Chemometric approach for development, optimization and validation of HILIC methods used for the determination of alkaloids from poppy straw
Keywords:Chemometry, Design of Experiments, HILIC/DAD, opium poppy alkaloids
Two hydrophilic interaction liquid chromatography (HILIC) methods for simultaneous determination of the major alkaloids (morphine, codeine, thebaine, oripavine, papaverine and noscapine) in opium poppy straw (Papaver somniferum L., Papaveraceae) were developed.
The chromatographic behavior of target alkaloids was investigated on two different HILIC stationary phases: bare silica (Si-HILIC) and zwitterionic (ZIC-HILIC). Systematic optimization of the methods was carried out by use of chemometrics. A full factorial design of the experiments was utilized for assessment of the influence of acetonitrile share, ionic strength and the pH value of the mobile phase buffer on several chromatographic responses. The central composite circumscribed design of experiments was used for the robustness testing during the method validation.
The separation of the alkaloids was obtained within close retention window on both columns with optimized gradient elution. The ZIC-HILIC method had advantage over Si-HILIC method in terms of sensitivity, robustness and cost. This method was found suitable for determination of the morphinane alkaloids from poppy straw.
International Narcotics Control Board—technical report 2011 and estimated world requirements for 2012—Statistics for 2010, United Nations Publication, 2012
A. Gümüoçü, N. Arslan, & E.O. SarВhan, Evaluation of selected poppy (Papaver somniferum L.) lines by their morphine and other alkaloids contents, Eur Food Res Technol 226,1213–1220 (2008).
S. Frick, R. Kramell, J. Schmidt, A.J. Fist & T.M. Kutchan, Comparative Qualitative and Quantitative Determination of Alkaloids in Narcotic and Condiment Papaver somniferum Cultivars, J Nat Prod 68 (5), 666–673 (2005).
Z. Szucs, B. Szabady, M. Szatmáry, G. Cimpan & Sz. Nyiredy, High-throughput analytical strategy with combined planar and column liquid chromatography for improvement of the poppy (Papaver somniferum L.) with a high alkaloid content, Chromatographia 56, S49-S54 (2002).
M. Anyzewska, E. Wojtasik & I. Arent, The development and validation of the HPLC method for morphine content determination in poppy straw, Acta Pol Pharm - Drug research 58 (2), 121-126 (2001).
M. Espinosa Bosch, A. Ruiz Sanchez, F. Sanchez Rojas & C. Bosch Ojeda, Morphine and its metabolites: Analytical methodologies for its determination, J Pharmaceut Biomed Anal 43, 799–815 (2007).
S. Honoré Hansen, Sample preparation and separation techniques for bioanalysis of morphine and related substances, J Separ Sci 32(5-6), 825 – 834 (2009).
R. Dams, T. Benijts, W.E. Lambert & A.P. De Leenheer, Simultaneous determination of in total 17 opium alkaloids andopioids in blood and urine by fast liquid chromatography–diode array detection–fluorescence detection, after solid-phase extraction, J Chrom B, 773 53–61 (2002).
C. Sproll, R.C. Perz & D.W. Lachenmeier, High-performance liquid chromatographic assay for morphine in small plasma samples: application to pharmacokinetic studies in rats, J Agric Food Chem 54 (15), 5292 (2006).
H.A. Claessens, Trends and progress in the characterization of stationary phases for reversed-phase liquid chromatography, Trends in Analytical Chemistry 20 (10), 563-583 (2001).
M. Cooke, C.F. Poole, I.D. Wilson & E.R. Adlard, Encyclopedia of separation science, Academic Press, 2000.
J. Аcevska, G. Stefkov, R, Petkovska, S. Kulevanova & A. Dimitrovska, Chemometric approach for development, optimization and validation of different chromatographic methods for separation of opium alkaloids, Anal Bioanal Chem 403, 1117-1129 (2012).
J. Acevska, A. Dimitrovska, G. Stefkov, K. Brezovska, M. Karapandzova & S. Kulevanova, Development and validation of RP-HPLC method for determination of alkaloids from Papaver somniferum L., Papaveraceae, J AOAC Int 95 (2), 399-405 (2012).
R. Li, Y. Zhanga, C.C. Leeb, R. Lua & Y. Huanga, Development and validation of a hydrophilic interaction liquid chromatographic method for determination of aromatic amines in environmental water, J Chrom A 1217, 1799–1805 (2010).
W. Jiang, G. Fischer, Y. Girmay & K. Irguma, Zwitterionic stationary phase with covalently bonded phosphorylcholine type polymer grafts and its applicability to separation of peptides in the hydrophilic interaction liquid chromatography mode J Chrom A 1127, 82–91 (2006).
V.V. Tolstikov & O. Fiehn, Analysis of Highly Polar Compounds of Plant Origin: Combination of Hydrophilic Interaction Chromatography and Electrospray Ion Trap Mass Spectrometry, Anal Biochem 301, 298–307 (2002).
E.S. Grumbach, D.M. Wagrowski-Diehl, J.R. Mazzeo, B. Alden & P.C. Iraneta, Hydrophilic Interaction Chromatography Using Silica Columns for the Retention of Polar Analytes and Enhanced ESI-MS Sensitivity, LCGC Notrh America 22 (10), 1010-1023 (2004).
G.A. Leweis, D. Mathieu & R. Phan-Tan-Luu, Pharmaceutical experimental design, New York: Marcel Decker, 1999.
R.L. Mason, R.F. Gunst & J.L. Hess, Statistical design and analysis of experiments, 2nd edn, New Jersey: Wiley, 2003.
S.N. Deming & S.L. Morgan, Experimental design: a chemometric approach, 2nd edn New York: Elsevier Sci. Publishing, 1993.
T. Lundstedt, E. Seifert, L. Abramo, B. Thelin, A. Nystrom, J. Oettersen & R. Bergman, Experimental design and optimization Chemom Intell Lab Syst 42, 3-40 (1998).
D.C. Montgomery, Design and analysis of experiments, New Jersey: John Wiley&Sons Inc., 1976.
M.A. Sharaf & D.L. Illman, Chemometrics, New York: Wiley, 1986.
D.L. Massart, B.G.M. Vandeginste, S.N. Deming, Y. Michotte & L. Kaufman, Chemometrics: a textbook, New York: Elsevier Sci.Publishing Company inc., 1998.
R.G. Brereton, Chemometrics – Data analysis for the laboratory and chemical plant, The Atrium, Chichester, England: John Wiley & Sons Ltd., 2003.
ICH on Technical Requirements for Registration of Pharmaceuticals for Human Use, Guideline on Validation of Analytical Procedures: Text and methodology Q2(R1), Harmonized Tripartite Guideline, Switzerland, 2005.
B. Dejagher, X. Carpon, J. Smeyers-Verbeke & Y. Vander Heyden, Randomization tests to identify significant effects in designs for robustness testing, Anal Chim Acta 564, 184-200 (2006).
How to Cite
The authors agree to the following licence: Attribution-NonCommercial 4.0 International (CC BY-NC 4.0)
- Share — copy and redistribute the material in any medium or format
- Adapt — remix, transform, and build upon the material
- for any purpose, even commercially.
Under the following terms:
Attribution — You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use.
- NonCommercial — You may not use the material for commercial purposes.