Concepts of sustainability have received attention from people involved in investigation of nature-derived matrices. The effects of concomitant pollutant activities are cumulative and harmful to the environment from which these matrices are obtained. High performance liquid chromatography analyses generate millions of litters of chemical waste worldwide every year. Reduction of organic solvent consumption during the analyses and replacement of harmful solvents with greener options are the main approaches to mitigate this problem. This work explored the strategy of employing monolithic columns when the problematic acetonitrile is intended to be replaced with the greener but more viscous ethanol in fingerprinting a leaf extract of Lippia sidoides Cham., Verbenaceae, by high performance liquid chromatography. Two monolithic columns were coupled in series to test a more critical backpressure condition while doubling the number of theoretical plates, which can be useful to separate the hundreds of compounds present in plant extracts. All work was conducted by employing design of experiments. A mathematical model indicated an optimum point in which ethanol was the only organic solvent of the mobile phase. However, the use of a proper metric, which considered environmental parameters together with separation parameters, evidenced that an experimental condition of the original central composite design should be preferred over the former even if containing 20% acetonitrile in the organic modifier mixture. Flow rates of up to 3 ml/min were accommodated with two coupled monolithic columns without exceeding 250 bar. These findings reinforced that no state-of-the-art instruments are needed to shift from traditional harmful solvents to greener ones, but only require a shift in researchers’ approach toward sustainability.
Almeida, M.C.S.De., Alves, L.A., Gregório, L., Souza, S., Machado, L.L., Matos, M.C.De., Conceição, M., Oliveira, F.De., Lemos, T.L.G., Braz-filho, R., 2010. Flavonoides e outras substâncias de Lippiasidoides e suas atividades antioxidantes. Quim. Nova 33, 1877–1881.
Castro, A.C.C.M., Oda, F.B., Almeida-Cincotto, M.G.J., Davanço, M.G., Chiari-Andréo, B.G., Cicarelli, R.M.B., Peccinini, R.G., Zocolo, G.J., Ribeiro, P.R.V., Corrêa, M.A., Isaac, V.L.B., Santos, A.G., 2018. Green coffee seed residue: a sustainable source of antioxidant compounds. Food Chem. 246, 48–57.
Causon, T.J., Cortes, H.J., Shellie, R.A., Hilder, E.F., 2012. Temperature pulsing for controlling chromatographic resolution in capillary liquid chromatography. Anal. Chem. 84, 3362–3368.
Destandau, E., Lesellier, E., 2008. Chromatographic properties of ethanol/water mobile phases on silica based monolithic C18. Chromatographia 68, 985–990.
Funari, C.S., Carneiro, R.L., Andrade, A.M., Hilder, E.F., Cavalheiro, A.J., 2014a. Green chromatographic fingerprinting: an environmentally friendly approach for the development of separation methods for fingerprinting complex matrices. J. Sep. Sci. 37, 37–44.
Funari, C.S., Carneiro, R.L., Cavalheiro, A.J., Hilder, E.F., 2014b. A trade off between separation, detection and sustainability in liquid chromatographic fingerprinting. J. Chromatogr. A 1354, 34–42.
Funari, C.S., Carneiro, R.L., Khandagale, M.M., Cavalheiro, A.J., Hilder, E.F., 2015. Acetone as a greener alternative to acetonitrile in liquid chromatographic fingerprinting. J. Sep. Sci. 38, 1458–1465.
Gaber, Y., Tornvall, U., Kumar, M.A., Ali Amin, M., Hatti-Kaul, R., 2011. HPLCEAT (Environmental Assessment Tool): a tool for profiling safety, health and environmental impacts of liquid chromatography methods. Green Chem. 13, 2021–2025.
Gałuszka, A., Migaszewski, Z., Namiesnik, J., 2013. The 12 principles of green analytical chemistry and the SIGNIFICANCE mnemonic of green analytical practices. TrAC - Trends Anal. Chem. 50, 78–84.
Gritti, F., Guiochon, G., 2012. The current revolution in column technology: how it began, where is it going? J. Chromatogr. A 1228, 2–19.
Guardia, M.D.La., Garrigues, S., 2011. Challenges in Green Analytical Chemistry. RSC Green Chemistry. Royal Society of Chemistry, Great Britain, https://doi.org/10.1039/9781849732963.
Lima, B.S., Ramos, C.S., Santos, J.P.A., Rabelo, T.K., Serafini, M.R., Souza, C.A.S., Soares, L.A.L., Quintans, L.J., Moreira, J.C.F., Gelain, D.P., Araújo, A.A.S., Silva, F.A., 2015. Development of standardized extractive solution from Lippia sidoides by factorial design and their redox active profile. Rev. Bras. Farmacogn. 25, 301–306.
Ministério da Saúde, 2008. RENISUS - Relação Nacional de Plantas Medicinais de Interesse ao SUS [WWW Document]. Ministério da Saúde, URL file:///C:/Users/HP/Downloads/RENISUS-2009.pdf.
Pereira, A., dos, S., Girón, A.J., Admasu, E., Sandra, P., 2010. Green hydrophilic interaction chromatography using ethanol-water-carbon dioxide mixtures. J. Sep. Sci. 33, 834–837.
Płotka, J., Tobiszewski, M., Sulej, A.M., Kupska, M., Górecki, T., Namieśnik, J., 2013. Green chromatography. J. Chromatogr. A 1307, 1–20.
Prat, D., Wells, A., Hayler, J., Sneddon, H., Mcelroy, C.R., Abou-shehada, S., Dunn, P.J., 2016. CHEM21 selection guide of classical- and less classical-solvents. Green Chem. 18, 288–296.
Sandra, P., Sandra, K., Pereira, A., Vanhoenacker, G., David, F., 2010. Green chromatography, Part 1: Introduction and liquid chromatography. LC-GC Eur. 23, 242–259.
Shaaban, H., Górecki, T., 2012. Fast ultrahigh performance liquid chromatographic method for the simultaneous determination of 25 emerging contaminants in surface water and wastewater samples using superficially porous sub-3μm particles as an alternative to fully porous sub-2μm particles. Talanta 100, 80–89.
Shen, Y., Chen, B., van Beek, T., 2015. Alternative solvents can make preparative liquid chromatography greener. GreenChem. 17, 4073–4081.
Sutton, A.T., Fraige, K., Leme, G.M., Bolzani, V.S., Hilder, E.F., Cavalheiro, A.J., Arrua, D.R., Funari, C.S., 2018. Natural deep eutectic solvents as the major mobile phase components in high performance liquid chromatography - searching for alternatives to organic solvents. Anal. Bional. Chem., https://doi.org/10.1007/s00216-018-1027-5.
Tistaert, C., Dejaegher, B., Vander Heyden, Y., 2011. Chromatographic separation techniques and data handling methods for herbal fingerprints: a review. Anal. Chim. Acta 690, 148–161.
Tobiszewski, M., Mechlinska, A., Namiesnik, J., 2010. Green analytical chemistry -theory and practice. Chem. Soc. Rev. 39, 2869–2878.
Tobiszewski, M., Namiesnik, J., 2017. Greener organic solvents in analytical chemistry. Curr. Opin. Green Sustain. Chem. 5, 1–4.
Welch, C.J., Wu, N., Biba, M., Hartman, R., Brkovic, T., Gong, X., Helmy, R., Schafer, W., Cuff, J., Pirzada, Z., Zhou, L., 2010. Greening analytical chromatography. TrAC -Trends Anal. Chem. 29, 667–680.
Yehia, A.M., Mohamed, H.M., 2016. Green approach using monolithic column for simultaneous determination of coformulated drugs. J. Sep. Sci. 39, 2114–2122.
CSF performed all the experimental work, analyzed the data and wrote the manuscript. RLC and AJC contributed to experimental design, data analysis, and drafting of the manuscript. All the authors read the final manuscript and approved the submission.
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Funari, C.S., Cavalheiro, A.J. & Carneiro, R.L. Coupled monolithic columns as an alternative for the use of viscous ethanol-water mobile phases on chromatographic fingerprinting complex samples. Rev. Bras. Farmacogn. 28, 261–266 (2018). https://doi.org/10.1016/j.bjp.2018.04.010
- Experimental design
- Chromatographic fingerprint
- Green analytical chemistry
- Green solvents