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Graphene oxide/Fe3O4@polythionine nanocomposite as an efficient sorbent for magnetic solid-phase extraction followed by high-performance liquid chromatography for the determination of duloxetine in human plasma

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Abstract

Herein, an efficient graphene oxide/Fe3O4@polythionine (GO/Fe3O4/PTh) nanocomposite sorbent was introduced for magnetic solid-phase extraction combined with high-performance liquid chromatography–ultraviolet detection of duloxetine (DLX) in human plasma. To prepare the sorbent, an oxidative polymerization of thionine on the surface of magnetic GO was utilized while PTh was simply used as a surface modifier to improve extraction efficiency. Transmission electron microscopy, scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray analysis, vibrating sample magnetometry, Fourier transform-infrared spectroscopy and Brunauer–Emmett–Teller technique were applied to characterize the prepared nanoparticles. Firstly, effective parameters controlling the performance of the extraction process were evaluated in detail and optimized. Under the optimized conditions, calibration curve showed linearity in the range of 2–2500 ng mL−1 with regression coefficient corresponding to 0.998. Limits of detection (LOD, S/N = 3) and quantification (LOQ, S/N = 10) were 0.5 and 2 ng mL−1, respectively. Reasonable intra-assay (3.5–4.5%, n = 6) and inter-assay (3.8–6.7%, n = 9) precision represented acceptable performance of the procedure. The applicability of the method was successfully extended to the determination of DLX in human plasma after oral administration of 60 mg single dose of the drug and finally some pharmacokinetic data was achieved.

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References

  • Ammar RA, Otaif H, Al-Warthan A (2012) A novel ion-selective membrane electrode for the determination of duloxetine. Anal Methods 4:1427–1431. doi:10.1039/C2AY05884G

    Article  CAS  Google Scholar 

  • Anderson D, Reed S, Lintemoot J, Kegler S, DeQuintana S, Sandberg M, Muto J (2006) A first look at duloxetine (Cymbalta®) in a postmortem laboratory. J Anal Toxicol 30:576–580. doi:10.1093/jat/30.8.576

    Article  CAS  Google Scholar 

  • Asgharinezhad AA, Ebrahimzadeh H, Mirbabaei F, Mollazadeh N, Shekari N (2014) Dispersive micro-solid-phase extraction of benzodiazepines from biological fluids based on polyaniline/magnetic nanoparticles composite. Anal Chim Acta 844:80–89. doi:10.1016/j.aca.2014.06.007

    Article  CAS  Google Scholar 

  • Bagheri H, Ayazi Z, Naderi M (2013) Conductive polymer-based microextraction methods: a review. Anal Chim Acta 767:1–13. doi:10.1016/j.aca.2012.12.013

    Article  CAS  Google Scholar 

  • Ball S, Marangell LB, Lipsius S, Russell JM (2013) Brain-derived neurotrophic factor in generalized anxiety disorder: results from a duloxetine clinical trial. Prog Neuropsychopharmacol Biol Psychiatry 43:217–221. doi:10.1016/j.pnpbp.2013.01.002

    Article  CAS  Google Scholar 

  • Bennett R, Russell IJ, Choy E, Spaeth M, Mease P, Kajdasz D, Walker D, Wang F, Chappell A (2012) Evaluation of patient-rated stiffness associated with fibromyalgia: a post hoc analysis of 4 pooled, randomized clinical trials of duloxetine. Clin Ther 34:824–837. doi:10.1016/j.clinthera.2012.02.013

    Article  CAS  Google Scholar 

  • Cao X, Shen L, Ye X, Zhang F, Chen J, Mo W (2014) Ultrasound-assisted magnetic solid-phase extraction based ionic liquid-coated Fe3O4@graphene for the determination of nitrobenzene compounds in environmental water samples. Analyst 139:1938–1944. doi:10.1039/c3an01937c

    Article  CAS  Google Scholar 

  • Chaves AR, Júnior GC, Queiroz MEC (2009) Solid-phase microextraction using poly (pyrrole) film and liquid chromatography with UV detection for analysis of antidepressants in plasma samples. J Chromatogr B 877:587–893. doi:10.1016/j.jchromb.2008.12.070

    Article  CAS  Google Scholar 

  • Chen X, You X, Liu F, Hou F, Zhang X (2015) Ionic-liquid-based, manual-shaking-and ultrasound-assisted, surfactant-enhanced emulsification microextraction for the determination of three fungicide residues in juice samples. J Sep Sci 38:93–99. doi:10.1002/jssc.201400970

    Article  Google Scholar 

  • D’Archivio AA, Maggi MA, Ruggieri F, Carlucci M, Ferrone V, Carlucci G (2016) Optimisation by response surface methodology of microextraction by packed sorbent of non steroidal anti-inflammatory drugs and ultra-high performance liquid chromatography analysis of dialyzed samples. J Pharm Biomed Anal 125:114–121. doi:10.1016/j.jpba.2016.03.045

    Article  Google Scholar 

  • Dhaneshwar SS, Deshpande P, Patil M, Vadnerkar G, Dhaneshwar SR (2008) Development and validation of a HPTLC method for estimation of duloxetine hydrochloride in bulk drug and in tablet dosage form. Indian J Pharm Sci 70:233–236. doi:10.4103/0250-474X.41463

    Article  Google Scholar 

  • Dimiev AM, Eigler S (2016) Graphene oxide: fundamentals and applications. Wiley, New York. ISBN 978-1-119-06940-9

    Book  Google Scholar 

  • Ding J, Mao LJ, Guo N, Yu L, Feng YQ (2016) Determination of endogenous brassinosteroids using sequential magnetic solid phase extraction followed by in situ derivatization/desorption method coupled with liquid chromatography–tandem mass spectrometry. J Chromatogr A 1446:103–113. doi:10.1016/j.chroma.2016.04.012

    Article  CAS  Google Scholar 

  • Farahani H, Shokouhi M, Rahimi-Nasrabadi M, Zare-Dorabei R (2016) Green chemistry approach to analysis of formic acid and acetic acid in aquatic environment by headspace water-based liquid-phase microextraction and high-performance liquid chromatography. Toxicol Environ Chem 98:714–726. doi:10.1080/02772248.2015.1126283

    CAS  Google Scholar 

  • Freeman MP, Hirschberg AM, Wang B, Petrillo LF, Connors S, Regan S, Joffe H, Cohen LS (2013) Duloxetine for major depressive disorder and daytime and nighttime hot flashes associated with the menopausal transition. Maturitas 75:170–174. doi:10.1016/j.maturitas.2013.03.007

    Article  CAS  Google Scholar 

  • Gołębiowski M, Stepnowski P, Leszczyńska D (2017) Application of carbon nanotubes as solid-phase extraction sorbent for analysis of chlorophenols in water samples. Chem Pap Chem Zvesti 71:831–839. doi:10.1007/s11696-016-0098-z

    Article  Google Scholar 

  • Herrero-Latorre C, Barciela-García J, García-Martín S, Peña-Crecente RM, Otárola-Jiménez J (2015) Magnetic solid-phase extraction using carbon nanotubes as sorbents: a review. Anal Chim Acta 892:10–26. doi:10.1016/j.aca.2015.07.046

    Article  CAS  Google Scholar 

  • Huang Y, Zheng Z, Huang L, Yao H, Wu X, Li S, Lin D (2017) Optimization of dispersive liquid-phase microextraction based on solidified floating organic drop combined with high-performance liquid chromatography for the analysis of glucocorticoid residues in food. J Pharm Biomed Anal 138:363–372. doi:10.1016/j.jpba.2017.02.026

    Article  CAS  Google Scholar 

  • Hunziker ME, Suehs BS, Bettinger TL, Crismon ML (2005) Duloxetine hydrochloride: a new dual-acting medication for the treatment of major depressive disorder. Clin Ther 27:1126–1143. doi:10.1016/j.jpba.2017.02.026

    Article  CAS  Google Scholar 

  • Karpavičiūtė D, Murkovic M, Vinauskienė R, Venskutonis R (2017) Determination of non-polar heterocyclic aromatic amines in roasted coffee by SPE-HPLC-FLD. Chem Pap Chem Zvesti 71:67–70. doi:10.1007/s11696-016-0039-x

    Article  Google Scholar 

  • Lantz RJ, Gillespie TA, Rash TJ, Kuo F, Skinner M, Kuan HY, Knadler MP (2003) Metabolism, excretion, and pharmacokinetics of duloxetine in healthy human subjects. Drug Metab Dispos 31:1142–1150. doi:10.1124/dmd.31.9.1142

    Article  CAS  Google Scholar 

  • Leeuwen JHS, Lange RR, Jonasson AF, Chen WJ, Viktrup L (2008) Efficacy and safety of duloxetine in elderly women with stress urinary incontinence or stress-predominant mixed urinary incontinence. Maturitas 60:138–147. doi:10.1016/j.maturitas.2008.04.012

    Article  Google Scholar 

  • Li N, Chen J, Shi YP (2017) Magnetic polyethyleneimine functionalized reduced graphene oxide as a novel magnetic solid-phase extraction adsorbent for the determination of polar acidic herbicides in rice. Anal Chim Acta 949:23–34

    Article  CAS  Google Scholar 

  • Li X, Wang Y, Yang X, Chen J, Fu H, Cheng T (2012) Conducting polymers in environmental analysis. TrAC Trends Anal Chem 39:163–179. doi:10.1016/j.trac.2012.06.003

    Article  CAS  Google Scholar 

  • Liu L, Nussbaum MA (1999) Systematic screening approach for chiral separations of basic compounds by capillary electrophoresis with modified cyclodextrins. J Pharm Biomed Anal 19:679–694. doi:10.1016/S0731-7085(98)00295-7

    Article  CAS  Google Scholar 

  • Liu L, Feng T, Wang C, Wu Q, Wang Z (2014) Magnetic three-dimensional graphene nanoparticles for the preconcentration of endocrine-disrupting phenols. Microchim Acta 181:1249–1255. doi:10.1007/s00604-014-1234-5

    Article  CAS  Google Scholar 

  • Ma N, Zhang BK, Chen BM, Xu P, Wang F, Zhu RH, Feng S, **ang DX, Zhu Y-G (2007) Determination of duloxetine in human plasma via LC/MS and subsequent application to a pharmacokinetic study in healthy Chinese volunteers. Clin Chim Acta 380:100–105. doi:10.1016/j.cca.2007.01.018

    Article  CAS  Google Scholar 

  • Malfará WR, Bertucci C, Queiroz MEC, Carvalho SAD, Bianchi MLP, Cesarino EJ, Crippa JA, Queiroz RHC (2007) Reliable HPLC method for therapeutic drug monitoring of frequently prescribed tricyclic and nontricyclic antidepressants. J Pharm Biomed Anal 44:955–962. doi:10.1016/j.jpba.2007.04.005

    Article  Google Scholar 

  • Mallinckrodt CH, Prakash A, Andorn AC, Watkin JG, Wohlreich MM (2006) Duloxetine for the treatment of major depressive disorder: a closer look at efficacy and safety data across the approved dose range. J Psychiatr Res 40:337–348. doi:10.1016/j.jpsychires.2005.08.010

    Article  Google Scholar 

  • Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z, Slesarev A, Alemany LB, Lu W, Tour JM (2010) Improved synthesis of graphene oxide. ACS Nano 4:4806–4814. doi:10.1021/nn1006368

    Article  CAS  Google Scholar 

  • Mehdinia A, Roohi F, Jabbari A (2011) Rapid magnetic solid phase extraction with in situ derivatization of methylmercury in seawater by Fe3O4/polyaniline nanoparticle. J Chromatogr A 1218:4269–4274. doi:10.1016/j.chroma.2011.04.070

    Article  CAS  Google Scholar 

  • Mercolini L, Mandrioli R, Cazzolla R, Amore M, Raggi MA (2007) HPLC analysis of the novel antidepressant duloxetine in human plasma after an original solid-phase extraction procedure. J Chromatogr B 856:81–87. doi:10.1016/j.jchromb.2007.05.031

    Article  CAS  Google Scholar 

  • Mihaylova B, Pitman R, Tincello D, Der Vaart HV, Tunn R, Timlin L, Quail D, Johns A, Sculpher M (2010) Cost-effectiveness of duloxetine: the Stress Urinary Incontinence Treatment (SUIT) study. Value Health 13:565–572. doi:10.1111/j.1524-4733.2010.00729.x

    Article  Google Scholar 

  • Mitra S (2003) Sample preparation techniques in analytical chemistry. Wiley, New York. ISBN 978-0-471-32845-2

    Book  Google Scholar 

  • Moldoveanu SC (2004) Solutions and challenges in sample preparation for chromatography. J Chromatogr Sci 42:1–14. doi:10.1093/chromsci/42.1.1

    Article  CAS  Google Scholar 

  • Moldoveanu SC, David D (2002) Sample preparation in chromatography, vol 65. Elsevier, Amsterdam. ISBN 9780080540702

    Google Scholar 

  • Musenga A, Amore M, Mandrioli R, Kenndler E, Martino LD, Raggi MA (2009) Determination of duloxetine in human plasma by capillary electrophoresis with laser-induced fluorescence detection. J Chromatogr B 877:1126–1132. doi:10.1016/j.jchromb.2009.02.059

    Article  CAS  Google Scholar 

  • Pastor-Belda M, Bastida D, Campillo N, Pérez-Cárceles MD, Motas M, Viñas P (2016) A study of the influence on diabetes of free and conjugated bisphenol A concentrations in urine: development of a simple microextraction procedure using gas chromatography–mass spectrometry. J Pharm Biomed Anal 129:458–465. doi:10.1016/j.jpba.2016.07.042

    Article  CAS  Google Scholar 

  • Pavlović DM, Babić S, Horvat AJM, Kaštelan-Macan M (2007) Sample preparation in analysis of pharmaceuticals. TrAC Trends Anal Chem 26:1062–1075. doi:10.1016/j.trac.2007.09.010

    Article  Google Scholar 

  • Pawliszyn J (2002) Sampling and sample preparation for field and laboratory: fundamentals and new directions in sample preparation, vol 37. Elsevier, Amsterdam. ISBN 9780080929453

    Google Scholar 

  • Płotka-Wasylka J, Szczepańska N, Guardia M, Namieśnik J (2015) Miniaturized solid-phase extraction techniques. TrAC Trends Anal Chem 73:19–38. doi:10.1016/bs.coac.2017.03.001

    Article  Google Scholar 

  • Rickard EC, Bopp RJ (1994) Optimization of a capillary electrophoresis method to determine the chiral purity of a drug. J Chromatogr A 680:609–621. doi:10.1016/0021-9673(94)85161-1

    Article  CAS  Google Scholar 

  • Shi Y, Wu H, Wang C, Guo X, Du J, Du L (2016) Determination of polycyclic aromatic hydrocarbons in coffee and tea samples by magnetic solid-phase extraction coupled with HPLC–FLD. Food Chem 199:75–80. doi:10.1016/j.foodchem.2015.11.137

    Article  CAS  Google Scholar 

  • Suh JH, Lee YY, Lee HJ, Kang M, Hur Y, Lee SN, Yang D-H, Han SB (2013) Dispersive liquid–liquid microextraction based on solidification of floating organic droplets followed by high performance liquid chromatography for the determination of duloxetine in human plasma. J Pharm Biomed Anal 75:214–219. doi:10.1016/j.jpba.2012.11.041

    Article  CAS  Google Scholar 

  • Sultan A, Gaskell H, Derry S, Moore RA (2008) Duloxetine for painful diabetic neuropathy and fibromyalgia pain: systematic review of randomised trials. BMC Neurol 8:29. doi:10.1186/1471-2377-8-29

    Article  Google Scholar 

  • Taghvimi A, Hamishehkar H (2017) Carbon coated magnetic nanoparticles as a novel magnetic solid phase extraction adsorbent for simultaneous extraction of methamphetamine and ephedrine from urine samples. J Chromatogr B 1041:113–119. doi:10.1016/j.jchromb.2016.11.039

    Article  Google Scholar 

  • Wang L, Zhang Z, Zhang J, Zhang L (2016) Magnetic solid-phase extraction using nanoporous three dimensional graphene hybrid materials for high-capacity enrichment and simultaneous detection of nine bisphenol analogs from water sample. J Chromatogr A 1463:1–10. doi:10.1016/j.chroma.2016.08.003

    Article  CAS  Google Scholar 

  • Yan S, Qi T-T, Chen D-W, Li Z, Li X-J, Pan S-Y (2014) Magnetic solid phase extraction based on magnetite/reduced graphene oxide nanoparticles for determination of trace isocarbophos residues in different matrices. J Chromatogr A 1347:30–38. doi:10.1016/j.chroma.2014.04.073

    Article  CAS  Google Scholar 

  • Zeeb M, Mirza B, Zare-Dorabei R, Farahani H (2014) Ionic liquid-based ultrasound-assisted in situ solvent formation microextraction combined with electrothermal atomic absorption spectrometry as a practical method for preconcentration and trace determination of vanadium in water and food samples. Food Anal Methods 7:1783–1790. doi:10.1007/s12161-014-9820-z

    Article  Google Scholar 

  • Zeeb M, Farahani H, Papan MK (2016) Determination of atenolol in human plasma using ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography. J Sep Sci 39:2138–2145. doi:10.1002/jssc.201501365

    Article  CAS  Google Scholar 

  • Zhao R, Cheng G, Tang J, Song J, Peng W-X (2009) Pharmacokinetics of duloxetine hydrochloride enteric-coated tablets in healthy Chinese volunteers: a randomized, open-label, single-and multiple-dose study. Clin Ther 31:1022–1036. doi:10.1016/j.clinthera.2009.05.005

    Article  CAS  Google Scholar 

  • Zhao C, Jiang Z, Cai X, Lin L, Lin X, Weng S (2015) Ultrasensitive and reliable dopamine sensor based on polythionine/AuNPs composites. J Electroanal Chem 748:16–22. doi:10.1016/j.jelechem.2015.04.025

    Article  CAS  Google Scholar 

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Acknowledgements

This work has been supported by grants from the Islamic Azad University South Tehran Branch which is hereby gratefully acknowledged. The authors greatly appreciate Miss Farnaz Bahman for cooperating to carry out the HPLC analysis, and also thank the volunteers for enrolling in this study and taking their valuable time.

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  1. Department of Applied Chemistry, Faculty of Science, Islamic Azad University, South Tehran Branch, Tehran, Iran

    Mohsen Zeeb

  2. Research Institute of Petroleum Industry (RIPI), P. O. Box 1485733111, Tehran, Iran

    Hadi Farahani

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  1. Mohsen Zeeb
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Correspondence to Mohsen Zeeb.

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Zeeb, M., Farahani, H. Graphene oxide/Fe3O4@polythionine nanocomposite as an efficient sorbent for magnetic solid-phase extraction followed by high-performance liquid chromatography for the determination of duloxetine in human plasma. Chem. Pap. 72, 15–27 (2018). https://doi.org/10.1007/s11696-017-0253-1

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