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  • Electrochemistry of immobilized hemes and heme proteins

    Citation for published version (APA): Groot, de, M. T. (2007). Electrochemistry of immobilized hemes and heme proteins. Eindhoven: Technische Universiteit Eindhoven. https://doi.org/10.6100/IR626249

    DOI: 10.6100/IR626249

    Document status and date: Published: 01/01/2007

    Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers)

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    Download date: 11. Jun. 2020

    https://doi.org/10.6100/IR626249 https://doi.org/10.6100/IR626249 https://research.tue.nl/en/publications/electrochemistry-of-immobilized-hemes-and-heme-proteins(1c8a0837-9d79-410a-95ce-ca39b9d5b7b2).html

  • Electrochemistry of Immobilized

    Hemes and Heme Proteins

    PROEFSCHRIFT

    ter verkrijging van de graad van doctor aan de

    Technische Universiteit Eindhoven, op gezag van de

    Rector Magnificus, prof.dr.ir. C.J. van Duijn, voor een

    commissie aangewezen door het College voor

    Promoties in het openbaar te verdedigen

    op donderdag 14 juni 2007 om 16.00 uur

    door

    Matheus Theodorus de Groot

    geboren te Deurne

  • Dit proefschrift is goedgekeurd door de promotoren:

    prof.dr. M.T.M. Koper

    en

    prof.dr. R.A. van Santen

    Copromotor:

    dr. M. Merkx

    A catalogue record is available from the Library Eindhoven University of Technology

    ISBN: 978-90-386-0985-0

    Copyright © 2007 by Matheus T. de Groot

    The work described in this thesis has been carried out at the Schuit Institute of Catalysis within the

    Laboratory of Inorganic Chemistry and Catalysis, Eindhoven University of Technology and the

    Leiden Institute of Chemistry, Leiden University, The Netherlands. Financial support has been

    supplied by the National Research School Combination Catalysis (NRSC-C).

    Design cover: Thijs de Groot and Paul Verspaget

    Printed at the Universiteitsdrukkerij, Eindhoven University of Technology

  • Life is not measured by the number of breaths you take,

    but by the number of moments that take your breath away.

  • ——————————————————————————————————————————

    Contents ——————————————————————————————————————————

    Chapter 1 Introduction

    Chapter 2 Electrochemical reduction of NO by hemin adsorbed at pyrolitic

    graphite

    Chapter 3 Heme release in myoglobin-DDAB films and its role in

    electrochemical NO reduction

    A. Heme release in myoglobin-DDAB films and its role in

    electrochemical NO reduction

    B. Additional evidence for heme release in myoglobin-DDAB

    films on pyrolitic graphite

    Chapter 4 Heme release and adsorption in layer-by-layer assemblies of

    polystyrenesulfonate and myoglobin on pyrolitic graphite

    Chapter 5 Electron transfer and ligand binding to cytochrome c’

    immobilized on self-assembled monolayers

    Chapter 6 Reorganization of immobilized horse and yeast cytochrome c

    induced by pH changes or nitric oxide binding

    Chapter 7 Redox transitions of chromium, manganese, iron, cobalt and

    nickel protoporphyrins in aqueous solution

    Chapter 8 Conclusions and future prospects

    Summary

    Samenvatting

    List of publications

    Curriculum vitae

    Dankwoord

    1

    11

    33

    35

    61

    73

    85

    109

    131

    161

    165

    168

    170

    171

    172

  • —————————————————————————————————————————————

    Chapter 1 —————————————————————————————————————————————

    Introduction

    1.1 The search for better catalysts

    Catalysts are of great value to mankind, since they enable reactions that would

    otherwise not occur or would occur at a very slow rate. The best-known example of a

    catalyst is the catalytic converter located in the exhaust of a car. It converts toxic gases

    such as carbon monoxide (CO), nitric oxide (NO) and nitrogen dioxide (NO2), which are

    formed in the car engine, into the relatively harmless gases nitrogen (N2) and carbon

    dioxide (CO2). In this way the catalytic converter contributes to the improvement of the

    air quality in urban areas, which in turn has a positive influence on public health. The

    catalytic converter consists of a support with small metal particles, on which the reaction

    occurs in three steps (Figure 1.1). Firstly, the toxic gas molecules are adsorbed on the

    metal particles, next the reaction occurs, and finally the molecules are desorbed from the

    particles. The metal particles play an important role in the reaction, but they are not

    consumed. Therefore, the metal particles can in principle be used to convert an infinite

    number of toxic molecules and do not have to be replaced over the lifetime of a car.

    Without the metal particles the reaction would either not occur or occur at a very slow

    rate. This is the essence of every catalyst, which is defined as a substance that increases

    the rate of a reaction without being consumed. Although less known to the general

    public, catalysts are being used in many other processes. These include oil refinery,

    production of fertilizers, production of plastics and the production of drugs.

    Figure 1.1 The catalytic converter in a car. The figure depicts its location (top left), its

    macroscopic shape (bottom left) and a schematic representation of the reactions that

    occur on the small metal particles of the catalytic converter (right).

  • 2 Chapter 1 —————————————————————————————————————————————

    Catalysis is big business, as reflected in the fact that the global catalyst market is

    worth $ 210 billion annually.1 Finding the right catalyst for an industrial process can

    determine whether such a process is economically feasible. Therefore, there is a

    continuous search for better and cheaper catalysts to improve the competitiveness of

    chemical processes. When considering the use of a catalyst for a particular reaction, one

    has to take into account the following important properties:

    • Activity. This corresponds to the rate of the reaction that occurs on the

    catalyst. Ideally, a catalyst should be very active, which means that only a

    small amount of catalyst is needed to convert many molecules in a relatively

    short time.

    • Selectivity. The selectivity of a catalyst indicates what products are formed

    in the reaction. In many chemical reactions more than one product can be

    formed and normally only one of the products is desired. Selectivity is of

    particular importance in the drug industry, where one reaction product might

    be a good drug and another product might be toxic.

    • Stability. This relates to the lifetime of a catalyst. Ideally, a catalyst should

    be able to catalyze an endless number of reactions, but in practice the

    catalyst becomes inactive after a certain time. The lifetime of a catalyst

    depends on its specific properties, but al

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