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The influence of different parameters on electrokinetic supercharging performance was evaluated using both univariated and multivariated optimization processes. The parameters studied were sample pH, concentration, and length of the leading and terminating electrolytes, electrokinetic injection of the sample and composition and hydrodynamic injection of the solvent plug. The leading electrolyte (50 mM NaCl) was hydrodynamically injected (50 mbar \u00d7 120 s) prior to the sample that was adjusted to pH 9.6 and electrokinetically injected at \u22128.5 kV for 300 s. The terminating electrolyte (100 mM of 2\u2010(cyclohexylamino) ethanesulphonic acid) was then hydrodynamically injected (50 mbar \u00d7 140 s). The results showed that this strategy enhanced detection sensitivity around 1050\u2010fold compared with normal hydrodynamic injection, providing detection limits ranging between 1.5 and 2.1 ng\/mL for standard samples with good repeatability in terms of peak area (values of relative standard deviation, %<jats:styled-content style=\"fixed-case\">RSD<\/jats:styled-content> &lt; 3). The applicability of the optimized method was demonstrated by the analysis of human urine samples spiked with the studied compounds at different concentration levels and further liquid\u2013liquid extraction step. The estimated detection limits obtained in the urine samples extract ranged between 8 and 15 ng\/mL.<\/jats:p>","DOI":"10.1002\/jssc.201200690","type":"journal-article","created":{"date-parts":[[2013,1,9]],"date-time":"2013-01-09T15:41:00Z","timestamp":1357746060000},"page":"524-531","source":"Crossref","is-referenced-by-count":23,"title":["Electrokinetic supercharging in <scp>CE<\/scp> for the separation and preconcentration of barbiturate drugs in urine samples"],"prefix":"10.1002","volume":"36","author":[{"given":"Igor","family":"Botello","sequence":"first","affiliation":[{"name":"Departament de Qu\u00edmica Anal\u00edtica i Qu\u00edmica Org\u00e0nica, Faculty of Chemistry Universitat Rovira i Virgili Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Francesc","family":"Borrull","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica Anal\u00edtica i Qu\u00edmica Org\u00e0nica, Faculty of Chemistry Universitat Rovira i Virgili Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Marta","family":"Calull","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica Anal\u00edtica i Qu\u00edmica Org\u00e0nica, Faculty of Chemistry Universitat Rovira i Virgili Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Carme","family":"Aguilar","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica Anal\u00edtica i Qu\u00edmica Org\u00e0nica, Faculty of Chemistry Universitat Rovira i Virgili Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2013,1,9]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.200790073"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1080\/10826070903430175"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0378-4347(97)00555-0"},{"key":"e_1_2_7_5_1","first-page":"777","volume":"33","author":"Zhao H. 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