NMR Basic Principles and Progress

1. Introductory Aspects.- 1.1 General Properties of Halogens.- 1.2 Static Parameters.- 1.2.1 Quadrupole Splittings.- 1.2.2 Nuclear Shielding.- 1.2.3 Spin-Spin Couplings.- 1.3 Dynamic Parameters.- 1.3.1 Quadrupolar Relaxation.- 1.3.2 Other Relaxation Mechanisms.- 1.4 Chemical Exchange Effects.- 1.5 Experimental Aspects.- 2. Relaxation in Molecules or Ions With Covalently Bonded Halogens.- 2.1 Quadrupole Relaxation.- 2.1.1 General Aspects.- 2.1.2 On the Evaluation of the Correlation Time.- 2.1.3 Models for Molecular Rotation in Liquids.- 2.1.4 Survey of Experimental Results and Their Interpretation.- 2.2 Other Relaxation Mechanisms.- 3. Shielding Effects in Covalent Halogen Compounds.- 3.1 Theoretical Aspects.- 3.1.1 General Considerations.- 3.1.2 Approximate Calculations of Nuclear Shielding.- 3.1.3 Correlations Between Electronic Shielding and Quadrupolar Coupling Constants.- 3.1.4 Halide Ion Shielding in Crystals and Aqueous Solutions.- 3.2 Experimental Data.- 3.3 Medium Effects on Halogen Shielding Constants.- 3.3.1 General Considerations.- 3.3.2 Medium Effects on Chlorine Shielding Values.- 4. Scalar Spin Couplings.- 4.1 General Considerations.- 4.2 Experimental Data on Cl, Br and I Spin Couplings.- 5. Relaxation of Chloride, Bromide and Iodide Ions.- 5.1 Quadrupole Relaxation.- 5.1.1 General Aspects.- 5.1.2 Halide Ion Quadrupole Relaxation in Infinitely Dilute Aqueous Solutions.- 5.1.2.1 Experimental Results.- 5.1.2.2 Electrostatic Models.- 5.1.2.3 Electronic Distortion Model.- 5.1.3 Aqueous Solutions of Alkali Halides.- 5.1.3.1 Experimental Concentration Dependences.- 5.1.3.2 Electrostatic Model.- 5.1.3.3 Electronic Distortion Model.- 5.1.3.4 Water Isotope Effect.- 5.1.3.5 Mixed Alkali Halide Solutions.- 5.1.3.6 Temperature Dependence.- 5.1.4 Aqueous Solutions of Other Inorganic Halides.- 5.1.4.1 Hydrogen Halides.- 5.1.4.2 Ammonium Halides.- 5.1.4.3 Alkaline Earth Halides.- 5.1.4.4 Other Metal Halides.- 5.1.5 Aqueous Solutions Containing Small Hydrophobic Ions or Molecules.- 5.1.6 Halide Ions in Surfactant Systems.- 5.1.7 Halide Ions in Mixed Solvent and Non-Aqueous Solutions.- 5.2 Relaxation Rates and Chemical Shifts in Paramagnetic Systems.- 5.2.1 General Comments.- 5.2.2 Experimental Studies.- 5.3 Chemical Exchange of Halide Ions.- 5.3.1 General Considerations.- 5.3.2 Effects of Different Isotopes.- 5.3.3 Exchange Rates Accessible for Study.- 5.3.4 Ligand Exchange Mechanisms in Inorganic Halide Complexes.- 5.3.5 Experimental Studies of Halide Ion Exchange: Systems Involving Halogen Molecules.- 5.3.6 Experimental Studies of Halide Ion Exchange: Metal-Halide Complexes.- 6. Shielding of Halide Ions.- 6.1 Absolute Shielding Values of Ions in Aqueous Solutions.- 6.1.1 Theoretical Calculations of Shieldings in Alkali Halide Crystals.- 6.1.2 Estimates of Absolute Ion Shieldings from Relaxation Rates and Solvent Isotope Shifts.- 6.1.3 Molecular Beam and Atomic Beam Data.- 6.1.4 Discussion of the Absolute Shielding Values in Table 6.1.- 6.2 Shielding in Aqueous Alkali Halide Solutions.- 6.3 Shielding in Other Aqueous Solutions.- 6.4 Shielding in Mixed Solvent and Non-Aqueous Solution.- 6.5 Water Solvent Isotope Effect on Shielding.- 7. Quadrupole Splittings in Liquid Crystals.- 7.1 General Aspects on Static Quadrupole Effects of Mesomorphous Systems.- 7.2 Halogen Quadrupole Splittings of Covalent Compounds in Liquid Crystals.- 7.3 Quadrupole Splittings of Halide Ions in Amphiphilic Mesophases.- 8. Halide Ions in Biological Systems.- 8.1 General Principles.- 8.1.1 Introduction.- 8.1.2 Quadrupolar Relaxation of I = 3/2 Nuclei.- 8.1.3 Chemical Exchange of a Spin I = 3/2 Nucleus.- 8.1.4 The Influence of Chemical Exchange on the Correlation Time ?C.- 8.1.5 Effects of Internal Motion at the Macromolecular Binding Site.- 8.1.6 Halide Exchange in Multi-Site Systems.- 8.1.7 General Types of Biological Halide NMR Studies and Parameters Attainable.- 8.1.8 Evaluation of Rate Parameters.- 8.1.9 Determination of Binding Constants and Related Parameters.- 8.1.10 Competition Experiments Between Different Ligands.- 8.1.11 Evaluation of Rotational Correlation Times.- 8.2 Small Molecules or Ions of Biological Interest.- 8.3 Polypeptides.- 8.4 Proteins.- 8.4.1 Carbonic Anhydrase.- 8.4.2 Alcohol Dehydrogenase.- 8.4.3 Alkaline Phosphates.- 8.4.4 Serum Albumin.- 8.4.5 Hemoglobin.- 8.4.6 Other Proteins.- 8.5 Miscellaneous Systems.- 9. Studies of the Perchlorate Ion.- 9.1 Introduction.- 9.2 Shielding.- 9.3 Quadrupole Effects.- 10. Recent Work.- 11. References.- 12. Subject Index.