Provides deep insight into the concepts and recent developments in the area of supramolecular chemistry in water
Written by experts in their respective field, this comprehensive reference covers various aspects of supramolecular chemistry in water?from fundamental aspects to applications. It provides readers with a basic introduction to the current understanding of the properties of water and how they influence molecular recognition, and examines the different receptor types available in water and the types of substrates that can be bound. It also looks at areas to where they can be applied, such as materials, optical sensing, medicinal imaging, and catalysis.
Supramolecular Chemistry in Water offers five major sections that address important topics like water properties, molecular recognition, association and aggregation phenomena, optical detection and imaging, and supramolecular catalysis. It covers chemistry and physical chemistry of water; water-mediated molecular recognition; peptide and protein receptors; nucleotide receptors; carbohydrate receptors; and ion receptors. The book also teaches readers all about coordination compounds; self-assembled polymers and gels; foldamers; vesicles and micelles; and surface-modified nanoparticles. In addition, it provides in-depth information on indicators and optical probes, as well as probes for medical imaging.
-Covers, in a timely manner, an emerging area in chemistry that is growing more important every day
-Addresses topics such as molecular recognition, aggregation, catalysis, and more
-Offers comprehensive coverage of everything from fundamental aspects of supramolecular chemistry in water to its applications
-Edited by one of the leading international scientists in the field
Supramolecular Chemistry in Water is a one-stop-resource for all polymer chemists, catalytic chemists, biochemists, water chemists, and physical chemists involved in this growing area of research.
Preface xv
1 Water Runs Deep 1
Nicholas E. Ernst and Bruce C. Gibb
1.1 The Control of Water 1
1.2 The Shape of Water 2
1.3 The Matrix of Life as a Solvent 4
1.4 Solvation Thermodynamics 6
1.5 The Three Effects 9
1.5.1 The Hydrophobic Effect 11
1.5.2 The Hofmeister Effect 19
1.5.3 The Reverse Hofmeister Effect 23
1.6 Conclusions and Future Work 24
Acknowledgments 25
References 25
2 WaterCompatible Host Systems 35
Frank Biedermann
2.1 General Overview 35
2.2 Acyclic Systems 36
2.2.1 Acyclic Molecular Recognition Units 36
2.2.2 Molecular Tweezers 38
2.2.3 Foldamers 39
2.2.4 Compartmentalized Structures Formed by SurfactantLike Molecules 40
2.3 Macrocyclic Receptors that Bind Charged Guests 42
2.3.1 Crown Ethers, Cryptands, and Spherands 42
2.3.2 Bambus[n]urils 44
2.3.3 Calix[n]arenes 45
2.3.4 Pillar[n]arenes 48
2.4 Macrocyclic Receptors that (also) Bind Noncharged Organic Guests 50
2.4.1 Cyclodextrins 50
2.4.2 Cucurbit[n]urils 54
2.4.3 Deep Cavitands 58Contents
2.4.4 Molecular Tubes 62
2.5 Practitioners Guidelines for Choosing a WaterCompatible Host 64
2.5.1 Guest Binding Affinity and Selectivity 64
2.5.2 Availability/Scalability 65
2.5.3 Functionality 65
2.5.4 Solubility 66
2.5.5 Biocompatibility/Toxicity 67
References 67
3 Artificial Peptide and Protein Receptors 79
Joydev Hatai and Carsten Schmuck
3.1 Introduction 79
3.2 Peptide Recognition 79
3.2.1 Calixarenes 80
3.2.2 Guanidiniocarbonyl Pyrroles 80
3.2.3 Cucurbiturils 82
3.2.4 Metal Complexes 84
3.2.5 Phosphonates 86
3.2.6 ThioureaContaining Copolymers 87
3.3 Protein Recognition 88
3.3.1 Molecular Tweezer: Huntingtin Protein (htt) 89
3.3.2 Foldamer: Human Carbonic Anhydrase 89
3.3.3 Tetravalent Peptide: Tryptase 90
3.3.4 Semisynthetic Fusicoccin Derivative: 1433/Gab2 Protein 91
3.3.5 Ruthenium Complex: Cytochrome C 92
3.3.6 Nitrilotriacetic AcidPeptide Conjugate: HisTag Calmodulin 93
3.3.7 Cucurbit[7]uril: Native Insulin and Human Growth Hormone 95
3.3.8 Phosphonated Calix[6]arene: Cytochrome C 96
3.3.9pSulfonatocalixarene: Human Insulin 96
3.3.10 Multivalent Calixarene: PlateletDerived Growth Factor 97
3.4 Sensor Arrays for Proteins 99
3.4.1 Tripodal PeptideContaining Receptors: Proteins and Glycoproteins 99
3.4.2 Substituted Porphyrins: Proteins and Metalloproteins 100
3.4.3 Poly(pphenyleneethynylene)s: Proteins 101
3.4.4 Chemiluminescent Nanomaterials: Proteins and Cells 103
3.5 Combinatorial Fluorescent Molecular Sensors for Proteins 104
3.5.1 Probe for MMP, GST, and PDGF Protein Families 104
3.5.2 Probe for Amyloid Beta Proteins 107
3.6 Conclusions and Future Directions 108
References 109
4 Recognition, Transformation, Detection of Nucleotides and Aqueous NucleotideBased Materials 115
Isabel Pont, Cristina GalianaRosello, Alberto Lopera, Jorge GonzálezGarcía, and Enrique GarcíaEspaña
4.1 Introduction 115
4.2 Nucleotide Structures 118
4.3 Nucleotide Receptors 119
4.3.1 Receptors without Aromatic Units 119
4.3.2 Receptors with Aromatic Units 123
4.3.3 Metal Complexes as Nucleotide Receptors 131
4.3.4 Catalytic Aspects 134
4.4 Nucleotide Sensing 140
4.4.1 General Aspects 140
4.4.2 UVvis Sensing 140
4.4.3 Fluorescence Sensing 142
4.5 Soft Materials Incorporating Nucleotides, Nucleosides, and Nucleobases 147
4.6 Biomedical Applications 150
4.7 Challenges and Future Perspectives 151
Acknowledgment 152
References 153
5 Carbohydrate Receptors 161
Anthony P. Davis
5.1 Introduction 161
5.2 Organic Molecular Receptors 163
5.2.1 Acyclic Receptors 164
5.2.2 Macrocyclic Receptors 167
5.2.3 Macropolycyclic Cage Receptors 171
5.3 Metal Complexes as Carbohydrate Receptors 178
5.4 BoronBased Receptors 180
5.5 Conclusions 184
References 186
6 Ion Receptors 193
Luca Leoni, Antonella Dalla Cort, Frank Biedermann, and Stefan Kubik
6.1 Introduction 193
6.1.1 Potential Applications for Ion Receptors 194
6.1.2 Binding Modes of Ion Receptors 194
6.2 Cation Receptors 197
6.2.1 Neutral Receptors 197
6.2.1.1 Crown Ethers and Cryptands 197
6.2.1.2 Cyclodextrins 198
6.2.1.3 Cucurbiturils 199
6.2.1.4 Cavitands 201
6.2.2 Negatively Charged Receptors 202
6.2.2.1 Cyclophanes 202
6.2.2.2 Cryptophanes 204
6.2.2.3 Calixarenes 204
6.2.2.4 Pillararenes 205
6.2.2.5 Molecular Tweezers 206
6.2.2.6 Acyclic Cucurbiturils 208
6.2.3.1 Metallacycles 209
6.2.3.2 Coordination Cages 210
6.3 Anion Receptors 211
6.3.1 MetalContaining Receptors 211
6.3.1.1 Coordination Cages 212
6.3.1.2 TetraazamacrocycleBased Receptors 214
6.3.1.3 Diethylenetriamine and Bis(2pyridylmethyl)amineBased Receptors 215
6.3.1.4 Tris(2aminoethyl)amine and Tris(2pyridylmethyl)amineBased Receptors 218
6.3.1.5 Miscellaneous 220
6.3.2 Positively Charged Receptors 221
6.3.2.1 Receptors with Quaternary Ammonium Groups 221
6.3.2.2 AmineBased Receptors 223
6.3.2.3 GuanidineBased Receptors 225
6.3.2.4 ImidazoliumBased Receptors 227
6.3.3 Negatively Charged Receptors 228
6.3.4 Neutral Receptors 231
6.4 Zwitterion Receptors 236
6.5 Conclusion and Future Challenges 238
References 239
7 Coordination Compounds 249
Anna J. McConnell and Marc Lehr
7.1 Introduction 249
7.2 Organometallic Compounds 249
7.2.1 Macrocycles 251
7.2.2 Cages 252
7.3 Metallomacrocycles 253
7.4 Metallosupramolecular Helicates 255
7.4.1 Transition Metal Helicates 255
7.4.2 Lanthanide Helicates 257
7.5 Metallosupramolecular Bowls and Tubes 260
7.6 Metallosupramolecular Cages 262
7.6.1 Design Considerations 263
7.6.2 Thermodynamics of Guest Binding 263
7.6.3 Cage and Guest Dynamics upon Encapsulation 265
7.6.4 Chiral Recognition 266
7.6.5 Encapsulation of Biorelevant Molecules 266
7.6.6 Stabilization of Encapsulated Species 269
7.6.7 Controlling Reactivity 269
7.6.8 Catalysis 270
7.7 MetalOrganic Frameworks 272
7.8 Challenges and Future Directions 273
8 Aqueous Supramolecular Polymers and Hydrogels 285
Daniel Spitzer and Pol Besenius
8.1 Introduction 285
8.2 HydrogenBonded Supramolecular Systems 287
8.3 HostGuest Induced Supramolecular Polymers and Hydrogels 292
8.4 MetalLigand Coordinated Systems 296
8.5 Conjugated Systems 301
8.6 Low Molecular Weight Hydrogelator Systems 307
8.7 PeptideBased Molecular Amphiphiles and Their Supramolecular Systems 314
8.8 Bioinspired Systems 321
8.9 Challenges and Future Directions 326
References 326
9 Foldamers 337
Morgane Pasco, Christel Dolain, and Gilles Guichard
9.1 Introduction 337
9.2 Discrete ProteinLike Architectures by Lateral Assemblies of Helical Foldamers 338
9.2.1 Bioinspired Helix Assemblies: TopDown Approaches 340
9.2.2 Bioinspired Helix Assemblies: BottomUp Approaches 344
9.3 Helix Duplexes in Aqueous Solution 350
9.4 Assemblies of Extended Chains 355
9.5 Elongated Nanostructures by SelfAssembly 357
9.6 Applications 359
9.6.1 HostGuest Interactions With and Within Helix Bundles 359
9.6.2 SelfAssembling Foldamers Targeting Heparin 362
9.6.3 Catalysis with SelfAssembled Foldamers 363
9.6.4 FoldamerMediated Protein Oligomerization 364
9.6.5 Nanopores by Insertion of Foldamers into Phospholipid Membranes 366
9.7 Challenges and Future Directions 366
Acknowledgments 367
References 367
10 Vesicles and Micelles 375
Wilke C. de Vries and Bart Jan Ravoo
10.1 Introduction 375
10.2 Building Blocks and Structure of Vesicles and Micelles 376
10.2.1 Conventional Building Blocks and Packing Parameter 376
10.2.2 Driving Forces and Dynamics 379
10.2.3 Nonconventional Building Blocks 382
10.3 StimulusResponsive Vesicles and Micelles 387
10.3.1 Endogenous Stimuli: Redox and pH 387
10.3.1.1 Redox 387
10.3.1.2 pH 389
10.3.2 Exogenous Stimuli: Light and Temperature 391
10.3.2.1 Light 391
10.3.2.2 Temperature 392
10.4 Vesicles and Micelles as Template Structures for Nanomaterials 393
10.4.1 Condensation and Polymerization Reactions Using Template Structures 393
10.4.2 Stabilization of Vesicle and Micelle Structures by CrossLinking 394
10.4.3 Polymer Shells Enclosing Vesicle Templates 395
10.5 Molecular Recognition of Vesicles and Micelles in Biomimetic Systems and Nanomaterials 397
10.5.1 Macrocyclic Amphiphiles 397
10.5.2 Carbohydrate and PeptideBased Recognition 399
10.5.3 DNABased Recognition 402
10.6 Challenges and Future Directions 404
References 405
11 MonolayerProtected Gold Nanoparticles for Molecular Sensing and Catalysis 413
Fabrizio Mancin, Leonard J. Prins, Federico Rastrelli, and Paolo Scrimin
11.1 Introduction 413
11.2 Analytical Techniques 414
11.2.1 Nuclear Magnetic Resonance Spectroscopy 414
11.2.2 Electron Paramagnetic Resonance Spectroscopy 416
11.2.3 Fluorescence Spectroscopy 417
11.2.4 Isothermal Titration Calorimetry 417
11.2.5 SurfaceEnhanced Raman Scattering 418
11.3 Molecular Recognition and Chemosensing of Small Molecules 418
11.3.1 Multivalent Binding Interactions at the Monolayer Surface 419
11.3.2 Binding Pockets in the Monolayer 420
11.3.3 Gold NanoparticleBased Chemosensors 426
11.3.3.1 Indicator Displacement Assays 426
11.3.3.2 NMR Chemosensing 428
11.4 Catalysis by Nanozymes 430
11.5 Controlling Molecular Recognition Processes at the Monolayer 435
11.5.1 Regulatory Mechanisms 435
11.5.2 Adaptive Multivalent Surfaces 438
11.6 Challenges and Future Directions 442
References 442
12 Optical Probes and Sensors 449
Pavel Anzenbacher, Jr and Lorenzo M. Mosca
12.1 Introduction and Lexicon 449
12.2 Brief Fundamentals of Molecular Photoprocesses 451
12.3 Some Comments on the Design of Probes and Sensors 455
12.3.1 General Aspects 455
12.3.2 Fighting with Water 457
12.4 Probes and Sensors for Electroneutral Species 459
12.4.1 Carbohydrates 459
12.5 Probes and Sensor for Cations 462
12.5.1 Alkali and AlkaliEarth Cations 462
12.5.2 FirstRow Transition Metal Ions 464
12.5.3 Heavy Metal Ions, Particularly Cadmium and Mercury 467
12.6 Probes and Sensors for Anions 469
12.6.1 Fluoride 469
12.6.2 Cyanide 472
12.6.3 Inorganic and Organic Phosphates 473
12.6.4 Carboxylates 482
12.6.5 Other Anions of Interest 487
12.6.6 Sensors for Multiple Anions 487
12.7 Sensing of Biomacromolecules 489
12.8 Challenges and Future Directions 491
References 492
13 Probes for Medical Imaging 501
Felicia M. Roland and Bradley D. Smith
13.1 Medical Imaging 501
13.2 Structure and Supramolecular Properties of Molecular Probes 503
13.2.1 Structure 503
13.2.2 Linkers 503
13.2.3 Reporter Groups 504
13.2.4 Design Aspects 504
13.3 Targeting Groups for Receptors 506
13.3.1 DrugLike Molecules 506
13.3.2 Vitamins 507
13.3.3 Peptides 508
13.3.4 Antibodies 508
13.3.5 Aptamers 510
13.4 Signal Enhancement Strategies 511
13.4.1 Intracellular Accumulation 511
13.4.2 Signal Activation by Enzymes 512
13.5 Targeting Cell Surface Biomolecules 513
13.5.1 Anionic Phospholipids 513
13.5.2 Glycans 514
13.5.3 Antigens 515
13.6 Clinical Development 516
13.6.1 Government Approval 516
13.6.2 Multimodal Approaches 518
13.6.3 Theranostic Approaches 519
13.7 Future Role of Supramolecular Chemistry 520
Acknowledgments 521
References 521
14 Supramolecular Catalysis in Water 525
Piet W. N. M. van Leeuwen and Matthieu Raynal
14.1 Introduction 525
14.2 Classification of Supramolecular Catalysts Operating in Water 527
14.2.1 Mass Transfer Promotion through Substrate Sequestration (S1) 529
14.2.2 Catalysis by Confinement (S2) 529
14.2.3 Directed Substrate Reactivity (S3) 531
14.2.4 Construction and Modulation of the Catalytic Structure (S4) 532
14.3 Synthetic Hosts for Catalysis in Water 533
14.3.1 Cyclodextrins (CDs) 536
14.3.2 Cucurbit[n]urils (CBn) 536
14.3.3 Hosts with Aromatic Walls 537
14.3.4 Velcrands 538
14.3.5 Octaacid 538
14.3.6 Metallocages 538
14.3.7 Hyperbranched Polymers 539
14.3.8 Dendrimers 539
14.3.9 Micelles 540
14.3.10 Vesicles 541
14.4 Supramolecular Catalysts for the Aqueous Biphasic Hydroformylation Reaction 542
14.5 Supramolecular Catalysts for Other Organometallic Reactions in Water 547
14.6 Future Directions 550
References 551
Index 567
