Au NPs) that can be electrochemically modulated and reversibly activated is reported. The catalytic activity relies on the presence of metal ions (Cd(2+) and Cu(2+) ), which can be complexed by the nanoparticle-bound monolayer. This activates the system towards the catalytic cleavage of 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP), which can be monitored by UV/Vis spectroscopy. It is shown that Cu(2+) metal ions can be delivered to the system by applying an oxidative potential to an electrode on which Cu(0) was deposited. By exploiting the different affinity of Cd(2+) and Cu(2+) ions for the monolayer, it was also possible to upregulate the catalytic activity after releasing Cu(2+) from an electrode into a solution containing Cd(2+) . Finally, it is shown that the activity of this supramolecular nanosystem can be reversibly switched on or off by oxidizing/reducing Cu/Cu(2+) ions under controlled conditions.
authors.affiliation: Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.
authors.forename: Flavio
authors.identifier: 0000-0002-6142-9869
authors.initials: F
authors.lastname: Della Sala
authors.affiliation: Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.
authors.forename: Jack L-Y
authors.initials: JL
authors.lastname: Chen
authors.affiliation: Chemistry Department, University of Rome Tor Vergata, Via della Ricerca Scientifica, 00133, Rome, Italy.
authors.forename: Simona
authors.initials: S
authors.lastname: Ranallo
authors.affiliation: Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.
authors.forename: Denis
authors.identifier: 0000-0001-6270-7966
authors.initials: D
authors.lastname: Badocco
authors.affiliation: Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy.
authors.forename: Paolo
authors.identifier: 0000-0003-1448-0175
authors.initials: P
authors.lastname: Pastore
authors.affiliation: Chemistry Department, University of Rome Tor Vergata, Via della Ricerca Scientifica, 00133, Rome, Italy. francesco.ricci@uniroma2.it.
authors.forename: Francesco
authors.identifier: 0000-0003-4941-8646
authors.initials: F
authors.lastname: Ricci
authors.affiliation: Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy. leonard.prins@unipd.it.
authors.forename: Leonard J
authors.identifier: 0000-0001-6664-822X
authors.initials: LJ
authors.lastname: Prins
keywords: gold nanoparticles; nanocatalysis; nanozymes; supramolecular catalysis; supramolecular chemistry