Skip to content

Research at St Andrews

Laccase redox potentials: pH dependence and mutants, a QM/MM study

Research output: Contribution to journalArticle

Author(s)

Jan Philipp Goetze, Michael Buehl

School/Research organisations

Abstract

We have studied the T. versicolor laccase T1 site redox potential (RP) at the M06/6-311++G**/SDD(Cu) level of theory, employing QM/MM optimised geometries (RI-BP86/def2-SVP/def2-TZVP(Cu):CHARMM) of the whole protein system with electronic embedding. The oxidation state of the trinuclear cluster was found to affect the T1 site RP by about 0.2-0.3 V, depending on the protein protonation state. The computed laccase RP can be drastically lowered upon introduction of a protonation state corresponding to a neutral environment, by up to -1.37 V, which is likely an overestimation of the effect in vivo. The gradual change of the protonation state by single points without optimisation or equilibration results in a change that is even larger, namely up to about -2.6 V. Thus, the preferred protein conformation supports a high redox potential, compensating for the RP-lowering effect of surface charges. The predicted change in RP on going to the F463M mutant, ca. -0.1 V, is consistent with observations for a related laccase. Based on our results, we also propose and test a D206N mutant, but find it to be locked in a conformation with slightly lower RP.
Close

Details

Original languageEnglish
Pages (from-to)9265-9276
Number of pages12
JournalJournal of Physical Chemistry B
Volume120
Issue number35
Early online date17 Aug 2016
DOIs
Publication statusPublished - 8 Sep 2016

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Structure and dynamics of iron pentacarbonyl

    Portius, P., Buehl, M., George, M., Grevels, F-W. & Turner, J., 11 Nov 2019, In : Organometallics. 38, 21, p. 4288-4297 10 p.

    Research output: Contribution to journalArticle

  2. Conjugated, rigidified bibenzimidazole ancillary ligands for enhanced photoluminescence quantum yields of orange/red-emitting iridium(III) complexes

    Henwood, A. F., Antón-García, D., Morin, M., Rota Martir, D., Cordes, D. B., Casey, C., Slawin, A. M. Z., Lebl, T., Buehl, M. & Zysman-Colman, E., 14 Jul 2019, In : Dalton Transactions. 48, 26

    Research output: Contribution to journalArticle

  3. Acetyl coenzyme A analogues as rationally designed inhibitors of citrate synthase

    Bello, D., Rubanu, M. G., Bandaranayaka, N., Götze, J. P., Bühl, M. & O'Hagan, D., 2 May 2019, In : ChemBioChem. 20, 9, p. 1174-1182

    Research output: Contribution to journalArticle

Related by journal

  1. Efficient singlet oxygen photogeneration by zinc porphyrin-dimers upon one- and two-photon excitation

    Mazur, L. M., Roland, T., Leroy-Lhez, S., Sol, V., Samoc, M., Samuel, I. D. W. & Matczyszyn, K., 16 May 2019, In : Journal of Physical Chemistry B. 123, 19, p. 4271-4277 7 p.

    Research output: Contribution to journalArticle

  2. Photochemically induced dynamic nuclear polarization observed by solid-state NMR in a uniformly 13C-isotope labeled photosynthetic reaction center

    Paul, S., Bode, B. E., Matysik, J. & Alia, A., 29 Oct 2015, In : Journal of Physical Chemistry B. 119, 43, p. 13897-13903

    Research output: Contribution to journalArticle

  3. Analysis of influenza A virus NS1 dimer interfaces in solution by pulse EPR distance measurements

    Kerry, P. S., Turkington, H. L., Ackermann, K., Jameison, S. A. & Bode, B. E., 22 Aug 2014, In : Journal of Physical Chemistry B. 118, 37, p. 10882-10888 7 p.

    Research output: Contribution to journalArticle

  4. Multielement NMR Studies of the Liquid-Liquid Phase Separation and the Metal-to-Nonmetal Transition in Fluid Lithium- and Sodium-Ammonia Solutions

    Lodge, M. T. J. H., Cullen, P., Rees, N. H., Spencer, N., Maeda, K., Harmer, J. R., Jones, M. O. & Edwards, P. P., 24 Oct 2013, In : Journal of Physical Chemistry B. 117, 42, p. 13322-13334 13 p.

    Research output: Contribution to journalArticle

ID: 245112100

Top