Design and evaluation of seven-coordinate manganese and iron complexes, and fullerene derivatives, as SOD mimetics [Elektronische Ressource] / vorgelegt von Gao-Feng Liu

<C1f5b8dfb7e5>

Informations

• Publié par: friedrich-alexander-universitat_erlangen-nurnberg
• Publié le: 01 janvier 2008
• Nombre de lectures: 7
• Langue: English
• Poids de l'ouvrage: 2 Mo

Extrait

Design and Evaluation of Seven-coordinate
Manganese and Iron Complexes, and Fullerene
derivatives, as SOD mimetics


Der Naturwissenschaftlichen Fakultät
der Friedrich-Alexander-Universität Erlangen-Nürnberg
zur
Erlangung des Doktorgrades

vorgelegt von
Gao-Feng Liu
aus
VR China


IDesign and Evaluation of Seven-coordinate Manganese and Iron Complexes, and
Fullerene derivatives, as SOD mimics

Als Dissertation genehmigt von den Naturwissenschftlichen Fakultäten der Friedrich
-Alexander-Universität Erlangen-Nürnberg.

















Tag der mündlichen Prüfung: 02.05.2008

Vorsitzender der Promotionskommission: Prof. Dr. E. Bänsch

Erstberichterstatter: Prof. Dr. Dr. h. c. R. van Eldik

Zweitberichterstatter: Prof. Dr. Lutz Dahlenburg

IIAcknowledgements

This study was carried out from February 2003 to February 2008 at the
Institute of Inorganic Chemistry at the Friedrich-Alexander-University of
Erlangen-Nürnberg under the supervision of Prof. Dr. Dr. h. c. mult Rudi van
Eldik.

I would like to express my sincere gratitude to my supervisor, Dr. Ivana
Ivanovi ć-Burmazovi ć for her essential guidance, her never-ending enthusiasm, and
permanent encouragement throughout my study. At the same time I am thankful to
Prof. Dr. Dr. h. c. mult Rudi van Eldik for his kind and helpful discussion.

Warm thanks are given to the whole group for the friendly working
atmosphere.

Thanks to the Friedrich-Alexander-University of Erlangen-Nürnberg and the
DFG within SFB 583 “Redox-active Metal Complexes” for the financial support.

Finally I am grateful to my parents and to my wife for endless support which
has been valuable during my study.


Gao-Feng Liu


IIIDesign and Evaluation of Seven-coordinate Manganese and Iron Complexes, and
Fullerene derivatives, as SOD mimics

Publications

1 Gao-Feng Liu, Ralph Puchta, Frank W. Heinemann, Ivana Ivanovi ć-Burmazovi ć,
Ligand Electronic Properties in the Control of Redox Behavior and Reactivity
toward Superoxide in Seven-Coordinate Manganese Complexes, Chemical
Communication (Submitted)

2 Gao-Feng Liu, Miloš Filipovi ć, Ivana Ivanovi ć-Burmazovi ć, Florian Beuerle, Patrick
Witte, Andreas Hirsch, Highly Catalytic Metal-Free Superoxide Dismutation mimics
from Dendritic Monoadducts of C Angewandte Chemie (in print) 60,

3 Gao-Feng Liu, Miloš Filipovi ć, Frank W. Heinemann and Ivana Ivanovi ć-Burmazovi ć
Seven-Coordinate Iron and Manganese Complexes with Acyclic and Rigid Pentadentate
Chelates and their Superoxide Dismutase Activity, Inorganic Chemistry, 2007, 46,
8825-8835.

4 David Sarauli, Roland Meier, Gao-Feng Liu, Ivana Ivanovic-Burmazovic, Rudi van
Eldik, Effect of Pressure on Proton-Coupled Electron Transfer Reactions of
Seven-Coordinate Iron Complexes in Aqueous Solutions, Inorganic Chemistry, 2005,
44, 7624-7633.


Conference contributions

1 Poster “Sub-millisecond Mixing Stopped-Flow Configuration to SOD Activity”,
Inorganic Reaction Mechanism Meeting, organised by the Royal Society of
Chemistry, Athens, Greece, January 2004.

2 Poster “Cryo-stopped-flow measurements for rapid inorganic reactions”,
Inorganic Reaction Mechanism Meeting, organised by the Royal Society of
Chemistry, Athens, Greece, January, 2004.
IV
3 Oral Presentation “Seven-coordinate Iron and Manganese Complexes and
Reactivity towards Superoxide”, Conference on Coordination Chemistry of
China, organised by the Chinese Society of Chemistry, Guangzhou, China,
October, 2005.

4 Poster “Superoxide Dismutase Mimetics. From Seven-coordinate Iron and
Manganese Complexes to Fullerenes”, Inorganic Reaction Mechanism Meeting,
organised by the Royal Society of Chemistry, Krakow, Poland, January, 2006.

5 Poster “Design and Evaluation of Seven-coordinate Iron and Manganese
Complexes, Fullerenes as SOD mimics”, SFB-Symposium on Redox-Active
Metal complexes: Control of Reactivity via Molecular Architecture, Erlangen,
Germany, March, 2007.

Abbreviations

SODs superoxide dismutases
ROS reactive oxygen species
RNS reactive nitrogen species
SAR Structure-Activity-Relationship
His L-Histidine
Asp L-Aspartic acid
Me [15]pyridinaneN trans-2,13-dimethyl-3,6,9,12,18-pentaazabicyclo 2 5
[12.3.1]-octadeca-1(18),14,16-triene)
Hdapsox 2,6-diacetylpyridine-bis(semioxamazide) 2
HDcphp Pyridine-2,6-biscarboxylic acid-bis((N ′-2-pyridine-2-yl) 2
hydrazide)
Daphp 2,6-diacetylpyridine-bis(2-pyridylhydrazone)
Hdapmp [1-(6-acetyl-2-pyridinyl) ethylidene] hydrazone
VDesign and Evaluation of Seven-coordinate Manganese and Iron Complexes, and
Fullerene derivatives, as SOD mimics
salen N,N´-ethylenebis(salicylideniminate)
TBAP tetrakis(4-benzoic acid)porphyrin
Tempol 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl
t half life 1/2
λ wavelength (nm)
δ chemical shift(NMR)
ν stretching mode(IR)
A absorbance
PBP pentagonal-bipyramidal
DD distorted-dodecahedron
IC half maximal inhibitory concentration 50
K equilibrium constant
k catalytic rate constant cat
k observed rate constant obs
OPs oxidation potentials
NHE normal hydrogen electrode
SHE standard hydrogen electrode
CV cyclic voltammetry
NBT nitro blue tetrazolium
UV ultraviolet
DFT density functional theory
IR infrared spectroscopy
NMR nuclear magnetic resonance
MS mass spectrometry
VI
Contents
ACKNOWLEDGEMENTS......................................................................................................................................III
PUBLICATIONS................... IV
CONFERENCE CONTRIBUTIONS ........................................................................................................................ IV
ABBREVIATIONS..................V
CHAPTER 1 ...........................................................................................................................................................1
INTRODUCTION..................................................................................................................................................1
1.1 SUPEROXIDE AND SUPEROXIDE DISMUTASES (SODS) ...........................................................................1
1.1.1 Superoxide and its toxic effects to damage the cell ............................................................................1
1.1.2 Superoxide Dismutases (SODs) and their Active Metal Center Structures ..........................................3
1.2 DEVELOPMENT AND CONSIDERATIONS OF SYNZYMES AS SOD MIMICS ..............................................6
1.2.1. Manganese(III) Metalloporphyrins ..................................................................................................8
1.2.2. Manganese(III) salen Complexes .....................................................................................................9
1.2.3. Nitroxide...................10
1.2.4. Manganese(II) (pentaazamacrocyclic ligand)-Based Complexes ..................................................11
1.3 CHARACTERIZATION ARRAYS OF SOD ACTIVITY...............................................................................12
1.3.1 Indirect Assay.................................................................................................................................12
1.3.2 Direct Arrays..................................................................................................................12
1.3.3 Cyclic Voltammetry Method ...........................................................................................................13
1.4 FULLERENE AND ITS ANTIOXIDANT ABILITY ........................................................................................14
1.5 AIMS OF THIS THESIS .............................................................................................................................18
1.6 REFERENCES..........................................................................................................................................19
CHAPTER 2 .........................................................................................................................................................25
SEVEN-COORDINATE IRON AND MANGANESE COMPLEXES WITH ACYCLIC AND RIGID
PENTADENTATE CHELATES AND THEIR SUPEROXIDE DISMUTASE ACTIVITY.........................25
2.1 ABSTRACT...............25
2.2 INTRODUCTION.......26
2.3 EXPERIMENTAL SECTION29
2.4 RESULTS AND DISCUSSION ....................................................................................................................35
2.4.1 Stability of Superoxide Anion in H O-DMSO.................................................................................35 2
2.4.2 Structures ..............................................................................................................................