Abstract
In this review we introduce the advantages and limitations of electromigrative separation techniques in forensic toxicology. We thus present a summary of illustrative studies and our own experience in the field together with established methods from the German Federal Criminal Police Office rather than a complete survey. We focus on the analytical aspects of analytes’ physicochemical characteristics (e.g. polarity, stereoisomers) and analytical challenges including matrix tolerance, separation from compounds present in large excess, sample volumes, and orthogonality. For these aspects we want to reveal the specific advantages over more traditional methods. Both detailed studies and profiling and screening studies are taken into account. Care was taken to nearly exclusively document well-validated methods outstanding for the analytical challenge discussed. Special attention was paid to aspects exclusive to electromigrative separation techniques, including the use of the mobility axis, the potential for on-site instrumentation, and the capillary format for immunoassays. The review concludes with an introductory guide to method development for different separation modes, presenting typical buffer systems as starting points for different analyte classes. The objective of this review is to provide an orientation for users in separation science considering using capillary electrophoresis in their laboratory in the future.
Similar content being viewed by others
References
Favretto D, Pascali JP, Tagliaro F (2013) New challenges and innovation in forensic toxicology: focus on the ’New psychoactive substances'. J Chromatogr A 1287:84–95
Rosenbaum C, Carreiro S, Babu K (2012) Here today, gone tomorrow…and back again? A review of herbal marijuana alternatives (k2, spice), synthetic cathinones (bath salts), kratom, salvia divinorum, methoxetamine, and piperazines. J Med Toxicol 8(1):15–32
Theobald DS, Pütz M, Schneider E, Maurer HH (2006) New designer drug 4-iodo-2,5-dimethoxy-beta-phenethylamine (2C-I): studies on its metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric and capillary electrophoretic/mass spectrometric techniques. J Mass Spectrom 41(7):872–886
Chee GL, Wan TSM (1993) Reproducible and high-speed separation of basic drugs by capillary zone electrophoresis. J Chromatogr B 612(1):172–177
Mohr S, Pilaj S, Schmid MG (2012) Chiral separation of cathinone derivatives used as recreational drugs by cyclodextrin-modified capillary electrophoresis. Electrophoresis 33(11):1624–1630
Weinberger R, Lurie IS (1991) Micellar electrokinetic capillary chromatography of illicit drug substances. Anal Chem 63(8):823–827
Iwamuro Y, Iio-Ishimaru R, Chinaka S, Takayama N, Kodama S, Hayakawa K (2010) Reproducible chiral capillary electrophoresis of methamphetamine and its related compounds using a chemically modified capillary having diol groups. Forensic Toxicol 28(1):19–24
Iio R, Chinaka S, Tanaka S, Takayamaa N, Hayakawab K (2003) Simultaneous chiral determination of methamphetamine and its metabolites in urine by capillary electrophoresis-mass spectrometry. Analyst 128:646–650
Iio R, Chinaka S, Takayama N, Hayakawa K (2005) Simultaneous chiral analysis of methamphetamine and related compounds by capillary electrophoresis/mass spectrometry using anionic cyclodextrin. Anal Sci 21(1):15–19
Iwata YT, Kanamori T, Ohmae Y, Tsujikawa K, Inoue H, Kishi T (2003) Chiral analysis of amphetamine-type stimulants using reversed-polarity capillary electrophoresis/positive ion electrospray ionization tandem mass spectrometry. Electrophoresis 24(11):1770–1776
Iio R, Chinaka S, Takayama N, Hayakawa K (2005) Simultaneous chiral analysis of methamphetamine and its metabolites by capillary electrophoresis/mass spectrometry with direct injection of urine. J Health Sci 51(6):693–701
Liotta E, Gottardo R, Seri C, Rimondo C, Miksik I, Serpelloni G, Tagliaro F (2012) Rapid analysis of caffeine in “smart drugs” and “energy drinks” by microemulsion electrokinetic chromatography (MEEKC). Forensic Sci Int 220(1–3):279–283
Lurie IS, Meyers RP, Conver TS (1998) Capillary electrochromatography of cannabinoids. Anal Chem 70(15):3255–3260
Ho Y-H, Wang C-C, Hsiao Y-T, Ko W-K, Wu S-M (2013) Analysis of ten abused drugs in urine by large volume sample stacking–sweeping capillary electrophoresis with an experimental design strategy. J Chromatogr A 1295:136–141
Rittgen J, Pütz M, Zimmermann R (2012) Identification of fentanyl derivatives at trace levels with nonaqueous capillary electrophoresis-electrospray-tandem mass spectrometry (MSn, n = 2, 3): Analytical method and forensic applications. Electrophoresis 33(11):1595–1605
Pütz M, Martin N Application of CE-ESI-MS in forensic toxicology: Identification of piperazine-derived designer drugs in Ecstasy tablets and of food colorants in illicit drugs. In: Pragst F, Aderjan R (eds) XV. GTFCh-Symposium 2007 Aktuelle Beiträge zur Forensischen und Klinischen Toxikologie, Bad Vibel, 2008. pp 487–501
Lurie IS, Hays PA, Parker K (2004) Capillary electrophoresis analysis of a wide variety of seized drugs using the same capillary with dynamic coatings. Electrophoresis 25(10–11):1580–1591
Lurie IS, Hays PA, Garcia AE, Panicker S (2004) Use of dynamically coated capillaries for the determination of heroin, basic impurities and adulterants with capillary electrophoresis. J Chromatogr A 1034(1–2):227–235
Wen T, Zhao X, Luo G, Wang J, Wang Y, Yao B, Zhao J, Zhu J, Yu Z (2007) Comparison of microemulsion electrokinetic chromatography and solvent modified micellar electrokinetic chromatography on rapid separation of heroin, amphetamine and their basic impurities. Talanta 71(2):854–860
Posch TN, Müller A, Schulz W, Pütz M, Huhn C (2012) Implementation of a design of experiments to study the influence of the background electrolyte on separation and detection in non-aqueous capillary electrophoresis–mass spectrometry. Electrophoresis 33(4):583–598
Lurie IS, Panicker S, Hays PA, Garcia AD, Geer BL (2003) Use of dynamically coated capillaries with added cyclodextrins for the analysis of opium using capillary electrophoresis. J Chromatogr A 984(1):109–120
Meng L, Wang B, Luo F, Shen G, Wang Z, Guo M (2011) Application of dispersive liquid–liquid microextraction and CE with UV detection for the chiral separation and determination of the multiple illicit drugs on forensic samples. Forensic Sci Int 209(1–3):42–47
Lim J-T, Zare RN, Bailey CG, Rakestraw DJ, Yan C (2000) Separation of related opiate compounds using capillary electrochromatography. Electrophoresis 21(4):737–742
Aturki Z, D’Orazio G, Rocco A, Bortolotti F, Gottardo R, Tagliaro F, Fanali S (2010) CEC-ESI ion trap MS of multiple drugs of abuse. Electrophoresis 31(7):1256–1263
Aturki Z, D’Orazio G, Fanali S, Rocco A, Bortolotti F, Gottardo R, Tagliaro F (2009) Capillary electrochromatographic separation of illicit drugs employing a cyano stationary phase. J Chromatogr A 1216(17):3652–3659
Kohler I, Schappler J, Rudaz S (2013) Highly sensitive capillary electrophoresis-mass spectrometry for rapid screening and accurate quantitation of drugs of abuse in urine. Anal Chim Acta 780:101–109
Wey AB, Zhang C-X, Thormann W (1999) Head-column field-amplified sample stacking in binary system capillary electrophoresis: preparation of extracts for determination of opioids in microliter amounts of body fluids. J Chromatogr A 853(1–2):95–106
Lurie IS, Jason Bethea M, McKibben TD, Hays PA, Pellegrini P, Sahai R, Garcia AD, Weinberger R (2001) Use of dynamically coated capillaries for the routine analysis of methamphetamine, amphetamine, MDA, MDMA, MDEA, and cocaine using capillary electrophoresis. J Forensic Sci 46(5):1025–1032
Unger M, Stöckigt D, Belder D, Stöckigt J (1997) General approach for the analysis of various alkaloid classes using capillary electrophoresis and capillary electrophoresis-mass spectrometry. J Chromatogr A 767(1–2):263–276
Posch TN, Martin N, Pütz M, Huhn C (2012) Nonaqueous capillary electrophoresis–mass spectrometry: a versatile, straightforward tool for the analysis of alkaloids from psychoactive plant extracts. Electrophoresis 33(11):1557–1566
Lurie IS, Conver TS, Ford VL (1998) Simultaneous separation of acidic, basic, and neutral organic compounds, including strong and moderate acids and bases, by capillary electrochromatography. Anal Chem 70(21):4563–4569
Tagliaro F, Bortolotti F (2006) Recent advances in the applications of CE to forensic sciences (2001–2004). Electrophoresis 27(1):231–243
Tagliaro F, Bortolotti F (2008) Recent advances in the applications of CE to forensic sciences (2005–2007). Electrophoresis 29(1):260–268
Tagliaro F, Pascali J, Fanigliulo A, Bortolotti F (2010) Recent advances in the application of CE to forensic sciences: a update over years 2007–2009. Electrophoresis 31(1):251–259
Pascali JP, Bortolotti F, Tagliaro F (2012) Recent advances in the application of CE to forensic sciences, an update over years 2009–2011. Electrophoresis 33(1):117–126
Riekkola M-L, Jönsson JÅ, Smith RM (2004) Terminology for analytical capillary electromigration techniques. Pure Appl Chem 76(2):443–451
Tagliaro F, Manetto G, Crivellente F, Smith FP (1998) A brief introduction to capillary electrophoresis. Forensic Sci Int 92(2–3):75–88
Lauer HH, Rozing G (eds) High Performance Capillary Electrophoresis - A Primer. Agilent Technologies
Engelhardt H, Beck W, Schmitt T, Gutnikov G (1996) Capillary electrophoresis: Methods and potentials. Vieweg, Wiesbaden
Tagliaro F, Smith FP (1996) Forensic capillary electrophoresis. TrAC Trends Anal Chem 15(10):513–525
Tagliaro F, Bortolotti F, Pascali J (2007) Current role of capillary electrophoretic/electrokinetic techniques in forensic toxicology. Anal Bioanal Chem 388(7):1359–1364
Cruces-Blanco C, García-Campaña AM (2012) Capillary electrophoresis for the analysis of drugs of abuse in biological specimens of forensic interest. TrAC Trends Anal Chem 31:85–95
Smyth WF, Brooks P (2004) A critical evaluation of high performance liquid chromatography-electrospray ionisation-mass spectrometry and capillary electrophoresis- electrospray-mass spectrometry for the detection and determination of small molecules of significance in clinical and forensic science. Electrophoresis 25(10–11):1413–1446
Fanigliulo A, Bortolotti F, Pascali J, Tagliaro F (2008) Chapter 15 Forensic toxicological screening with capillary electrophoresis and related techniques. In: Bogusz MJ (ed) Handbook of analytical separations, vol 6. Elsevier Science B.V, Amsterdam, pp 513–534
Petersen JR, Okorodudu AO, Mohammad A, Payne DA (2003) Capillary electrophoresis and its application in the clinical laboratory. Clin Chim Acta 330(1–2):1–30
Smyth WF, McClean S (1998) A critical evaluation of the application of capillary electrophoresis to the detection and determination of 1,4-benzodiazepine tranquilizers in formulations and body materials. Electrophoresis 19(16–17):2870–2882
Smyth WF (2006) Recent applications of capillary electrophoresis-electrospray ionisation-mass spectrometry in drug analysis. Electrophoresis 27(11):2051–2062
Smyth WF (2005) Recent applications of capillary electrophoresis-electrospray ionisation-mass spectrometry in drug analysis. Electrophoresis 26(7–8):1334–1357
Northrop DM, McCord B, Butler JM (1994) Forensic applications of capillary electrophoresis. J Capillary Electrophor 001(2):158–168
Bjørnsdottir I, Tjørnelund J, Hansen SH (1998) Nonaqueous capillary electrophoresis - its applicability in the analysis of food, pharmaceuticals and biological fluids. Electrophoresis 19(12):2179–2186
Lurie IS (1998) Capillary electrophoresis of illicit drug seizures. Forensic Sci Int 92(2–3):125–136
von Heeren F, Thormann W (1997) Capillary electrophoresis in clinical and forensic analysis. Electrophoresis 18(12–13):2415–2426
Lemos NP, Bortolotti F, Manetto G, Anderson RA, Cittadini F, Tagliaro F (2001) Capillary electrophoresis: a new tool in forensic medicine and science. Sci Justice 41(3):203–210
Deyl Z, Mikik I, Tagliaro F (1998) Advances in capillary electrophoresis. Forensic Sci Int 92(2–3):89–124
Thormann W, Aebi Y, Lanz M, Caslavska J (1998) Capillary electrophoresis in clinical toxicology. Forensic Sci Int 92(2–3):157–183
Manetto G, Crivellente F, Tagliaro F (2000) Capillary electrophoresis: a new analytical tool for forensic toxicologists. Ther Drug Monit 22(1):84–88
Boone CM, Franke J-P, de Zeeuw RA, Ensing K (1999) Evaluation of capillary electrophoretic techniques towards systematic toxicological analysis. J Chromatogr A 838(1–2):259–272
Anastos N, Barnett NW, Lewis SW (2005) Capillary electrophoresis for forensic drug analysis: a review. Talanta 67(2):269–279
Cruces-Blanco C, Gámiz–Gracia L, García-Campaña AM (2007) Applications of capillary electrophoresis in forensic analytical chemistry. TrAC Trends Anal Chem 26(3):215–226
Thormann W, Molteni S, Caslavska J, Schmutz A (1994) Clinical and forensic applications of capillary electrophoresis. Electrophoresis 15(1):3–12
Thormann W, Caslavska J (1998) Capillary electrophoresis in drug analysis. Electrophoresis 19(16–17):2691–2694
Plaut O, Staub C (2002) Capillary electrophoresis in forensic toxicology. CHIMIA Int J Chem 56(3):96–100
Porras SP, Riekkola M-L, Kenndler E (2003) The principles of migration and dispersion in capillary zone electrophoresis in nonaqueous solvents. Electrophoresis 24(10):1485–1498
Porras SP, Riekkola M-L, Kenndler E (2001) Electrophoretic mobilities of cationic analytes in non-aqueous methanol, acetonitrile and their mixtures - influence of ionic strength and ion-pair formation. J Chromatogr A 924:31–42
Porras SP, Kenndler E (2004) Capillary zone electrophoresis in non-aqueous solutions: pH of the background electrolyte. J Chromatogr A 1037(1–2):455–465
Porras SP, Kenndler E (2005) Are the asserted advantages of organic solvents in capillary electrophoresis real? A critical discussion. Electrophoresis 26(17):3203–3220
Geiser L, Veuthey J-L (2009) Non-aqueous capillary electrophoresis 2005–2008. Electrophoresis 30(1):36–49
Riekkola M-L, Jussila M, Porras SP, Valko IE (2000) Non-aqueous capillary electrophoresis. J Chromatogr A 892(1–2):155–170
Szumski M, Buszewski B (2013) Non-aqueous capillary electrophoresis. In: Buszewski B, Dziubakiewicz E, Szumski M (eds) Electromigration techniques, vol 105, Springer series in chemical physics. Springer, Berlin-Heidelberg, pp 203–213
Bjørnsdottir I, HonoréHansen S (1995) Comparison of separation selectivity in aqueous and non-aqueous capillary electrophoresis. J Chromatogr A 711(2):313–322
Amini A (2001) Recent developments in chiral capillary electrophoresis and applications of this technique to pharmaceutical and biomedical analysis. Electrophoresis 22(15):3107–3130
Chankvetadze B (1997) Separation selectivity in chiral capillary electrophoresis with charged selectors. J Chromatogr A 792(1–2):269–295
Pyell U (2006) Electrokinetic chromatography: theory, instrumentation, and applications. John Wiley & Sons, Chichester
Somsen GW, Mol R, de Jong GJ (2003) On-line micellar electrokinetic chromatography–mass spectrometry: feasibility of direct introduction of non-volatile buffer and surfactant into the electrospray interface. J Chromatogr A 1000(1–2):953–961
Watarai H (1991) Microemulsion capillary electrophoresis. Chem Lett 20(3):391–394
Marsh A, Altria K, Clark B (2007) Microemulsion electrokinetic chromatography. In: Electrokinetic chromatography. John Wiley & Sons, Ltd, Hoboken, pp 115–135
Yang H, Ding Y, Cao J, Li P (2013) Twenty-one years of microemulsion electrokinetic chromatography (1991–2012): a powerful analytical tool. Electrophoresis 34(9–10):1273–1294
Ryan R, Donegan S, Power J, McEvoy E, Altria K (2009) Recent advances in the methodology, optimisation and application of MEEKC. Electrophoresis 30(1):65–82
Altria KD, Mahuzier P-E, Clark BJ (2003) Background and operating parameters in microemulsion electrokinetic chromatography. Electrophoresis 24(3):315–324
Hansen SH, Sheribah ZA (2005) Comparison of CZE, MEKC, MEEKC and non-aqueous capillary electrophoresis for the determination of impurities in bromazepam. J Pharm Biomed Anal 39(1–2):322–327
Mistry K, Krull I, Grinberg N (2002) Capillary electrochromatography: an alternative to HPLC and CE. J Sep Sci 25(15–17):935–958
Bartle KD, Myers P (eds) (2001) Capillary electrochromatography. Royal Society of Chemistry, Cambridge
Deyl Z, Svec F (eds) (2001) Capillary electrochromatography, Journal of chromatography library. Elsevier, Amsterdam
Boček P (1981) Analytical isotachophoresis. In: Analytical Problems, vol 95, Topics in Current Chemistry. Springer, Berlin Heidelberg, pp 131–177
Bocek P (1988) Analytical isotachophoresis. Electrophoresis library. VCH Verl. Ges., Weinheim
Everaerts FM, Becker JL, Verheggen TPEM (1976) Isotachophoresis: theory, instrumentation, and applications, vol 6, Journal of chromatography library. Elsevier Scientific Pub. Co, Amsterdam
Danková M, Kaniansky D, Fanali S, Iványi F (1999) Capillary zone electrophoresis separations of enantiomers present in complex ionic matrices with on-line isotachophoretic sample pretreatment. J Chromatogr A 838(1–2):31–43
Tomás-Barberán FA (1995) Capillary electrophoresis: a new technique in the analysis of plant secondary metabolites. Phytochem Anal 6(4):177–192
Frost M, Köhler H (1998) Analysis of lysergic acid diethylamide: comparison of capillary electrophoresis with laser-induced fluorescence (CE-LIF) with conventional techniques. Forensic Sci Int 92(2–3):213–218
Huhn C, Pütz M, Martin N, Dahlenburg R, Pyell U (2005) Determination of tryptamine derivatives in illicit synthetic drugs by capillary electrophoresis and ultraviolet laser-induced fluorescence detection. Electrophoresis 26(12):2391–2401
Bishop SC, Lerch M, McCord BR (2007) Detection of nitrated benzodiazepines by indirect laser-induced fluorescence detection on a microfluidic device. J Chromatogr A 1154(1–2):481–484
Bailey CG, Wallenborg SR (2000) Indirect laser-induced fluorescence detection of explosive compounds using capillary electrochromatography and micellar electrokinetic chromatography. Electrophoresis 21(15):3081–3087
Melanson JE, Boulet CA, Lucy CA (2001) Indirect laser-induced fluorescence detection for capillary electrophoresis using a violet diode laser. Anal Chem 73(8):1809–1813
Wallenborg SR, Bailey CG (2000) Separation and detection of explosives on a microchip using micellar electrokinetic chromatography and indirect laser-induced fluorescence. Anal Chem 72(8):1872–1878
Páez X, Hernández L (2001) Biomedical applications of capillary electrophoresis with laser-induced fluorescence detection. Biopharm Drug Dispos 22(7–8):273–289
Swinney K, Bornhop DJ (2000) Detection in capillary electrophoresis. Electrophoresis 21(7):1239–1250
Zemann AJ, Schnell E, Volgger D, Bonn GK (1998) Contactless conductivity detection for capillary electrophoresis. Anal Chem 70(3):563–567
Vio L, Crétier G, Chartier F, Geertsen V, Gourgiotis A, Isnard H, Rocca J-L (2012) Separation and analysis of lanthanides by isotachophoresis coupled with inductively coupled plasma mass spectrometry. Talanta 99:586–593
Schmitt-Kopplin P, Frommberger M (2003) Capillary electrophoresis - mass spectrometry: 15 years of developments and applications. Electrophoresis 24(22–23):3837–3867
Reinhoud NJ, Schroder E, Tjaden UR, Niessen WMA, de Brauw MCTN, Van der Greef J (1990) Static and scanning array detection in capillary electrophoresis-mass spectrometry. J Chromatogr A 516(1):147–155
Verheij ER, Tjaden UR, Niessen WMA, Van der Greef J (1991) Pseudo-electrochromatography-mass spectrometry: a new alternative. J Chromatogr A 554(1–2):339–349
Chang SY, Yeung ES (1997) Laser vaporization/ionization interface for capillary electrophoresis-time-of-flight mass spectrometry. Anal Chem 69(13):2251–2257
Hirabayashi Y, Hirabayashi A, Koizumi H (1999) A sonic spray interface for capillary electrophoresis/mass spectrometry. Rapid Commun Mass Spectrom 13(8):712–715
Gusev AI (2000) Interfacing matrix-assisted laser desorption/ionization mass spectrometry with column and planar separations. Fresenius J Anal Chem 366(6–7):691–700
Musyimi Harrison K, Guy J, Narcisse Damien A, Soper Steven A, Murray Kermit K (2005) Direct coupling of polymer-based microchip electrophoresis to online MALDI-MS using a rotating ball inlet. Electrophoresis 26(24):4703–4710
Preisler J, Foret F, Karger BL (1998) On-Line MALDI-TOF MS using a continuous vacuum deposition interface. Anal Chem 70(24):5278–5287
Maxwell EJ, Chen DDY (2008) Twenty years of interface development for capillary electrophoresis–electrospray ionization–mass spectrometry. Anal Chim Acta 627(1):25–33
Whitt JT, Moini M (2003) Capillary electrophoresis to mass spectrometry interface using a porous junction. Anal Chem 75(9):2188–2191
Maxwell EJ, Zhong X, Zhang H, van Zeijl N, Chen DDY (2010) Decoupling CE and ESI for a more robust interface with MS. Electrophoresis 31(7):1130–1137
Schmitt-Kopplin P, Englmann M (2005) Capillary electrophoresis - mass spectrometry: survey on developments and applications 2003–2004. Electrophoresis 26(7–8):1209–1220
Scriba GKE (2007) Nonaqueous capillary electrophoresis-mass spectrometry. J Chromatogr A 1159(1–2):28–41
Av B, Nicholson G, Bayer E (2001) Recent advances in capillary electrophoresis/electrospray-mass spectrometry. Electrophoresis 22(7):1251–1266
Unger M, Stöckigt J (1997) Improved detection of alkaloids in crude extracts applying capillary electrophoresis with field amplified sample injection. J Chromatogr A 791(1–2):323–331
Bjørnsdottir I, Hansen SH (1995) Determination of opium alkaloids in crude opium using non-aqueous capillary electrophoresis. J Pharm Biomed Anal 13(12):1473–1481
Bjørnsdottir I, Hansen SH (1997) Comparison of aqueous and non-aqueous capillary electrophoresis for quantitative determination of morphine in pharmaceuticals. J Pharm Biomed Anal 15(8):1083–1089
Bjørnsdottir I, Hansen SH (1999) Fast separation of 16 seizure drug substances using non-aqueous capillary electrophoresis. J Biochem Bioph Methods 38(2):155–161
Bjørnsdottir I, Hansen SH (1995) Determination of opium alkaloids in opium by capillary electrophoresis. J Pharm Biomed Anal 13(4–5):687–693
Nielsen MKK, Johansen SS, Dalsgaard PW, Linnet K (2010) Simultaneous screening and quantification of 52 common pharmaceuticals and drugs of abuse in hair using UPLC–TOF-MS. Forensic Sci Int 196(1–3):85–92
Badawi N, Simonsen KW, Steentoft A, Bernhoft IM, Linnet K (2009) Simultaneous screening and quantification of 29 drugs of abuse in oral fluid by solid-phase extraction and ultraperformance LC-MS/MS. Clin Chem 55(11):2004–2018
Dresen S, Ferreirós N, Gnann H, Zimmermann R, Weinmann W (2010) Detection and identification of 700 drugs by multi-target screening with a 3200 Q TRAP LC-MS/MS system and library searching. Anal Bioanal Chem 396(7):2425–2434
Pyell U (2007) Theory of electrokinetic chromatography. In: Electrokinetic chromatography. John Wiley & Sons, Ltd, Hoboken, pp 1–31
Terabe S (1992) Selectivity manipulation in micellar electrokinetic chromatography. J Pharm Biomed Anal 10(10–12):705–715
Beckers JL, Boček P (2000) Sample stacking in capillary zone electrophoresis: principles, advantages and limitations. Electrophoresis 21(14):2747–2767
Malá Z, Křivánková L, Gebauer P, Boček P (2007) Contemporary sample stacking in CE: a sophisticated tool based on simple principles. Electrophoresis 28(1–2):243–253
Huhn C (2007) Optimierung von Probeninjektion und Trennung in der Kapillarelektrophorese, der micellaren elektrokinetischen Chromatographie und der Säulenkopplung Isotachophorese-Kapillarelektrophorese zur Analyse komplexer Proben in der forensischen Analytik. Philipps-Universität Marburg, Marburg an der Lahn
Himes S, Concheiro M, Scheidweiler K, Huestis M (2014) Validation of a novel method to identify in utero ethanol exposure: simultaneous meconium extraction of fatty acid ethyl esters, ethyl glucuronide, and ethyl sulfate followed by LC-MS/MS quantification. Anal Bioanal Chem 406(7):1945–1955
Albermann ME, Musshoff F, Madea B (2012) A high-performance liquid chromatographic–tandem mass spectrometric method for the determination of ethyl glucuronide and ethyl sulfate in urine validated according to forensic guidelines. J Chromatogr Sci 50(1):51–56
Cherkaoui S, Bekkouche K, Christen P, Veuthey J-L (2001) Non-aqueous capillary electrophoresis with diode array and electrospray mass spectrometric detection for the analysis of selected steroidal alkaloids in plant extracts. J Chromatogr A 922(1–2):321–328
Huhn C, Pütz M, Holthausen I, Pyell U (2008) Separation of very hydrophobic analytes by micellar electrokinetic chromatography. Electrophoresis 29(2):526–537
Poole CF, Poole SK (1997) Interphase model for retention and selectivity in micellar electrokinetic chromatography. J Chromatogr A 792(1–2):89–104
Poole SK, Poole CF (1997) Characterization of surfactant selectivity in micellar electrokinetic chromatography. Analyst 122:267–274
Poole CF, Poole SK, Abraham MH (1998) Recommendations for the determination of selectivity in micellar electrokinetic chromatography. J Chromatogr A 798(1–2):207–222
Cherkaoui S, Mateus L, Christen P, Veuthey J (1999) Nonaqueous capillary electrophoresis for the analysis of selected tropane alkaloids in a plant extract. Chromatographia 49(1):54–60
Cherkaoui S, Varesio E, Christen P, Veuthey J-L (1998) Selectivity manipulation using nonaqueous capillary electrophoresis. Application to tropane alkaloids and amphetamine derivatives. Electrophoresis 19(16–17):2900–2906
Vindevogel J, Sandra P (1992) Introduction to micellar electrokinetic chromatography. Hüthig, Heidelberg
Lucangioli SE, Hermida LG, Tripodi VP, Rodríguez VG, López EE, Rouge PD, Carducci CN (2000) Analysis of cis–trans isomers and enantiomers of sertraline by cyclodextrin-modified micellar electrokinetic chromatography. J Chromatogr A 871(1–2):207–215
Huhn C, Pütz M, Pyell U (2008) Separation of very hydrophobic analytes by MEKC. II. Carbon number equivalents as analyte descriptors – influence of the composition of the separation electrolyte. Electrophoresis 29:567–575
Bjørnsdottir I, Hansen SH, Terabe S (1996) Chiral separation in non-aqueous media by capillary electrophoresis using the ion-pair principle. J Chromatogr A 745(1–2):37–44
Hansen SH, Bjørnsdottir I, Tjørnelund J (1997) Separation of cationic cis-trans (Z-E) isomers and diastereoisomers using non-aqueous capillary electrophoresis. J Chromatogr A 792(1–2):49–55
Iwata YT, Inoue H, Kuwayama K, Kanamori T, Tsujikawa K, Miyaguchi H, Kishi T (2006) Forensic application of chiral separation of amphetamine-type stimulants to impurity analysis of seized methamphetamine by capillary electrophoresis. Forensic Sci Int 161(2–3):92–96
Lee JS, Yang WK, Han EY, Lee SY, Park YH, Lim MA, Chung HS, Park JH (2007) Monitoring precursor chemicals of methamphetamine through enantiomer profiling. Forensic Sci Int 173(1):68–72
Inoue H, Iwata YT, Kuwayama K (2008) Characterization and profiling of methamphetamine seizures. J Health Sci 54(6):615–622
Fanali S (2000) Enantioselective determination by capillary electrophoresis with cyclodextrins as chiral selectors. J Chromatogr A 875(1–2):89–122
Zaugg S, Thormann W (2000) Enantioselective determination of drugs in body fluids by capillary electrophoresis. J Chromatogr A 875(1–2):27–41
Caslavska J, Thormann W (2011) Stereoselective determination of drugs and metabolites in body fluids, tissues and microsomal preparations by capillary electrophoresis (2000–2010). J Chromatogr A 1218(4):588–601
Fillet M, Servais A-C, Crommen J (2003) Effects of background electrolyte composition and addition of selectors on separation selectivity in nonaqueous capillary electrophoresis. Electrophoresis 24(10):1499–1507
Blanco M, Valverde I (2003) Choice of chiral selector for enantioseparation by capillary electrophoresis. TrAC Trends Anal Chem 22(7):428–439
Sabbah S, Süß F, Scriba GKE (2001) pH-dependence of complexation constants and complex mobility in capillary electrophoresis separations of dipeptide enantiomers. Electrophoresis 22(15):3163–3170
Sabbah S, Scriba GKE (2000) Influence of the structure of cyclodextrins and amino acid sequence of dipeptides and tripeptides on the pH-dependent reversal of the migration order in capillary electrophoresis. J Chromatogr A 894(1–2):267–272
Süß F, Poppitz W, de Griend CES-v, Scriba GKE (2001) Influence of the amino acid sequence and nature of the cyclodextrin on the separation of small peptide enantiomers by capillary electrophoresis using randomly substituted and single isomer sulfated and sulfonated cyclodextrins. Electrophoresis 22(12):2416–2423
Sidamonidze N, Süß F, Poppitz W, Scriba GKE (2001) Influence of the amino acid sequence and nature of the cyclodextrin on the separation of small peptide enantiomers by capillary electrophoresis using α-, β-, and γ-cyclodextrin and the corresponding hydroxypropyl derivatives. J Sep Sci 24(9):777–783
Loukas YL, Sabbah S, Scriba GKE (2001) Method development and validation for the chiral separation of peptides in the presence of cyclodextrins using capillary electrophoresis and experimental design. J Chromatogr A 931(1–2):141–152
Sabbah S, Scriba GKE (2001) Separation of dipeptide and tripeptide enantiomers in capillary electrophoresis using carboxymethyl-β-cyclodextrin and succinyl-β-cyclodextrin: influence of the amino acid sequence, nature of the cyclodextrin and pH. Electrophoresis 22(7):1385–1393
Süß F, Kahle C, Holzgrabe U, Scriba GKE (2002) Studies on the chiral recognition of peptide enantiomers by neutral and sulfated β-cyclodextrin and heptakis-(2,3-di-O-acetyl)-β-cyclodextrin using capillary electrophoresis and nuclear magnetic resonance. Electrophoresis 23(9):1301–1307
Rudaz S, Calleri E, Geiser L, Cherkaoui S, Prat J, Veuthey J-L (2003) Infinite enantiomeric resolution of basic compounds using highly sulfated cyclodextrin as chiral selector in capillary electrophoresis. Electrophoresis 24(15):2633–2641
Dieckmann S, Pütz M, Pyell U (2008) Enantiomeric identification of chiral drugs, adulterants and impurites by capillary electrophoresis-ESI-mass spectrometry (CE-ESI-MS). Paper presented at the XVI. Symposium der GTFCh, Mosbach
Cherkaoui S, Rudaz S, Varesio E, Veuthey J-L (2001) On-line capillary electrophoresis-electrospray mass spectrometry for the stereoselective analysis of drugs and metabolites. Electrophoresis 22(15):3308–3315
Jung B, Caslavska J, Thormann W (2009) Determination of ethyl glucuronide in human serum by capillary zone electrophoresis and an immunoassay. J Sep Sci 32(20):3497–3506
Schmitt T, Engelhardt H (1995) Optimization of enantiomeric separations in capillary electrophoresis by reversal of the migration order and using different derivatized cyclodextrins. J Chromatogr A 697(1–2):561–570
Caslavska J, Jung B, Thormann W (2011) Confirmation analysis of ethyl glucuronide and ethyl sulfate in human serum and urine by CZE-ESI-MSn after intake of alcoholic beverages. Electrophoresis 32(13):1760–1764
Iwata YT, Garcia A, Kanamori T, Inoue H, Kishi T, Lurie IS (2002) The use of a highly sulfated cyclodextrin for the simultaneous chiral separation of amphetamine-type stimulants by capillary electrophoresis. Electrophoresis 23(9):1328–1334
Dahlén J, von Eckardstein S (2006) Development of a capillary zone electrophoresis method including a factorial design and simplex optimisation for analysis of amphetamine, amphetamine analogues, cocaine, and heroin. Forensic Sci Int 157(2–3):93–105
Varesio E, Gauvrit JY, Longeray R, Lantéri P, Veuthey JL (1999) Optimization of fast CE analyses of ecstasy derivatives by use of experimental designs. Chromatographia 50(3–4):195–201
Tagliaro F, Antonioli C, Moretto S, Archetti S, Ghielmi S, Marigo M (1993) High-sensitivity low-cost methods for determination of cocaine in hair: high-performance liquid chromatography and capillary electrophoresis. Forensic Sci Int 63(1–3):227–238
Weinmann W, Schaefer P, Thierauf A, Schreiber A, Wurst FM (2004) Confirmatory analysis of ethylglucuronide in urine by liquid-chromatography/electrospray ionization/tandem mass spectrometry according to forensic guidelines. J Am Soc Mass Spectrom 15(2):188–193
Jung B, Caslavska J, Thormann W (2008) Determination of ethyl sulfate in human serum and urine by capillary zone electrophoresis. J Chromatogr A 1206(1):26–32
Krivankova L, Caslavska J, Malaskova H, Gebauer P, Thormann W (2005) Analysis of ethyl glucuronide in human serum by capillary electrophoresis with sample self-stacking and indirect detection. J Chromatogr A 1081(1):2–8
Nováková M, Křivánková L (2008) Determination of ethyl glucuronide in human serum by hyphenation of capillary isotachophoresis and zone electrophoresis. Electrophoresis 29(8):1694–1700
Tagliaro F, Manetto G, Crivellente F, Scarcella D, Marigo M (1998) Hair analysis for abused drugs by capillary zone electrophoresis with field-amplified sample stacking. Forensic Sci Int 92(2–3):201–211
Zhang C-X, Thormann W (1996) Head-column field-amplified sample stacking in binary system capillary electrophoresis: a robust approach providing over 1000-fold sensitivity enhancement. Anal Chem 68(15):2523–2532
Zhang C-X, Thormann W (1998) Head-column field-amplified sample stacking in binary system capillary electrophoresis. 2. Optimization with a preinjection plug and application to micellar electrokinetic chromatography. Anal Chem 70(3):540–548
Gottardo R, Bortolotti F, De Paoli G, Pascali JP, Miksik I, Tagliaro F (2007) Hair analysis for illicit drugs by using capillary zone electrophoresis-electrospray ionization-ion trap mass spectrometry. J Chromatogr A 1159(1–2):185–189
Guzman NA, Blanc T, Phillips TM (2008) Immunoaffinity capillary electrophoresis as a powerful strategy for the quantification of low-abundance biomarkers, drugs, and metabolites in biological matrices. Electrophoresis 29(16):3259–3278
Thormann W, Lanz M, Caslavska J, Siegenthaler P, Portmann R (1998) Screening for urinary methadone by capillary electrophoretic immunoassays and confirmation by capillary electrophoresis-mass spectrometry. Electrophoresis 19(1):57–65
Lanz M, Thormann W (1996) Characterization of the stereoselective metabolism of methadone and its primary metabolite via cyclodextrin capillary electrophoretic determination of their urinary enantiomers. Electrophoresis 17(12):1945–1949
Bao J, Regnier FE (1992) Ultramicro enzyme assays in a capillary electrophoretic system. J Chromatogr A 608(1–2):217–224
Wey AB, Caslavska J, Thormann W (2000) Analysis of codeine, dihydrocodeine and their glucuronides in human urine by electrokinetic capillary immunoassays and capillary electrophoresis-ion trap mass spectrometry. J Chromatogr A 895(1–2):133–146
Wey AB, Thormann W (2001) Capillary electrophoresis-electrospray ionization ion trap mass spectrometry for analysis and confirmation testing of morphine and related compounds in urine. J Chromatogr A 916(1–2):225–238
W-R- B, Perez SB, El-Khadra-Kluth N, Fritsch R, Hindorf G, Jacobsen-Bauer A, Klein B, Naujoks E, Standke U, Stein K, Westphal F, Zerell U (2012) Richtlinie zur qualitätssicherung bei forensisch-chemischen untersuchungen von betäubungs- und arzneimitteln. Toxichem Krimtech 79(3):42
Castaneda Penalvo G, Julien E, Fabre H (1996) Cross validation of capillary electrophoresis and high-performance liquid chromatography for cefotaxime and related impurities. Chromatographia 42(3–4):159–164
Sadeghipour F, Varesio E, Giroud C, Rivier L, Veuthey JL (1997) Analysis of amphetamines by capillary electrophoresis and liquid chromatography: application to drug seizures and cross-validation. Forensic Sci Int 86(1–2):1–13
Tagliaro F, Smith FP, Turrina S, Equisetto V, Marigo M (1996) Complementary use of capillary zone electrophoresis and micellar electrokinetic capillary chromatography for mutual confirmation of results in forensic drug analysis. J Chromatogr A 735(1–2):227–235
Schmitt-Kopplin P, Garmash AV, Kudryavtsev AV, Menzinger F, Perminova IV, Hertkorn N, Freitag D, Petrosyan VS, Kettrup A (2001) Quantitative and qualitative precision improvements by effective mobility-scale data transformation in capillary electrophoresis analysis. Electrophoresis 22(1):77–87
Schmitt-Kopplin P, Fekete A (2008) The CE way of thinking. In: Schmitt-Kopplin P (ed) Capillary electrophoresis, vol 384, Methods in molecular biology. Humana Press, Totowa, pp 611–629
Nevedomskaya E, Derks R, Deelder A, Mayboroda O, Palmblad M (2009) Alignment of capillary electrophoresis–mass spectrometry datasets using accurate mass information. Anal Bioanal Chem 395(8):2527–2533
Lewis AP, Cranny A, Harris NR, Green NG, Wharton JA, Wood RJK, Stokes KR (2013) Review on the development of truly portable and in-situ capillary electrophoresis systems. Meas Sci Technol 24(4):042001
Wallenborg SR, Lurie IS, Arnold DW, Bailey CG (2000) On-chip chiral and achiral separation of amphetamine and related compounds labeled with 4-fluoro-7-nitrobenzofurazane. Electrophoresis 21(15):3257–3263
Fernández-la-Villa A, Sánchez-Barragán D, Pozo-Ayuso DF, Castaño-Álvarez M (2012) Smart portable electrophoresis instrument based on multipurpose microfluidic chips with electrochemical detection. Electrophoresis 33(17):2733–2742
da Costa ET, Neves CA, Hotta GM, Vidal DTR, Barros MF, Ayon AA, Garcia CD, do Lago CL (2012) Unmanned platform for long-range remote analysis of volatile compounds in air samples. Electrophoresis 33(17):2650–2659
Blanco GA, Nai YH, Hilder EF, Shellie RA, Dicinoski GW, Haddad PR, Breadmore MC (2011) Identification of inorganic improvised explosive devices using sequential injection capillary electrophoresis and contactless conductivity detection. Anal Chem 83(23):9068–9075
Sarazin C, Delaunay N, Varenne A, Vial J, Costanza C, Eudes V, Minet J-J, Gareil P (2010) Identification and determination of inorganic anions in real extracts from pre- and post-blast residues by capillary electrophoresis. J Chromatogr A 1217(44):6971–6978
Sarazin C, Delaunay N, Costanza C, Eudes V, Gareil P (2013) On the use of capillary electrophoresis for the determination of inorganic anions and cations, and carbohydrates in residues collected after a simulated suicide bombing attack. Talanta 103:301–305
Kobrin E-G, Lees H, Fomitšenko M, Kubáň P, Kaljurand M (2014) Fingerprinting postblast explosive residues by portable capillary electrophoresis with contactless conductivity detection. Electrophoresis 35(8):1165–1172
Manetto G, Tagliaro F, Crivellente F, Pascali VL, Marigo M (2000) Field-amplified sample stacking - capillary zone electrophoresis applied to the analysis of opiate drugs in hair. Electrophoresis 21(14):2891–2898
Foret F, Thompson TJ, Vouros P, Karger BL, Gebauer P, Bocek P (1994) Liquid sheath effects on the separation of proteins in capillary electrophoresis/electrospray mass spectrometry. Anal Chem 66(24):4450–4458
Huhn C, Pyell U (2008) Separation of very hydrophobic analytes by micellar electrokinetic chromatography: IV. Modeling of the effective electrophoretic mobility from carbon number equivalents and octanol-water partition coefficients. J Chromatogr A 1198–1199:208–214
Reijenga JC, Verheggen TPEM, Martens JHPA, Everaerts FM (1996) Buffer capacity, ionic strength and heat dissipation in capillary electrophoresis. J Chromatogr A 744(1–2):147–153
Huhn C, Ramautar R, Wuhrer M, Somsen GW (2010) Relevance and use of capillary coatings in capillary electrophoresis–mass spectrometry. Anal Bioanal Chem 396:297–314
Kenndler E (1998) Dependence of analyte separation on electroosmotic flow in capillary zone electrophoresis: quantitative description by the reduced mobility. J Microcolumn Sep 10(3):273–279
Acknowledgments
We thank the Helmholtz Initiative and Networking Fund for financial support. This article was funded within the program “Forschung für die zivile Sicherheit” of the Federal Ministry of Education and Research (BMBF; 13 N12012). C.H. also thanks the German Excellence Initiative commissioned by the German Research Foundation (DFG).
Author information
Authors and Affiliations
Corresponding author
Additional information
ABC Highlights: authored by Rising Stars and Top Experts.
Rights and permissions
About this article
Cite this article
Posch, T.N., Pütz, M., Martin, N. et al. Electromigrative separation techniques in forensic science: combining selectivity, sensitivity, and robustness. Anal Bioanal Chem 407, 23–58 (2015). https://doi.org/10.1007/s00216-014-8271-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-014-8271-0