Verfügbarkeit: Chiral analysis

Chiral analysis:

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Bibliographische Detailangaben
Format:	Buch
Sprache:	English
Veröffentlicht:	Amsterdam [u.a.] Elsevier 2006
Ausgabe:	1. ed.
Schlagworte:	Chirality Enantioselective catalysis Chemische Analyse Chirale Verbindungen
Online-Zugang:	Inhaltsverzeichnis
Beschreibung:	XVI, 704 S. Ill., graph. Darst.
ISBN:	9780444516695 0444516697

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Datensatz im Suchindex

_version_	1804137008385228800
adam_text	νπ Contents Preface ................... Parti Chapter 1. A history of chirality Seymour Mauskopf..................... 3 1.1 The concept of chirality ............ 3 1.2 The background to Pasteur ..................... 4 1.3 Towards a chemistry in space ................... 13 1.4 Van t Hoff, Le Bel, and the tetrahedral carbon atom ......... 13 1.5 Reception of the tetrahedral carbon model .............. 18 1.6 Chirality and life .......................... 19 1.7 Optical activity and drug action ................... 20 References ............................. 21 Chapter 2. Chiral asymmetry in nature Dilip Kondepudi and Kouichi Asakura ............ 25 2.1 Introduction ............................ 25 2.2 Chirality: terminology and quantification issues ............ 25 2.2.1 Cahn-Ingold-Prelog classification of chiral molecules ..... 27 2.2.2 Optical rotation ....................... 29 2.2.3 Enantiomeric excess ..................... 29 2.2.4 Crystal enantiomeric excess ................. 29 2.2.5 Chirality measures ..................... 30 2.3 Chiral asymmetry in nature ..................... 31 2.3.1 Asymmetry in nuclear processes ............... 31 2.3.2 Asymmetry in atoms .................... 32 2.3.3 Asymmetry in molecules ................... 33 viii Contents 2.3.4 Biomolecular asymmetry .................. 33 2.3.5 Morphological asymmetry .................. 34 2.3.6 Astrophysical asymmetries .................. 34 2.4 Theory of spontaneous chiral symmetry breaking ........... 35 2.5 Sensitivity of chiral symmetry-breaking transitions to asymmetric interactions ....................... 38 2.6 Examples of spontaneous chiral symmetry breaking .......... 40 2.7 Concluding remarks ......................... 42 2.8 Acknowledgments .......................... 43 References ............................. 43 Chapter 3. Physical properties and enantiomeric composition Chong-Hui Gu and David J.W. Grant ............ 47 3.1 Introduction ............................ 47 3.2 Nature of racemates ......................... 47 3.3 Optical activity ........................... 49 3.4 Solid-state analysis of properties and compositions of chiral compounds ............................. 50 3.4.1 Thermal properties ..................... 50 3.4.2 Thermodynamic stability relationship between racemates ... 51 3.4.3 Crystal structure of chiral compounds ............ 52 3.4.4 Powder X-ray diffraction (PXRD) patterns .......... 54 3.4.5 Infrared, Raman, and solid-state nuclear magnetic resonance spectra ...................... 57 3.5 Solubility and dissolution ...................... 57 3.6 Polymorphism and pseudopolymorphism of chiral crystals ...... 59 3.7 Racemization ............................ 64 3.8 Influence of chiral impurity on physical properties of host chiral crystals ............................... 64 3.9 Concluding remarks ......................... 71 References ............................. 72 Chapter 4. Emerging high-throughput screening methods for asymmetric induction M.G. Finn ......................... 79 4.1 Introduction ............................ 79 4.2 Strategies .............................. 81 4.3 Methods .............................. 82 4.3.1 Separation or direct detection of enantiomers ........ 82 4.3.2 Absorbance or fluorescence spectra with nonchiral reporter molecules derived from enantioenriched substrates ...... 83 4.3.3 Absorbance or fluorescence spectra with chiral reporter molecules .......................... 84 Contents ix 4.3.4 Mass spectrometry with nonchiral reporter molecules derived from enantioenriched substrates ........... 85 4.3.5 Mass spectrometry with chiral reporter molecules ....... 85 4.3.6 Detection methods based on antibodies and enzymes ..... 86 4.3.7 Detection methods based on other instrumentation ...... 88 4.3.8 The wave of the future? ................... 89 References ............................. 90 Part II Chapter 5. Analysis of chiral Chromatographie separations by molecular modeling Kenny B. Lipkowitz ..................... 97 5.1 Introduction ............................ 97 5.2 Atomistic modeling ......................... 97 5.3 Structure-property relationships ................... 98 5.4 Describing molecular structure .................... 99 5.4.1. Graph theory ........................ 99 5.4.2. 3D descriptors ....................... 100 5.5 Quantitative structure enantioselectivity relationships (QSERR) .............................. 101 5.6 Comparative molecular field analysis (CoMFA) ........... 104 5.7 Computation of selector-selectand interactions ............ 109 5.8 Quantum mechanics-based studies .................. 110 5.9 Force field (FF)-based studies .................... 113 5.10 Summary and prospectus ...................... 125 5.11 Acknowledgments .......................... 126 References ............................. 126 Chapter 6. Gas Chromatographie enantioseparation of chiral pollutants — techniques and results Walter Vetter and Kai Bester................. 131 6.1 Direct gas Chromatographie enantioseparation of chiral pollutants .............................. 131 6.2 Gas Chromatographie enantioseparations with modified cyclodextrins ............................ 133 6.2.1 Native cyclodextrins ..................... 134 6.2.2 Modified cyclodextrins in gas chromatography ........ 135 6.2.3 Nomenclature of modified cyclodextrins ........... 136 6.2.4 Quality of modified cyclodextrins .............. 137 6.2.5 CSPs suggested for the enantioseparation of chiral pollutants .......................... 140 6.2.6 Practical recommendations ................. 145 6.2.7 Quality assurance (QA) in EF determinations ........ 145 x Contents 6.3 Definitions of terms to describe deviations from the racemate..... 155 6.3.1 Suitable terms to describe deviations from the racemate for chiral pollutants ..................... 155 6.3.2 Thermodynamical considerations and classification of enantioseparations ..................... 158 6.3.3 Chiral resolution ...................... 159 6.4 Chiral pollutants .......................... 160 6.4.1 Atropisomeric polychlorinated biphenyls (PCBs), their metabolites (МеЅОг-РСВѕ), and polybrominated analogs (PBBs) ....................... 161 6.4.2 DDT and DDT-related compounds ............. 169 6.4.3 aaeeee-1, 2,3,4,5, o-Hexachlorocyclohexane (a-HCH) and related compounds ..................... 172 6.4.4 Chlordane-related compounds ................ 176 6.4.5 Endosulfan ......................... 182 6.4.6 Compounds of technical toxaphene (CTT) .......... 182 6.4.7 Bromocyclene ........................ 189 6.4.8 Modern pesticides ...................... 189 6.4.9 Environmentally relevant Pharmaceuticals .......... 191 6.4.10 Polycyclic musks ...................... 192 6.5 Conclusions ............................. 195 References ............................. 196 Chapter 7. HPLC resolution using polysaccharide derivatives as CSP Chiyo Yamamoto and Yoshio Okamoto ........... 215 7.1 Introduction ............................ 215 7.2 Chiral stationary phase (CSP) for HPLC ............... 215 7.3 Polysaccharide-based CSPs ..................... 217 7.3.1 Cellulose esters ....................... 218 7.3.2 Cellulose and amylose phenylcarbamates ........... 221 7.3.3 Amylose benzylcarbamates ................. 223 7.3.4 Other poylsaccharide derivatives ............... 225 7.4 Selection of a suitable column and eluent for enantioseparation .......................... 226 7.5 Separation of several typical racemates ................ 228 7.5.1 Chiral acids ......................... 228 7.5.2 Chiral amines ........................ 228 7.5.3 Chiral alcohols ....................... 230 7.5.4 Chiral aromatic hydrocarbons ................ 230 7.5.5 Non-aromatic chiral compounds ............... 233 7.6 Conclusion ............................. 233 References ............................. 233 Contents xi Chapter 8. Chiral separations by capillary electrophoresis A.M. Stalcup ........................ 241 8.1 Introduction ............................ 241 8.2 Capillary electrophoresis: the experiment ............... 242 8.2.1 Capillary electrophoresis: the experimental data ....... 243 8.3 The column ............................. 249 8.4 Sample injection .......................... 250 8.5 Detection .............................. 250 8.6 Chiral separation theory in capillary electrophoresis ......... 252 8.6.1 Chiral separation strategies: neutral enantiomeric pairs . . . . 254 8.6.2 Chiral separation strategies: charged enantiomeric pairs. . . . 257 8.7 Chiral selectors in capillary electrophoresis .............. 258 8.7.1 Chiral selectors based on cyclodextrins ............ 258 8.7.2 Chiral selectors based on noncyclic polysaccharides ...... 260 8.7.3 Chiral selectors based on crown ethers ............ 261 8.7.4 Chiral selectors based on ligand exchange .......... 262 8.7.5 Chiral selectors based on chiral surfactants .......... 263 8.7.6 Chiral selectors based on proteins .............. 264 8.7.7 Chiral selectors based on macrocyclic antibiotics ....... 265 8.8 Conclusions ............................. 267 References ............................. 267 Chapter 9. Chiral separations in microfluidic devices Detlev Belder........................ 277 9.1 Introduction ............................ 277 9.2 Methodology and instrumentation .................. 278 9.2.1 Injection .......................... 279 9.2.2 Detection .......................... 282 9.2.3 Chiral electrolytes ...................... 286 9.2.4 Enhancing resolution and performance ............ 287 9.3 Outlook .............................. 292 References ............................. 292 Part III Chapter 10. Instrumental aspects of chiroptical detection Kenneth W. Busch, Marianna A. Busch and Carlos Calleja-Amador.................... 299 Part A—The polarization of light 10.1 Light as a wave ........................... 300 10.2 Types of polarized light ....................... 301 10.2.1 Linearly polarized light ................... 303 10.2.2 Circularly polarized light .................. 303 10.2.3 Effiptically polarized light .................. 304 xii Contents 10.3 Production of linearly polarized light ................. 306 10.3.1 Polarization by scattering .................. 308 10.3.2 Polarization by reflection .................. 309 10.3.3 Polarization by birefringence ................ 312 10.3.4 Polarization by wire grids .................. 318 10.3.5 Polarization by dichroism .................. 320 10.4 Production of circularly polarized light ................ 321 10.5 Production of elliptically polarized light ............... 323 10.6 Photoelastic modulators ....................... 324 Part В — Signal handling 10.7 Phase-sensitive detection ....................... 327 Appendix A. Basic optics ......................... 335 1A. Refractive index ........................ 335 2A. Snell slaw .......................... 335 Appendix B. The law of Malus...................... 337 Appendix C. Lissajous figures and forms of polarization .......... 338 References ............................. 341 Chapter 11. Micro-scale polarimetry Darryl J. Bornhop and Stephen Dotson ............ 343 11.1 Conventional micro-scale polarimetry ................ 344 11.2 RI compensation .......................... 345 11.3 Molasses analysis .......................... 346 11.4 Advanced laser polariméter ..................... 348 11.5 Imaging polariméter ......................... 349 11.6 Automated polariméter ....................... 350 11.7 Backscatter technique ........................ 352 11.7.1 Capillary polarimetrie detector (CPD) ............ 352 11.7.2 CPD: analysis by Fourier transform ............. 354 11.7.3 CPD: absolute optical activity measurements ......... 355 11.8 Conclusion ............................. 357 References ............................. 360 Chapter 12. Chiral analysis by regression modeling of spectral data Kenneth W. Busch and Marianna A. Busch .......... 363 12.1 Introduction ............................ 363 12.2 Introduction to multivariate calibration ............... 364 12.3 Introduction to principal component analysis ............. 366 12.3.1 Principal component analysis revisited ............ 369 12.3.2 Multivariate regression ................... 372 12.4 Use of chemometrics in determining enantiomeric composition .... 377 12.4.1 Use of a chiral auxiliary ................... 377 Contents xiii 12.5 Chiral analysis by multivariate regression modeling of spectral data ............................ 379 12.5.1 Initial studies with amino acids ............... 381 12.5.2 Studies with pharmaceutical compounds ........... 382 12.5.3 Studies with modified cyclodextrins ............. 385 12.5.4 Studies using fluorescence .................. 386 12.6 Conclusions ............................. 389 Appendix A. Matrix algebra ........................ 391 References ............................. 394 Chapter 13. Electronic circular dichroism for chiral analysis Jacek Gawronski and Pawel Skowronek........... 397 13.1 Introduction — the exciton coupling mechanism ............ 397 13.2 Absolute configuration determination ................ 407 13.2.1 Internal chromophores ................... 409 13.2.2 External chromophores ................... 410 13.3 Conformational analysis ....................... 414 13.3.1 Atropisomers ........................ 415 13.3.2 Chiral polymers ....................... 419 13.3.3 Protein secondary structure ................. 425 13.3.4 Nucleic acids ........................ 431 13.4 Analysis of chiral interactions by induced circular dichroism ..... 436 13.4.1 Self-association ....................... 437 13.4.2 Host-guest association ................... 440 13.5 Miscellaneous analytical applications ................. 446 13.6 Acknowledgment .......................... 449 References ............................. 449 Chapter 14. Determination of molecular stereochemistry using optical rotatory dispersion, vibrational circular dichroism and vibrational Raman optical activity Prasad L. Polavarapu .................... 461 14.1 Optical rotatory dispersion ..................... 461 14.1.1 Introduction ........................ 461 14.1.2 Experimental methods .................... 462 14.1.3 Theoretical methods ..................... 465 14.1.4 Protocol for determining molecular stereochemistry ...... 467 14.1.5 Applications ........................ 469 14.1.6 Commercial polarimétere and quantum mechanical software . 470 14.2 Vibrational circular dichroism .................... 471 14.2.1 Introduction ........................ 471 14.2.2 Experimental methods .................... 472 14.2.3 Theoretical methods ..................... 476 xiv Contents 14.2.4 Protocol for determining molecular stereochemistry ...... 477 14.2.5 Applications ........................ 479 14.2.6 Commercial VCD spectrometers and quantum mechanical software ..................... 481 14.2.7 Books on VCD ....................... 481 14.3 Vibrational Raman optical activity .................. 481 14.3.1 Introduction ........................ 481 14.3.2 Experimental methods .................... 483 14.3.3 Theoretical methods ..................... 485 14.3.4 Protocol for determining molecular stereochemistry ...... 486 14.3.5 Applications ........................ 488 14.3.6 Commercial VROA spectrometers and quantum mechanical software ..................... 489 14.3.7 Books on VROA ...................... 489 14.4. Summary .............................. 490 14.5 Acknowledgments .......................... 490 References ............................. 491 Appendix A. Literature articles on quantum mechanically predicted specific rotations for evaluating molecular stereochemistry ....... 495 Appendix B. Literature articles (1999-2005) on quantum mechanically predicted VCD spectra for evaluating molecular stereochemistry ........................ 498 Appendix C. Literature articles on quantum mechanically predicted VROA spectra for evaluating molecular stereochemistry .... 502 Chapter 15. Vibrational optical activity in chiral analysis Laurence A. Nafie and Rina К. Dukor ............ 505 15.1 Introduction ............................ 505 15.2 Definitions of vibrational optical activity ............... 507 15.3 Measurement of vibrational optical activity .............. 509 15.4 Theoretical basis of vibrational optical activity ............ 510 15.4.1 Theory of vibrational circular dichroism ........... 511 15.4.2 Theory of Raman optical activity .............. 512 15.5 Calculation of vibrational optical activity ............... 515 15.6 Determination of absolute configuration ............... 517 15.7 Determination of enantiomeric excess of multiple chiral species .... 524 15.8 Vibrational optical activity of solids and formulated products ..... 532 15.9 Summary and conclusions ...................... 535 References ............................. 536 Chapter 16. Raman optical activity Ewan W. Blanch, Lutz Hecht and Laurence D. Barron .... 545 16.1 Introduction ............................ 545 Contents xv 16.2 Fundamental theory of ROA .................... 547 16.2.1 Distinction between ROA and optical rotation ........ 547 16.2.2 Electric and magnetic properties ............... 548 16.2.3 Discovery of ROA ..................... 550 16.2.4 ROA observables ...................... 550 16.2.5 The scattered circular polarization strategy .......... 552 16.3 Resonance ROA (RROA) ...................... 553 16.4 Second harmonic scattering from chiral interfaces ........... 555 16.5 Magnetic ROA ........................... 556 16.6 Computation of ROA observables.................. 557 16.6.1 ROA of archetypal helical molecules ............. 558 16.7 Instrumentation ........................... 559 16.8 Studies on small molecules ...................... 561 16.9 Enhanced sensitivity of ROA to biomolecular structure and dynamics .............................. 562 16.9.1 ROA spectra of polypeptides and proteins .......... 563 16.9.2 PolyÍL-lysine) ........................ 564 16.9.3 ROA spectra of proteins .................. 568 16.9.4 Studies on nucleic acids ................... 576 16.9.5 Studies on viruses ...................... 578 16.10 Surface-enhanced ROA ....................... 581 16.11 Application of chemometrics to ROA data .............. 585 16.12 Bright future ............................ 588 16.13 Acknowldgments .......................... 589 References ............................. 589 Chapter 17. Mass spectral methods of chiral analysis Brandy L. Young, Lianming Wu and R. Graham Cooks . . . 595 17.1 Background to chiral analysis by mass spectrometry ......... 595 17.2 Fundamental interactions leading to chiral recognition ........ 598 17.3 Mass spectrometric methods for chiral analysis ............ 599 17.3.1 Kinetic resolution in solution with mass-tagged reagents . . . 601 17.3.2 Single-stage mass spectrometry ............... 605 17.3.3 Ion/molecule reactions ................... 613 17.3.4 Dissociation of cluster ions ................. 619 17.4 Applications ............................ 633 17.4.1 Chiral analysis of ternary mixtures .............. 633 17.4.2 Chiral analysis of complex mixtures ............. 635 17.4.3 Chiral morphing ...................... 636 17.4.4 Chiral drag analysis ..................... 637 17.4.5 Method development and validation for chiral purity determination ........................ 637 17.4.6 Online chiral analysis .................... 641 xvi Contents 17.5 Concluding remarks ......................... 643 17.5.1 Emerging methods ..................... 643 17.5.2 Advantages and challenges ahead .............. 650 17.6 Acknowledgments .......................... 651 References ............................. 651 Chapter 18. Novel chiral derivatizing agents powerful for enantioresolution and determination of absolute stereochemistry by X-ray crystallographic and Н NMR anisotropy methods Nobuyuki Harada, Masataka Watanabe and Shunsuke Kuwahara ..................... 661 18.1 Introduction ............................ 661 18.2 Methodologies for determining absolute configuration and their evaluations .......................... 662 18.2.1 Nonempirical methods for determining absolute configurations of chiral compounds ............. 662 18.2.2 Relative methods for determining absolute configuration using an internal reference with known absolute configuration 662 18.3 Methodologies for chiral synthesis and their evaluations ....... 664 18.3.1 Enantioresolution of racemates ............... 664 18.3.2 Asymmetric syntheses .................... 665 18.4 Camphorsultam dichlorophthalic acid [CSDP acid (-)-!] and camphorsultam phthalic acid [CSP acid (-)-4] useful for enantioresolution of alcohols by HPLC and determination of their absolute configurations by X-ray crystallography ........... 665 18.5 A novel chiral molecular tool, 2-methoxy-2-(l-naphthyl)propionic acid [MaNP acid (S)-(+)-2], useful for enantioresolution of alcohols and determination of their absolute configurations by the Ή NMR anisotropy method ......................... 676 18.5.1 Facile synthesis of MaNP acid (2) and its extraordinary enantioresolution with natural (-)-menthol .......... 678 18.5.2 The Ή NMR anisotropy method for determining the absolute configuration of secondary alcohols: the sector rule and applications ...................... 679 18.5.3 Enantioresolution of various alcohols using MaNP acid and simultaneous determination of their absolute configurations. . 682 18.6 Complementary use of CSDP acid {-)- and MaNP acid (S)-(+)-2 for enantioresolution of alcohols and determination of their absolute confi¬ gurations by X-ray crystallographic and Ή NMR anisotropy methods 686 18.7 Conclusions ............................. 690 18.8 Acknowledgments .......................... 691 References ............................. 691 Index ................................... 693
adam_txt	νπ Contents Preface . Parti Chapter 1. A history of chirality Seymour Mauskopf. 3 1.1 The concept of chirality . 3 1.2 The background to Pasteur . 4 1.3 Towards a "chemistry" in space . 13 1.4 Van't Hoff, Le Bel, and the tetrahedral carbon atom . 13 1.5 Reception of the tetrahedral carbon model . 18 1.6 Chirality and life . 19 1.7 Optical activity and drug action . 20 References . 21 Chapter 2. Chiral asymmetry in nature Dilip Kondepudi and Kouichi Asakura . 25 2.1 Introduction . 25 2.2 Chirality: terminology and quantification issues . 25 2.2.1 Cahn-Ingold-Prelog classification of chiral molecules . 27 2.2.2 Optical rotation . 29 2.2.3 Enantiomeric excess . 29 2.2.4 Crystal enantiomeric excess . 29 2.2.5 Chirality measures . 30 2.3 Chiral asymmetry in nature . 31 2.3.1 Asymmetry in nuclear processes . 31 2.3.2 Asymmetry in atoms . 32 2.3.3 Asymmetry in molecules . 33 viii Contents 2.3.4 Biomolecular asymmetry . 33 2.3.5 Morphological asymmetry . 34 2.3.6 Astrophysical asymmetries . 34 2.4 Theory of spontaneous chiral symmetry breaking . 35 2.5 Sensitivity of chiral symmetry-breaking transitions to asymmetric interactions . 38 2.6 Examples of spontaneous chiral symmetry breaking . 40 2.7 Concluding remarks . 42 2.8 Acknowledgments . 43 References . 43 Chapter 3. Physical properties and enantiomeric composition Chong-Hui Gu and David J.W. Grant . 47 3.1 Introduction . 47 3.2 Nature of racemates . 47 3.3 Optical activity . 49 3.4 Solid-state analysis of properties and compositions of chiral compounds . 50 3.4.1 Thermal properties . 50 3.4.2 Thermodynamic stability relationship between racemates . 51 3.4.3 Crystal structure of chiral compounds . 52 3.4.4 Powder X-ray diffraction (PXRD) patterns . 54 3.4.5 Infrared, Raman, and solid-state nuclear magnetic resonance spectra . 57 3.5 Solubility and dissolution . 57 3.6 Polymorphism and pseudopolymorphism of chiral crystals . 59 3.7 Racemization . 64 3.8 Influence of chiral impurity on physical properties of host chiral crystals . 64 3.9 Concluding remarks . 71 References . 72 Chapter 4. Emerging high-throughput screening methods for asymmetric induction M.G. Finn . 79 4.1 Introduction . 79 4.2 Strategies . 81 4.3 Methods . 82 4.3.1 Separation or direct detection of enantiomers . 82 4.3.2 Absorbance or fluorescence spectra with nonchiral reporter molecules derived from enantioenriched substrates . 83 4.3.3 Absorbance or fluorescence spectra with chiral reporter molecules . 84 Contents ix 4.3.4 Mass spectrometry with nonchiral reporter molecules derived from enantioenriched substrates . 85 4.3.5 Mass spectrometry with chiral reporter molecules . 85 4.3.6 Detection methods based on antibodies and enzymes . 86 4.3.7 Detection methods based on other instrumentation . 88 4.3.8 The wave of the future? . 89 References . 90 Part II Chapter 5. Analysis of chiral Chromatographie separations by molecular modeling Kenny B. Lipkowitz . 97 5.1 Introduction . 97 5.2 Atomistic modeling . 97 5.3 Structure-property relationships . 98 5.4 Describing molecular structure . 99 5.4.1. Graph theory . 99 5.4.2. 3D descriptors . 100 5.5 Quantitative structure enantioselectivity relationships (QSERR) . 101 5.6 Comparative molecular field analysis (CoMFA) . 104 5.7 Computation of selector-selectand interactions . 109 5.8 Quantum mechanics-based studies . 110 5.9 Force field (FF)-based studies . 113 5.10 Summary and prospectus . 125 5.11 Acknowledgments . 126 References . 126 Chapter 6. Gas Chromatographie enantioseparation of chiral pollutants — techniques and results Walter Vetter and Kai Bester. 131 6.1 Direct gas Chromatographie enantioseparation of chiral pollutants . 131 6.2 Gas Chromatographie enantioseparations with modified cyclodextrins . 133 6.2.1 Native cyclodextrins . 134 6.2.2 Modified cyclodextrins in gas chromatography . 135 6.2.3 Nomenclature of modified cyclodextrins . 136 6.2.4 Quality of modified cyclodextrins . 137 6.2.5 CSPs suggested for the enantioseparation of chiral pollutants . 140 6.2.6 Practical recommendations . 145 6.2.7 Quality assurance (QA) in EF determinations . 145 x Contents 6.3 Definitions of terms to describe deviations from the racemate. 155 6.3.1 Suitable terms to describe deviations from the racemate for chiral pollutants . 155 6.3.2 Thermodynamical considerations and classification of enantioseparations . 158 6.3.3 Chiral resolution . 159 6.4 Chiral pollutants . 160 6.4.1 Atropisomeric polychlorinated biphenyls (PCBs), their metabolites (МеЅОг-РСВѕ), and polybrominated analogs (PBBs) . 161 6.4.2 DDT and DDT-related compounds . 169 6.4.3 aaeeee-1, 2,3,4,5, o-Hexachlorocyclohexane (a-HCH) and related compounds . 172 6.4.4 Chlordane-related compounds . 176 6.4.5 Endosulfan . 182 6.4.6 Compounds of technical toxaphene (CTT) . 182 6.4.7 Bromocyclene . 189 6.4.8 Modern pesticides . 189 6.4.9 Environmentally relevant Pharmaceuticals . 191 6.4.10 Polycyclic musks . 192 6.5 Conclusions . 195 References . 196 Chapter 7. HPLC resolution using polysaccharide derivatives as CSP Chiyo Yamamoto and Yoshio Okamoto . 215 7.1 Introduction . 215 7.2 Chiral stationary phase (CSP) for HPLC . 215 7.3 Polysaccharide-based CSPs . 217 7.3.1 Cellulose esters . 218 7.3.2 Cellulose and amylose phenylcarbamates . 221 7.3.3 Amylose benzylcarbamates . 223 7.3.4 Other poylsaccharide derivatives . 225 7.4 Selection of a suitable column and eluent for enantioseparation . 226 7.5 Separation of several typical racemates . 228 7.5.1 Chiral acids . 228 7.5.2 Chiral amines . 228 7.5.3 Chiral alcohols . 230 7.5.4 Chiral aromatic hydrocarbons . 230 7.5.5 Non-aromatic chiral compounds . 233 7.6 Conclusion . 233 References . 233 Contents xi Chapter 8. Chiral separations by capillary electrophoresis A.M. Stalcup . 241 8.1 Introduction . 241 8.2 Capillary electrophoresis: the experiment . 242 8.2.1 Capillary electrophoresis: the experimental data . 243 8.3 The column . 249 8.4 Sample injection . 250 8.5 Detection . 250 8.6 Chiral separation theory in capillary electrophoresis . 252 8.6.1 Chiral separation strategies: neutral enantiomeric pairs . . . . 254 8.6.2 Chiral separation strategies: charged enantiomeric pairs. . . . 257 8.7 Chiral selectors in capillary electrophoresis . 258 8.7.1 Chiral selectors based on cyclodextrins . 258 8.7.2 Chiral selectors based on noncyclic polysaccharides . 260 8.7.3 Chiral selectors based on crown ethers . 261 8.7.4 Chiral selectors based on ligand exchange . 262 8.7.5 Chiral selectors based on chiral surfactants . 263 8.7.6 Chiral selectors based on proteins . 264 8.7.7 Chiral selectors based on macrocyclic antibiotics . 265 8.8 Conclusions . 267 References . 267 Chapter 9. Chiral separations in microfluidic devices Detlev Belder. 277 9.1 Introduction . 277 9.2 Methodology and instrumentation . 278 9.2.1 Injection . 279 9.2.2 Detection . 282 9.2.3 Chiral electrolytes . 286 9.2.4 Enhancing resolution and performance . 287 9.3 Outlook . 292 References . 292 Part III Chapter 10. Instrumental aspects of chiroptical detection Kenneth W. Busch, Marianna A. Busch and Carlos Calleja-Amador. 299 Part A—The polarization of light 10.1 Light as a wave . 300 10.2 Types of polarized light . 301 10.2.1 Linearly polarized light . 303 10.2.2 Circularly polarized light . 303 10.2.3 Effiptically polarized light . 304 xii Contents 10.3 Production of linearly polarized light . 306 10.3.1 Polarization by scattering . 308 10.3.2 Polarization by reflection . 309 10.3.3 Polarization by birefringence . 312 10.3.4 Polarization by wire grids . 318 10.3.5 Polarization by dichroism . 320 10.4 Production of circularly polarized light . 321 10.5 Production of elliptically polarized light . 323 10.6 Photoelastic modulators . 324 Part В — Signal handling 10.7 Phase-sensitive detection . 327 Appendix A. Basic optics . 335 1A. Refractive index . 335 2A. Snell'slaw . 335 Appendix B. The law of Malus. 337 Appendix C. Lissajous figures and forms of polarization . 338 References . 341 Chapter 11. Micro-scale polarimetry Darryl J. Bornhop and Stephen Dotson . 343 11.1 Conventional micro-scale polarimetry . 344 11.2 RI compensation . 345 11.3 Molasses analysis . 346 11.4 Advanced laser polariméter . 348 11.5 Imaging polariméter . 349 11.6 Automated polariméter . 350 11.7 Backscatter technique . 352 11.7.1 Capillary polarimetrie detector (CPD) . 352 11.7.2 CPD: analysis by Fourier transform . 354 11.7.3 CPD: absolute optical activity measurements . 355 11.8 Conclusion . 357 References . 360 Chapter 12. Chiral analysis by regression modeling of spectral data Kenneth W. Busch and Marianna A. Busch . 363 12.1 Introduction . 363 12.2 Introduction to multivariate calibration . 364 12.3 Introduction to principal component analysis . 366 12.3.1 Principal component analysis revisited . 369 12.3.2 Multivariate regression . 372 12.4 Use of chemometrics in determining enantiomeric composition . 377 12.4.1 Use of a chiral auxiliary . 377 Contents xiii 12.5 Chiral analysis by multivariate regression modeling of spectral data . 379 12.5.1 Initial studies with amino acids . 381 12.5.2 Studies with pharmaceutical compounds . 382 12.5.3 Studies with modified cyclodextrins . 385 12.5.4 Studies using fluorescence . 386 12.6 Conclusions . 389 Appendix A. Matrix algebra . 391 References . 394 Chapter 13. Electronic circular dichroism for chiral analysis Jacek Gawronski and Pawel Skowronek. 397 13.1 Introduction — the exciton coupling mechanism . 397 13.2 Absolute configuration determination . 407 13.2.1 Internal chromophores . 409 13.2.2 External chromophores . 410 13.3 Conformational analysis . 414 13.3.1 Atropisomers . 415 13.3.2 Chiral polymers . 419 13.3.3 Protein secondary structure . 425 13.3.4 Nucleic acids . 431 13.4 Analysis of chiral interactions by induced circular dichroism . 436 13.4.1 Self-association . 437 13.4.2 Host-guest association . 440 13.5 Miscellaneous analytical applications . 446 13.6 Acknowledgment . 449 References . 449 Chapter 14. Determination of molecular stereochemistry using optical rotatory dispersion, vibrational circular dichroism and vibrational Raman optical activity Prasad L. Polavarapu . 461 14.1 Optical rotatory dispersion . 461 14.1.1 Introduction . 461 14.1.2 Experimental methods . 462 14.1.3 Theoretical methods . 465 14.1.4 Protocol for determining molecular stereochemistry . 467 14.1.5 Applications . 469 14.1.6 Commercial polarimétere and quantum mechanical software . 470 14.2 Vibrational circular dichroism . 471 14.2.1 Introduction . 471 14.2.2 Experimental methods . 472 14.2.3 Theoretical methods . 476 xiv Contents 14.2.4 Protocol for determining molecular stereochemistry . 477 14.2.5 Applications . 479 14.2.6 Commercial VCD spectrometers and quantum mechanical software . 481 14.2.7 Books on VCD . 481 14.3 Vibrational Raman optical activity . 481 14.3.1 Introduction . 481 14.3.2 Experimental methods . 483 14.3.3 Theoretical methods . 485 14.3.4 Protocol for determining molecular stereochemistry . 486 14.3.5 Applications . 488 14.3.6 Commercial VROA spectrometers and quantum mechanical software . 489 14.3.7 Books on VROA . 489 14.4. Summary . 490 14.5 Acknowledgments . 490 References . 491 Appendix A. Literature articles on quantum mechanically predicted specific rotations for evaluating molecular stereochemistry . 495 Appendix B. Literature articles (1999-2005) on quantum mechanically predicted VCD spectra for evaluating molecular stereochemistry . 498 Appendix C. Literature articles on quantum mechanically predicted VROA spectra for evaluating molecular stereochemistry . 502 Chapter 15. Vibrational optical activity in chiral analysis Laurence A. Nafie and Rina К. Dukor . 505 15.1 Introduction . 505 15.2 Definitions of vibrational optical activity . 507 15.3 Measurement of vibrational optical activity . 509 15.4 Theoretical basis of vibrational optical activity . 510 15.4.1 Theory of vibrational circular dichroism . 511 15.4.2 Theory of Raman optical activity . 512 15.5 Calculation of vibrational optical activity . 515 15.6 Determination of absolute configuration . 517 15.7 Determination of enantiomeric excess of multiple chiral species . 524 15.8 Vibrational optical activity of solids and formulated products . 532 15.9 Summary and conclusions . 535 References . 536 Chapter 16. Raman optical activity Ewan W. Blanch, Lutz Hecht and Laurence D. Barron . 545 16.1 Introduction . 545 Contents xv 16.2 Fundamental theory of ROA . 547 16.2.1 Distinction between ROA and optical rotation . 547 16.2.2 Electric and magnetic properties . 548 16.2.3 Discovery of ROA . 550 16.2.4 ROA observables . 550 16.2.5 The scattered circular polarization strategy . 552 16.3 Resonance ROA (RROA) . 553 16.4 Second harmonic scattering from chiral interfaces . 555 16.5 Magnetic ROA . 556 16.6 Computation of ROA observables. 557 16.6.1 ROA of archetypal helical molecules . 558 16.7 Instrumentation . 559 16.8 Studies on small molecules . 561 16.9 Enhanced sensitivity of ROA to biomolecular structure and dynamics . 562 16.9.1 ROA spectra of polypeptides and proteins . 563 16.9.2 PolyÍL-lysine) . 564 16.9.3 ROA spectra of proteins . 568 16.9.4 Studies on nucleic acids . 576 16.9.5 Studies on viruses . 578 16.10 Surface-enhanced ROA . 581 16.11 Application of chemometrics to ROA data . 585 16.12 Bright future . 588 16.13 Acknowldgments . 589 References . 589 Chapter 17. Mass spectral methods of chiral analysis Brandy L. Young, Lianming Wu and R. Graham Cooks . . . 595 17.1 Background to chiral analysis by mass spectrometry . 595 17.2 Fundamental interactions leading to chiral recognition . 598 17.3 Mass spectrometric methods for chiral analysis . 599 17.3.1 Kinetic resolution in solution with mass-tagged reagents . . . 601 17.3.2 Single-stage mass spectrometry . 605 17.3.3 Ion/molecule reactions . 613 17.3.4 Dissociation of cluster ions . 619 17.4 Applications . 633 17.4.1 Chiral analysis of ternary mixtures . 633 17.4.2 Chiral analysis of complex mixtures . 635 17.4.3 Chiral morphing . 636 17.4.4 Chiral drag analysis . 637 17.4.5 Method development and validation for chiral purity determination . 637 17.4.6 Online chiral analysis . 641 xvi Contents 17.5 Concluding remarks . 643 17.5.1 Emerging methods . 643 17.5.2 Advantages and challenges ahead . 650 17.6 Acknowledgments . 651 References . 651 Chapter 18. Novel chiral derivatizing agents powerful for enantioresolution and determination of absolute stereochemistry by X-ray crystallographic and 'Н NMR anisotropy methods Nobuyuki Harada, Masataka Watanabe and Shunsuke Kuwahara . 661 18.1 Introduction . 661 18.2 Methodologies for determining absolute configuration and their evaluations . 662 18.2.1 Nonempirical methods for determining absolute configurations of chiral compounds . 662 18.2.2 Relative methods for determining absolute configuration using an internal reference with known absolute configuration 662 18.3 Methodologies for chiral synthesis and their evaluations . 664 18.3.1 Enantioresolution of racemates . 664 18.3.2 Asymmetric syntheses . 665 18.4 Camphorsultam dichlorophthalic acid [CSDP acid (-)-!] and camphorsultam phthalic acid [CSP acid (-)-4] useful for enantioresolution of alcohols by HPLC and determination of their absolute configurations by X-ray crystallography . 665 18.5 A novel chiral molecular tool, 2-methoxy-2-(l-naphthyl)propionic acid [MaNP acid (S)-(+)-2], useful for enantioresolution of alcohols and determination of their absolute configurations by the Ή NMR anisotropy method . 676 18.5.1 Facile synthesis of MaNP acid (2) and its extraordinary enantioresolution with natural (-)-menthol . 678 18.5.2 The Ή NMR anisotropy method for determining the absolute configuration of secondary alcohols: the sector rule and applications . 679 18.5.3 Enantioresolution of various alcohols using MaNP acid and simultaneous determination of their absolute configurations. . 682 18.6 Complementary use of CSDP acid {-)-\ and MaNP acid (S)-(+)-2 for enantioresolution of alcohols and determination of their absolute confi¬ gurations by X-ray crystallographic and Ή NMR anisotropy methods 686 18.7 Conclusions . 690 18.8 Acknowledgments . 691 References . 691 Index . 693
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spelling	Chiral analysis ed. by Kenneth W. Busch ... 1. ed. Amsterdam [u.a.] Elsevier 2006 XVI, 704 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Chirality Enantioselective catalysis Chemische Analyse (DE-588)4009840-0 gnd rswk-swf Chirale Verbindungen (DE-588)4348527-3 gnd rswk-swf Chirale Verbindungen (DE-588)4348527-3 s Chemische Analyse (DE-588)4009840-0 s b DE-604 Busch, Kenneth W. Sonstige oth Digitalisierung UB Regensburg application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=015965508&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis
spellingShingle	Chiral analysis Chirality Enantioselective catalysis Chemische Analyse (DE-588)4009840-0 gnd Chirale Verbindungen (DE-588)4348527-3 gnd
subject_GND	(DE-588)4009840-0 (DE-588)4348527-3
title	Chiral analysis
title_auth	Chiral analysis
title_exact_search	Chiral analysis
title_exact_search_txtP	Chiral analysis
title_full	Chiral analysis ed. by Kenneth W. Busch ...
title_fullStr	Chiral analysis ed. by Kenneth W. Busch ...
title_full_unstemmed	Chiral analysis ed. by Kenneth W. Busch ...
title_short	Chiral analysis
title_sort	chiral analysis
topic	Chirality Enantioselective catalysis Chemische Analyse (DE-588)4009840-0 gnd Chirale Verbindungen (DE-588)4348527-3 gnd
topic_facet	Chirality Enantioselective catalysis Chemische Analyse Chirale Verbindungen
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