AJAC  Vol.2 No.4 , August 2011
Trace Determination of Tamoxifen in Biological Fluids Using Hollow Fiber Liquid-Phase Microextraction Followed by High-Performance Liquid Chromatography-Ultraviolet Detection
Abstract: The applicability of hollow fiber liquid-phase microextraction (HF-LPME) combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) was evaluated for the extraction and determination of tamoxifen (TAM) in biological fluids including human urine and plasma. The drug was extracted from a 15 mL aqueous sample (source phase; SP) into an organic phase impregnated in the pores of the hollow fiber (membrane phase; MP) followed by the back-extraction into a second aqueous solution (receiving phase; RP) located in the lumen of the hollow fiber. The effects of several factors such as the nature of organic solvent, compositions of SP and RP solutions, extraction time, ionic strength and stirring rate on the extraction efficiency were examined and optimized. An enrichment factor of 360 along with substantial sample clean up was obtained under the optimized conditions. The calibration curve showed linearity in the range of 1 - 500 ng?mL–1 and the limit of detection was found to be 0.5 ng?mL–1 in aqueous medium. A reasonable relative recovery (≥89%) and satisfactory intra-assay (3.7% - 4.2%, n = 3) and inter-assay (7.5% - 7.8%, n = 3) precision illustrated good performance of the analytical procedure in spiked human urine and plasma samples.
Cite this paper: nullA. Kashtiaray, H. Farahani, S. Farhadi, B. Rochat and H. Sobhi, "Trace Determination of Tamoxifen in Biological Fluids Using Hollow Fiber Liquid-Phase Microextraction Followed by High-Performance Liquid Chromatography-Ultraviolet Detection," American Journal of Analytical Chemistry, Vol. 2 No. 4, 2011, pp. 429-436. doi: 10.4236/ajac.2011.24052.

[1]   S. C. Moldoveanu and V. David, “Sample Preparation in Chromatography,” Elsevier, Amsterdam, 2002.

[2]   J. Pawliszyn, “Sampling and Sample Preparation for Field and Laboratory,” Elsevier, Amsterdam, 2002.

[3]   J. Pawliszyn, “Sample Preparation: Quo Vadis?” Analyt-ical Chemistry, Vol. 75, No. 11, 2003, pp. 2543-2558. doi:10.1021/ac034094h

[4]   R. M. Smith, “Before the Injection-Modern Methods of Sample Preparation for Separation Techniques,” Journal of Chromatography A, Vol. 1000, No. 1-2, 2003, pp. 3-27. doi:10.1016/S0021-9673(03)00511-9

[5]   D. E. Raynie, “Modern Extraction Techniques,” Analytical Chemistry, Vol. 76, No. 16, 2004, pp. 4659-4664. doi:10.1021/ac040117w

[6]   D. E. Raynie, “Modern Extraction Techniques,” Analytical Chemistry, Vol. 78, No. 12, 2006, pp. 3997-4004. doi:10.1021/ac060641y

[7]   C. L. Arthur and J. Pawliszyn, “Solid Phase Microextrac-tion with Thermal Desorption Using Fused Silica Optical Fibers,” Analytical Chemistry, Vol. 62, No. 19, 1990, pp. 2145-2148. doi:10.1021/ac00218a019

[8]   J. Pawliszyn, “Solid Phase Microextraction: Theory and Practice,” Wiley-VCH Inc., New York, 1997.

[9]   J. Pawliszyn, “Applications of Solid Phase Microextrac-tion,” Royal Society of Chemistry, London, 1999.

[10]   H. Liu and P. K. Dasgupta, “Analytical Chemistry in a Drop. Solvent Extraction in a Microdrop,” Analytical Chemistry, Vol. 68, No. 11, 1996, pp.1817-1821. doi:10.1021/ac960145h

[11]   F. F. Cantwell and M. A. Jeannot, “Solvent Microextrac-tion into a Single Drop,” Analytical Chemistry, Vol. 68, No. 13, 1996, pp. 2236-2240.

[12]   Y. Wang, Y. C. Kwok, Y. He and H. K. Lee, “Application of Dynamic Liquid-Phase Microextraction to the Analysis of Chlorobenzenes in Water by Using a Conventional Microsyringe,” Analytical Chemistry, Vol. 70, No. 21, 1998, pp. 4610-4614. doi:10.1021/ac9804339

[13]   L. Xu, C. Basheer and H. K. Lee, ?Developments in Sin-gle-Drop Microextraction,” Journal of Chromatography A, Vol. 1152, No. 1-2, 2007, pp. 184-192. doi:10.1016/j.chroma.2006.10.073

[14]   L. Meng, X. Liu, B. Wang, G. Shen, Z. Wang and M. Guo, “Simultaneous Derivatization and Extraction of Free Cyanide in Biological Samples with Home-Made Hollow Fiber-Protected Headspace Liquid-Phase Microextraction Followed by Capillary Electrophoresis with UV Detection,” Journal of Chromatography B, Vol. 877, No. 29, 2009, pp. 3645-3651. doi:10.1016/j.jchromb.2009.09.006

[15]   Y. Li, Y. Xiong, J. Fang, L. Wang and Q. Liang, “Appli-cation of Hollow Fiber Liquid-Phase Microextraction in Identification of Oil Spill Sources,” Journal of Chroma-tography A, Vol. 1216, No. 34, 2009, pp. 6155-6161. doi:10.1016/j.chroma.2009.06.069

[16]   N. Sharma, A. K. K. V. Pillai, N. Pathak, A. Jain and K. K. Verma, “Liquid-Phase Microextraction and Fibre-Op- tics-Based Cuvetteless CCD-Array Micro-Spectropho- tometry for Trace Analysis,” Analytica Chimica Acta, Vol. 648, No. 2, 2009, pp. 183-193. doi:10.1016/j.aca.2009.07.006

[17]   Q. Zhou, H. Bai, G. Xie and J. Xiao, “Trace Determination of Organophosphorus Pesticides in Environmental Samples by Temperature-Controlled Ionic Liquid Disper-sive Liquid-Phase Microextraction,” Journal of Chroma-tography A, Vol. 1188, No. 2, 2008, pp. 148-153. doi:10.1016/j.chroma.2008.02.094

[18]   H. Bagheri, F. Khalilian, E. Babanezhad, A. Eshaghi and M.-R. Rouini, “Modified Solvent Microextraction with Back Extraction Combined with Liquid Chromatogra-phy-Fluorescence Detection for the Determination of Ci-talopram in Human Plasma,” Analytica Chimica Acta, Vol. 610, No. 2, 2008, pp. 211-216. doi:10.1016/j.aca.2008.01.047

[19]   A. L. Theis, J. W. Waldack, S. M. Hansen and M. A. Jeannot, “Headspace Solvent Microextraction,” Analytical Chemistry, Vol. 73, No. 23, 2001, pp. 5651-5654. doi:10.1021/ac015569c

[20]   L. Zhao and H. K. Lee, “Liquid-Phase Microextraction Combined with Hollow Fiber as a Sample Preparation Technique Prior to Gas Chromatography/Mass Spectro-metry,” Analytical Chemistry, Vol. 74, No. 11, 2002, 2486-2492. doi:10.1021/ac011124c

[21]   M. H. Ma and F. F. Cantwell, “Solvent Microextraction with Simultaneous Back-Extraction for Sample Cleanup and Preconcentration: Quantitative Extraction,” Analytical Chemistry, Vol. 70, No. 18, 1998, pp. 3912-3919. doi:10.1021/ac980174n

[22]   M. H. Ma and F. F. Cantwell, “Solvent Microextraction with Simultaneous Back-Extraction for Sample Cleanup and Preconcentration into a Single Microdrop,” Analytical Chemistry, Vol. 71, No. 2, 1999, pp. 388-393. doi:10.1021/ac9805899

[23]   S. Pedersen-Bjergaard and K. E. Rasmussen, “Liquid- Liquid-Liquid Microextraction for Sample Preparation of Biological Fluids Prior to Capillary Electrophoresis,” Analytical Chemistry, Vol. 71, No. 14, 1999, pp. 2650- 2656. doi:10.1021/ac990055n

[24]   T. G. Halvorsen, S. Pedersen-Bjergaard and K. E. Ras-mussen, “Reduction of Extraction Times in Liquid-Phase Microextraction,” Journal of Chromatography B, Vol. 71, No. 2, 2001, pp. 219-226.

[25]   K. E. Rasmussen and S. Pedersen-Bjergaard, “Develop-ments in Hollow Fibre Based Liquid-Phase Microextrac-tion,” Trends in Analytical Chemistry, Vol. 23, No. 1, 2004, pp. 1-10. doi:10.1016/S0165-9936(04)00105-0

[26]   H. G. Ugland, M. Krogh and K. E. Rasmussen, “Liquid- Phase Microextraction as a Sample Preparation Technique Prior to Capillary Gas Chromatographic-Deter- mination Ofbenzodiazepines in Biological Matrices,” Journal of Chromatography B, Vol. 749, No. 1, 2000, pp. 85-92. doi:10.1016/S0378-4347(00)00382-0

[27]   K. E. Rasmussen, S. Pedersen-Bjergaard, M. Krogh, H. Ugland and T. Gr?nhaug, “Development of a Simple in-Vial Liquid-Phase Microextraction Device for Drug Analysis Compatible with Capillary Gas Chromatography, Capillary Electrophoresis and High-Performance Liquid Chromatography,” Journal of Chromatography A, Vol. 873, No. 1, 2000, pp. 3-11. doi:10.1016/S0021-9673(99)01163-2

[28]   T. G. Halvorsen, S. Pedersen-Bjergaard and K. E. Ras-mussen, “Liquid-Phase Microextraction and Capillary Electrophoresis of Citalopram, an Antidepressant Drug,” Journal of Chromatography A, Vol. 909, No. 1, 2001, pp. 87-93. doi:10.1016/S0021-9673(00)00868-2

[29]   E. Robinson, G. G. Kimmick and H. B. Muss, “Tamox-ifen in Postmenopausal Women: A Safety Perspective,” Drugs & Aging, Vol. 8, No. 5, 1996, pp. 329-337. doi:10.2165/00002512-199608050-00002

[30]   J. V. Kemp, H. K. Adam, A. E. Wakeling and R. Slater, “Identification and Biological Activity of Tamoxifen Me- tabolites in Human Serum,” Biochemical Pharmacology, Vol. 32, No. 13, 1983, pp. 2045-2052. doi:10.1016/0006-2952(83)90425-2

[31]   R. Mihailescu, H. Y. Aboul-Enein and M. D. Efstatide, “Identification of Tamoxifen and Metabolites in Human Male Urine by GC/MS,” Biomedical Chromatography, Vol. 14, No. 3, 2000, pp.180-183. doi:10.1002/1099-0801(200005)14:3<180::AID-BMC958>3.0.CO;2-T

[32]   R. T. Sane, S. V. Desai, K. K. Sonawne and V. G. Nayak, “Quantitative Gas Chromatographic Determination of Ta- moxifen Citrate in Pharmaceuticals,” Journal of Chroma- tography A, Vol. 331, No. 2, 1985, pp. 432-436. doi:10.1016/0021-9673(85)80052-2

[33]   R. R. Brown, R. Bain and V. C. Jordan, “Determination of Tamoxifen and Metabolites in Human Serum by High- -Performance Liquid Chromatography with Post-Column Fluorescence Activation,” Journal of Chromatography B, Vol. 272, 1983, pp. 351-358. doi:10.1016/S0378-4347(00)86138-1

[34]   J. E. Manns, S. Hanks and J. E. Brown, “Optimised Se-paration of E- and Z-Isomers of Tamoxifen, and Its Prin-cipal Metabolites Using Reversed-Phase High Perfor-mance Liquid Chromatography,” Journal of Pharma-ceutical and Biomedical Analysis, Vol. 16 , No. 5, 1998, pp. 847-852. doi:10.1016/S0731-7085(97)00116-7

[35]   Y.-B. Zhu, Q. Zhang, J.-J. Zou, C.-X. Yu and D.-W. Xiao, “Optimizing High-Performance Liquid Chromatography Method with Fluorescence Detection for Quantification of Tamoxifen and Two Metabolites in Human Plasma: Application to a Clinical Study,” Journal of Pharmaceut-ical and Biomedical Analysis, Vol. 46, No. 2, 2008, pp. 349-355. doi:10.1016/j.jpba.2007.10.012

[36]   J. M. Sanders, L. T. Burka, M. D. Shelby, R. R. Newbold and M. L. Cunningham, “Determination of Tamoxifen and Metabolites in Serum by Capillary Electrophoresis Using a Nonaqueous Buffer System,” Journal of Chromatography B, Vol. 695, No. 1, 1997, pp. 181-185. doi:10.1016/S0378-4347(97)00099-6

[37]   X. F. Li, S. J. Carter and N. J. Dovichi, “Non-Aqueous Capillary Electrophoresis of Tamoxifen and Its Acid Hy-drolysis Products,” Journal of Chromatography A, Vol. 895, No. 1-2, 2000, pp. 81-85. doi:10.1016/S0021-9673(00)00661-0

[38]   J. Rodríguez Flores, J. J. Berzas Nevado, A. M. Contento Salcedo and M. P. Cabello Díaz, “Nonaqueous Capillary Electrophoresis Method for the Analysis of Tamoxifen, Imipramine and Their Main Metabolites in Urine,” Talanta, Vol. 65, No. 1, 2005, pp. 155-162.

[39]   C. Murphy, T. Fotsis, P. Pantzar, H. Adlercreutz and F. Martin, “Analysis of Tamoxifen, N-Desmethyltamoxifen and 4-Hydroxytamoxifen Levels in Cytosol and KCl- -Nuclear Extracts of Breast Tumours from Tamoxifen Treated Patients by Gas Chromatoraphy-Mass Spectro-metry (GC-MS) Using Selected Ion Monitoring (SIM),” Journal of Steroid Biochemistry, Vol. 28, No. 6, 1987, pp. 609-618. doi:10.1016/0022-4731(87)90387-6

[40]   H. K. Lim, S. Stellingweif, S. Sisenwine and K. W. Chan, “Rapid Drug Metabolite Profiling Using Fast Liquid Chromatography, Automated Multiple-Stage Mass Spec-trometry and Receptor-Binding,” Journal of Chromato-graphy A, Vol. 83, No. 2, 1999, pp. 227-241. doi:10.1016/S0021-9673(98)00956-X

[41]   Z. L. Zhang and J. L. Zhou, “Simultaneous Determination of Various Pharmaceutical Compounds in Water by Sol-id-Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry,” Journal of Chromatography A, Vol. 1154, No. 1-2, 2007, pp. 205-213. doi:10.1016/j.chroma.2007.03.105

[42]   W. Lu, G. K. Poon, P. L. Carmichael and R. B. Cole, “Analysis of Tamoxifen and Its Metabolites by on-Line Capillary Electrophoresis-Electrospray Ionization Mass Spectrometry Employing Nonaqueous Media Containing Surfactants,” Analytical Chemistry, Vol. 68, No. 4, 1996, pp. 668-674. doi:10.1021/ac950786x

[43]   P. Daneshgar, P. Norouzi, M. R. Ganjali and H. A. Za-mani, “Ultrasensitive Flow-Injection Electrochemical Method for Detection of Anticancer Drug Tamoxifen,” Talanta, Vol. 77, No. 3, 2009, pp. 1075-1080. doi:10.1016/j.talanta.2008.08.027

[44]   S. Palmarsdottir, E. Thordarson, L. E. Edholm, J. A. Jonsson and L. Mathiasson, “Miniaturized Supported Li- quid Membrane Device for Selective on-Line Enrichment of Basic Drugs in Plasma Combined with Capillary Zone Electrophoresis,” Analytical Chemistry, Vol. 69, No. 9, 1997, pp. 1732-1737.

[45]   S. C. Paterson, C. K. Lim and K. D. Smith, “Analysis of the Interaction between Alpha-1-Acid Glycoprotein and Tamoxifen and Its Metabolites,” Biomedical Chromato-graphy, Vol. 17, No. 2-3, 2003, pp. 143-148. doi:10.1002/bmc.230