Frans_M_Everaerts_Isotachophoresis_378342.pdf

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SUBJECT INDEX 41 5 Detection limit 129, 278 --_ , high-resolution detectors 193-199 ___ , improvements 195 Detectors, specific 11 8 --_ , synchronous, UV detection 163 --_ , universal 1 18 Detectors used in analytical isotachophoresis, survey 122 Determination of conductivity circuit suitable, ax.-method 146, 148 Determination of effective mobilities 392 Determination of trace amounts 168 Diameter of the narrow-bore tube 395ff Differential signal peaks 20 Differentiating thermometric signals, circuit 123 Differentiator for the a.c. conductivity detector 154 Diffusion, influence on the zone boundaries 74,75 ‘Dilution’ principle of isotachophoretic analyses 378 ‘Dilution’ technique 352 --_ , UV detector 169 Disc electrophoresis 17, 265-267 Disc electrophoretic system 67 Dissociation, partial 3 1-35 Disturbances caused by hydrogen and hydroxyl ions 253-263 Disturbances due to the presence of carbon dioxide 263, 264 Disturbances due to the presence of hydrogen and hydroxyl ions in buffered systems 260-263 Disturbances from the leading zone 257-260 ‘Dole polynomals’, modification 389 E Electrode, activated 187 -_ _ , bipolar sensing 176 --_ , charge-transfer 175, 176 _-- , ‘ideally’ polarized 175, 176 _-- , metallic 174 -__ , micro-sensing, coating 19 1 - 193 _-_ , --_ , effect of coating 192, 194 --- , (partially) passivated 186 --_ , passivated 185 --_ , polarized 174 --_ , reversible 174 Electrode reactions 256 Electroendosmosis 171, 173 Electroendosmotic flow, effect of additives 171-173 Electrolyte, background 7 ___ , de-gassing of 252 --- , leading 13 __- , supporting 7 ___ , terminating 13 Electrolyte systems, choice 83ff -__ --- ,scheme 101 Electroneutrality, principle 15,60 Electroneutrality equations 47, 48, 388 Electrophoresis, disc 17, 265-267 __- , moving-boundary 9-12, 387ff --- , -__ , procedure of computation 389 __- , stacking 18 -_- ,zone 7 Electrophoretic system, disc 67 Enforced isotachophoresis 264-267 Enzymatic conversion 348-360 Enzymatic reactions 347ff Equilibrium equations 45-47,58 Equipment 217-229 Equivalent weight 29 F Fatty acids 103 _-- , separation in a methanolic system 108 Friction factor 27, 38 Friction force 27 Funktion, beharrliche 2, 41 Galvanic separation 150 Gas bubbles 252, 253 H Halides, qualitative information 366 Heights, step 20 Henderson-Hasselbalch equation 33 High-frequency conductivity detection 130-133 __- , construction 131-133 High-resolution detectors, detection limits 193-199 , isotachophoretic equipment with 224-229
416 SUBJECT INDEX I Identification 20 --_ , reference materials 99 Impurities, influence on counter-flow of electrolyte 23 1 --_ , marking a zone boundary 165 --_ , zones of 96 Indirect UV method 166 Inhibitors, corrosion 184 Injection block 208-211 --- , simplified 211, 212 Injection systems 203-21 1 --_ , four-way tap 204, 205 --_ , six-way valve 205-208 Ionic atmosphere 28 Isoelectric focusing 23, 24 Isoelectric point 23 Isotachopherograms 20-22 --- , influence of current density 195 <strong>Isotachophoresis</strong>, computation procedure 62 --- , enforced 264-267 , mathematical model 41ff, 58-62 --_ , principle 13-23 -_- , steady state 55-69 --- , _-_ , computer program 74 Isotachophoretic analysis, resolution 1 89 Isotachophoretic condition 14, 15, 58, 260 Isotachophoretic equipment 11 7 Is0 tachophore tic equipment with high-resolution detectors 224-229 Isotachophoretic equipment with thermostating via aluminium block 221-224 Isotachophoretic equipment with water-jacket 219-221 Isotachophoretic model, check 76-81 Isotachophoretically separated system 13, 57 Isotachophoretic separations, concept 5 5 -5 8 --- , influence of additives 183 --_ , influence of surfactants 189 Isotachophoretic separations in non-aqueous systems 361ff Iteration procedure 62-69 L Law of independent migration 31 Leading electrolyte 13 -_- , pH, choice 93-96 Leading ionic species, choice 96-99 Leading zone, enlarged 255 Leak current 188 Length of a zone 18 Linearity of two conductimeters, a.c. method 152 M Mass balance of the buffer 59, 60 Mass balances 48-50, 388 Measurement of effective mobilities 387ff Mechanical construction of the UV source 158 Membrane pump 24 1-245 -__ , circuit for counter flow regulation via 242, 24 5 ‘Memory’ effect 182 Methanol, alkali metals in 104 _-- , separation of anionic species using a thermometric detector 362-364 --_ , separation of cationic species using a thermometric detector 364-373 Methanol as solvent 87-92 Methanolic system, separation of some fatty acids 108 Micro-sensing electrodes, coatinq 191-193 --_ , effect of additives 174-1 80 --- , effect of coating 192, 194 --_ , polarization 176 Migration, independent, law 3 1 Migration paths 50 Mixed zones 9,13 Mobility, absolute ionic 30, 31 --_ , concept 27ff -__ ,ionic 29-31 --- _-- ,effective 31-37,49, 83, 86 - - - - - - - - - , determination 392 - - - - - - , - - - , measurement 3 87 ff --- , --- , relationship with entropy 39 --- , __- , relationship with volume 37, 38 -__ , separations according to 83, 98, 100 Mobility at infinite dilution 30 Moving-boundary electrophoresis 9-12, 387ff -__ , procedure of computation 389 Moving-boundary procedure 13 N Narrow-bore tube; diameter 395ff Non-aqueous systems, isotachophoretic separations 361ff Nucleotides, qualitative information 342, 344
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Journal of Chromatogaphy Library -
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Journal of Chromatography Library -
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Dedicated to Pr0f.Dr.h. A.I.M. Keul
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Contents Preface ..................
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CONTENTS IX 6.4.2. The d.c. method
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CONTENTS XI 12.2.2. Applications ..
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It is very well known that charged
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Chapter 1 Historical review SUMMARY
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HISTORICAL REVIEW 3 Independently i
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THEORY
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Chapter 2 Principles of electrophor
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MOVINGBOUNDARY ELECTROPHORESIS a S
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MOVINGBOUNDARY ELECTROPHORESIS 0 iu
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ISOTACHOPHORESIS 13 2.4. PRINCIPLE
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ISOTACHOPHORESIS 15 As the anionic
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ISOTACHOPHORESIS velocities, so tha
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ISOTACHOPHORESIS 19 d.t ’.t I Fig
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ISOTACHOPHORESIS 21 t Fig.2.8. Isot
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ISOELECTRIC FOCUSING 23 The four is
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DISCUSSION 25 Fig.2.11. Survey of t
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Chapter 3 Concept of mobility SUMMA
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IONIC MOBILITY AND IONIC EQUIVALENT
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EFFECTIVE IONIC MOBILITY 31 obtain
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EFFECTIVE IONIC MOBILITY 33 compari
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EFFECTIVE IONIC MOBILITY Fig.3.4. R
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DETERMINATION OF IONIC MOBILITIES 3
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DETERMINATION OF IONIC MOBILITIES 3
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Chapter 4 Mathematical model for is
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GENERAL EQUATIONS 43 anionic specie
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GENERAL EQUATIONS 4.2.1. Equilibriu
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GENERAL EQUATIONS 41 i Similar equa
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GENERAL EQUATIONS 49 Uthzone (U-llt
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GENERAL EQUATIONS 4.2.4. Modified O
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GENERAL EQUATIONS TABLE 4.2 REDUCED
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MATHEMATICAL MODEL FOR THE STEADY S
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VALIDITY OF THE ISOTACHOPHORETIC MO
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CHECK OF THE ISOTACHOPHORETIC MODEL
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CHECK OF THE ISOTACHOPHORETIC MODEL
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REFERENCES 81 Fig.4.17. Relationshi
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Chapter 5 Choice of electrolyte sys
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CHOICE OF THE SOLVENT 85 In general
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CHOICE OF THE SOLVENT TABLE 5.2 THE
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CHOICE OF THE SOLVENT pH and pKvalu
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CHOICE OF THE SOLVENT 91 TABLE 5.4
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CHOICE OF THE pH OF THE LEADING ELE
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CHOICE OF THE pH OF THE LEADING ELE
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CHOICE OF THE TERMINATING AND LEADI
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ADDITIONS TO THE ELECTROLYTE SOLUTI
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EXAMPLES Choice of solvent. Can wat
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EXAMPLES 103 solvent, hoping that a
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EXAMPLES TABLE 5.11 STEP HEIGHTS OF
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EXAMPLES TABLE 5.12 STEP HEIGHTS OF
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Fig.5.9. Isotachopherograms of the
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EXAMPLES II 4 3 Fig.5.11. Isotachop
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REFERENCES 113 Example I. As exampl
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INSTRUMENTATION
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Chapter 6 Detection systems SUMMARY
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THERMOMETRIC RECORDING 6.1.3. Combi
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THERMOMETRIC RECORDING Potential gr
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THERMOMETRIC RECORDING /2 Fig.6.1.
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THERMOMETRIC RECORDING T t l Fig.6.
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THERMOMETRIC RECORDING 7 127 It-- I
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THERMOMETRIC RECORDING a concentrat
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HIGH-FREQUENCY CONDUCTIVITY DETECTI
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CONDUCTIVITY DETECTION 133 Fig.6.9.
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CONDUCTIVITY DETECTION 135 The d.c.
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CONDUCTIVITY DETECTION 137 Hi V 1kR
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CONDUCTIVITY DETECTION Fig.6.12. Co
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CONDUCTIVITY DETECTION Fig.6.14. Th
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CONDUCTIVITY DETECTION 143 6.4.4. T
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CONDUCTIVITY DETECTION 145 contact
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CONDUCTIVITY DETECTION 147 We can n
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CONDUCTIVITY DETECTION 149 N.Y., U.
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CONDUCTIVITY DETECTION 151 achieved
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UV ABSORPTION METER 153 -_-.- +- R
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UV ABSORPTION METER Fig.6.22. Contr
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W ABSORPTION METER r +15V -15V Mod
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W ABSORPTION METER 159 TABLE 6.4 PR
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W ABSORPTION METER 230 240 2% m zm
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to Mod (Fig 6.24) oscillator I sync
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UV ABSORPTION METER 165 dicular to
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Fig.6.31. Isotachopherograms for th
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UV ABSORPTION METER 169 50 Fig.6.33
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ADDITIVES TO THE ELECTROLYTES 171 6
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ADDITIVES TO THE ELECTROLYTES 173 e
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ADDITIVES TO THE ELECTROLYTES 175 a
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ADDITIVES TO THE ELECTROLYTES 177 o
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ADDITIVES TO THE ELECTROLYTES 179 d
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ADDITIVES TO THE ELECTROLYTES 181 T
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ADDITIVES TO THE ELECTROLYTES Fig.6
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ADDITIVES TO THE ELECTROLYTES 185 F
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ADDITIVES TO THE ELECTROLYTES 1 2 3
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ADDITIVES TO THE ELECTROLYTES 189 n
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COATING OF THE MICRO-SENSING ELECTR
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DETECTION LIMITS 193 electric drivi
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DETECTION LIMITS 195 Fig.6.48. Infl
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DETECTION LIMITS 197 TABLE 6.6 SURV
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CONCLUSION 199 average length of a
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REFERENCES 201 seen. Again it is cl
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Chapter 7 Instrumentation SUMMARY T
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INJECTION SYSTEMS I! I n Fig.7.1. P
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INJECTION SYSTEMS Fig.7.3. Exploded
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INJECTION SYSTEMS Fig.7.5. Injectio
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COUNTER ELECTRODE COMPARTMENTS 21 1
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COUNTER ELECTRODE COMPARTMENTS Even
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COUNTER ELECTRODE COMPARTMENTS 21 5
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EQUIPMENT the large bore, a more di
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EQUIPMENT 219 belonging to three cl
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EQUIPMENT 221 signal of the thermoc
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EQUIF'MENT 223 No effect on the res
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EQUIPMENT 225 Fig.7.14. Electrophor
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EQUIPMENT Fig.7.16. Photograph of t
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EQUIPMENT 229 mounted equiplanar, w
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COUNTER FLOW OF ELECTROLYTE 231 ins
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COUNTER FLOW OF ELECTROLYTE p High
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COUNTER FLOW OF ELECTROLYTE Fig.7.2
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COUNTER FLOW OF ELECTROLYTE 231 aro
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COUNTER FLOW OF ELECTROLYTE p high
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COUNTER FLOW OF ELECTROLYTE 24 1 7.
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COUNTER FLOW OF ELECTROLYTE I I 31
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COUNTER FLOW OF ELECTROLYTE max. 15
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APPLICATIONS
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Chapter 8 Introduction SUMMARY In t
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INTRODUCTION 25 1 the various ionic
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Chapter 9 Practical aspects SUMMARY
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DISTURBANCES CAUSED BY H+ AND OH 25
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DISTURBANCES CAUSED BY H+ AND OH- 2
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DISTURBANCES DUE TO CO, 263 Electro
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ENFORCED ISOTACHOPHORESIS 265 t T T
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WATER AS TERMINATOR 267 function of
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PURIFICATION OF THE TERMINATOR 7 4
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REFERENCES 271 AS an example, the c
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Chapter 10 Quantitative aspects SUM
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THERMOMETRIC MEASUREMENTS 215 vj c
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THERMOMETRIC MEASUREMENTS TABLE 10.
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CONDUCTIMETRIC MEASUREMENTS factor
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CONCLUSION 28 1 Tables 10.3-10.5 wa
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Chapter 11 Separation of cationic s
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SEPARATION USING A THERMOCOUPLE AS
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I SEPARATION USING A THERMOCOUPLE A
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SEPARATION USING CONDUCTIVITY AND U
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Chapter I2 Separation of anionic sp
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SEPARATION USING A THERMOMETRIC DET
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SEPARATION USING CONDUCTIVITY AND W
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Chapter 13 Amino acids, peptides an
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AMINO ACIDS TABLE 13.1 OPERATIONAL
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AMINO ACIDS 8- ?- 6- 5- 4- 3- 2- f-
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AMINO ACIDS 317 TABLE 13.5 STEP HEI
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AMINO ACIDS Fig.13.3. Schematic dia
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AMINO ACIDS TABLE 13.6 DETERMINATIO
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SEPARATION OF PROTEINS IN AMPHOLYTE
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SEPARATION OF SMALL PEPTIDES reprod
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Chapter I4 Separation of nucleotide
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Chapter 15 Enzymatic reactions SUMM
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ENZYMATIC CONVERSION OF GLUCOSE (FR
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ENZYMATIC CONVERSION OF PYRUVATE 35
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Chapter 16 Separations in non-aqueo
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SEPARATION OF ANIONIC SPECIES IN ME
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Page 388 and 389: EXPERIMENTS IN AQUEOUS METHANOLIC S
Page 390 and 391: Chapter I7 Counter flow of electrol
Page 392 and 393: INTRODUCTION 317 In various operati
Page 394 and 395: EXPERIMENTAL 0% 10 % a b 60 % a b a
Page 396 and 397: EXPERIMENTAL 381 caused by the coun
Page 398 and 399: CONCLUSION 383 c t r ’r; I I"
Page 400 and 401: APPENDICES
Page 402 and 403: Appendix A Simplified model of movi
Page 404 and 405: PROCEDURE OF COMPUTATION A.3. PROCE
Page 406 and 407: EXPERIMENTAL 39 1 TABLE A1 THEORETI
Page 408 and 409: DISCUSSION E I I Fig.A2. Graphical
Page 410 and 411: Appendix B Diameter of the narrow-b
Page 412 and 413: Appendix C Literature 1897-1966 F.
Page 414 and 415: LITERATURE 399 B.P. Konstantinov an
Page 416 and 417: LITERATURE 401 1971 L. Arlinger, Is
Page 418 and 419: LITERATURE 403 1973 L. Arlinger and
Page 420 and 421: LITERATURE 405 A. Chrambach and J.S
Page 422 and 423: LITERATURE 407 M. Coxon and M.J. Bi
Page 424 and 425: Symbols and abbreviations SYMBOLS A
Page 426 and 427: SYMBOLS AND ABBREVIATIONS SUPERSCRI
Page 428 and 429: Subject index A Absorption meter, U
Page 432 and 433: SUBJECT INDEX 41 7 --_ , separation
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