SIMULTANEOUS DETERMINATION OF CHLOROGENIC ACIDS AND CAFFEINE BY REVERSED-PHASE HPLC
Abstract
A variant of simultaneous determination of chlorogenic (monocaffeoylquinic and dicaffeoylquinic) acids and caffeine in coffee (drink) using reversed-phase chromatography with spectrophotometric detection has been developed. For separation, a gradient mode is proposed exploring of two components of the mobile phase containing 3 vol.% of formic acid and 6 and 20 vol.% acetonitrile in distilled water and chromatographic column 150×4.6 mm Symmetry C18, 3.5 μm. Column thermostat temperature is 30 °C. The choice of the type and concentration of the acidifier of the mobile phase is justified in the work. It has been established that the acidity of the mobile phases should not be lower than pH 2 in order to transfer most of the chlorogenic acids to the non-ionized state. The dependences of the retention of monocaffeoylquinic acids and caffeine on the concentration of acetonitrile and formic acid, which is more effective in the selectivity of separation compared to orthophosphoric acid in the mobile phase, are determined. The selectivity of the separation of these compounds depends more on the concentration of formic acid than on the concentration of acetonitrile. Concentrations of chlorogenic acids and caffeine were determined in drinks from two varieties of coffee, coffee husk (dried pericarp of coffee fruits) (produced in Vietnam) and for comparison of two more variants – Arabica coffee from roasted grains and from green decaffeinated grains from other manufacturers. It is shown that coffee husk is a valuable raw material for the preparation of an alternative drink. Thus, when using 1 g of coffee husk when brewing 100 ml of boiling water, a drink containing about 10 mg (per 100 ml) of monocaffeoylquinic acids, about 6 mg of dicaffeoylquinic acids and about 3 mg of caffeine was obtained.
For citation:
Blinova I.P., Oleinits E.Yu., Salasina Ya.Yu., Deineka V.I., Vu Thi Ngoc Anh, Nguyen Van Anh Simultaneous determination of chlorogenic acids and caffeine by reversed-phase HPLC. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 2. P. 45-52. DOI: 10.6060/ivkkt.20236602.6711.
References
Girma B. Simultaneous Determination of Some Biochemical Contents of Coffee Arabica (Coffea arabica L.) Varieties and Correlation with Organoleptic Cup Quality in Contrasting Al-titudes in Southwest Ethiopia. Food Sci. Quality Manag. 2020. V. 93. P. 22-34. DOI: 10.7176/FSQM/93-03.
Farah A., Monteiro M.C., Calado V., Franca A.S., Trugo L.C. Correlation between cup quality and chemical attributes of Brazilian coffee. Food Chem. 2006. V. 98. P. 373–380. DOI: 10.1016/j.foodchem.2005.07.032.
Belay A., Gholap A.V. Characterization and determination of chlorogenic acids (CGA) in coffee beans by UV-Vis spectroscopy. African J. Pure Appl. Chem. 2009. V. 3. P. 234-240. DOI: 10.5897/AJPAC.
Navarra G., Moschetti M., Guarrasi V., Mangione M.R., Militello V., Leone M. Simultaneous Determination of Caffeine and Chlorogenic Acids in Green Coffee by UV/Vis Spectroscopy. J. Chem. 2017. V. 2017. Art. ID 6435086. DOI: 10.1155/2017/6435086.
Atlabachew M., Abebe A., Wubieneh T.A., Habtemariam Y.T. Rapid and simultaneous determination of trigonelline, caffeine, and chlorogenic acid in green coffee bean extract. Food Sci. Nutr. 2021. V. 9. P. 5028–5035. DOI: 10.1002/fsn3.2456.
Murata M., Okada H., Homma S. Hydroxycinnamic Acid Derivatives and p-Coumaroyl-(L)-trypropban, A Novel Hydroxycinnamic Acid Derivative, from Coffee Beans. Biosci. Biotech. Biochem. 1995. V. 59. P. 1887-1890. DOI: 10.1271/bbb.59.1887.
Jeszka‑Skowron M., Sentkowska A., Pyrzyńska K., De Peсa M.P. Chlorogenic acids, caffeine content and antioxidant properties of green coffee extracts: influence of green coffee bean preparation. Eur. Food Res. Technol. 2016. V. 242. P. 1403–1409. DOI: 10.1007/s00217-016-2643-y.
Jeon J.-S., Kim H.-T., Jeong I.-H., Hong S.-R., Oh M.-S., Park K.-H., Shim J.-H., Abd El-Aty A.M. Determination of chlorogenic acids and caffeine in homemade brewed coffee prepared under various conditions. J. Chromat. B. 2017. V. 1064. P. 115–123. DOI: 10.1016/j.jchromb.2017.08.041.
Rodrigues N.P., Bragagnolo N. Identification and quantification of bioactive compounds in coffee brews by HPLC–DAD–MSn. J. Food Comp. Anal. 2013. V. 32. P. 105–115. DOI: 10.1016/j.jfca.2013.09.002.
Vinson J.A., Chen X., Garver D.D. Determination of Total Chlorogenic Acids in Commercial Green Coffee Extracts. Med. Food. 2019. V. 22. P. 314–320. DOI: 10.1089/jmf.2018.0039.
Higdon J.V., Frei B. Coffee and health: a review of recent human research. Crit. Rev. Food Sci. Nutr. 2006. V. 46. P. 101–123. DOI: 10.1080/10408390500400009.
Watanabe T., Arai Y., Mitsui Y., Kusaura T., Okawa W., Kajihara Y., Saito I. The blood pressure-lowering effect and safety of chlorogenic acid from green coffee bean extract in essential hypertension. Clin. Exp. Hypertens. 2006. V. 28. P. 439–449. DOI: 10.1080/10641960600798655.
Menshutina N.V., Kazeev I.V., Artemiev A.I., Bocharova O.A., Khudeev I.I. Application of supercritical extraction for isolation of chemical compounds. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2021. V. 64. N 6. P. 4-19 (in Russian). DOI: 10.6060/ivkkt.20216406.6405.
Spiro M., Grandoso D.M., Price W.E. Protonation constant of caffeine in aqueous solution. J. Chem. Soc., Faraday Trans. 1. 1989. V. 85. P. 4259-4267. DOI: 10.1039/F19898504259.
Dai J., Mendonsa S.D., Bowser M.T., Lucy C.A., Carr P.W. Effect of anionic additive type on ion pair formation constants of basic pharmaceuticals. J. Chromatogr. A. 2005. V. 1069. P. 225–234. DOI: 10.1016/j.chroma.2005.02.030.
Deineka V.I., Oleinits E.Yu., Blinova I.P., Deineka L.A. Selectivity of the Separa-tion of Isomeric Chlorogenic Acids under the Conditions of Reversed-Phase HPLC. J. Analyt. Chem. 2019. V. 74. P. 778–783. DOI: 10.1134/S1061934819080057.
Clifford M.N., Wight J. The Measurement of Feruloylquinic Acids and Caffeoylquinic Acids in Coffee Beans. Development of the Technique and its Preliminary Application to Green Coffee Beans. J. Sci. Food Agric. 1976. V. 27. P. 13-84. DOI: 10.1002/jsfa.2740270112.
Schrader K., Kiehne A., Engelhardt U.H., Maier H.G. Determination of Chlorogenic Acids with Lactones in Roasted Coffee. J. Sci. Food Agric. 1996. 71. P. 392-398. DOI: 10.1002/(SICI)1097-0010(199607)71:3<392::AID-JSFA597>3.0.CO;2-X.
Deineka V.I., Oleinits E.Yu., Chulkov A.N., Deineka L.A. Control of the selectivity of the separation of dicofeo-ilchinic acids in reverse-phase chromatography. Journal. analyte. chemistry. 2022. V. 77. P. 569-575. DOI: 10.31857/S0044450222060068.
Farah A., de Paulis T., Trugo L.C., Martin P.R. Effect of Roasting on the Formation of Chlorogenic Acid Lactones in Coffee. J. Agric. Food Chem. 2005. 53. P. 1505-1513. DOI: 10.1021/jf048701t.
Ky C.-L., Louarn J., Dussert S., Guyot B., Hamon S., Noirot M. Caffeine, trigonelline, chlorogenic acids and su-crose diversity in wild Coffea arabica L. and C. canephora P. Accessions. Food Chem. 2001. V. 75. P. 223–230. doi.org/10.1016/S0308-8146(01)00204-7
Klingel T., Kremer J.I., Gottstein V., de Rezende T.R., Schwarz S., Lachenmeier D.W. A Review of Co_ee By-Products Including Leaf, Flower, Cherry, Husk, Silver Skin, and Spent Grounds as Novel Foods within the European Un-ion. Foods. 2020. V. 9. P. 665. DOI: 10.3390/foods9050665.
Cangussu L.B., Melo J.C., Franca A.S., Oliveira L.S. Chemical Characterization of Coffee Husks, a By-Product of Coffea arabica Production. Foods. 2021. 10. P. 3125. DOI: 10.3390/foods10123125.
Lachenmeier D.W., Schwarz S., Rieke-Zapp J., Cantergiani E., Rawel H., Martín-Cabrejas M.A., Martuscelli M., Gottstein V., Angeloni S. Coffee By-Products as Sus-tainable Novel Foods: Report of the 2nd International Elec-tronic Conference on Foods—“Future Foods and Food Technologies for a Sustainable World”. Foods. 2022. V. 11. P. 3. DOI: 10.3390/foods11010003.
Sholichah E., Desnilasari D., Subekti R.J., Karim M.A., Purwono B. The influence of coffee cherry fermentation on the properties of Cascara arabica from Subang, West Java. IOP Conf. Ser.: Mater. Sci. Eng. 2011. V. 1011. P. 012006. DOI: 10.1088/1757-899X/1011/1/012006.
