Determination of valproic acid in human plasma using dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection

Document Type : Original Article

Authors

1 Liver and Gastrointestinal Diseases Research Center, Tabriz University of Medical Sciences, Tabriz, Iran

2 Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran

3 Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz, Iran

4 Pharmaceutical Analysis Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences, Tabriz, Iran

Abstract

Objective(s): Dispersive liquid-liquid microextraction coupled with gas chromatography (GC)-flame ionization detector was developed for the determination of valproic acid (VPA) in human plasma.
Materials and Methods: Using a syringe, a mixture of suitable extraction solvent (40 µl chloroform) and disperser (1 ml acetone) was quickly added to 10 ml of diluted plasma sample containing VPA (pH, 1.0; concentration of NaCl, 4% (w/v)), resulting in a cloudy solution. After centrifugation (6000 rpm for 6 min), an aliquot (1 µl) of the sedimented organic phase was removed using a 1-µl GC microsyringe and injected into the GC system for analysis. One variable at a time optimization method was used to study various parameters affecting the extraction efficiency of target analyte. Then, the developed method was fully validated for its accuracy, precision, recovery, stability, and robustness.
Results: Under the optimum extraction conditions, good linearity range was obtained for the calibration graph, with correlation coefficient higher than 0.998. Limit of detection and lower limit of quantitation were 3.2 and 6 μg/ml, respectively. The relative standard deviations of intra and inter-day analysis of examined compound were less than 11.5%. The relative recoveries were found in the range of 97 to 107.5%. Finally, the validated method was successfully applied to the analysis of VPA in patient sample.
Conclusion: The presented method has acceptable levels of precision, accuracy and relative recovery and could be used for therapeutic drug monitoring of VPA in human plasma.

Keywords

References

1. Macdonald RL, Kelly KM. Antiepileptic drug mechanisms of action. Epilepsia 1995; 36:S2–S12.
2. Johannessen CU, Johannessen SI. Valproate: past, present, and future. CNS Drug Rev 2003; 9:199–216.
3. Warner A, Privitera M, Bates D. Standards of laboratory practice: antiepileptic drug monitoring. Clin Chem 1998; 44:1085–1095.
4. Löscher W. Valproate: a reappraisal of its pharmacodynamic properties and mechanisms of action. Prog Neurobiol 1999; 58:31–59.
5. Arranz Peña MI. Rapid gas chromatographic determination of valproic acid in serum. J Chromatogr 1981; 225:459–462.
6. Kumps AH. Therapeutic drug monitoring: a comprehensive and critical review of analytical methods for anticonvulsive drugs. J Neurol 1982; 228:1–16.
7. Krasowski MD. Therapeutic drug monitoring of the newer anti-epilepsy medications. Pharmaceu-ticals 2010; 3:1909–1935.
8. Musenga A, Saracino MA, Sani G, Raggi MA. Antipsychotic and antiepileptic drugs in bipolar disorder: the importance of therapeutic drug monitoring. Curr Med Chem 2009; 16:1463–1481.
9. Kang J, Park YS, Kim SH, Kim SH, Jun MY. Modern methods for analysis of antiepileptic drugs in the biological fluids for pharmacokinetics, bioequival-ence and therapeutic drug monitoring. Korean J Physiol Pharmacol 2011; 15:67–81.
10.Regenthal R, Krueger M, Koeppel C, Preiss R. Drug Levels: therapeutic and toxic serum/plasma concentrations of common drugs. J Clin Monit Comput 1999; 15:529–544.
11.Amini H, Javan M, Ahmadiani A. Development and validation of a sensitive assay of valproic acid in human plasma by high-performance liquid chromatography without prior derivatization. J Chromatogr B 2006; 830:368–371.
12.Kushida K, Ishizaki T. Concurrent determination of valproic acid with other antiepileptic drugs by high-performance liquid chromatography. J Chromatogr 1985; 338:131–139.
13.Lin MC, Kou HS, Chen CC, Wu SM, Wu HL. Simple and sensitive fluorimetric liquid chromatography method for the determination of valproic acid in plasma. J Chromatogr B 2004; 810:169–172.
14.Wolf JH, Veenma-van der Duin L, Korf J. Automated analysis procedure for valproic acid in blood, serum and brain dialysate by high-performance liquid chromatography with bromomethylmethoxycoumarin as fluorescent label. J Chromatogr 1989; 487:496–502.
15.Jain D, Subbaiah G, Sanyal M, Shrivastav P. A high throughput and selective method for the estimation of valproic acid an antiepileptic drug in human plasma by tandem LC–MS/MS. Talanta 2007; 72:80–88.
16.Gao S, Miao H, Tao X, Jiang B, Xiao Y, Cai F, et al. LC–MS/MS method for simultaneous determination of valproic acid and major metabolites in human plasma. J Chromatogr B 2011; 879:1939–1944.
17. Cheng H, Liu Z, Blum W, Byrd JC, Klisovic R, Grever MR, et al. Quantification of valproic acid and its metabolite 2-propyl-4-pentenoic acid in human plasma using HPLC-MS/MS. J Chromatogr B 2007; 850:206–212.
18. Belin GK, Krähenbühl S, Hauser PC. Direct determination of valproic acid in biological fluids by capillary electrophoresis with contactless conductivity detection. J Chromatogr B 2007; 847:205–209.
19. Pham TTT, See HH, Morand R, Krähenbühl S, Hauser PC. Determination of free and total valproic acid in human plasma by capillary electrophoresis with contactless conductivity detection. J Chromatogr B 2012; 907:74–78.
20. Degel F, Heidrich R, Schmid RD, Weidemann G. Quantitative determination of valproic acid by means of gas chromatographic headspace analysis. Clin Chim Acta 1984; 139:29–36.
21. Cooreman S, Cuypers E, De Doncker M, Van Hee P, Uyttenbroeck W, Neels H. Comparison of three immunoassays and one GC-MS method for the determination of valproic acid. Immuno-Anal Biol Spe 2008; 23:240–244.
22. Ahmadkhaniha R, Rastkari N, Kobarfard F, Pakdaman H, Ahmadkhaniha O, Kebriaeezadeh A. An improved GC method for rapid analysis of valproic acid in human plasma without derivatization. Iran J Pharm Sci 2007; 9:37-42.
23. Deng C, Li N, Ji J, Yang B, Duan G, Zhang X. Development of water-phase derivatization           followed by solid-phase microextraction and gas chromatography/mass spectrometry for fast determination of valproic acid in human plasma. Rapid Commun Mass Spectrom 2006; 20:1281–1287.
24. Ho TS, Pedersen-Bjergaard S, Rasmussen KE. Liquid-phase microextraction of protein-bound drugs under non-equilibrium conditions. Analyst 2002; 127:608–613.
25. Krogh M, Johansen K, Tønnesen F, Rasmussen KE. Solid-phase microextraction for the determination of the free concentration of valproic acid in human plasma by capillary gas chromatography. J Chromatogr B 1995; 673:299–305.
26. Matin AA, Biparva P, Amanzadeh H, Farhadi K. Zinc/Aluminum layered double hydroxide–titanium dioxide composite nanosheet film as novel solid phase microextraction fiber for the gas chromatographic determination of valproic acid. Talanta 2013; 103:207–213.
27. Farajzadeh MA, Farhadi K, Matin AA, Hashemi P, Jouyban A. Headspace solid-phase microextraction-gas chromatography method for the determination of valproic acid in human serum, and formulations using hollow-fiber coated wire. Anal Sci 2009; 25:875–879.
28. Jahangiri S, Hatami M, Farhadi K, Bahram M. Hollow-fiber-based LPME as a reliable sampling method for gas chromatographic determination of pharmacokinetic parameters of valproic acid in rat plasma. Chromatographia 2013; 76:663–669.
29. Sobhi HR, Kashtiaray A, Farahani H, Abrahimpour F, Esrafili A. Quantitation of valproic acid in pharmaceutical preparations using dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection without prior derivatization. Drug Test Anal 2010; 2:362–366.
30. Namera A, Saito T. Recent advances in unique sample preparation techniques for bioanalysis. Bioanalysis 2013; 5:915–932.
31. Ashri NY, Abdel-Rehim M. Sample treatment based on extraction techniques in biological matrices. Bioanalysis 2011; 3:2003–2018.
32. Lord H, Pawliszyn J. Evolution of solid-phase microextraction technology. J Chromatogr A 2000; 885:153–193.
33. Arthur CL, Pawliszyn J. Solid phase microextraction with thermal desorption using fused silica optical fibers. Anal Chem 1990; 62:2145–2148.
34. Jeannot MA, Cantwell FF. Solvent microextraction into a single drop. Anal Chem 1996; 68:2236–2240.
35. He Y, Lee HK. Liquid-phase microextraction in a single drop of organic solvent by using a conventional microsyringe. Anal Chem 1997; 69:4634–4640.
36. Sarafraz -Yazdi A, Amiri A. Liquid-phase microextraction. Trends Anal Chem 2010; 29:1-14.
37. Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S. Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A 2006; 1116:1–9.
38. Berijani S, Assadi Y, Anbia M, Milani Hosseini MR, Aghaee E. Dispersive liquid-liquid microextraction combined with gas chromatography-flame photometric detection. Very simple, rapid and sensitive method for the determination of organophosphorus pesticides in water. J Chromatogr A 2006; 1123:1–9.
39. Volmut J, Matisová E, Pham Thi Ha. Simultaneous determination of six antiepileptic drugs by capillary gas chromatography. J Chromatogr B 1990; 527:428–435.
40. Shahdousti P, Mohammadi A, Alizadeh N. Determination of valproic acid in human serum and pharmaceutical preparations by headspace liquid-phase microextraction gas chromatography-flame ionization detection without prior derivatization. J Chromatogr B 2007; 850:128–133.
Iranian Journal of Basic Medical Sciences
Volume 18, Issue 10 - Serial Number 10
October 2015
Pages 979-988

Files

Share

How to cite

Statistics