Metal complexes of amino acids which form tridentate N-chelates [Elektronische Ressource] = Metallkomplexe mit dreizähnig chelatisierenden Aminosäuren / vorgelegt von Slobodan Novokmet

Slobodan

Description

Metal complexes of amino acids which form tridentate N-chelates Metallkomplexe mit Dreizähnig Chelatisirenden Aminosäuren Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Vorgelegt von Slobodan Novokmet aus Kragujevac, Serbien und Montenegro. Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 22.12.2005 Vorsitzender der Promotionskommission: Prof. Dr. D. –P. Häder Erstberichtstatter: PD Dr. R. Alsfasser Zweiteberichtstatter: Prof. Dr. Dr. h. c. R. van Eldik Acknowledgements This work was carried out from August 2002 until September 2005 at the Institute of Inorganic Chemistry at the Friedrich–Alexander–University of Erlangen–Nürnberg under supervision of PD Dr. Ralf Alsfasser to whom I would especially like to thank for a very productive time in his group, his permanent interest in my work, and his financial support during my work. Sincere thanks are given to my group co-workers Dipl. Chem. Christian Schickaneder and Dr. Nicole Niklas for having a good time during the work in the lab, useful discussions, and advices. I would like to thank to Prof. Dr. Dr. h. c. Rudi van Eldik for his great support and the possibility to finish my work in his group. Special thanks are also given to: Dr.

Informations

• Publié par: friedrich-alexander-universitat_erlangen-nurnberg
• Publié le: 01 janvier 2006
• Nombre de lectures: 30
• Langue: English
• Poids de l'ouvrage: 6 Mo

Extrait

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Metal complexes of amino acids which form tridentate

N-chelates 

Metallkomplexe mit Dreizähnig Chelatisirenden

Aminosäuren

Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades

Vorgelegt von Slobodan Novokmet aus Kragujevac, Serbien und Montenegro.

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Als Dissertation genehmigt von den

Naturwissenschaftlichen Fakultäten der Universität

        Tag  Vorsitzender der Promotionskommission:  Erstberichtstatter:

Erlangen-Nürnberg

der mündlichen Prüfung:

 Zweiteberichtstatter:

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22.12.2005

Prof. Dr. D. P. Häder

PD Dr. R. Alsfasser

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

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Acknowledgements

This work was carried out from August 2002 until September 2005 at the Institute of

Inorganic Chemistry at the FriedrichAlexanderUniversity of ErlangenNürnberg

under supervision of PD Dr. Ralf Alsfasser to whom I would especially like to thank for

a very productive time in his group, his permanent interest in my work, and his financial

support during my work. Sincere thanks are given to my group co-workers Dipl. Chem.

Christian Schickaneder and Dr. Nicole Niklas for having a good time during the work in

the lab, useful discussions, and advices.

I would like to thank to Prof. Dr. Dr.h. c.Rudi van Eldik for his great support and the

possibility to finish my work in his group.

Special thanks are also given to: Dr. Frank Heinemann for x-ray analyses, Dr. Achim

Zahl for NMR measurements, Susanne Hoffmann for IR measurements, Christina

Wrona for elemental analyses, Dr. Jörg Sutter and Martin Bachmüller for mass

spectrometry measurements, Prof. Dr. Paul Müller and Sahabul Alam (Department of

Physics) for the STM measurements, the people from workshop of the Institute and

glassblower Mr. Zöbelein, for their excellent technical support. Dr. Jürgen Limmer, Dr.

Anton Neubrand, Dr. Carlos Dücker-Benfer, Dr. Ivana Ivanovic-Burmazovic, PD Dr.

Roland Meier, Ariane Brausam, David Sarauli, Hakan Ertürk, Joachim Maigut, Nadine

Summa, Patrick Witte, Peter Illner, Wolfgang Schiessel, Usrula Niegratschka (secretary

of the institute) for their continuous support during my work. Dr. Diana Utz and Dr.

Markus Weitzer for a wonderful time that we spent toghether on lunch-brakes. Prof. Dr.

ivadin Bugarčić (Universityfor helping me to get the oportunity to of Kragujevac)

study in Germany.

City of Erlangen and Germany for hosting me and my family during my PhD studies.

Finally, I would like to thank my familly, wife Danijela and son Aleksa, that supported

me all of this PhD-time.

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wife Da

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nijela and son Aleksa.

List of publications   1.Z. Bugarčić, S. Novokmet, . Senić, . Bugarčić, Chem. Mon.,2000,131(7), 799-802. 

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2.S. Novokmet, V. Mujović, V. Jakovljević, D. Djurić,Perfusion,2001,2, 93-94.

3.Z. Bugarčić, S. Novokmet, V. Kostić,J. Serb. Chem. Soc.,2005,70(5), 681-686.

4.S. Novokmet, S. Alam, V. Dremov, F. W. Heinemann, P. Müller, R. Alsfasser,

Angew. Chem. Int. Ed. Engl.,2005,44, 803-806.  5.S. Novokmet, F. W. Heinemann, A. Zahl, R. Alsfasser,Inorg. Chem.,2005, 44(13), 4796-4805.   Conference contributions   1.Annual meeting of the German Atherosclerosis Society, 29.03.-31.03.2001, Blaubeuren, Germany.

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2.Annual meeting of the German Chemical Society, 06.1011.10. 2003, Munich, Germany.

3.The 2004 Yonger European Chemists Conference,Short-talk, 25.08- 29.08.2004, Torino, Italy.

4.Joint SFB Workshop, SFB 436, SFB 583, SFB 623, SFB 624, "Advances ion Molecular Catalysis", 12-14.10.2004, Lauterbad (Schwarzwald), Germany.

5.SFB 583-Minisymposium, February 2005,

Erlangen, Germany.

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1.4. 1.4.1. 1.5. 

2.

2.1. 2.2. 2.3. 2.4.   3. 3.1. 3.2. 3.3. 3.4. 3.4.1.    

Table of Contents

Chapter 1 General Introduction Aromatic Interactions ππInteractions CationπInteractions Investigation of aromatic interactions in peptide model systems Coordination Polymers Preliminary work done in our research group Synthesis of peptide type metal complexes: chelating ligand + biomolecule- metal Helical Coordination Polymers pH dependent switch of peptidic amide group from oxygen to anionic nitrogen coordination Goals and tasks of this work Dipeptide Ligands Containing the Amino Acid Dipicolylglycine (Dpg) References and Notes Chapter 2

The Deposition of Metallopeptide Based Coordination Polymers on Graphite Substrates: Effects of Side Chain Functional Groups and Local Surface Structure Introduction Results and Discusion Experimental Section References and Notes Chapter 3

Aromatic Interactions in Unusual Backbone N-Coordinated Zinc Peptide Complexes: A Crystallographic and Spectroscopic Study Introduction Results and discussion Conclusions

Experimental Section General Methods

1

1 2

2

3

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8 9 9 11

13 13 14 20 26 27

27 27 29 38

39 39

  3.4.2. 3.4.3. 3.4.4. 3.4.5. 3.4.6. 3.4.7. 3.5.  4.1. 4.1.1. 4.1.2. 4.2. 4.3.

4.4.

4.5. 4.6.

4.7.

5. 6. 7.

Table of Contents

Bromoacetylated Amino Acid Esters. Ligands [(Dpg-Xaa-OMe)(H 2 O)Zn](CF 3 SO 3 ) 2  Synthesis of[(Dpg-Xaa) -H Zn]

X-ray crystallography Apendix References and Notes Chapter 4 Synthesis of chiral quadridentate ligands derived from L-alanine and L-leucine Bromoacetylated Amino Acid Esters Ligands Synthesis of chiral quadridentate ligands Dpg-Xaa  type Synthesis of Zn(II) complexes using chiral quadridentate ligands Dpg-Ala-OMe and Dpg-Leu-OMe Synthesis of Zn(II)peptide based coordination polymer and N-anionic coordinated monomer derived from leucine Synthesis of Cu(II)peptide based coordination polymer derived from leucine Synthesis of Ni(II)peptide based coordination dimer derived from phenylalanine Synthesis of Cd(II), Co(II) and Mn(II) complexes using chiral quadridentate ligand Dpg-Phe-OMe Summary Zusammenfassung Curiculum Vitae

40 43 45 47 51

55 57

61 61

62 63

67

70 72 74

76 81

82 83

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Chapter 1

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1. General Introduction

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1.1. Aromatic Interactions

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Aromatic rings are important structural and functional elements both in biological and

in synthetic supramolecular architectures, and contribute to the intramolecular

stabilization of structures such as enzyme-substrate complexes. Aromatic interactions play a key role in biomolecular recognition processes 1 and protein aggregation. The

redox-active aromatic amino acids tyrosine and tryptophan are known to participate in

metalloenzyme-catalysed substrate oxidations. Recent results demonstrate their importance for the activation of coordinated ligands. 2  model complexes, aromatic In rings are well known to form close contacts with metal centers in planar complexes. 3 

They can thereby significantly contribute to the stabilization of ternary amino acid

complexes. Depending on the nature of the rings, aromatic groups can interact in one of

several geometries. Those interactions are expected to be strong in water because of the

hydrophobic component of the interaction, and the interaction should be selective if the

electrostatic component is significant. Several geometries have been proposed on the 4 basis of the electrostatic component of the interaction (Figure 1).

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a

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Figure 1. Geometries of aromatic interactions:

(a) edge-face; (b) offset stacked; (c) face-to-face stacked.

1