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Reduction thermodynamics of the T1 Cu site in plant and fungal laccases

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Abstract

The thermodynamic parameters for reduction of the type-1 (T1) copper site in Rhus vernicifera and Trametes versicolor laccases and for the derivative of the former protein from which the type-2 copper has been selectively removed (T2D) have been determined with UV–vis spectroelectrochemistry. In all cases, the enthalpic term turns out to be the main determinant of the E o′ of the T1 site. Also the difference between the reduction potentials of the two laccases is enthalpy-based and reflects differences in the coordination features of the T1 sites and their protein environment. The T1 sites in native R. vernicifera laccase and its T2D derivative show the same E o′, as a result of compensatory differences in the reduction thermodynamics. This suggests that removal of the type-2 (T2) copper results in modification of the reduction-induced solvent reorganization effects, with no influence in the structure of the multicopper protein site. This conclusion is supported by NMR data recorded on the native, the T2D, and Hg-substituted T1 derivatives of R. vernicifera laccase, which show that the T1 and T2/T3 sites are largely noninteracting.

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Abbreviations

EPR:

Electron paramagnetc resonance

OTTLE:

Optically transparent thin layer electrochemical

T1:

Type 1

T1(Hg):

Laccase derivative in which the type-1 copper has been replaced with Hg

T2:

Type 2

T2D:

Type-2 copper depleted form of laccase

T3:

Type 3

ΔH orc ′:

Enthalpy change for reduction

ΔS orc ′:

Entropy change for reduction

E o′:

Standard reduction potential

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Acknowledgements

This work was supported in part by the Ministero dell’Universitá e della Ricerca Scientifica e Tecnologica of Italy (Programmi di Ricerca Scientifica di Rilevante Interesse Nazionale, PRIN 2003), by the Fondazione Cassa di Risparmio di Modena 16/4/2002 and by the COST D21 action of the EC (WG D21/0011/01). A.D.C. and R.P. thank the EC (QLK3-99-590) for financial support. A.J.V. thanks NIH (R01-GM068682) and ANPCyT (PICT 01-11625) for financial support and Fundacion Antorchas for a travel grant. Lucia Banci (University of Florence) is gratefully acknowledged for stimulating discussions. Lorenzo Sorace of the LAMM of the University of Florence is gratefully acknowledged for assistance in recording the EPR spectra.

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Authors and Affiliations

  1. Department of Chemistry—Centro SCS, University of Modena and Reggio Emilia, Via Campi 183, 41100, Modena, Italy

    Gianantonio Battistuzzi, Marzia Bellei, Alan Leonardi & Marco Sola

  2. CERM and Department of Chemistry, University of Florence, Via Luigi Sacconi 6, 50019, Sesto Fiorentino, Florence, Italy

    Roberta Pierattelli

  3. Molecular Biology Division, Instituto de Biología Molecular y Celular de Rosario, CONICET, and Biophysics Section, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK, Rosario, Argentina

    Ariel De Candia & Alejandro J. Vila

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  1. Gianantonio Battistuzzi
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Correspondence to Gianantonio Battistuzzi.

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Battistuzzi, G., Bellei, M., Leonardi, A. et al. Reduction thermodynamics of the T1 Cu site in plant and fungal laccases. J Biol Inorg Chem 10, 867–873 (2005). https://doi.org/10.1007/s00775-005-0035-z

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