Assessing the functional structure of molecular transporters by EPR spectroscopy:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Berlin [u.a.]
Springer
2012
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| Schriftenreihe: | Springer Theses
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| Schlagworte: | |
| Online-Zugang: | Inhaltstext Inhaltsverzeichnis |
| Beschreibung: | XVI, 212 S. Ill., graph. Darst. 235 mm x 155 mm |
| ISBN: | 9783642251344 364225134X |
Internformat
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Datensatz im Suchindex
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IMAGE 1
CONTENTS
1 GENERAL INTRODUCTION 1
REFERENCES 4
2 ELECTRON PARAMAGNETIC RESONANCE THEORY 7
2.1 HISTORICAL REVIEW 7
2.2 EPR FUNDAMENTALS 8
2.2.1 PREFACE 8
2.2.2 RESONANCE PHENOMENON 9
2.2.3 MAGNETIZATION 10
2.2.4 BLOCH EQUATIONS 11
2.2.5 CONTINUOUS MICROWAVE IRRADIATION 12
2.3 TYPES O F INTERACTIONS AND SPIN HAMILTONIAN 14
2.3.1 ELECTRON ZEEMAN INTERACTION 15
2.3.2 NUCLEAR ZEEMAN INTERACTION 16
2.3.3 HYPERFINE INTERACTION 16
2.3.4 NUCLEAR QUADRUPOLE INTERACTION 17
2.3.5 NUCLEAR SPIN-SPIN INTERACTION 18
2.3.6 ZERO-FIELD SPLITTING 18
2.3.7 WEAK COUPLING BETWEEN ELECTRON SPINS 18
2.4 ANISOTROPY IN EPR SPECTRA 20
2.4.1 G ANISOTROPY 20
2.4.2 COMBINED ANISOTROPICS IN REAL SPECTRA 22
2.5 DYNAMIC EXCHANGE 23
2.6 NITROXIDES AS SPIN PROBES 26
2.6.1 SPIN PROBE VERSUS SPIN LABEL 27
2.6.2 QUANTUM MECHANICAL DESCRIPTION 27
2.6.3 NITROXIDE DYNAMICS 28
2.6.4 ENVIRONMENTAL INFLUENCES 30
2.7 C W SPECTRAL ANALYSIS VIA SIMULATIONS 31
2.8 TIME EVOLUTION O F SPIN ENSEMBLES 33
X I
HTTP://D-NB.INFO/101610412X
IMAGE 2
XII C O N T E N T S
2.8.1 THE DENSITY MATRIX 33
2.8.2 PRODUCT OPERATOR FORMALISM 35
2.8.3 APPLICATION TO EPR 36
2.8.4 THE VECTOR MODEL 37
2.8.5 THE (S = 1/2, I = 1/2) MODEL SYSTEM 37
2.9 PULSE EPR METHODS BASED ON THE PRIMARY ECHO 39
2.9.1 ESE DETECTED SPECTRA 4 0
2.9.2 2-PULSE ELECTRON SPIN ECHO ENVELOPE MODULATION (ESEEM) 41
2.10 PULSE EPR METHODS BASED ON THE STIMULATED ECHO 4 2
2.10.1 3-PULSE ESEEM 42
2.10.2 HYPERFINE SUBLEVEL CORRELATION (HYSCORE) SPECTROSCOPY 4 4
2.10.3 BLIND SPOTS 44
2.10.4 PHASE CYCLING 4 5
2.11 DOUBLE ELECTRON-ELECTRON RESONANCE (DEER) 4 6
REFERENCES 50
3 THE FUNCTIONAL STRUCTURE OF HUMAN SERUM ALBUMIN 53
3.1 INTRODUCTION 54
3.2 THE DISTRIBUTION O F FATTY ACIDS IN HUMAN SERUM ALBUMIN IN SOLUTION
56
3.2.1 RESULTS 56
3.2.2 DISCUSSION 59
3.3 MULTISPIN CONTRIBUTIONS TO DEER SPECTRA 62
3.3.1 SPIN COUNTING 62
3.3.2 QUANTIFICATION O F MULTISPIN ARTIFACTS 65
3.4 ORIENTATION SELECTIVITY IN DEER: BEYOND DISTANCES 68
3.5 CONCLUSIONS 76
3.6 MATERIALS AND METHODS 76
REFERENCES 79
4 COPPER COMPLEXES O F STAR-SHAPED CHOLIC ACID OLIGOMERS WITH
1,2,3-TRIAZOLE MOIETIES 83
4.1 INTRODUCTION 84
4.2 TRIAZOLE-SUBSTITUTED OLIGOMER T3T AS METAL ION SENSOR 87
4.2.1 FLUORESCENCE QUENCHING ENHANCEMENT BY T3T 87
4.2.2 T3T: A TRIDENTATE LIGAND FOR COPPER 88
4.2.3 DERIVING A MOLECULAR PICTURE FROM THE EPR RESULTS 93
4.2.4 COMPARATIVE FLUORESCENCE QUENCHING STUDIES O F T3T AND TO 93
4.2.5 SUMMARY 95
IMAGE 3
CONTENTS XIII
4.3 INFLUENCE O F THE MOLECULAR STRUCTURE ON THE METAL
ION COMPLEXATION 95
4.3.1 FLUORESCENCE QUENCHING OF T3B 95
4.3.2 COPPER COORDINATION IN T3B 96
4.3.3 INFLUENCE OF A FOURTH CHOLIC ACID ARM 100
4.3.4 OBSERVATION O F A FOURTH SPECIES IN A 2:1 MIXTURE O F CUCL 2 AND
Q8TB 102
4.3.5 SUMMARY 103
4.4 SELF-ASSEMBLY OF MONOMERIC CHOLIC ACID DERIVATIVES 103
4.4.1 CU 2+ COORDINATION BY S2 103
4.4.2 CU 2+ MEDIATED SPATIAL ASSEMBLY O F SINGLE CHOLIC ACID CHAINS 105
4.5 CONCLUSIONS 109
4.6 MATERIALS AND METHODS 110
REFERENCES I L L
5 NANO-INHOMOGENEITIES IN STRUCTURE AND REACTIVITY OF THERMORESPONSIVE
HYDROGELS 115
5.1 INTRODUCTION 116
5.2 RESULTS 118
5.2.1 THE TEMPERATURE INDUCED HYDROGEL COLLAPSE AS SEEN BY PROBE
MOLECULES 118
5.2.2 CHEMICAL DECOMPOSITION OF SPIN PROBES IN HYDROPHILIC REGIONS O F
THE HYDROGEL 121
5.3 DISCUSSION 124
5.3.1 THE HYDROGEL COLLAPSE ON A MOLECULAR LEVEL 124
5.3.2 HYDROGEL INHOMOGENEITIES ON THE NANOSCALE LEAD TO NANOREACTORS AND
NANOSHELTERS 126
5.3.3 NANOREACTORS WITH LOCALIZED ACID GROUPS 127
5.4 CONCLUSIONS 129
5.5 MATERIALS AND METHODS 129
REFERENCES 131
6 THERMORESPONSIVE SPIN-LABELED HYDROGELS AS SEPARABLE DNP POLARIZING
AGENTS 133
6.1 INTRODUCTION 134
6.2 THEORY OF OVERHAUSER DNP 136
6.3 RESULTS AND DISCUSSION 137
6.3.1 STRATEGY FOR THE PREPARATION OF THERMORESPONSIVE SPIN-LABELED
HYDROGELS 137
6.3.2 C W EPR CHARACTERIZATION OF THE SPIN-LABELED HYDROGELS 138
6.3.3 CHARACTERISTIC DNP FACTORS AND ' H RELAXATION TIMES . . . 139
IMAGE 4
XIV C O N T E N T S
6.3.4 TEMPERATURE-DEPENDENT DNP PERFORMANCE OF
SPIN-LABELED HYDROGELS 141
6.4 CONCLUSIONS 143
6.5 OUTLOOK 143
6.6 MATERIALS AND METHODS 144
REFERENCES 146
7 LOCAL NANOSCOPIC HETEROGENEITIES IN THERMORESPONSIVE DENDRONIZED
POLYMERS 149
7.1 INTRODUCTION 150
7.2 LOCAL HETEROGENEITIES ABOVE THE CRITICAL TEMPERATURE 151
7.3 PRE-COLLAPSE O F THE DENDRONIZED POLYMERS BELOW THE CRITICAL
TEMPERATURE 157
7.4 FORMATION AND INFLUENCE OF A DENSE PERIPHERAL POLYMERIC LAYER 159
7.4.1 RESULTS 159
7.4.2 DISCUSSION 162
7.5 CONCLUSIONS 167
7.6 MATERIALS AND METHODS 169
REFERENCES 170
8 CONCLUSION 173
APPENDIX 177
CURRICULUM VITAE 209 |
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| author | Junk, Matthias J. N. 1983- |
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| spelling | Junk, Matthias J. N. 1983- Verfasser (DE-588)141472340 aut Assessing the functional structure of molecular transporters by EPR spectroscopy Matthias J. N. Junk Berlin [u.a.] Springer 2012 XVI, 212 S. Ill., graph. Darst. 235 mm x 155 mm txt rdacontent n rdamedia nc rdacarrier Springer Theses Carrier (DE-588)4602818-3 gnd rswk-swf Molekülstruktur (DE-588)4170383-2 gnd rswk-swf Elektronenspinresonanzspektroskopie (DE-588)4151888-3 gnd rswk-swf 1\p (DE-588)4113937-9 Hochschulschrift gnd-content Carrier (DE-588)4602818-3 s Molekülstruktur (DE-588)4170383-2 s Elektronenspinresonanzspektroskopie (DE-588)4151888-3 s DE-604 X:MVB text/html http://deposit.dnb.de/cgi-bin/dokserv?id=3896815&prov=M&dok_var=1&dok_ext=htm Inhaltstext DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=024761633&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis 1\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk |
| spellingShingle | Junk, Matthias J. N. 1983- Assessing the functional structure of molecular transporters by EPR spectroscopy Carrier (DE-588)4602818-3 gnd Molekülstruktur (DE-588)4170383-2 gnd Elektronenspinresonanzspektroskopie (DE-588)4151888-3 gnd |
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| title | Assessing the functional structure of molecular transporters by EPR spectroscopy |
| title_auth | Assessing the functional structure of molecular transporters by EPR spectroscopy |
| title_exact_search | Assessing the functional structure of molecular transporters by EPR spectroscopy |
| title_full | Assessing the functional structure of molecular transporters by EPR spectroscopy Matthias J. N. Junk |
| title_fullStr | Assessing the functional structure of molecular transporters by EPR spectroscopy Matthias J. N. Junk |
| title_full_unstemmed | Assessing the functional structure of molecular transporters by EPR spectroscopy Matthias J. N. Junk |
| title_short | Assessing the functional structure of molecular transporters by EPR spectroscopy |
| title_sort | assessing the functional structure of molecular transporters by epr spectroscopy |
| topic | Carrier (DE-588)4602818-3 gnd Molekülstruktur (DE-588)4170383-2 gnd Elektronenspinresonanzspektroskopie (DE-588)4151888-3 gnd |
| topic_facet | Carrier Molekülstruktur Elektronenspinresonanzspektroskopie Hochschulschrift |
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