Analytical methods in supramolecular chemistry:
Gespeichert in:
| Weitere Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Weinheim
Wiley-VCH-Verl.
2007
|
| Schlagworte: | |
| Online-Zugang: | Inhaltstext Inhaltsverzeichnis |
| Beschreibung: | Literaturangaben |
| Beschreibung: | XVI, 484 S. Ill., graph. Darst. 25 cm |
| ISBN: | 9783527315055 3527315055 |
Internformat
MARC
| LEADER | 00000nam a2200000 c 4500 | ||
|---|---|---|---|
| 001 | BV022518994 | ||
| 003 | DE-604 | ||
| 007 | t | ||
| 008 | 070719s2007 gw ad|| |||| 00||| eng d | ||
| 015 | |a 07,A08,0853 |2 dnb | ||
| 020 | |a 9783527315055 |c Pp. : EUR 149.00 (freier Pr.), ca. sfr 235.00 (freier Pr.) |9 978-3-527-31505-5 | ||
| 020 | |a 3527315055 |c Pp. : EUR 149.00 (freier Pr.), ca. sfr 235.00 (freier Pr.) |9 3-527-31505-5 | ||
| 024 | 3 | |a 9783527315055 | |
| 028 | 5 | 2 | |a 1131505 000 |
| 035 | |a (OCoLC)71348102 | ||
| 035 | |a (DE-599)BVBBV022518994 | ||
| 040 | |a DE-604 |b ger |e rakddb | ||
| 041 | 0 | |a eng | |
| 044 | |a gw |c XA-DE-BW | ||
| 049 | |a DE-19 |a DE-703 |a DE-20 |a DE-11 |a DE-188 | ||
| 050 | 0 | |a QD878 | |
| 082 | 0 | |a 547.1226 |2 22 | |
| 082 | 0 | |a 547.1226 |2 22/ger | |
| 084 | |a UK 7500 |0 (DE-625)145803: |2 rvk | ||
| 084 | |a VK 7150 |0 (DE-625)147416:253 |2 rvk | ||
| 084 | |a 540 |2 sdnb | ||
| 245 | 1 | 0 | |a Analytical methods in supramolecular chemistry |c ed. by Christoph Schalley |
| 264 | 1 | |a Weinheim |b Wiley-VCH-Verl. |c 2007 | |
| 300 | |a XVI, 484 S. |b Ill., graph. Darst. |c 25 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 500 | |a Literaturangaben | ||
| 650 | 7 | |a Supramoleculaire systemen |2 gtt | |
| 650 | 4 | |a Instrumental analysis | |
| 650 | 4 | |a Supramolecular chemistry | |
| 650 | 0 | 7 | |a Analytische Chemie |0 (DE-588)4129906-1 |2 gnd |9 rswk-swf |
| 650 | 0 | 7 | |a Supramolekulare Chemie |0 (DE-588)4306141-2 |2 gnd |9 rswk-swf |
| 689 | 0 | 0 | |a Supramolekulare Chemie |0 (DE-588)4306141-2 |D s |
| 689 | 0 | 1 | |a Analytische Chemie |0 (DE-588)4129906-1 |D s |
| 689 | 0 | |5 DE-604 | |
| 700 | 1 | |a Schalley, Christoph A. |d 1968- |0 (DE-588)115419969 |4 edt | |
| 856 | 4 | 2 | |q text/html |u http://deposit.dnb.de/cgi-bin/dokserv?id=2843897&prov=M&dok_var=1&dok_ext=htm |3 Inhaltstext |
| 856 | 4 | 2 | |m HBZ Datenaustausch |q application/pdf |u http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015725764&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |3 Inhaltsverzeichnis |
| 943 | 1 | |a oai:aleph.bib-bvb.de:BVB01-015725764 | |
Datensatz im Suchindex
| _version_ | 1805089213232709632 |
|---|---|
| adam_text |
Contents
Preface XIII
ListofContributors XV
1 Introduction 1
Christoph A. Schalley
1.1 Some Historical Remarks on Supramolecular Chemistry 1
1.2 The Noncovalent Bond: A Brief Overview 2
1.3 Basic Concepts in Supramolecular Chemistry 4
1.3.1 Molecular Recognition: Molecular Complementarity 5
1.3.2 Chelate Effects and Preorganization: Entropy Factors 5
1.3.3 Cooperativity and Multivalency 7
1.3.4 Self-assembly and Self-organization 8
1.3.5 Template Effects 10
1.3.6 Self-replication and Supramolecular Catalysis 11
1.3.7 Molecular Devices and Machines: Implementing Function 13
1.4 Condusions: Diverse Methods for a Diverse Research Area 14
References and Notes 15
2 Determination of Binding Constants 17
Keiji Hirose
2.1 Theoretical Principles 17
2.1.1 The Binding Constants and Binding Energies 17
2.1.2 A General View on the Determination of Binding Constants 18
2.1.3 Guideline for Experiments 19
2.2 A Practical Course of Binding Constant Determination by UV/vis
Spectroscopy 19
2.2.1 Determination of Stoichiometry 19
2.2.2 Evaluation of Complex Concentration 23
2.2.3 Precautions to be Taken when Serting Up Concentration Conditions of
the Titration Experiment 25
2.2.3.1 Correlation between [H]o, [G]o, x and K 25
2.2.3.2 How to Set Up [H]o 27
Analytical Methods in Supramolecular Chemistry. Edited by Christoph Schalley
Copyright © 2007 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim
ISBN: 978-3-527-31505-5
VI Contents
2.2.3.3 How to Set Up [G]o 27
2.2.4 Data Treatment 32
2.2.4.1 General View 32
2.2.4.2 Rose-Drago Method for UV/vis Spectroscopy 33
2.2.4.3 Estimation of Error 35
2.2.5 Conclusion for UV/vis Spectroscopic Method 35
2.3 Practical Course of Action for NMR Spectroscopic Binding Constant
Determination 36
2.3.1 Determination of Stoichiometry 37
2.3.2 Evaluation of Complex Concentration 39
2.3.3 Data Treatment for NMR Method 39
2.3.3.1 Rose-Drago Method for NMR Spectroscopy 39
2.3.3.2 Estimation of Error for NMR Method 40
2.3.3.3 Nonlinear Least Square Data Treatment of NMR Titration Method 40
2.3.3.4 Estimation of Error for Nonlinear Least Square Method of NMR
Spectroscopy 44
2.4 Conclusion 45
References and Notes 54
3 Isothermal Titration Calorimetry in Supramolecular Chemistry 55
Franz P. Schmidtchen
3.1 Introduction 55
3.2 The Thermodynamic Platform 56
3.3 Acquiring Calorimetric Data 60
3.4 Extending the Applicability 70
3.5 Perspectives 75
Acknowledgement 76
References 77
4 Extraction Methods 79
Holger Stephan, Stefanie Juran, Bianca Antonioli, Kerstin Cloe and Karsten Cloe
4.1 Introduction 79
4.2 The Extraction Technique 80
4.3 The Technical Process 83
4.4 The Extraction Equilibrium 84
4.5 Principles of Supramolecular Extraction 87
4.6 Examples of Supramolecular Extraction 89
4.7 Conclusions and Future Perspectives 100
Acknowledgements 100
References 101
5 Mass Spectrometry and Gas Phase Chemistry of Supramolecules 104
Michael Kogej and Christoph A. Schalley
5.1 Introduction 104
5.2 Instrumentation 105
5.2.1 Ionization Techniques Suitable for Noncovalent Species 106
Contents I VII
5.2.1.1 Matrix-assisted Laser Desorption/Ionization (MALDI) 106
5.2.1.2 Electrospray Ionization (ESI) 108
5.2.1.3 Resonance-enhanced Multiphoton Ionization (REMPI) 110
5.2.1.4 Ionization of Noncovalent Species 110
5.2.2 Mass Analyzers 111
5.2.2.1 Quadrupole Instruments and Quadrupole Ion Traps 111
5.2.2.2 Time-of-flight (TOF) 113
5.2.2.3 Ion Cyclotron Resonance (ICR) 115
5.3 Particuliarities and Limitations of Mass Spectrometry 117
5.4 Beyond Analytical Characterization: Tandem MS Experiments for the
Examination of the Gas-phase Chemistry of Supramolecules 119
5.4.1 Collision-induced Decay (CID) 220
5.4.2 Infrared-multiphoton Dissociation (IRMPD) 120
5.4.3 Blackbody Infrared Dissociation (BIRD) 121
5.4.4 Electron-capture Dissociation (ECD) and Electron Transfer Dissociation
(ETD) 122
5.4.5 Bimolecular Reactions: H/D-exchange and Gas-phase Equilibria 122
5.5 Selected Examples 123
5.5.1 Analytical Characterization: Exact Mass, Isotope Patterns, Charge State,
Stoichiometry, Impurities 125
5.5.2 Structural Characterization of Supramolecules 226
5.5.2.1 The Mechanical Bond: How to Distinguish Molecules with Respect to
Their Topology 126
5.5.2.2 Encapsulation of Guest Molecules in Self-assembling Capsules 127
5.5.3 Ion Mobility: A Zwitterionic Serine Octamer? 138
5.5.4 Mass Spectrometry for the Detection of Chirality 140
5.5.5 Reactivity Studies of Supramolecules in Solution 242
5.5.6 Reactivity in the Gas Phase: Isolated Species instead of Dynamic
Interconverting Complexes 147
5.5.6.1 Metallosupramolecular Squares: A Supramolecular Equivalent to
Neighbor Group Assistance 147
5.5.6.2 A Surprising Dendritic Effect: Switching Fragmentation
Mechanisms 151
5.5.7 Determining Thermochemical Data: The Influence of the
Environment 154
5.5.7.1 Crown Ether - Alkali Complexes: Questioning the Best-fit Model 154
5.5.7.2 BIRD: Arrhenius Kinetics of Oligonucleotide Strand Separation in the
Gas Phase 257
5.6 Conclusions 157
References and Notes 159
6 Diffusion NMR in Supramolecular Chemistry 163
Yoram Cohen, Liat Avram, Tamar Evan-Salem and Limor Frish
6.1 Introduction 163
6.2 Concepts of Molecular Diffusion 164
6.3 Measuring Diffusion with NMR 264
VIIII Contents
6.3.1 The Basic Pulse Sequence 164
6.3.2 The Stimulated Echo (STE) Diffusion Sequence 168
6.3.3 Technical Issues in Diffusion NMR 169
6.3.4 The LED and BPLED Sequences 171
6.3.5 DOSY-Diffusion Ordered Spectroscopy 173
6.4 Applications of Diffusion NMR in Supramolecular Chemistry: Selected
Examples 175
6.4.1 Binding and Association Constants 175
6.4.2 Encapsulation and Molecular Capsules 182
6.4.3 Molecular Size, Shape and Self-aggregation 193
6.4.4 Diffusion as a Filter: Virtual Separation and Ligand Screening 203
6.4.5 From Organometallics to Supercharged Supramolecular Systems 207
6.5 Advantages and Limitations of Diffusion NMR 209
6.6 Diffusion NMR and Chemical Exchange 210
6.7 Summary and Outlook 215
References and Notes 216
7 Photophysics and Photochemistry of Supramolecular Systems 220
Bernard Valeur, Mario Nuno Berberan-Santos and Monique M. Martin
7.1 Introduction 220
7.2 Spectrophotometry and Spectrofluorometry 221
7.2.1 Determination of the Stoichiometry and Association Constant of
Supramolecular Complexes from Spectrophotornetric or
Spectrofluorometric Titrations 221
7.2.2 Cooperativity and Anticooperativity 224
7.2.3 Possible Differences in Binding Constants in the Ground State and in
the Excited State 226
7.2.4 Information on Photoinduced Processes frorn Fluorescence
Spectra 227
7.2.4.1 Photoinduced Electron Transfer in a Calixarene-based Supermolecule
Designed for Mercury Ion Sensing [10] 227
7.2.4.2 Excitation Energy Transfer in an Indusion Complex of a
Multichromophoric Cyclodextrin with a Fluorophore 229
7.3 Time-resolved Fluorescence Techniques 230
7.3.1 General Principles 231
7.3.2 Pulse Fluorometry 233
7.3.3 Phase-modulation Fluorometry 235
7.3.3.1 Phase Fluorometers using a Continuous Light Source and an Electro-
optic Modulator 235
7.3.3.2 Phase Fluorometers using the Harmonie Content of a Pulsed
Laser 237
7.3.4 Data Analysis 237
7.3.5 Examples 238
7.3.5.1 Photoinduced Electron Transfer in a Self-assembled Zinc
Naphthalocyanine-Fullerene Diad 238
Contents I IX
7.3.5.2 Excitation Energy Transfer in a Self-assembled Zinc Porphyrin-Free Base
Porphyrin Diad 240
7.3.5.3 Excitation Energy Transfer in an Inclusion Complex of a
Multichromophoric Cyclodextrin with a Fluorophore 241
7.3.5.4 Excimer Formation of Cyanobiphenyls in a Calix[4]resorecinarene
Derivative 241
7.4 Fluorescence Anisotropy 243
7.4.1 Principles 244
7.4.2 Examples 249
7.4.2.1 Supramolecular Polymer Length 249
7.4.2.2 Excitation Energy Hopping in Multichromophoric Cydodextrins 251
7.5 Transient Absorption Spectroscopy 253
7.5.1 General Principles 253
7.5.2 Pump-probe Spectroscopy with Subpicosecond Laser Excitation 254
7.5.2.1 White Light Continuum Generation 254
7.5.2.2 Subpicosecond Pump-continuum Probe Set-up 255
7.5.2.3 Time-resolved Differential Absorption Measurements 257
7.5.2.4 Data Analysis 257
7.5.3 Examples of Application 258
7.5.3.1 Charge Separation in Porphyrin-Fullerene Diads 258
7.5.3.2 Cation Photorelease from a Crown-ether Complex 260
7.6 Concluding Remarks 262
References and Notes 262
8 Circular Dichroism Spectroscopy 265
Marie Urbanovä and Petr Mahn
8.1 Basic Considerations 265
8.1.1 Circular Dichroism 265
8.1.2 Variants of Chiroptical Methods 268
8.1.3 Advantages and Limits of Circular Dichroism Spectroscopies 269
8.1.3.1 Chiral and Parent Non-chiral Spectroscopies 269
8.1.3.2 Electronic and Vibrational Circular Dichroism 269
8.1.3.3 Instrumentation 270
8.1.3.4 Calculations 270
8.2 Measurement Techniques (Methodology of CD Measurement) 270
8.2.1 Electronic Circular Dichroism Measurements 272
8.2.2 Vibrational Circular Dichroism Measurements 272
8.3 Processing of Circular Dichroism Spectra 275
8.3.1 Intensity Calibration in VCD Spectroscopy 276
8.3.2 Baseline Corrections and Reliability in VcD 277
8.3.3 Advanced Processing of Circular Dichroism Spectra 277
8.4 Theory 279
8.4.1 Rotational Strength 279
8.4.2 Mechanisms Generating Optical Activity 280
8.4.3 Ab initio Calculations 282
X I Contents
8.5 Examples of Vibrational Circular Dichroism Applications 283
8.5.1 Absolute Configuration and Detailed Structural Parameters 283
8.5.2 Solution Structure of Biomolecules 287
8.5.3 Supramolecular Systems 292
8.6 Concluding Remarks 299
Abbreviations 299
References and Notes 300
9 Crystallography and Crystal Engineering 305
Kari Rissanen
9.1 Introduction 305
9.2 Crystallography 306
9.2.1 Introduction 306
9.2.2 A Walk through a Single Crystal Structural Determination 308
9.2.2.1 The (Single) Crystal 309
9.2.2.2 Mounting of the Crystal 310
9.2.2.3 Unit Cell Determination and Preliminary Space Group Selection 312
9.2.2.4 Data Collection, Data Processing and Final Space Group
Determination 318
9.2.2.5 Data Reduction, Structure Solution and Refinement 322
9.2.2.6 Analysis of Structure 327
9.3 Crystal Engineering 331
9.3.1 Introduction 331
9.3.2 Definition 331
9.4 Conclusions 334
Acknowledgements 335
References and Notes 335
10 Scanning Probe Microscopy 337
B. A. Hermann
10.1 Introduction: What is the Strength of Scanning Probe Techniques? 337
10.2 How do Scanning Probe Microscopes Work? 339
10.2.1 Scanning Tunneling Microscopy (STM) 341
10.2.1.1 Working Principle of STM 341
10.2.1.2 Operation Modes of STM 344
10.2.1.3 Imaging with STM 346
10.2.1.4 Tunneling Spectroscopy 350
10.2.1.5 Manipulating Atoms and Molecules with STM 359
10.2.2 Atomic Force Microscopy (AFM) 363
10.2.2.1 Function Principle of AFM 363
10.2.2.2 Various Operation Modes of AFM 364
10.2.2.3 Single Molecule Force Spectroscopy - Force-Distance
Measurements 367
10.3 Which Molecules can be Studied? 369
10.3.1 Differences between STM and AFM 370
Contents I XI
10.3.2 Exemplary Results on Smaller Molecules 371
10.4 What Results have been Obtained in the Field of Supramolecular
Chemistry? 374
10.4.1 Coronenes, Crown ethers, Cryptands, Macrocycles, Squares,
Rectangles 375
10.4.2 Calixarenes, Cyclodextrins, Molecular Sieves and Boxes 378
10.4.3 Porphyrins and Phorphyrin Oligomers 380
10.4.4 Complex Interconnected Supermolecules: Rotaxanes and
Catenanes 382
10.4.5 Supramolecular Assemblies, Grids, Arrays, Chains 382
Acknowledgements 384
References 384
11 The Characterization of Synthetic Ion Channels and Pores 391
Stefan Matile and Naomi Sakai
11.1 Introduction 391
11.2 Methods 392
11.2.1 Planar Bilayer Conductance 394
11.2.2 Fluorescence Spectroscopy with Labeled Vesicles 396
11.2.3 Miscellaneous 398
11.3 Characteristics 399
11.3.1 pH Gating 399
11.3.2 Concentration Dependence 400
11.3.3 Size Selectivity 402
11.3.4 Voltage Gating 403
11.3.5 Ion Selectivity 404
11.3.6 Blockage and Ligand Gating 407
11.3.7 Miscellaneous 410
11.4 Structural Studies 412
11.4.1 Binding to the Bilayer 413
11.4.2 Location in the Bilayer 414
11.4.3 Self-Assembly 414
11.4.4 Molecular Recognition 415
11.5 Concluding Remarks 415
Acknowledgement 416
References 416
12 Theoretical Methods for Supramolecular Chemistry 419
Barbara Kirchner and Markus Reiher
12.1 Introduction 419
12.2 A Survey of Theoretical Methods 422
12.2.1 First-principles Methods 424
12.2.2 The Supramolecular Approach and Total Interaction Energies 430
12.2.3 The Time Dimension: Molecular Dynamics 433
12.2.4 A Technical Note: Linear Scaling and Multiscale Modeling 437
XII Contents
12.2.5 How to Make the Connection to Experiment? 439
12.3 Standard Classification of Intermolecular Interactions 443
12.3.1 A Complication: Cooperative Effects 445
12.3.2 Distributed Multipoles and Polarizabilities 446
12.3.3 Local Multipole Expansions in MD Simulations 447
12.4 Qualitative Understanding and Decomposition Scheines 450
12.4.1 Interaction Energy Decomposition 451
12.4.2 A Core-electron Probe for Hydrogen Bond Interactions 452
12.4.3 The SEN Approach to Hydrogen Bond Energies 452
12.5 General Mechanism for a Static, Step-wise View on Host-Guest
Recognition 455
12.5.1 Template-free Pre-orientation Processes 457
12.5.2 Rearrangement Reactions 458
12.5.3 The Host-controlled Association Reaction 459
12.5.4 The Transformation Step 460
12.5.5 Inclusion of Environmental Effects 460
12.5.6 General Aspects of Template Thermodynamics and Kinetics 460
12.6 Conclusions and Perspective 462
Acknowledgments 463
References and Notes 463
Index 472 |
| adam_txt |
Contents
Preface XIII
ListofContributors XV
1 Introduction 1
Christoph A. Schalley
1.1 Some Historical Remarks on Supramolecular Chemistry 1
1.2 The Noncovalent Bond: A Brief Overview 2
1.3 Basic Concepts in Supramolecular Chemistry 4
1.3.1 Molecular Recognition: Molecular Complementarity 5
1.3.2 Chelate Effects and Preorganization: Entropy Factors 5
1.3.3 Cooperativity and Multivalency 7
1.3.4 Self-assembly and Self-organization 8
1.3.5 Template Effects 10
1.3.6 Self-replication and Supramolecular Catalysis 11
1.3.7 Molecular Devices and Machines: Implementing Function 13
1.4 Condusions: Diverse Methods for a Diverse Research Area 14
References and Notes 15
2 Determination of Binding Constants 17
Keiji Hirose
2.1 Theoretical Principles 17
2.1.1 The Binding Constants and Binding Energies 17
2.1.2 A General View on the Determination of Binding Constants 18
2.1.3 Guideline for Experiments 19
2.2 A Practical Course of Binding Constant Determination by UV/vis
Spectroscopy 19
2.2.1 Determination of Stoichiometry 19
2.2.2 Evaluation of Complex Concentration 23
2.2.3 Precautions to be Taken when Serting Up Concentration Conditions of
the Titration Experiment 25
2.2.3.1 Correlation between [H]o, [G]o, x and K 25
2.2.3.2 How to Set Up [H]o 27
Analytical Methods in Supramolecular Chemistry. Edited by Christoph Schalley
Copyright © 2007 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim
ISBN: 978-3-527-31505-5
VI Contents
2.2.3.3 How to Set Up [G]o 27
2.2.4 Data Treatment 32
2.2.4.1 General View 32
2.2.4.2 Rose-Drago Method for UV/vis Spectroscopy 33
2.2.4.3 Estimation of Error 35
2.2.5 Conclusion for UV/vis Spectroscopic Method 35
2.3 Practical Course of Action for NMR Spectroscopic Binding Constant
Determination 36
2.3.1 Determination of Stoichiometry 37
2.3.2 Evaluation of Complex Concentration 39
2.3.3 Data Treatment for NMR Method 39
2.3.3.1 Rose-Drago Method for NMR Spectroscopy 39
2.3.3.2 Estimation of Error for NMR Method 40
2.3.3.3 Nonlinear Least Square Data Treatment of NMR Titration Method 40
2.3.3.4 Estimation of Error for Nonlinear Least Square Method of NMR
Spectroscopy 44
2.4 Conclusion 45
References and Notes 54
3 Isothermal Titration Calorimetry in Supramolecular Chemistry 55
Franz P. Schmidtchen
3.1 Introduction 55
3.2 The Thermodynamic Platform 56
3.3 Acquiring Calorimetric Data 60
3.4 Extending the Applicability 70
3.5 Perspectives 75
Acknowledgement 76
References 77
4 Extraction Methods 79
Holger Stephan, Stefanie Juran, Bianca Antonioli, Kerstin Cloe and Karsten Cloe
4.1 Introduction 79
4.2 The Extraction Technique 80
4.3 The Technical Process 83
4.4 The Extraction Equilibrium 84
4.5 Principles of Supramolecular Extraction 87
4.6 Examples of Supramolecular Extraction 89
4.7 Conclusions and Future Perspectives 100
Acknowledgements 100
References 101
5 Mass Spectrometry and Gas Phase Chemistry of Supramolecules 104
Michael Kogej and Christoph A. Schalley
5.1 Introduction 104
5.2 Instrumentation 105
5.2.1 Ionization Techniques Suitable for Noncovalent Species 106
Contents I VII
5.2.1.1 Matrix-assisted Laser Desorption/Ionization (MALDI) 106
5.2.1.2 Electrospray Ionization (ESI) 108
5.2.1.3 Resonance-enhanced Multiphoton Ionization (REMPI) 110
5.2.1.4 Ionization of Noncovalent Species 110
5.2.2 Mass Analyzers 111
5.2.2.1 Quadrupole Instruments and Quadrupole Ion Traps 111
5.2.2.2 Time-of-flight (TOF) 113
5.2.2.3 Ion Cyclotron Resonance (ICR) 115
5.3 Particuliarities and Limitations of Mass Spectrometry 117
5.4 Beyond Analytical Characterization: Tandem MS Experiments for the
Examination of the Gas-phase Chemistry of Supramolecules 119
5.4.1 Collision-induced Decay (CID) 220
5.4.2 Infrared-multiphoton Dissociation (IRMPD) 120
5.4.3 Blackbody Infrared Dissociation (BIRD) 121
5.4.4 Electron-capture Dissociation (ECD) and Electron Transfer Dissociation
(ETD) 122
5.4.5 Bimolecular Reactions: H/D-exchange and Gas-phase Equilibria 122
5.5 Selected Examples 123
5.5.1 Analytical Characterization: Exact Mass, Isotope Patterns, Charge State,
Stoichiometry, Impurities 125
5.5.2 Structural Characterization of Supramolecules 226
5.5.2.1 The Mechanical Bond: How to Distinguish Molecules with Respect to
Their Topology 126
5.5.2.2 Encapsulation of Guest Molecules in Self-assembling Capsules 127
5.5.3 Ion Mobility: A Zwitterionic Serine Octamer? 138
5.5.4 Mass Spectrometry for the Detection of Chirality 140
5.5.5 Reactivity Studies of Supramolecules in Solution 242
5.5.6 Reactivity in the Gas Phase: Isolated Species instead of Dynamic
Interconverting Complexes 147
5.5.6.1 Metallosupramolecular Squares: A Supramolecular Equivalent to
Neighbor Group Assistance 147
5.5.6.2 A Surprising Dendritic Effect: Switching Fragmentation
Mechanisms 151
5.5.7 Determining Thermochemical Data: The Influence of the
Environment 154
5.5.7.1 Crown Ether - Alkali Complexes: Questioning the Best-fit Model 154
5.5.7.2 BIRD: Arrhenius Kinetics of Oligonucleotide Strand Separation in the
Gas Phase 257
5.6 Conclusions 157
References and Notes 159
6 Diffusion NMR in Supramolecular Chemistry 163
Yoram Cohen, Liat Avram, Tamar Evan-Salem and Limor Frish
6.1 Introduction 163
6.2 Concepts of Molecular Diffusion 164
6.3 Measuring Diffusion with NMR 264
VIIII Contents
6.3.1 The Basic Pulse Sequence 164
6.3.2 The Stimulated Echo (STE) Diffusion Sequence 168
6.3.3 Technical Issues in Diffusion NMR 169
6.3.4 The LED and BPLED Sequences 171
6.3.5 DOSY-Diffusion Ordered Spectroscopy 173
6.4 Applications of Diffusion NMR in Supramolecular Chemistry: Selected
Examples 175
6.4.1 Binding and Association Constants 175
6.4.2 Encapsulation and Molecular Capsules 182
6.4.3 Molecular Size, Shape and Self-aggregation 193
6.4.4 Diffusion as a Filter: Virtual Separation and Ligand Screening 203
6.4.5 From Organometallics to Supercharged Supramolecular Systems 207
6.5 Advantages and Limitations of Diffusion NMR 209
6.6 Diffusion NMR and Chemical Exchange 210
6.7 Summary and Outlook 215
References and Notes 216
7 Photophysics and Photochemistry of Supramolecular Systems 220
Bernard Valeur, Mario Nuno Berberan-Santos and Monique M. Martin
7.1 Introduction 220
7.2 Spectrophotometry and Spectrofluorometry 221
7.2.1 Determination of the Stoichiometry and Association Constant of
Supramolecular Complexes from Spectrophotornetric or
Spectrofluorometric Titrations 221
7.2.2 Cooperativity and Anticooperativity 224
7.2.3 Possible Differences in Binding Constants in the Ground State and in
the Excited State 226
7.2.4 Information on Photoinduced Processes frorn Fluorescence
Spectra 227
7.2.4.1 Photoinduced Electron Transfer in a Calixarene-based Supermolecule
Designed for Mercury Ion Sensing [10] 227
7.2.4.2 Excitation Energy Transfer in an Indusion Complex of a
Multichromophoric Cyclodextrin with a Fluorophore 229
7.3 Time-resolved Fluorescence Techniques 230
7.3.1 General Principles 231
7.3.2 Pulse Fluorometry 233
7.3.3 Phase-modulation Fluorometry 235
7.3.3.1 Phase Fluorometers using a Continuous Light Source and an Electro-
optic Modulator 235
7.3.3.2 Phase Fluorometers using the Harmonie Content of a Pulsed
Laser 237
7.3.4 Data Analysis 237
7.3.5 Examples 238
7.3.5.1 Photoinduced Electron Transfer in a Self-assembled Zinc
Naphthalocyanine-Fullerene Diad 238
Contents I IX
7.3.5.2 Excitation Energy Transfer in a Self-assembled Zinc Porphyrin-Free Base
Porphyrin Diad 240
7.3.5.3 Excitation Energy Transfer in an Inclusion Complex of a
Multichromophoric Cyclodextrin with a Fluorophore 241
7.3.5.4 Excimer Formation of Cyanobiphenyls in a Calix[4]resorecinarene
Derivative 241
7.4 Fluorescence Anisotropy 243
7.4.1 Principles 244
7.4.2 Examples 249
7.4.2.1 Supramolecular Polymer Length 249
7.4.2.2 Excitation Energy Hopping in Multichromophoric Cydodextrins 251
7.5 Transient Absorption Spectroscopy 253
7.5.1 General Principles 253
7.5.2 Pump-probe Spectroscopy with Subpicosecond Laser Excitation 254
7.5.2.1 White Light Continuum Generation 254
7.5.2.2 Subpicosecond Pump-continuum Probe Set-up 255
7.5.2.3 Time-resolved Differential Absorption Measurements 257
7.5.2.4 Data Analysis 257
7.5.3 Examples of Application 258
7.5.3.1 Charge Separation in Porphyrin-Fullerene Diads 258
7.5.3.2 Cation Photorelease from a Crown-ether Complex 260
7.6 Concluding Remarks 262
References and Notes 262
8 Circular Dichroism Spectroscopy 265
Marie Urbanovä and Petr Mahn
8.1 Basic Considerations 265
8.1.1 Circular Dichroism 265
8.1.2 Variants of Chiroptical Methods 268
8.1.3 Advantages and Limits of Circular Dichroism Spectroscopies 269
8.1.3.1 Chiral and Parent Non-chiral Spectroscopies 269
8.1.3.2 Electronic and Vibrational Circular Dichroism 269
8.1.3.3 Instrumentation 270
8.1.3.4 Calculations 270
8.2 Measurement Techniques (Methodology of CD Measurement) 270
8.2.1 Electronic Circular Dichroism Measurements 272
8.2.2 Vibrational Circular Dichroism Measurements 272
8.3 Processing of Circular Dichroism Spectra 275
8.3.1 Intensity Calibration in VCD Spectroscopy 276
8.3.2 Baseline Corrections and Reliability in VcD 277
8.3.3 Advanced Processing of Circular Dichroism Spectra 277
8.4 Theory 279
8.4.1 Rotational Strength 279
8.4.2 Mechanisms Generating Optical Activity 280
8.4.3 Ab initio Calculations 282
X I Contents
8.5 Examples of Vibrational Circular Dichroism Applications 283
8.5.1 Absolute Configuration and Detailed Structural Parameters 283
8.5.2 Solution Structure of Biomolecules 287
8.5.3 Supramolecular Systems 292
8.6 Concluding Remarks 299
Abbreviations 299
References and Notes 300
9 Crystallography and Crystal Engineering 305
Kari Rissanen
9.1 Introduction 305
9.2 Crystallography 306
9.2.1 Introduction 306
9.2.2 A Walk through a Single Crystal Structural Determination 308
9.2.2.1 The (Single) Crystal 309
9.2.2.2 Mounting of the Crystal 310
9.2.2.3 Unit Cell Determination and Preliminary Space Group Selection 312
9.2.2.4 Data Collection, Data Processing and Final Space Group
Determination 318
9.2.2.5 Data Reduction, Structure Solution and Refinement 322
9.2.2.6 Analysis of Structure 327
9.3 Crystal Engineering 331
9.3.1 Introduction 331
9.3.2 Definition 331
9.4 Conclusions 334
Acknowledgements 335
References and Notes 335
10 Scanning Probe Microscopy 337
B. A. Hermann
10.1 Introduction: What is the Strength of Scanning Probe Techniques? 337
10.2 How do Scanning Probe Microscopes Work? 339
10.2.1 Scanning Tunneling Microscopy (STM) 341
10.2.1.1 Working Principle of STM 341
10.2.1.2 Operation Modes of STM 344
10.2.1.3 Imaging with STM 346
10.2.1.4 Tunneling Spectroscopy 350
10.2.1.5 Manipulating Atoms and Molecules with STM 359
10.2.2 Atomic Force Microscopy (AFM) 363
10.2.2.1 Function Principle of AFM 363
10.2.2.2 Various Operation Modes of AFM 364
10.2.2.3 Single Molecule Force Spectroscopy - Force-Distance
Measurements 367
10.3 Which Molecules can be Studied? 369
10.3.1 Differences between STM and AFM 370
Contents I XI
10.3.2 Exemplary Results on Smaller Molecules 371
10.4 What Results have been Obtained in the Field of Supramolecular
Chemistry? 374
10.4.1 Coronenes, Crown ethers, Cryptands, Macrocycles, Squares,
Rectangles 375
10.4.2 Calixarenes, Cyclodextrins, Molecular Sieves and Boxes 378
10.4.3 Porphyrins and Phorphyrin Oligomers 380
10.4.4 Complex Interconnected Supermolecules: Rotaxanes and
Catenanes 382
10.4.5 Supramolecular Assemblies, Grids, Arrays, Chains 382
Acknowledgements 384
References 384
11 The Characterization of Synthetic Ion Channels and Pores 391
Stefan Matile and Naomi Sakai
11.1 Introduction 391
11.2 Methods 392
11.2.1 Planar Bilayer Conductance 394
11.2.2 Fluorescence Spectroscopy with Labeled Vesicles 396
11.2.3 Miscellaneous 398
11.3 Characteristics 399
11.3.1 pH Gating 399
11.3.2 Concentration Dependence 400
11.3.3 Size Selectivity 402
11.3.4 Voltage Gating 403
11.3.5 Ion Selectivity 404
11.3.6 Blockage and Ligand Gating 407
11.3.7 Miscellaneous 410
11.4 Structural Studies 412
11.4.1 Binding to the Bilayer 413
11.4.2 Location in the Bilayer 414
11.4.3 Self-Assembly 414
11.4.4 Molecular Recognition 415
11.5 Concluding Remarks 415
Acknowledgement 416
References 416
12 Theoretical Methods for Supramolecular Chemistry 419
Barbara Kirchner and Markus Reiher
12.1 Introduction 419
12.2 A Survey of Theoretical Methods 422
12.2.1 First-principles Methods 424
12.2.2 The Supramolecular Approach and Total Interaction Energies 430
12.2.3 The Time Dimension: Molecular Dynamics 433
12.2.4 A Technical Note: Linear Scaling and Multiscale Modeling 437
XII Contents
12.2.5 How to Make the Connection to Experiment? 439
12.3 Standard Classification of Intermolecular Interactions 443
12.3.1 A Complication: Cooperative Effects 445
12.3.2 Distributed Multipoles and Polarizabilities 446
12.3.3 Local Multipole Expansions in MD Simulations 447
12.4 Qualitative Understanding and Decomposition Scheines 450
12.4.1 Interaction Energy Decomposition 451
12.4.2 A Core-electron Probe for Hydrogen Bond Interactions 452
12.4.3 The SEN Approach to Hydrogen Bond Energies 452
12.5 General Mechanism for a Static, Step-wise View on Host-Guest
Recognition 455
12.5.1 Template-free Pre-orientation Processes 457
12.5.2 Rearrangement Reactions 458
12.5.3 The Host-controlled Association Reaction 459
12.5.4 The Transformation Step 460
12.5.5 Inclusion of Environmental Effects 460
12.5.6 General Aspects of Template Thermodynamics and Kinetics 460
12.6 Conclusions and Perspective 462
Acknowledgments 463
References and Notes 463
Index 472 |
| any_adam_object | 1 |
| any_adam_object_boolean | 1 |
| author2 | Schalley, Christoph A. 1968- |
| author2_role | edt |
| author2_variant | c a s ca cas |
| author_GND | (DE-588)115419969 |
| author_facet | Schalley, Christoph A. 1968- |
| building | Verbundindex |
| bvnumber | BV022518994 |
| callnumber-first | Q - Science |
| callnumber-label | QD878 |
| callnumber-raw | QD878 |
| callnumber-search | QD878 |
| callnumber-sort | QD 3878 |
| callnumber-subject | QD - Chemistry |
| classification_rvk | UK 7500 VK 7150 |
| ctrlnum | (OCoLC)71348102 (DE-599)BVBBV022518994 |
| dewey-full | 547.1226 |
| dewey-hundreds | 500 - Natural sciences and mathematics |
| dewey-ones | 547 - Organic chemistry |
| dewey-raw | 547.1226 |
| dewey-search | 547.1226 |
| dewey-sort | 3547.1226 |
| dewey-tens | 540 - Chemistry and allied sciences |
| discipline | Chemie / Pharmazie Physik |
| discipline_str_mv | Chemie / Pharmazie Physik |
| format | Book |
| fullrecord | <?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>00000nam a2200000 c 4500</leader><controlfield tag="001">BV022518994</controlfield><controlfield tag="003">DE-604</controlfield><controlfield tag="007">t</controlfield><controlfield tag="008">070719s2007 gw ad|| |||| 00||| eng d</controlfield><datafield tag="015" ind1=" " ind2=" "><subfield code="a">07,A08,0853</subfield><subfield code="2">dnb</subfield></datafield><datafield tag="020" ind1=" " ind2=" "><subfield code="a">9783527315055</subfield><subfield code="c">Pp. : EUR 149.00 (freier Pr.), ca. sfr 235.00 (freier Pr.)</subfield><subfield code="9">978-3-527-31505-5</subfield></datafield><datafield tag="020" ind1=" " ind2=" "><subfield code="a">3527315055</subfield><subfield code="c">Pp. : EUR 149.00 (freier Pr.), ca. sfr 235.00 (freier Pr.)</subfield><subfield code="9">3-527-31505-5</subfield></datafield><datafield tag="024" ind1="3" ind2=" "><subfield code="a">9783527315055</subfield></datafield><datafield tag="028" ind1="5" ind2="2"><subfield code="a">1131505 000</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(OCoLC)71348102</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-599)BVBBV022518994</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-604</subfield><subfield code="b">ger</subfield><subfield code="e">rakddb</subfield></datafield><datafield tag="041" ind1="0" ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="044" ind1=" " ind2=" "><subfield code="a">gw</subfield><subfield code="c">XA-DE-BW</subfield></datafield><datafield tag="049" ind1=" " ind2=" "><subfield code="a">DE-19</subfield><subfield code="a">DE-703</subfield><subfield code="a">DE-20</subfield><subfield code="a">DE-11</subfield><subfield code="a">DE-188</subfield></datafield><datafield tag="050" ind1=" " ind2="0"><subfield code="a">QD878</subfield></datafield><datafield tag="082" ind1="0" ind2=" "><subfield code="a">547.1226</subfield><subfield code="2">22</subfield></datafield><datafield tag="082" ind1="0" ind2=" "><subfield code="a">547.1226</subfield><subfield code="2">22/ger</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">UK 7500</subfield><subfield code="0">(DE-625)145803:</subfield><subfield code="2">rvk</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">VK 7150</subfield><subfield code="0">(DE-625)147416:253</subfield><subfield code="2">rvk</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">540</subfield><subfield code="2">sdnb</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Analytical methods in supramolecular chemistry</subfield><subfield code="c">ed. by Christoph Schalley</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="a">Weinheim</subfield><subfield code="b">Wiley-VCH-Verl.</subfield><subfield code="c">2007</subfield></datafield><datafield tag="300" ind1=" " ind2=" "><subfield code="a">XVI, 484 S.</subfield><subfield code="b">Ill., graph. Darst.</subfield><subfield code="c">25 cm</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="b">n</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="b">nc</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="500" ind1=" " ind2=" "><subfield code="a">Literaturangaben</subfield></datafield><datafield tag="650" ind1=" " ind2="7"><subfield code="a">Supramoleculaire systemen</subfield><subfield code="2">gtt</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Instrumental analysis</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Supramolecular chemistry</subfield></datafield><datafield tag="650" ind1="0" ind2="7"><subfield code="a">Analytische Chemie</subfield><subfield code="0">(DE-588)4129906-1</subfield><subfield code="2">gnd</subfield><subfield code="9">rswk-swf</subfield></datafield><datafield tag="650" ind1="0" ind2="7"><subfield code="a">Supramolekulare Chemie</subfield><subfield code="0">(DE-588)4306141-2</subfield><subfield code="2">gnd</subfield><subfield code="9">rswk-swf</subfield></datafield><datafield tag="689" ind1="0" ind2="0"><subfield code="a">Supramolekulare Chemie</subfield><subfield code="0">(DE-588)4306141-2</subfield><subfield code="D">s</subfield></datafield><datafield tag="689" ind1="0" ind2="1"><subfield code="a">Analytische Chemie</subfield><subfield code="0">(DE-588)4129906-1</subfield><subfield code="D">s</subfield></datafield><datafield tag="689" ind1="0" ind2=" "><subfield code="5">DE-604</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Schalley, Christoph A.</subfield><subfield code="d">1968-</subfield><subfield code="0">(DE-588)115419969</subfield><subfield code="4">edt</subfield></datafield><datafield tag="856" ind1="4" ind2="2"><subfield code="q">text/html</subfield><subfield code="u">http://deposit.dnb.de/cgi-bin/dokserv?id=2843897&prov=M&dok_var=1&dok_ext=htm</subfield><subfield code="3">Inhaltstext</subfield></datafield><datafield tag="856" ind1="4" ind2="2"><subfield code="m">HBZ Datenaustausch</subfield><subfield code="q">application/pdf</subfield><subfield code="u">http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015725764&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA</subfield><subfield code="3">Inhaltsverzeichnis</subfield></datafield><datafield tag="943" ind1="1" ind2=" "><subfield code="a">oai:aleph.bib-bvb.de:BVB01-015725764</subfield></datafield></record></collection> |
| id | DE-604.BV022518994 |
| illustrated | Illustrated |
| index_date | 2024-07-02T18:02:36Z |
| indexdate | 2024-07-20T09:20:20Z |
| institution | BVB |
| isbn | 9783527315055 3527315055 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-015725764 |
| oclc_num | 71348102 |
| open_access_boolean | |
| owner | DE-19 DE-BY-UBM DE-703 DE-20 DE-11 DE-188 |
| owner_facet | DE-19 DE-BY-UBM DE-703 DE-20 DE-11 DE-188 |
| physical | XVI, 484 S. Ill., graph. Darst. 25 cm |
| publishDate | 2007 |
| publishDateSearch | 2007 |
| publishDateSort | 2007 |
| publisher | Wiley-VCH-Verl. |
| record_format | marc |
| spelling | Analytical methods in supramolecular chemistry ed. by Christoph Schalley Weinheim Wiley-VCH-Verl. 2007 XVI, 484 S. Ill., graph. Darst. 25 cm txt rdacontent n rdamedia nc rdacarrier Literaturangaben Supramoleculaire systemen gtt Instrumental analysis Supramolecular chemistry Analytische Chemie (DE-588)4129906-1 gnd rswk-swf Supramolekulare Chemie (DE-588)4306141-2 gnd rswk-swf Supramolekulare Chemie (DE-588)4306141-2 s Analytische Chemie (DE-588)4129906-1 s DE-604 Schalley, Christoph A. 1968- (DE-588)115419969 edt text/html http://deposit.dnb.de/cgi-bin/dokserv?id=2843897&prov=M&dok_var=1&dok_ext=htm Inhaltstext HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015725764&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Analytical methods in supramolecular chemistry Supramoleculaire systemen gtt Instrumental analysis Supramolecular chemistry Analytische Chemie (DE-588)4129906-1 gnd Supramolekulare Chemie (DE-588)4306141-2 gnd |
| subject_GND | (DE-588)4129906-1 (DE-588)4306141-2 |
| title | Analytical methods in supramolecular chemistry |
| title_auth | Analytical methods in supramolecular chemistry |
| title_exact_search | Analytical methods in supramolecular chemistry |
| title_exact_search_txtP | Analytical methods in supramolecular chemistry |
| title_full | Analytical methods in supramolecular chemistry ed. by Christoph Schalley |
| title_fullStr | Analytical methods in supramolecular chemistry ed. by Christoph Schalley |
| title_full_unstemmed | Analytical methods in supramolecular chemistry ed. by Christoph Schalley |
| title_short | Analytical methods in supramolecular chemistry |
| title_sort | analytical methods in supramolecular chemistry |
| topic | Supramoleculaire systemen gtt Instrumental analysis Supramolecular chemistry Analytische Chemie (DE-588)4129906-1 gnd Supramolekulare Chemie (DE-588)4306141-2 gnd |
| topic_facet | Supramoleculaire systemen Instrumental analysis Supramolecular chemistry Analytische Chemie Supramolekulare Chemie |
| url | http://deposit.dnb.de/cgi-bin/dokserv?id=2843897&prov=M&dok_var=1&dok_ext=htm http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015725764&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT schalleychristopha analyticalmethodsinsupramolecularchemistry |