Dimers of Azurin as model systems for electron transfer
Jongh, Thyra Estrid deCitation
Jongh, T. E. de. (2006, September 12). Dimers of Azurin as model systems for electron transfer. Retrieved from https://hdl.handle.net/1887/4554
Version: Corrected Publisher’s Version
License: Licence agreement concerning inclusion of doctoral thesis in theInstitutional Repository of the University of Leiden Downloaded from: https://hdl.handle.net/1887/4554
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Dimers of Azurin as model systems for electron transfer
1. A water-mediated hydrogen bond network between the redox centres is essential for efficient electron self-exchange in azurin (P.aeruginosa).
Chapter 5
2. Substitution of Cu(II) for Zn(II) allows the crystallization of H117G azurin without the risk of copper catalyzed oxidative damage to the Cys112 residue.
Chapter 6
3. The structures of cross-linked protein complexes are difficult to predict a priori as the relative orientation of the partners can be strongly influenced by many different parameters.
Chapters 4, 5 and 6
4. Ligand reconstitution of a cavity mutant of azurin using conductive molecular wires enables direct hotwiring of the copper site.
Chapter 7
5. Attributing the pH dependence of the electron self-exchange rate of M64E azurin to a direct electrostatic repulsion between the introduced charges overlooks the fact that in the presumed orientation of the reaction complex these residues are situated over 20 Å apart.
G. van Pouderoyen et al., Eur. J. Biochem (1994), 222 (2), 583-588
6. The increased fluxionality that was detected by 15N NMR relaxation studies in the
loop region between the residues 117 and 120 of Cu(I)-H117G azurin is consistent with the observed increase in the thermal factors for these same residues in Zn-H117G azurin.
7. The conflict between the Uniform Barrier model and the Tunnelling Pathway model for biological electron transfer has, through refinement of each, been largely reduced to a philosophical discussion on nature’s intentions.
D.N. Beratan et al., Science (1991), 252 (5010), 1285-1288 D.N. Beratan et al., Science (1992), 258 (5089), 1740-1741 C.C. Moser et al., Nature (1992), 353 (6363), 796-802 C.C. Moser et al., J. Bioinorg.Chem. (1997), 2, 393-398
8. Amongst bioinorganic chemists the paper by Marcus & Sutin on non-adiabatic electron transfer is likely the most frequently cited reference as well as the one that is actually read the least.
R.A. Marcus & N.Sutin, Biochim. Biophys. Acta (1985), 811 (3), 265-322
9. The phrase ‘time equals money’ does not survive the reality of laboratory life: whereas for Ph.D. students time is more valuable than money, for their supervisors the opposite is often true.
10. Protein engineering through site-directed mutagenesis is the biochemist’s version of the well-known adagium ‘think global, act local’.
11. 'Juvenile idealism' suggests that as we become older we become wiser. However, we merely become less willing to make certain sacrifices for the common good as we stand to loose more.
12. It is better to light a candle than to curse the darkness.
