Development and validation of an analytical method by HPLC-DAD for determination of caffeine in products based on guarana extracts (Paullinia cupana)
DOI:
https://doi.org/10.1590/s2175-97902023e22106Keywords:
Paullinia cupana, Caffeine; Guarana extract, High performance liquid chromatographyAbstract
Guarana (Paullinia cupana) is a native plant from the Amazon whose seeds contain a high concentration of caffeine. Aqueous extract of guarana is widely used in the world. In this study, the objective was to develop and validate a High-Performance Liquid Chromatography method for the determination of caffeine in extracts and commercial beverages based on guarana. A sensitive, simple, and viable high performance liquid chromatographic method without the need of an analyte extraction procedure was developed and validated according to Brazilian and international requirements. The method presented high performance, fulfilling Brazilian and international requirements, in addition to allowing product compliance tests. Results confirmed high selectivity and linearity (>0.999) between 5 to 135 ug/mL, with no significant matrix effect. Detection and quantification limits were 0.02 µg/mL and 2 µg/mL, respectively. Precision was less than 4 %, and accuracy varied from 99.9-120 %. Applicability of the method was demonstrated by conducting a limited evaluation in products containing caffeine. Commercial extracts showed quite different caffeine levels, while carbonated drinks follow Brazilian and American recommendations. Our results indicate that the developed method can be used to evaluate the quality of the guarana extract and of products containing caffeine.
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Ângelo PCS, Nunes-Silva CG, Brígido MM, Azevedo JSN, Assunção EN, Sousa ARB, et al. Guarana (Paullinia cupana var. sorbilis), an anciently consumed stimulant from the Amazon rain forest: the seeded-fruit transcriptome. Plant Cell Rep. 2008;27(1):117-124. https://doi.org/10.1007/ s00299-007-0456
» https://doi.org/10.1007/ s00299-007-0456
Arazi H, Hoseinihaji M, Eghbali E. The effects of different doses of caffeine on performance, rating of perceived exertion and pain perception in teenagers female karate athletes. Braz J Pharm Sci. 2016;52(4):685-692. https://doi. org/10.1590/s1984-82502016000400012
» https://doi. org/10.1590/s1984-82502016000400012
Armenta S, Garrigues S, De La Guardia M. Solid-phase FT-Raman determination of caffeine in energy drinks. Anal Chim Acta. 2005;547(2):197-203. https://doi.org/10.1016/j. aca.2005.05.032
» https://doi.org/10.1016/j. aca.2005.05.032
Armitage P, Berry G, Matthew JNS. Statistical methods in medical research (4th ed.). Wiley-Blackwell, 2001.
Bae IK, Ham HM, Jeong MH, Kim DH, Kim HJ. Simultaneous determination of 15 phenolic compounds and caffeine in teas and mate using RP-HPLC/UV detection: method development and optimization of extraction process. Food Chem. 2015;172:469-475. https://doi.org/10.1016/j. foodchem.2014.09.050
» https://doi.org/10.1016/j. foodchem.2014.09.050
Bertolín JR, Joy M, Blanco M. Malondialdehyde determination in raw and processed meat products by UPLC-DAD and UPLC-FLD. Food Chem. 2019;298:125009. https:// doi.org/10.1016/j.foodchem.2019.125009
» https:// doi.org/10.1016/j.foodchem.2019.125009
Bollinger G, Belsley DA, Kuh E, Welsch RE. Regression diagnostics: identifying influential data and sources of collinearity. J Mark Res. 1981; 18(3):392-393. https://doi. org/10.2307/3150985
» https://doi. org/10.2307/3150985
Brasil Ministério Da Agricultura. Laboratorial/CGAL, 2013. Intrução de trabalho: determinação de cafeína por CLAE (IT LABV 269). [citad 2020 December 07]. http://www.agricultura.gov.br/assuntos/laboratorios/legislacoes-e-metodos/arquivos-metodos-da-area-bev-iqa/it-labv-269-rev02-determinacao-de-cafeina-por-clae.pdf/@@download/file/ITLABV269Rev02-DeterminaçãodecafeínaporCLAE.pdf
Brasil Ministério da Saúde. Agência Nacional de Vigilância Sanitária (ANVISA). Resolução da Diretoria Colegiada (RDC) Nº 166 de 2017. [citad 2020 December 14]. http://portal.anvisa.gov.br/documents/10181/2721567/RDC_166_2017_COMP.pdf/d5f b92b3-6c6b-4130-8670-4e3263763401
» http://portal.anvisa.gov.br/documents/10181/2721567/RDC_166_2017_COMP.pdf/d5f b92b3-6c6b-4130-8670-4e3263763401
Brasil. Ministério da Saúde. Agência Nacional de Vigilância Sanitária(ANVISA).Resolução da Diretoria Colegiada (RDC) Nº 719 de 2022. [citad 2022 December 1]. https://anvisa.gov.br/documents/10181/6503647/%281%29RDC_719_2022_COMP.pdf/eec091a3-0699-4804-acba-3d6f9c3f72af
Brasil. Instituto Nacional de Metrologia e Normalização e Qualidade Industrial (INMETRO), 2011. Orientação Sobre Validação de Métodos de Ensaios Químicos DOQ-CGCRE-008. INMETRO. [citad 2020 December] [citad 2020 December] http://www.ufjf.br/baccan/files/2011/05/Validacao-Inmetro.pdf
» http://www.ufjf.br/baccan/files/2011/05/Validacao-Inmetro.pdf
Brown MB, Forsythe AB. Robust tests for the equality of variances. J Am Stat Assoc. 1974;69(346):364-367. https://doi.org/10.1080/01621459.1974.10482955
» https://doi.org/10.1080/01621459.1974.10482955
da Silva GS, Canuto KM, Ribeiro PR, de Brito ES, Nascimento MM, Zocolo GJ, et al. Chemical profiling of guarana seeds (Paullinia cupana) from different geographical origins using UPLC-QTOF-MS combined with chemometrics. Food Res Int. 2017;102:700-709. https://doi.org/10.1016/j.foodres.2017.09.055
» https://doi.org/10.1016/j.foodres.2017.09.055
Do T, Santi I, Reich E. A harmonized HPTLC method for identification of various caffeine containing herbal drugs, extracts, and products, and quantitative estimation of their caffeine content. J Liq Chromatog Relat Technol. 2019;42(9-10):274-281. https://doi.org/10.1080/10826076.2019.1585612
» https://doi.org/10.1080/10826076.2019.1585612
Draper NR, Smith H. Applied regression analysis. 1998;(3rd ed).. Wiley. https://doi.org/10.1002/9781118625590
» https://doi.org/10.1002/9781118625590
European Commission. 2017SANTE/11813/2017: Guidance document on analytical quality control and method validation procedures for pestice residues and analysis in food and feed [citad 2020 December 7] 2017SANTE/11813/2017: Guidance document on analytical quality control and method validation procedures for pestice residues and analysis in food and feed [citad 2020 December 7] https://ec.europa.eu/food/sites/food/files/plant/docs/pesticides_mrl_guidelines_wrkdoc_2017-11813.pdf
FDA Analytical procedures and methods validation for drugs and biologics. Guidance for Industry. 2015 July, 1-15.
Fekry AM, Shehata M, Azab SM., Walcarius A. Voltammetric detection of caffeine in pharmacological and beverages samples based on simple nano-Co (II, III) oxide modified carbon paste electrode in aqueous and micellar media. Sens Actuators B Chem. 2020;301,127172. https://doi. org/10.1016/j.snb.2019.12172
» https://doi. org/10.1016/j.snb.2019.12172
Horwitz W. Validation: An invisible component of measurement. AOAC International. 2003. [citad 2020 December 7] [citad 2020 December 7] http://scholar.google.com/scholar?hl=en&btnG=Search&q=intitle:Validation+:+An+invisible+Component+of+Measurement#0
Huber L. Validation of analytical methods: Review and strategy. LC GC Europe. 1998,11(2),96-105.http://www.scopus.com/inward/record.url?eid=2-FIg.00007433072&partnerID=40&md5=5ba3bf980084003aba10c935665b958c
Instituto Brasileiro de Geografia e Estatística (IBGE). Levantamento sistemático da produção agrícola: pesquisa mensal de previsão e acompanhamento das safras agrícolas no ano civil. In Levant. Sistem. Prod. Agríc.2017;30-12.
International Conference on Harmonization (ICH). Text on validation of analytical procedure: methodology: Q2(R1), 2005. [citad 2022 August] [citad 2022 August] http://www.ich.org
Kazusaki M, Ueda S, Takeuchi N, Ohgami Y. Validation of analytical procedures by high−performance liquid chromatography for pharmaceutical analysis. Chromatog. 2012;33(2), 65-73. https://doi.org/10.15583/ jpchrom.2012.005
» https://doi.org/10.15583/ jpchrom.2012.005
Klein T, Longhini R, de Mello JCP. Development of an analytical method using reversed-phase HPLC-PDA for a semipurified extract of Paullinia cupana var. sorbilis (guaraná). Talanta. 2012;88:502-506. https://doi.org/10.1016/j.talanta.2011.11.023
» https://doi.org/10.1016/j.talanta.2011.11.023
Kole J, Barnhill A. Caffeine content labeling: a missed opportunity for promoting personal and public health. J Caffeine Res. 2013;3:108-113. https://doi.org/10.1089/jcr.2013.0017
» https://doi.org/10.1089/jcr.2013.0017
Latosińska M, Latosińska JN. Introductory chapter: caffeine, a major component of nectar of the gods and favourite beverage of kings, popes, artists and revolutionists, a drug or a poison? In J. N. Latosinska & M. Latosinska (Eds.), The Question of Caffeine. 2017;1:1-26. InTech. https://doi.org/10.5772/intechopen.69693
» https://doi.org/10.5772/intechopen.69693
Machado KN, Freitas AA, de Cunha LH, Faraco AAG, Pádua RM, de Braga FC, et al. A rapid simultaneous determination of methylxanthines and proanthocyanidins in Brazilian guaraná (Paullinia cupana Kunth.). Food Chem. 2018;239:180-188. https://doi.org/10.1016/j.foodchem.2017.06.089
» https://doi.org/10.1016/j.foodchem.2017.06.089
Magnusson B, Ornemark U. The fitness for purpose of analytical methods a laboratory guide to method validation and related topics. In B. Magnusson & U. Örnemark (Eds.), Eurachem Guide. 2014, (2nd ed.). http://www.eurachem.org
Marques LLM, Ferreira EDF, Paula MN, Klein T, Mello JCP. Paullinia cupana: a multipurpose plant - a review. Rev Bras Farmacogn. 2019;29:77-110. https://doi.org/10.1016/j.bjp.2018.08.007
» https://doi.org/10.1016/j.bjp.2018.08.007
Nedeljković T, Pavlović Z, Dilber S, Šobajić S, Michaličkova D, Đorđević B. Determination of the content of caffeine and taurine in energy drinks and dietetic products by hplc method. Hrana I Ishrana. 2017;58:19-26. https://doi.org/10.5937/HraIsh1701019
» https://doi.org/10.5937/HraIsh1701019
Nour V, Trandafir I, Ionica ME. Chromatographic determination of caffeine contents in soft and energy drinks available on the romanian market. Scientific Study & Research Chemistry & Chemical Engineering, Biotechnology, Food Ind. 2010;11:351-358.
Ribani M, Bottoli CBG, Collins CH, Jardim ICSF, Melo LFC. Validação em métodos cromatográficos e eletroforéticos. Quim Nova. 2004;27(5):771-780. https://doi.org/10.1590/S0100-40422004000500017
» https://doi.org/10.1590/S0100-40422004000500017
Ryan TA, Joiner BL. Normal Probability Plots and Tests for Normality. Test. 1976, 10:1668-1675. [citad 2020 December 7]. http://scholar.google.com/scholar?hl=en&btnG=Search&q=intitle:Normal+probability+plots+and+tests+for+normality#0
Schimpl FC, da Silva JF, Gonçalves JF de C, Mazzafera P. Guarana: revisiting a highly caffeinated plant from the Amazon. J Ethnopharmacol. 2013;150(1):14-31. https://doi.org/10.1016/j.jep.2013.08.023
» https://doi.org/10.1016/j.jep.2013.08.023
Sereshti H, Samadi S. A rapid and simple determination of caffeine in teas, coffees and eight beverages. Food Chem. 2014;158:8-13. https://doi.org/10.1016/j.foodchem.2014.02.095
» https://doi.org/10.1016/j.foodchem.2014.02.095
Snedecor W, Cochran WG. Statistical methods (8th ed.). Wiley-Blackwell. 1991. [citad 2020 December 7]. https://www.wiley.com/en-us/Statistical+Methods%2C+8th+Edition-p-9780813815619
» https://www.wiley.com/en-us/Statistical+Methods%2C+8th+Edition-p-9780813815619
Sousa SA de, Pascoa H, Conceição EC da, Alves SF, Diniz DGA, Paula JR de, et al. Dissolution test of herbal medicines containing Paullinia cupana: validation of methods for quantification and assessment of dissolution. Braz J Pharm Sci. 2011;47:2,269-277. https://doi.org/10.1590/S1984-82502011000200008
» https://doi.org/10.1590/S1984-82502011000200008
Sun XD, Wu HL, Liu Z, Chen Y, Liu Q, Ding Y-J, et al. Rapid and Sensitive Detection of Multi-Class Food Additives in Beverages for Quality Control by Using HPLC-DAD and Chemometrics Methods. Food Anal Methods. 2019;12:381-393.
Turak F, Güzel R, Dinç E. Simultaneous determination of ascorbic acid and caffeine in commercial soft drinks using reversed-phase ultraperformance liquid chromatography. J Food Drug Anal. 2017; 25(2): 285-292. https://doi.org/10.1016/j.jfda.2016.09.004
» https://doi.org/10.1016/j.jfda.2016.09.004
Viana C, Zemolin GM, Dal Molin TR, Gobo L, Ribeiro SM, Leal GC, et al. Detection and determination of undeclared synthetic caffeine in weight loss formulations using HPLC-DAD and UHPLC-MS/MS. J Pharm Anal. 2018;8(6):366-372. https://doi.org/10.1016/j.jpha.2017.12.004
» https://doi.org/10.1016/j.jpha.2017.12.004
Watson J, Durbin, S. Testing for Serial Correlation in Least Squares Regression. Biometrika. 1950;37(1):409-428. http://www.jstor.org/stable/2332391
» http://www.jstor.org/stable/2332391
Yonekura L, Tamura H. A fast and sensitive isocratic high performance liquid chromatography method for determination of guaraná (Paullinia cupana) flavan-3-ols. MethodsX. 2019; 6:850-855. https://doi.org/10.1016/j.mex.2019.04.008
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