Frans_M_Everaerts_Isotachophoresis_378342.pdf

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HISTORICAL REVIEW 3 Independently in 1963, Everaerts [27] started, together with Martin, work that finally resulted in the appearance of this book on isotachophoresis. As Martin [ 151 , he used the term ‘displacement electrophoresis’. He performed the analysis in a narrow-bore tube of Pyrex glass of I.D. 0.5 mm and an O.D. of 0.8 mm. In order to prevent hydrodynamic flow between the two electrode compartments through the narrow-bore tube, caused by differences in levels, this tube was filled with an electrolyte the viscosity of which was increased up to 100 CP by addition of a watersoluble linear polymer, e.g., hydroxyethylcellulose. This polymer was purified by shaking it with a mixed-bed ion exchanger. A thermocouple (30-pm copper-25-pm constantan) was used as the detector. Independently, and unaware of this work, Kaimakov and Sharkov [28] reported on the use of microthermistors to detect zone boundaries. In 1964, Ornstein [29] and Davis [30] introduced disc electrophoresis. They placed a protein mixture between an electrolyte with an anion of low effective mobility and an electrolyte with an anion with a high effective mobility. Owing to the concentration phenomenon of isotachophoresis, the proteins are stacked in narrow zones between the two electrolytes (‘steady-state stacking’). The zones, however, are so narrow that even a high-resolution detector cannot detect them. Therefore, in the second stage of the analysis, the principle of zone electrophoresis was used, which allowed every protein to move at a different velocity. Cross-linked polyacrylamide was used as a stabilizing medium and as a molecular sieve. The mobilities of the proteins could be controlled, moreover, by varying the pore size in the gel. Ornstein [29] derived several equations, with which it was possible to calculate the mobilities and the pH values of the electrolyte systems. In 1966, Vesterrnark [31] introduced a new term, ‘cons electrophoresis’, for the electrophoretic technique that makes use of Kohlrausch’s regulating function [7] . Vestermark also used the spacer technique. In 1966, Preetz [32] gave a theoretical treatment of the use of a counter flow of electrolyte in isotachophoretic systems. In 1967, Preetz and Pfeifer [33] described an instrument that was specially designed for measurements of potential gradients and ion concentrations. Preetz also performed analyses in narrow-bore tubes. A further development was the continuous counter flow equipment described by Preetz and Pfeifer [34]. Based on work of Everaerts [35] and Martin and Everaerts [36], Verheggen and Everaerts built an instrument and introduced the technique in Bergstr6m’s department at the Karolinska Institute, Stockholm, Sweden, in 1968. This was the basis of the commercial production of isotachophoretic equipment, produced by LKB Produkter AB in Bromma, Sweden. In 1969, Everaerts and Verheggen introduced the technique at the Charles University in Prague, Czechoslovakia, in Vacik’s research group. Up to 1970, several names had been used for similar electrophoretic techniques, including ion migration method, Kendall [ 121 (1928); moving-boundary method, MacInnes and Longsworth [ 141 (1932); displacement electrophoresis, Martin [ 151 (1942) and Everaerts [27] (1964); steady-state stacking, Ornstein [29] (1964); cons electrophoresis, Vestermark [31] (1966); and ionophoresis, Preetz [32] (1966). Together with Haglund [37], a group of research workers in the field introduced a new name, based upon an important phenomenon of the electrophoretic technique, namely the identical velocities of the sample zones in the steady state: isotacho-electro-phoresis* , or isotachophoresis for short. *r LOO = equal; ~01x0~ = velocity; @peeueorc = to be dragged.
4 HISTORICAL REVIEW It is very difficult to summarize the individual contributions of the various scientists to the development of the technique after 1970. In Appendix B, we give an almost complete list of the relevant papers on the subject. Of all the papers, special note is made of two, in which new types of operational detector were described, representing land- marks in the development of isotachophoresis. In 1970, Arlinger and Routs [38] introduced an operational UV absorption detector, and in 1972, Verheggen et al. [39] introduced an operational conductivity detector. REFERENCES 1 G. Wiedeman, Pogg. Ann., 99 (1856) 197. 2 G. Wiedeman, Pogg. Ann., 104 (1858) 166. 3 H. Buff, Ann. Chem. Pharm., 105 (1858) 168. 4 0. Lodge, Brit. Ass. Advan. Sci., Rep., 56 (1886) 389. 5 W.C.D. Whetham, Phil. Trans. Roy. SOC. London, Ser. A, 184 (1893) 337. 6 W.C.D. Whetham,PhiI. Trans. Roy. SOC. London, Ser. A, 186 (1895) 507. 7 F. Kohlrausch,Ann. Phys. (Leipzig), 62 (1897) 209. 8 W.B. Hardy, Proc. Roy. Soc. London. 66 (1900) 110. 9 W.B. Hardy, J. Physiol. (London), 33 (1905) 251. 10 L. Michaelis, Biochem. Z., 16 (1909) 81. 11 J. Kendall and E.D. Crittenden, Proc. Nut. Acad. Sci. US., 9 (1923) 75. 12 J. Kendall, Science, 67 (1928) 163. 13 A. Lindemann, Proc. Roy. Soc., Ser. A, 99 (1921) 102. 14 D.A. MacInnes and L.G. Longsworth, Chem. Rev., 11 (1932) 171. 15 A.J.P. Martin, unpublished results, 1942. 16 L.G. Longsworth, Nut. Bur. Stand. (US.). Circ., No. 524 (1953) 59. 17 M.D. Poulik, Nature (London), 180 (1957) 1477. 18 E.A. Kaimakov, and V.B. Fiks, Rum. J. Phys. Chem., 35 (1961) 873. 19 E.A. Kairnakov, Russ. J. Phys. Chem., 36 (1961) 436. 20 B.P. Konstantinov and E.A. Kaimakov, Rum. J. Phys. Chem., 36 (1962) 437. 21 B.P. Konstantinov, E.A. Kaimakov and N.L. Varshovskaya, Russ. J. Phys. Chem., 36 (1962) 535. 22 B.P. Konstantinov, E.A. Kaimakov and N.L. Varshovskaya, Russ. J. Phys. Chem., 36 (1962) 540. 23 G.S. Hartley, Trans. Faraday SOC., 30 (1934) 648. 24 A.R. Gordon and R.L. Kay, J. Chem. Phys., 21 (1953) 131. 25 B.P. Konstantinov and O.V. Oshurkova, Dokl. Akad. Nauk. SSSR, 148 (1963) 11 10. 26 B.P. Konstantinov and O.V. Oshurkova, Sov. Phys.-Tech. Phys., 11 (1966) 693. 27 F.M. Everaerts, Graduation Rep., University of Technology, Eindhoven, 1964. 28 E.A. Kaimakov and V.I. Sharkov, Russ. J. Phys. Chem., 38 (1964) 893. 29 L. Ornstein, Ann. N. Y. Acad. Sci., 121 (1964) 321. 30 B.J. Davis, Ann. N. Y. Acad. Sci., 121 (1964) 404. 31 A. Vestermark, Cons Electrophoresis: An Experimental Study, unpublished results, 1966. 32 W. Preetz, Tdanta, 13 (1966) 1649. 33 W. Preetz and H.L. Pfeifer, Talanta, 14 (1967) 143. 34 W. Preetz and H.L. Pfeifer, Anal. aim. Acta, 38 (1967) 255. 35 F.M. Everaerts, Thesis, University of Technology, Eindhoven, 1968. 36 A.J.P. Martin and F.M. Everaerts,Anal. Chim. Acta, 38 (1967) 233. 37 H. Haglund, Sci. Tools, 17 (1970) 2. 38 L. Arlinger and R.J. Routs, Sci. Tools, 17 (1970) 21. 39 Th. P.E.M. Verheggen, E.C. van Ballegooijen, C.H. Massen and F.M. Everaerts, J. Chromatogr., 64 (1972) 185.
Page 2 and 3: Journal of Chromatogaphy Library -
Page 4 and 5: Journal of Chromatography Library -
Page 6 and 7: Dedicated to Pr0f.Dr.h. A.I.M. Keul
Page 8 and 9: Contents Preface ..................
Page 10 and 11: CONTENTS IX 6.4.2. The d.c. method
Page 12 and 13: CONTENTS XI 12.2.2. Applications ..
Page 14 and 15: It is very well known that charged
Page 16 and 17: Chapter 1 Historical review SUMMARY
Page 20 and 21: THEORY
Page 22 and 23: Chapter 2 Principles of electrophor
Page 24 and 25: MOVINGBOUNDARY ELECTROPHORESIS a S
Page 26 and 27: MOVINGBOUNDARY ELECTROPHORESIS 0 iu
Page 28 and 29: ISOTACHOPHORESIS 13 2.4. PRINCIPLE
Page 30 and 31: ISOTACHOPHORESIS 15 As the anionic
Page 32 and 33: ISOTACHOPHORESIS velocities, so tha
Page 34 and 35: ISOTACHOPHORESIS 19 d.t ’.t I Fig
Page 36 and 37: ISOTACHOPHORESIS 21 t Fig.2.8. Isot
Page 38 and 39: ISOELECTRIC FOCUSING 23 The four is
Page 40 and 41: DISCUSSION 25 Fig.2.11. Survey of t
Page 42 and 43: Chapter 3 Concept of mobility SUMMA
Page 44 and 45: IONIC MOBILITY AND IONIC EQUIVALENT
Page 46 and 47: EFFECTIVE IONIC MOBILITY 31 obtain
Page 48 and 49: EFFECTIVE IONIC MOBILITY 33 compari
Page 50 and 51: EFFECTIVE IONIC MOBILITY Fig.3.4. R
Page 52 and 53: DETERMINATION OF IONIC MOBILITIES 3
Page 54 and 55: DETERMINATION OF IONIC MOBILITIES 3
Page 56 and 57: Chapter 4 Mathematical model for is
Page 58 and 59: GENERAL EQUATIONS 43 anionic specie
Page 60 and 61: GENERAL EQUATIONS 4.2.1. Equilibriu
Page 62 and 63: GENERAL EQUATIONS 41 i Similar equa
Page 64 and 65: GENERAL EQUATIONS 49 Uthzone (U-llt
Page 66 and 67: GENERAL EQUATIONS 4.2.4. Modified O
Page 68 and 69:
GENERAL EQUATIONS TABLE 4.2 REDUCED
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MATHEMATICAL MODEL FOR THE STEADY S
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Page 78 and 79:
Page 80 and 81:
Page 82 and 83:
Page 84 and 85:
VALIDITY OF THE ISOTACHOPHORETIC MO
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Page 90 and 91:
Page 92 and 93:
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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Page 316 and 317:
SEPARATION USING CONDUCTIVITY AND W
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Page 320 and 321:
Page 322 and 323:
Page 324 and 325:
Page 326 and 327:
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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SEPARATION OF CATIONIC SPECIES IN M
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EXPERIMENTS IN AQUEOUS METHANOLIC S
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Chapter I7 Counter flow of electrol
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INTRODUCTION 317 In various operati
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EXPERIMENTAL 0% 10 % a b 60 % a b a
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EXPERIMENTAL 381 caused by the coun
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CONCLUSION 383 c t r ’r; I I"
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APPENDICES
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Appendix A Simplified model of movi
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PROCEDURE OF COMPUTATION A.3. PROCE
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EXPERIMENTAL 39 1 TABLE A1 THEORETI
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DISCUSSION E I I Fig.A2. Graphical
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Appendix B Diameter of the narrow-b
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Appendix C Literature 1897-1966 F.
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LITERATURE 399 B.P. Konstantinov an
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LITERATURE 401 1971 L. Arlinger, Is
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LITERATURE 403 1973 L. Arlinger and
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LITERATURE 405 A. Chrambach and J.S
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LITERATURE 407 M. Coxon and M.J. Bi
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Symbols and abbreviations SYMBOLS A
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SYMBOLS AND ABBREVIATIONS SUPERSCRI
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Subject index A Absorption meter, U
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SUBJECT INDEX 41 5 Detection limit
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SUBJECT INDEX 41 7 --_ , separation
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