Natural and artificial autonomous molecular machines operate by constantly dissipating energy coming from an external source to maintain a non-equilibrium state. Quantitative thermodynamic characterization of these dissipative states is highly challenging as they exist only as long as energy is provided. Here we report on the detailed physicochemical characterization of the dissipative operation of a supramolecular pump. The pump transduces light energy into chemical energy by bringing self-assembly reactions to non-equilibrium steady states. The composition of the system under light irradiation was followed in real time by 1H NMR for four different irradiation intensities. The experimental composition and photon flow were then fed into a theoretical model describing the non-equilibrium dissipation and the energy storage at the steady state. We quantitatively probed the relationship between the light energy input and the deviation of the dissipative state from thermodynamic equilibrium in this artificial system. Our results provide a testing ground for newly developed theoretical models for photoactivated artificial molecular machines operating away from thermodynamic equilibrium.

Kinetic and energetic insights into the dissipative non-equilibrium operation of an autonomous light-powered supramolecular pump / Corra, Stefano; Bakić, Marina Tranfić; Groppi, Jessica; Baroncini, Massimo; Silvi, Serena; Penocchio, Emanuele; Esposito, Massimiliano; Credi, Alberto. - In: NATURE NANOTECHNOLOGY. - ISSN 1748-3395. - STAMPA. - 17:(2022), pp. 746-751. [10.1038/s41565-022-01151-y]

Kinetic and energetic insights into the dissipative non-equilibrium operation of an autonomous light-powered supramolecular pump

Corra, Stefano;Groppi, Jessica;Baroncini, Massimo;Silvi, Serena;Credi, Alberto
2022

Abstract

Natural and artificial autonomous molecular machines operate by constantly dissipating energy coming from an external source to maintain a non-equilibrium state. Quantitative thermodynamic characterization of these dissipative states is highly challenging as they exist only as long as energy is provided. Here we report on the detailed physicochemical characterization of the dissipative operation of a supramolecular pump. The pump transduces light energy into chemical energy by bringing self-assembly reactions to non-equilibrium steady states. The composition of the system under light irradiation was followed in real time by 1H NMR for four different irradiation intensities. The experimental composition and photon flow were then fed into a theoretical model describing the non-equilibrium dissipation and the energy storage at the steady state. We quantitatively probed the relationship between the light energy input and the deviation of the dissipative state from thermodynamic equilibrium in this artificial system. Our results provide a testing ground for newly developed theoretical models for photoactivated artificial molecular machines operating away from thermodynamic equilibrium.
2022
Kinetic and energetic insights into the dissipative non-equilibrium operation of an autonomous light-powered supramolecular pump / Corra, Stefano; Bakić, Marina Tranfić; Groppi, Jessica; Baroncini, Massimo; Silvi, Serena; Penocchio, Emanuele; Esposito, Massimiliano; Credi, Alberto. - In: NATURE NANOTECHNOLOGY. - ISSN 1748-3395. - STAMPA. - 17:(2022), pp. 746-751. [10.1038/s41565-022-01151-y]
Corra, Stefano; Bakić, Marina Tranfić; Groppi, Jessica; Baroncini, Massimo; Silvi, Serena; Penocchio, Emanuele; Esposito, Massimiliano; Credi, Alberto
File in questo prodotto:
File Dimensione Formato  
Nat+Nano+postprint_Credi.pdf

Open Access dal 27/12/2022

Tipo: Postprint
Licenza: Licenza per Accesso Aperto. Creative Commons Attribuzione - Non commerciale - Non opere derivate (CCBYNCND)
Dimensione 2.37 MB
Formato Adobe PDF
2.37 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/890050
Citazioni
  • ???jsp.display-item.citation.pmc??? 9
  • Scopus 33
  • ???jsp.display-item.citation.isi??? 34
social impact