Document Type : Full research article


1 Department of Chemistry, Payam Noor University, P.O. Box 19395-4697, Tehran, Iran

2 Faculty of Chemistry, Razi University, Kermanshah 671496734, Iran


For the first time, an analytical methodology based ondifferential pulse voltammetry (DPV) at a glassy carbon electrode (GCE) assisted by two multivariate calibration (MVC) models including back propagation-artificial neural network (BP-ANN), non-linear class, and partial least squares-1 (PLS-1), classical class, thatthey have been constructed on the basis of non-bilinear first order differential pulse voltammetry (DPV) data,was developed and validated for the simultaneous determination of Ascorbic acid, Uric acid, Acetaminophen, and Noradrenalinto identify which approach offers the best predictions.The baselines of the DPV signals were corrected by asymmetric least square spline regression (AsLSSR) algorithm. Before applying the PLS-1,lack of bi-linearity was tackled by potential shift correction using correlation optimised warping (COW) algorithm. The multivariate calibration (MVC) model was developed as a quaternary calibration modelin a blank human serum sample (drug-free) provided by a healthy volunteer to regard the presence of a strong matrix effect which may be caused by the possible interferents present in the serum, and it was validated and tested with two independent sets of analytes mixtures in the blank and actual human serum samples, respectively.According to the obtained results, the PLS-1 was recommended for simultaneous determination of AA, UA, AC, and NA in both blank and actual human serum samples .


  • Andreu, S.D. Marcos, J.R. Castillo and J. Galbán, Sensor film for Vitamin C determination based on absorption properties of polyaniline, Talanta 65 (2005) 1045-1051.
  • J. O’Connell, C. Gormally, M. Pravda and G.G. Guilbault,Development of an amperometric l-ascorbic acid (Vitamin C) sensor based on electropolymerised aniline for pharmaceutical and food analysis, Anal. Chim. Acta, 431 (2001) 239-247.
  • X. Weng, Q.X. Cao, L.X. Liang, J.G. Chen, C.P. You, Y.M. Ruan, H.J. Lin and L.J.Wu, Simultaneous determination of dopamine and uri acid using layer-by-layer graphene and chitosan assembled multilayer films, Talanta, 117 (2013) 359-365.
  • V.V.S. Eswara and H.A. Mottola, Determination of Uric Acid at the Microgram Level by a Kinetic Procedure Based on a “Pseudo-Induction” Period, Anal. Chem., 46 (1974) 1777-1781.
  • G.M. Bessems and N.P.E. Vermeulen, Paracetamol (Acetaminophen)-Induced Toxicity: Molecular and Biochemical Mechanisms, Analogues and Protective Approaches, Crit. Rev. Toxicol. 31 (2001) 55-138.
  • T. Olaleye and B.T.J. Rocha, Acetaminophen-induced liver damage in mice: Effects of some medicinal plants on the oxidative defense system, Exp. Toxicol. Pathol. 59 (2008) 319-327.
  • C. Roberts, H.L. Phaneuf, J.G. Szakacs, R.T. Zera, J.G. Lamb and M.R. Franklin, Differential Chemoprotection against Acetaminophen-Induced Hepatotoxicity by Latentiated L-Cysteines, Chem. Res. Toxicol. 11 (1998) 1274-1282.
  • Mazer and J. Perrone, Acetaminophen-Induced Nephrotoxicity: Pathophysiology, Clinical Manifestations, and Management, J. Med. Toxicol. 4 (2008) 2-6.
  • Beitollahi, H. Karimi-Maleh and H. Khabazzadeh, Nanomolar and Selective Determination of Epinephrine in the Presence of Norepinephrine Using Carbon Paste Electrode Modified with Carbon Nanotubes and Novel 2-(4-Oxo-3-phenyl-3,4-dihydroquinazolinyl)-N′-phenyl-hydrazinecarbothioamide, Anal. Chem. 80 (2008) 9848-9851.
  •; 26, May, 2013.
  • G. Gioia, P. Andreatta, S. Boschetti and R. Gatti, Development and validation of a liquid chromatographic method for the determination of ascorbic acid, dehydroascorbic acid and acetaminophen in pharmaceuticals, J. Pharm. Biomed. Anal. 48 (2008) 331-339.
  • Carrera, E. Sabater, E. Vilanova and M.A. Sogorb,A simple and rapid HPLC–MS method for the simultaneous determination of epinephrine, norepinephrine, dopamine and 5-hydroxytryptamine: Application to the secretion of bovine chromaffin cell cultures, J. Chromatogr. B, 847 (2007) 88-94.
  • L. Kuhlenbeck, T.P.O. Neill, C.E. Mack, S.H. Hoke and K.R. Wehmeyer, Determination of norepinephrine in small volume plasma samples by stable-isotope dilution gas chromatography–tandem mass spectrometry with negative ion chemical ionization, J. Chromatogr. B, 738 (2000) 319-330.
  • Wu, Y. Guan and J. Ye, Determination of flavonoids and ascorbic acid in grapefruit peel and juice by capillary electrophoresis with electrochemical detection, Food Chem., 100 (2007) 1573-1579.
  • L. Guan, J. Quyang, Q.L. Li, B.H. Liu and W.R.G. Baeyens, Simultaneous determination of catecholamines by ion chromatography with direct conductivity detection, Talanta, 50 (2000) 1197-1203.
  • G. Kumar and R. Letha, Determination of Paracetamol in pure form and in dosage forms using N,N-dibromo dimethylhydantoin, J. Pharm. Biomed. Anal., 15 (1997) 1725-1728.
  • Rodenas, M.S. Garcia, C. Sanchez-Pedreno and M.I. Albero, Simultaneous determination of propacetamol and paracetamol by derivative spectrophotometry, Talanta, 52 (2000) 517-523.
  • Erk, Y. Ozkan, E. Banoglu, S.A. Ozkan and Z. Senturk, Simultaneous determination of paracetamol and methocarbamol in tablets by ratio spectra derivative spectrophotometry and LC, J. Pharm. Biomed. Anal., 24 (2001) 469-475.
  • Alberich, J.M. Diaz-Cruz, C. Arino and M. Esteban, Potential shift correction in multivariate curve resolution of voltammetric data. General formulation and application to some experimental systems, Analyst, 133 (2008) 112-125.
  • J. Bard, L.R. Faulkner, ELECTROCHEMICAL METHODS Fundamentals and Applications, John Wiley & Sons, Inc., New York, 2001.
  • B. Gholivand, A.R. Jalalvand and H.C. Goicoechea, Th. Skov, Chemometrics-assisted simultaneous voltammetric determination of ascorbic acid, uric acid, dopamine and nitrite: Application of non-bilinear voltammetric data for exploiting first-order advantage, Talanta, 119 (2014) 553-563.
  • Xu, J.H. Jiang, H.L. Wu, G.L. Shen and R.Q. Yu, Variable-weighted PLS, Chem. Intell. Lab. Syst., 85 (2007) 140-143.
  • Wold, H. Martens and H. Wold, The multivariate calibration problem in chemistry solved by the PLS method, Springer-Verlag, Heidelberg, 1983.
  • Wold, J. Cheney, N. Kettaneh and C. McCready, The chemometric analysis of point and dynamic data in pharmaceutical and biotech production (PAT) — some objectives and approaches, Chem. Intell. Lab. Syst., 84 (2006) 159-163.
  • Yang, P.R. Griffiths and J.D. Tate, Comparison of partial least squares regression and multi-layerneural networks for quantification of nonlinear systems and application to gas phase Fourier transform infrared spectra, Anal. Chim. Acta, 489 (2003) 125-136.
  • Centner, J. Verdú-Andrés, B. Walczak, D. Jouan-Rimbaud, F. Despagne, L. Pasti, D.L. Massart and O.E. de Noord, Comparison of Multivariate Calibration Techniques Applied to Experimental NIR Data Sets, Appl. Spectrosc., 54 (2000) 608-623.
  • Naes, T. Isakson, T. Fearn, T. Davies, A User-Friendly Guide to Multivariate Calibration and Classification, NIR. Publications, Chichester, 2002.
  • Wold, M. Sjostrom and L. Eriksson, PLS-regression: a basic tool of chemometrics, Chemom. Intell. Lab. Syst., 58 (2001) 109-130.
  • Geladi, D. MacDougall and H. Martens, Linearization and Scatter-Correction for Near-Infrared Reflectance Spectra of Meat, Appl. Spectrosc., 39 (1985) 491-500.
  • J. Barnes, M.S. Dhanoa and S.J. Lister, Standard Normal Variate Transformation and De-trending ofNear-Infrared Diffuse Reflectance Spectra, Appl. Spectrosc., 43 (1989) 772-777.
  • H. Suh, Y.Y. Lee, H.J. Lee, M. Kang, Y. Hur, S.N. Lee, D.H. Yang and S.B. Han, 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 (2013) 214-219.
  • B. Gholivand, A.R. Jalalvand, H.C. Goicoechea and R. Gargallo, Th. Skov, G. Paimard, Combination of electrochemistry with chemometrics to introduce an efficient analytical method for simultaneous quantification of five opium alkaloids in complex matrices, Talanta, 131 (2015) 26-37.
  • B. Gholivand, A.R. Jalalvand and H.C. Goicoechea, Th. Skov, Generation of non-multilinear three-way voltammetric arrays by an electrochemically oxidized glassy carbon electrode as an efficient electronic device to achieving second-order advantage: Challenges, and tailored applications, Talanta, 134 (2015) 607-618.
  • B. Gholivand, A.R. Jalalvand and H.C. Goicoechea, Th. Skov, Advanced and tailored applications of an efficient electrochemical approach assisted by AsLSSR–COW–rPLS and finding ways to cope with challenges arising from the nature of voltammetric data, Chemom. Intell. Lab. Syst., 146 (2015) 437-446.
  • M. De Zan, M.D. Gil García, M.J. Culzoni, R.G. Siano, H.C. Goicoechea and M. Martínez Galera, Solving matrix-effects exploiting the second order advantage in the resolution and determination of eight tetracycline antibiotics in effluent wastewater by modelling liquid chromatography data with multivariate curve resolution-alternating least squares and unfolded-partial least squares followed by residual bilinearization algorithms I. Effect of signal pre-treatment, J. Chromatogr. A, 1179 (2008) 106-114.
  • H.C. Eilers, I.D. Currie and M. Durban, Fast and compact smoothing on large multidimensional grids, Comput. Statist. Data Anal., 50 (2006) 61-67.
  • H.C. Eilers, Parametric Time Warping, Anal. Chem. 76 (2004) 404-411.
  • P.V. Nielsen, J.M. Carstensen and J. Smedsgaard, Aligning of single and multiple wavelength chromatographic profiles for chemometric data analysis using correlation optimized warping, J. Chromatogr. A, 805 (1998) 17-35.
  • Tomasi, F. Van den Berg and C. Andersson, Correlation optimized warping and dynamic time warping as preprocessing methods for chromatographic data, J. Chemom., 18 (2004) 231-241.
  • M. Haaland and E.V. Thomas, Partial Least-Squares Methods for Spectral Analyses. 1. Relation to Other Quantitative Calibration Methods and the Extraction of Qualitative Information, Anal. Chem., 60 (1988) 1193-1202.
  • G. Gonzalez, M.A. Herrador and A.G. Asuero, Intra-laboratory testing of method accuracy from recovery assays, Talanta, 48 (1999) 729-736.
  • A. Arancibia, G.M. Escandar, Two different strategies for the fluorimetric determination of piroxicam in serum, Talanta, 60 (2003) 1113-1121.