Oligo(phenylene-ethynylene) linker

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Table of contents

List of figures
List of schemes
List of tables
General introduction
Introduction: theory, literature review and aim of the project
1. Theoretical background
1.1 EPR: introduction and scope of application
1.2 Theoretical background
1.2.1 Magnetic moment of the electron
1.2.2 Interaction between a paramagnetic center and a magnetic field
1.2.3 Continuous-wave EPR
1.2.4 The case of a real EPR spectrum
1.3 Spin Hamiltonian for MnII
1.4 Continuous-wave high-field EPR
1.4.1 Design of the J-band cw-HFEPR spectrometer
1.4.2 Influence of the high-field on the EPR spectrum
1.4.2.1 The case of MnII
1.4.2.2 The case of TEMPO
1.5 Pulsed EPR
1.5.1 Introduction and main pulse sequences
1.5.2 The PELDOR pulse sequence
1.5.2.1 Theory
1.5.2.2 Pulse sequence
1.5.2.3 Optimization of parameters
1.5.2.3.1 Concentration
1.5.2.3.2 Pulses
1.5.2.3.3 Temperature
1.5.2.3.4 Solvent
1.5.2.4 High-spin metals vs nitroxide spin labels
1.5.2.5 MnII vs GdIII
2. Pulsed EPR measurements involving metals
2.1 Low-spin metals
2.1.1 CuII complexes
2.1.1.1 CuII-CuII distance measurements
2.1.1.2 CuII-nitroxide distance measurements
2.1.2 Fe-S clusters
2.1.3 Mn-tyrosyl measurements in the S2 state of PSII
2.2 High-spin GdIII complexes
2.2.1 PELDOR distance measurements between two GdIII complexes
2.2.1.1 Gd-Gd measurements on rigid models compounds
2.2.1.2 Gd-Gd measurements on biological objects
2.2.1.2.1 In vitro PELDOR
2.2.1.2.1.1 Gd-DPA-based tags
2.2.1.2.1.2 Gd-DO3A and Gd-DOTA-based tags
2.2.1.2.2 In-cell PELDOR
2.2.1.2.2.1 Gd-PyMTA tags
2.2.1.2.2.2 Gd-DOTA-based tags
2.2.1.3 Gd-nitroxide measurements
2.2.1.3.1 With Gd-Tpy or Gd-DTPA labels
2.2.1.3.2 With Gd-DOTA labels
2.2.2 RIDME
2.3 MnII complexes
2.3.1 Mn-Mn distance measurements
2.3.2 Mn-nitroxide measurements
3. Aim of the project
Chapter I – Synthesis of platforms with a constrained distance between two MnII complexes
1. Ligand screening
1.1 Bis(imino)pyridines
1.2 Terpyridines
1.3 Dipicolinic acid and derivatives (PyMTA and PyMDPDA)
1.4 PCTA and PCMA
1.5 DOTA and DO3A
2. Linkers and grafting of ligands
2.1 Oligo(piperidine) linker
2.1.1 Synthesis of the oligo(piperidine) linker
2.1.2 Coupling with ligands
2.1.2.1 Grafting of BImPs
2.1.2.2 Grafting of Tpys
2.2 Phenyl-piperazine linker
2.2.1 Symmetric version
2.2.2 Dissymmetric version
2.2.3 Elongation
2.2.4 Couplings with ligands
2.2.4.1 with terpyridines
2.2.4.2 with DPA, PyMTA and PyMDPDA derivatives
2.2.4.3 with DOTA derivatives
2.3 Oligo(phenylene-ethynylene) linker
2.3.1 Symmetric version
2.3.2 Dissymmetric version
2.3.3 Elongation
2.3.4 Coupling with ligands
2.3.4.1 with terpyridines
2.3.4.2 DPA and PyMTA derivatives
2.3.4.3 DO3A and DOTA derivatives
2.4 Polyprolines
3. Bis(nitroxides)
3.1 Platforms with a phenyl-piperazine linker
3.2 Platforms with an OPE linker
4. Dissymmetric platforms
4.1 With the phenyl-piperazine linker
4.2 With the OPE linker
Conclusion
Chapter II – PELDOR distance measurements between two high-spin MnII centers
1. General sample preparation for PELDOR measurements
2. Measurements on the bis-Mn-Tpy platforms
3. Measurements on the polyproline bis-dota platforms
3.1 Measurement of the ZFS interaction of Mn-DOTA
3.2 PELDOR results
3.3 Analysis of the pseudo-secular contribution
4. Measurements using rigid platforms
4.1 Phenyl-piperazine bis-DOTA platforms 149 and
4.2 OPE bis-DOTA platforms 202, 203 and
4.3 OPE bis-TEMPO platform
Conclusion
Chapter III – High-field EPR study of persistent substituted trityl radicals
1. Persistent trityl radicals
1.1 Origins of persistent trityl radicals
1.2 Reported synthesis and applications of PTM radicals
1.2.1 Synthesis
1.2.2 Applications
1.3 Reported synthesis and applications of TAM radicals
1.3.1 Synthesis
1.3.2 Applications
2. Towards TAM/PTM – MnII-DOTA model systems
2.1 Synthesis of PTMTE and PTMTC
2.2 Attempted couplings of PTM and TAM radicals
3. Accurate measurement of the g-anisotropy of substituted trityl radicals
3.1 Design of the experimental setup
3.2 Results and discussion
Conclusion
General conclusion and perspectives
Annexes
1. Glassing agents
2. PELDOR measurement process
3. Data Analysis
4. Final products
5. List of publications
Experimental part
1. Synthesis
2. ITC
3. CD
4. EPR
5. Computational methods
6. X-ray crystallography
References