JOURNAL OF CHROMATOGRAPHY LIBRARY — volume 69A chromatography 6th edition fundamentals and applications of chromatography and related differential migration methods part A: fundamentals and techniques The page is intentionally left blank JOURNAL OF CHROMATOGRAPHY LIBRARY — volume 69A chromatography 6th edition fundamentals and applications of chromatography and related differential migration methods part A: fundamentals and techniques edited by E. Heftmann 2004 Amsterdam–Boston–Heidelberg–London–New York–Oxford–Paris San Diego–San Francisco–Singapore–Sydney–Tokyo ELSEVIERB.V. ELSEVIERInc. ELSEVIERLtd ELSEVIERLtd SaraBurgerhartstraat25 525BStreet,Suite1900 TheBoulevard,LangfordLane 84TheobaldsRoad P.O.Box211,1000AEAmsterdam SanDiego,CA92101-4495 Kidlington,OxfordOX51GB LondonWC1X8RR TheNetherlands USA UK UK q2004ElsevierB.V.Allrightsreserved. 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ISBN: 0-444-51107-5 SetISBN: 0-444-51106-7 ISSN: 0-301-4770 W 1 ThepaperusedinthispublicationmeetstherequirementsofANSI/NISOZ39.48-1992(Permanenceof Paper).PrintedinTheNetherlands. TO BIBI The page is intentionally left blank VII CONTENTS List ofAuthors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI List ofAbbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . XIII List ofItalic Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . XXIX List ofGreek Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . XXXIII Foreword (S.Hjerte´n) . . . . . . . . . . . . . . . . . . . . . . . . . . XXXV Preface (E.Heftmann) . . . . . . . . . . . . . . . . . . . . . . . . . . XXXIX 1 Theory ofchromatography (V.L.McGuffin) . . . . . . . . . . . . . . . . 1 1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.2 Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.3 Principles of solute-zone dispersion . . . . . . . . . . . . . . . . 9 1.4 Principles of solute-zone separation . . . . . . . . . . . . . . . . 38 1.5 Optimization ofchromatographic separations . . . . . . . . . . . 72 1.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 2 Columnliquid chromatography (R.M. Smith) . . . . . . . . . . . . . . . . 95 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 2.2 Equipmentfor liquid-phase separations . . . . . . . . . . . . . . 98 2.3 Stationary-phase materials . . . . . . . . . . . . . . . . . . . . 104 2.4 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 2.5 Separation methods . . . . . . . . . . . . . . . . . . . . . . . 121 2.6 Liquid chromatography insample preparation . . . . . . . . . . . 128 2.7 High-temperature separations . . . . . . . . . . . . . . . . . . . 129 2.8 Miniaturization . . . . . . . . . . . . . . . . . . . . . . . . . 129 2.9 Large-scale separations . . . . . . . . . . . . . . . . . . . . . . 130 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 3 Affinity chromatography (F.B.Anspach) . . . . . . . . . . . . . . . . . . 139 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 3.2 Chromatographic operations . . . . . . . . . . . . . . . . . . . 141 VIII 3.3 Affinity interactions at solid interfaces . . . . . . . . . . . . . . 142 3.4 Affinity ligands . . . . . . . . . . . . . . . . . . . . . . . . . 153 3.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 4 Ion chromatography (C.A.Lucyand P. Hatsis) . . . . . . . . . . . . . . . 171 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 172 4.2 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . 173 4.3 Selectivityinion chromatography . . . . . . . . . . . . . . . . . 186 4.4 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . 203 4.5 Future directions . . . . . . . . . . . . . . . . . . . . . . . . . 207 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . 208 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209 5 Size-exclusionchromatography (J.Silberring, M. Kowalczuk, J.Bergquist, A. Kraj, P. Suder, T. Dylag, M. Smoluch, J.-P. Chervet, andJ. Ekman). . . . 213 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 213 5.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215 5.3 Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 5.4 Mobile phase . . . . . . . . . . . . . . . . . . . . . . . . . . 219 5.5 Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222 5.6 Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228 5.7 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 230 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . 241 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241 6 Planarchromatography(Sz. Nyiredy). . . . . . . . . . . . . . . . . . . . 253 6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 254 6.2 Classification ofplanar chromatographictechniques . . . . . . . . 255 6.3 Principles ofplanar chromatographicmethods . . . . . . . . . . . 257 6.4 Principal factorsinplanar chromatography . . . . . . . . . . . . 258 6.5 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . 273 6.6 Qualitativeand quantitative analysis . . . . . . . . . . . . . . . 277 6.7 Preparative planar chromatography . . . . . . . . . . . . . . . . 282 6.8 Special planar chromatographic techniques . . . . . . . . . . . . 285 6.9 Comparison ofvarious planar chromatographic techniques . . . . . 287 6.10 Trends in planar chromatography . . . . . . . . . . . . . . . . . 287 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291 7 Electrokineticchromatography (E. Kenndlerand A.Rizzi). . . . . . . . . . 297 7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 298 7.2 Electro-osmotic flowinopen andpacked capillaries . . . . . . . . 301 IX 7.3 Electrochromatographywith stationaryphases . . . . . . . . . . . 304 7.4 Electrokinetic chromatographywith pseudo-stationary phases . . . 310 7.5 Electricallydrivenvs. pressure-driven chromatography . . . . . . . 315 7.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . 316 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317 8 Gas chromatography (P.J. Marriott). . . . . . . . . . . . . . . . . . . . . 319 8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 320 8.2 Basic operating variables . . . . . . . . . . . . . . . . . . . . . 321 8.3 Enhanced and fast separations . . . . . . . . . . . . . . . . . . 332 8.4 Sample introduction . . . . . . . . . . . . . . . . . . . . . . . 340 8.5 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364 9 Capillaryzone electrophoresis (P.G. Righetti,A.Bossi, L. Castelletti,and B. Verzola) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369 9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 369 9.2 Theinstrument . . . . . . . . . . . . . . . . . . . . . . . . . . 370 9.3 Thecapillary . . . . . . . . . . . . . . . . . . . . . . . . . . . 374 9.4 Howto modulate the EOF . . . . . . . . . . . . . . . . . . . . 377 9.5 Thebuffers . . . . . . . . . . . . . . . . . . . . . . . . . . . 382 9.6 Modes ofoperation . . . . . . . . . . . . . . . . . . . . . . . 384 9.7 Micellar electrokinetic chromatography . . . . . . . . . . . . . . 390 9.8 Biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394 9.9 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . 394 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . 395 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395 10 Combinedtechniques (W.M.A.Niessen). . . . . . . . . . . . . . . . . . 403 10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 404 10.2 Coupled columns . . . . . . . . . . . . . . . . . . . . . . . . 405 10.3 Chromatography–spectrometry . . . . . . . . . . . . . . . . . 413 10.4 Liquid chromatography–mass spectrometry . . . . . . . . . . . 418 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425 11 Microfabricated analyticaldevices (A. Guttman andJ. Khandurina). . . . . 431 11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 431 11.2 Capillary electrophoresis onmicrochips . . . . . . . . . . . . . 432 11.3 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 437 11.4 System integration . . . . . . . . . . . . . . . . . . . . . . . 451 11.5 Modeling by computational fluid dynamics . . . . . . . . . . . . 461
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