Mass Spectrometry of Non-Covalent Complexes: Supramolecular Chemistry in the Gas Phase

List of Tutorials.

PART A: GENERAL ISSUES.

1. INTRODUCTION.

2. SUPRAMOLECULAR CHEMISTRY: SOME BACKGROUND.

2.1. The Nature of Non-Covalent Interactions.

2.2. Classical Building Blocks in Supramolecular Chemistry.

2.3. Key Areas and Key Concepts in Supramolecular Chemistry.

2.4. Biomolecules: Intra- and Intermolecular Non-Covalent Bonds.

References.

3 MASS SPECTROMETRY FOR THE EXAMINATION OF NON-COVALENT COMPLEXES.

3.1. Common Mass Spectrometric Instrumentation for the Examination of Non-Covalent Bonds.

3.2. How Non-Covalent Bonds Change on the Transition from Solution to the Gas Phase.

3.3. Ion Energetics Issues.

3.4. Tandem-MS-Experiments.

3.5. Potential Sources of Error or Misinterpretation.

References.

PART B: ARTIFICIAL SUPRAMOLECULAR SYSTEMS. 

4 FUNDAMENTAL STUDIES ON SMALLER NON-COVALENT COMPLEXES.

4.1. Ion Neutral Complexes.

4.2. High-Pressure Mass Spectrometry: Bridging the Gap Between Gas and Condensed Phase.

References.

5 DETERMINATION OF THE "SECONDARY STRUCTURE" OF SUPRAMOLECULES BY MASS SPECTROMETRY.

5.1. Mechanically Interlocked Molecules and Their Precursors.

5.2. Guest Encapsulation.

5.3. Gas-Phase Conformations.

5.4. Zwitterions and Salt-Bridges.

References.

6 CHIRAL RECOGNITION.

6.1. Tartrate Clusters.

6.2. Chiral Crown Ether-Ammonium Complexes: The Three-Point Model.

6.3. Cyclodextrin-Amino Acid Recognition.

6.4. Chiral Recognition in Amino Acid Clusters.

6.5. Homochiral Serine Octamers.

6.6. Resonant Two Photon Ionization Studies of Chiral Complexes: Spectroscopy of Diastereomeric Complexes in the Gas Phase.

References.

7 MONITORING SOLUTION REACTIVITY OF NON-COVALENT COMPLEXES BY MASS SPECTROMETRY.

7.1. Mass Spectrometric Characterization of Metallo-Supramolecular Aggregates.

7.2. Simple Ligand Exchanges in Metallo-Supramolecular Squares.

7.3. Titration Experiments with Helicates.

7.4. Helicates Again: Mechanistic Insight into Ligand Exchange Reactions.

7.5. Titration Experiments with Self-Sorting Tetraurea-Calixarenes.

7.6. Self-Sorting Reactions of Pseudorotaxane Assemblies.

7.7. Shorter Time-Scales: A Mixed-Flow Technique Applied to Self-Assembly.

References.

8. GAS-PHASE REACTIVITY OF SUPRAMOLECULES.

8.1. Molecular "Mouse Traps": Covalent Bond Formation Within Non-Covalent Complexes.

8.2. Fragmentation of Metallo-Supramolecular Helicates, Squares, and Cages.

8.3. Host-Guest Chemistry of Dendrimers in the Gas Phase.

8.4. H/D Exchange Reactions in Gaseous Non-Covalent Complexes.

References.

9 DETERMINATION OF THERMOCHEMICAL DATA.

9.1. Crown Ether Binding Affinities in Solution.

9.2. Ranking of Anion-Cavitand Gas-Phase Binding Energies.

9.3. Crown Ether-Ammonium Ion Complexes in the Gas Phase.

9.4. Crown Ether-Alkali Metal Ion Complexes and the Best-Fit Model.

References.

PART C NON-COVALENT COMPLEXES OF BIOMOLECULES.

10 NON-COVALENT COMPLEXES WITH PETIDES AND PROTEINS.

10.1. Metal-Ion Binding to Peptides and Small Proteins.

10.2. Probing Three-Dimensional Protein Structure and Protein-Protein Interactions.

10.3. Interactions of Proteins with Small Molecules.

10.4. Sugar-Peptide and Sugar-Protein Complexes.

10.5. Interactions of Proteins with Oligonucleotides, DNA, and RNA.

References.

11. NON-COVALENT COMPLEXES OF NUCLEOTIDES.

11.1. Metal-Ion Binding to DNA Bases and Oligonucleotides.

11.2. Are Watson-Crick Base Pairing and Double Helix Conserved in the Gas Phase?

11.3. G-Quartets.

11.4. The Folding of G-Rich Strands into Quadruplexes.

11.5. Minor Groove Binders and Intercalators: The Binding to Duplexes.

11.6. Non-Covalent Interactions With G-Quadruplexes.

References.

12. CARBOHYDRATES.

12.1 Carbohydrates: Their Importance and Analysis.

12.2. Stereodifferentiation of Small Carbohydrates.

12.3. Structural Aspects of Oligosaccharides by MS and IMS.

12.4. Carbohydrate Association.

12.5. Summary and Outlook.

References.

13. EPILOGUE.

Index.