THE OPTICAL ROTATING POWER OF ORGANIC SUBSTANCES AND ITS PRACTICAL APPLICATIONS

By AMELIA RODRIGUEZ

CONTENTS 1 POLARIZED LIGHT INTRODUCTION TO LIGHT POLARIZATION STATES DEPENDENCE ON PHASE DIFFERENCE DEPENDENCE ON AMPLITUDE DIFFERENCE DEPENDENCE ON BOTH PHASE AND AMPLITUDE DIFFERENCES GENERALIZATION ADVANCED REPRESENTATIONS ENERGIES REFERENCES 2 CHIRAL MOLECULES CLASSIFICATION OF MOLECULES CONFIGURATIONS OF CHIRAL MOLECULES CENTRAL CHIRALITY AXIAL CHIRALITY HELICAL CHIRALITY PLANAR CHIRALITY PROPELLER CHIRALITY OTHER SOURCES OF CHIRALITY CONFORMATIONS BIOMOLECULAR STRUCTURES 3 INTERACTION OF CIRCULARLY POLARIZED LIGHT WITH CHIRAL MOLECULES INTRODUCTION OPTICAL ROTATION CIRCULAR DICHROISM VIBRATIONAL RAMAN OPTICAL ACTIVITY (VROA) SUMMARY 4 QUANTUM CHEMICAL FORMULATION OF CHIROPTICAL SPECTROSCOPY INTERACTION OF MOLECULES WITH ELECTRIC FIELD TIME-INDEPENDENT PERTURBATION THEORY FIRST-ORDER CORRECTIONS MOLECULES IN STATIC ELECTRIC FIELD SECOND-ORDER CORRECTIONS TIME-DEPENDENT PERTURBATION THEORY MOLECULES IN DYNAMIC FIELDS ELECTRIC FIELD PERTURBATION DYNAMIC ELECTRIC DIPOLE–ELECTRIC DIPOLE POLARIZABILITY MAGNETIC FIELD PERTURBATION DYNAMIC ELECTRIC DIPOLE–MAGNETIC DIPOLE POLARIZABILITY INTERACTION OF MOLECULES WITH CPL ELECTRIC AND MAGNETIC FIELDS OF CPL ELECTRIC FIELD MAGNETIC FIELD ELECTRIC DIPOLE MOMENT INDUCED BY ELECTRIC AND MAGNETIC FIELDS OF CPL SPECIFIC OPTICAL ROTATION TRANSITION RATES FOR MOLECULES INTERACTING WITH CPL RELATION TO EXPERIMENTAL ABSORPTION AND CIRCULAR DICHROISM TRANSITION POLARIZABILITIES 5 PREDICTION OF CHIROPTICAL SPECTRA SPECTRAL PREDICTIONS USING QUANTUM CHEMICAL METHODS OPTICAL ROTATORY DISPERSION PRACTICAL CONSIDERATIONS ELECTRONIC ABSORPTION AND CIRCULAR DICHROISM SPECTRA VIBRATIONAL ABSORPTION AND CIRCULAR DICHROISM SPECTRA VIBRATIONAL RAMAN AND RAMAN OPTICAL ACTIVITY SPECTRA RESONANCE ROA SPECTRA SURFACE-ENHANCED VROA SPECTRA ROLE OF SOLVATION ON CHIROPTICAL SPECTRA APPROXIMATE METHODS FOR LARGE MOLECULES: CARTESIAN TENSOR TRANSFER AND FRAGMENTATION ACCURATE CALCULATIONS ON LARGE MOLECULES: MOLECULES-IN-MOLECULES FRAGMENTATION METHOD SPECTRAL PREDICTIONS USING APPROXIMATE MODELS ELECTRONIC CIRCULAR DICHROISM VIBRATIONAL CIRCULAR DICHROISM VIBRATIONAL RAMAN OPTICAL ACTIVITY 6 CONFORMATIONAL ANALYSIS 6 1 CONFORMATIONAL ANALYSIS OF SOLUTE MOLECULE 6 1 1 DESIGNATION OF BONDS 6 1 2 RING-PUCKERING ANGLES 6 1 3 SYMMETRIES OF GENERATED CONFORMATIONS 6 1 4 STRUCTURES WITH EQUIVALENT ENERGIES 6 1 5 ATROPISOMERS 6 1 6 MOLECULAR IONS AND RADICALS 6 1 7 DIMERIC STRUCTURES 6 1 8 ENANTIOMER STRUCTURES 6 1 9 BOLTZMANN POPULATIONS 6 2 CONFORMATIONAL ANALYSIS OF SOLUTE–SOLVENT CLUSTERS 6 3 SUMMARY 7 EXPERIMENTAL METHODS FOR MEASURING CHIROPTICAL SPECTRA OPTICAL ROTATION OF LIQUID SOLUTIONS OR OF GAS-PHASE SAMPLES TIME-RESOLVED ORD MEASUREMENTS EVANESCENT WAVE OR MEASUREMENTS CIRCULAR DICHROISM MEASUREMENTS DISPERSIVE SPECTROMETERS FT SPECTROMETERS POTENTIAL ARTIFACTS TUNABLE LASER-BASED SPECTROMETERS TIME-RESOLVED CIRCULAR DICHROISM NONLINEAR SPECTROSCOPIC METHODS INTERCONVERSION OF CD AND ORD VROA MEASUREMENTS NORMAL VROA MEASUREMENTS FT-VROA MEASUREMENTS RESONANCE VROA MEASUREMENTS INDUCED RESONANCE ROA MEASUREMENTS SURFACE-ENHANCED VROA MEASUREMENTS COHERENT ANTI-STOKES VROA MEASUREMENTS MAGNETIC VROA MEASUREMENTS RELATED METHODS 8 COMPARISON OF EXPERIMENTAL AND CALCULATED SPECTRA COMPARISON OF EXPERIMENTAL AND CALCULATED SPECTRA QUALITATIVE COMPARISONS QUANTITATIVE COMPARISONS NUMERICAL MEASURES OF SIMILARITY CARBÓ-SIMILARITY INDEX (SI) NEIGHBORHOOD SIMILARITY ENANTIOMERIC SIMILARITY INDEX (ESI) SPECTRAL SIMILARITY (SIM) SQUARE ROOT OF THE SQUARED DIFFERENCE COMPARISON OF EXPERIMENTAL AND CALCULATED RATIO SPECTRA SIGNIFICANCE OF SIMILARITY MEASURE VALUES 9 CHIRAL AGGREGATION, EQUILIBRIA, AND THE HOREAU EFFECT HOMOCHIRAL MONOMER–DIMER EQUILIBRIUM ANALYSIS OF SOR DATA ANALYSIS OF ABSORPTION SPECTRAL DATA ANALYSIS OF CD SPECTRAL DATA ANALYSIS OF VIBRATIONAL RAMAN AND VROA SPECTRAL DATA HETEROCHIRAL MONOMER–DIMER EQUILIBRIUM EQUILIBRIA WITH KHT = 2K EQUILIBRIA WITH KHT NOT EQUAL TO 2K ANALYSIS OF ABSORPTION/RAMAN SPECTRAL DATA FOR RACEMIC MIXTURES EQUILIBRIUM BETWEEN SECONDARY STRUCTURES OF BIOLOGICAL SYSTEMS 10 APPLICATIONS OF CHIROPTICAL SPECTRA 10 1 INTRODUCTION 10 2 SPECTRA–STRUCTURE CORRELATIONS 10 2 1 ORD SPECTRA 10 2 2 ECD SPECTRA 10 2 3 VCD SPECTRA 10 2 4 VROA SPECTRA 10 3 SPECTRAL PREDICTIONS USING APPROXIMATE MODELS 10 3 1 ORD SPECTRA 10 3 2 ECD SPECTRA 10 3 3 VCD SPECTRA 10 3 4 VROA SPECTRA 10 4 SPECTRAL PREDICTIONS USING QUANTUM CHEMICAL CALCULATIONS 10 4 1 DETERMINATION OF THE MOLECULAR STRUCTURES FLUORINATED ETHERS HALOMETHANES MOLECULES WITH CHIRALITY IMPARTED BY ISOTOPIC SUBSTITUTION METAL WIRES FULLERENES HELICENES METAL NANOPARTICLES ORGANIC NANOPARTICLES CRYPTOPHANES 10 4 1 10 CYCLOPHANES 10 4 1 11 ATROPISOMERS 10 4 1 12 SUPRAMOLECULAR AGGREGATES 10 4 1 13 PHARMACEUTICAL AND ANTIMICROBIAL COMPOUNDS 10 4 1 14 TRANSPORT ANTIBIOTICS 10 4 1 15 PESTICIDES AND HERBICIDES 10 4 1 16 THIOPHENES 10 4 1 17 CHIRAL SULPHUR COMPOUNDS 10 4 1 18 CHIRAL PHOSPHOROUS COMPOUNDS 10 4 1 19 CHIRAL SELENIUM COMPOUNDS 10 4 1 20 CHIRAL PHEROMONES 10 4 1 21 FUNGAL/PLANT METABOLITES 10 4 1 22 CARBOHYDRATES 10 4 1 23 TRANSITION METAL COMPLEXES 10 4 1 24 NATURAL PRODUCTS 10 4 1 25 POLYMERS 10 4 1 26 BIOMOLECULAR STRUCTURES 10 4 1 27 OTHER MOLECULES 10 4 1 28 ROLE OF INTRAMOLECULAR CT 10 4 2 CORRECTING THE INCORRECT OR AMBIGUOUS ACS 10 4 2 1 TROGER’S BASE 10 4 2 2 1,1-DIMETHYL-2-PHENYLETHYL PHENYL SULFOXIDE (DPPS) 10 4 2 3 2-(1-HYDROXYETHYL)-CHROMEN-4-ONE (HECO) 10 4 2 4 3,3?-DIPHENYL-[2,2?-BINAPHTHALENE]-1,1?-DIOL (VANOL) 10 4 2 5 CHROMANES 10 4 2 6 REMISPORINE B 10 4 2 7 NATURAL PRODUCTS 10 5 ANALYTICAL APPLICATIONS 10 6 CHIROPTICAL SPECTROSCOPY IN UNDERGRADUATE TEACHING LABORATORIES 10 6 1 INVERSION OF SUCROSE 10 6 2 MONOMER–DIMER EQUILIBRIUM 10 6 3 OTHER EXPERIMENTS 10 7 SUMMARY