Kinetic study of bioactive compound extraction from cacao shell waste by conventional and deep eutectic solvent
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Abstract
Cacao shells contain bioactive compounds such as phenolic acids and flavonoids. This study investigated the potential of bioactive compound extraction in cacao shells using conventional and green solvents like deep eutectic solvent (DES) (choline chloride: lactic acid). Specifically, it investigated the extraction kinetic models and parameters, which are critical to scale up the extraction process. The extraction of cacao shell was conducted using various conventional solvents (ethanol, methanol, n-hexane, and water) and DES (100 % and 70%) in which the result showed that DES 100% had the highest total phenolic content of 337.92?±?9.55 mg GAE/g dry weight. Meanwhile, pseudo-second order and Peleg’s model provided the best fit for the experimental data with higher R2 values. DES 70% showed a higher total flavonoid content of 76.51?±?1.59 mg RE/g dry weight. FT-IR and Raman spectroscopy confirmed the presence of bioactive compounds in DES-based extracts, which revealed characteristic vibrational bands associated with polyphenolic structures. These include bands corresponding to hydroxyl (–OH), carbonyl (C=O), and aromatic C=C stretching—functional groups commonly found in quercetin and other bioactive compounds.
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Irsal, M., Kusumastuti, Y., Ariyanto, T., & Putri, N. R. E. (2025). Kinetic study of bioactive compound extraction from cacao shell waste by conventional and deep eutectic solvent. Communications in Science and Technology, 10(1), 117-124. https://doi.org/10.21924/cst.10.1.2025.1606
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References
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F. A. González-Alejo, J. Barajas-Fernández, M. de los Á. Olán-Acosta, L. M. Lagunes-Gálvez, and P. García-Alamilla, Supercritical Fluid Extraction of Fat and Caffeine with Theobromine Retention in the Cocoa Shell, Processes 7(6) (2019) 385.
L. Valadez-Carmona, Plazola-Jacinto C. P., Hernández-Ortega M., Hernández-Navarro M. D., Villarreal F., Necoechea-Mondragón H., Ortiz-Moreno A., and Ceballos-Reyes G., Effects of microwaves, hot air and freeze-drying on the phenolic compounds, antioxidant capacity, enzyme activity and microstructure of cacao pod husks (Theobroma cacao L.), Innov. Food Sci. Emerg. Technol. 41 (2017) 378-386.
J. Xiao, Dietary flavonoid aglycones and their glycosides: Which show better biological significance?, Crit. Rev. Food Sci. Nutr. 57(9) (2017) 1874-1905.
E. L. Smith, A. P. Abbott, and K. S. Ryder, Deep Eutectic Solvents (DESs) and Their Applications, Chem. Rev. 114(21) (2014) 11060-11082.
X. Tang, M. Zuo, Z. Li, H. Liu, C. Xiong, X. Zeng, Y. Sun, L. Hu, S. Liu, T. Lei, and L. Lin, Green Processing of Lignocellulosic Biomass and Its Derivatives in Deep Eutectic Solvents, ChemSusChem 10(13) (2017) 2696-2706.
Q. Zhang, K. De Oliveira Vigier, S. Royer, and F. Jérôme, Deep eutectic solvents: syntheses, properties and applications, Chem. Soc. Rev. 41 (21) (2012) 7108-7146.
M. Francisco, A. Van Den Bruinhorst, and M. C. Kroon, New natural and renewable low transition temperature mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing, Green Chem. 14 (8) (2012) 2153-2157.
C. Fanali, V. Gallo, S. Della Posta, L. Dugo, L. Mazzeo, M. Cocchi, V. Piemonte, and L. De Gara, Choline Chloride–Lactic Acid-Based NADES As an Extraction Medium in a Response Surface Methodology-Optimized Method for the Extraction of Phenolic Compounds from Hazelnut Skin, Molecules 26(9) (2021) 2652.
A. Buci?-Koji?, H. Sovová, M. Planini?, and S. Tomas, Temperature-dependent kinetics of grape seed phenolic compounds extraction: Experiment and model, Food Chem. 136(3-4) (2013) 1136-1140.
Q. Xia, C. Chen, Y. Yao, J. Li, S. He, Y. Zhou, T. Li, X. Pan, Y. Yao, and L. Hu, A strong, biodegradable and recyclable lignocellulosic bioplastic, Nat. Sustain. 4(7) (2021) 627–635.
V. L. Singleton, R. Orthofer, and R. M. Lamuela-Raventós, Analysis of total phenols and other oxidation substrates and antioxidants by means of folin-ciocalteu reagent, Academic Press 299 (1999) 152-178.
M. Blasa, M. Candiracci, A. Accorsi, M. P. Piacentini, M. C. Albertini, and E. Piatti, “Raw Millefiori honey is packed full of antioxidants, Food Chem. 97(2) (2006) 217-222.
Y. S. Ho, H. A. Harouna-Oumarou, H. Fauduet, and C. Porte, Kinetics and model building of leaching of water-soluble compounds of Tilia sapwood, Sep. Purif. Technol. 45.3 (2005) 169-173.
Z. Reddad, C. Gerente, Y. Andres, and P. Le Cloirec, Adsorption of several metal ions onto a low-cost biosorbent: Kinetic and equilibrium studies, Environmental Sci. Technol. 36(9) (2002) 2067-2073.
Y. S. Ho and G. McKay, Pseudo-second order model for sorption processes, Process Biochem. 34(5) (1999) 451-465.
M. Peleg, An Empirical Model for the Description of Moisture Sorption Curves, J Food Sci. 53.4 (1988) 1216-1217.
C. Niamnuy, M. Charoenchaitrakool, P. Mayachiew, and S. Devahastin, Bioactive Compounds and Bioactivities of Centella asiatica (L.) Urban Prepared by Different Drying Methods and Conditions, Dry. Technol. 31(16) (2013) 2007-2015.
B. Hou, R. Durrani, A. Delavault, E. Durand, C. Jiang, Y. Long, L. Song, J. Song, W. Huan, and F. Gao, Application of deep eutectic solvents in protein extraction and purification, Front. Chem. 10 (2022) 912411.
Ul Abbas, Q. Qiao, M. T. Nguyen, J. Shi, and Q. Shao, Molecular dynamics simulations of heterogeneous hydrogen bond environment in hydrophobic deep eutectic solvents, AIChE J. 68 (2022) e17382.
M. K. Jha, A. Malik, and H. K. Kashyap, How hydrogen bond donor acceptor ratio and water content impact heterogeneity in microstructure and dynamics of N,N-diisooctylacetamide and decanol based hydrophobic deep eutectic solvent, J. Mol. Liq. 385 (2023) 122127.
M. Liu, D. Cao, W. Bi, and D. D. Y. Chen, Extraction of natural products by direct formation of eutectic systems, ACS Sustain. Chem. Eng. 9 (2021) 12049–12057.
Z. Reddad, C. Gerente, Y. Andres, and P. Le Cloirec, Adsorption of several metal ions onto a low-cost biosorbent: Kinetic and equilibrium studies, Environmental Sci. Technol. 36(9) (2002) 2067-2073.
E. Benítez-Correa, J. M. Bastías-Montes, S. Acuña-Nelson, and O. Muñoz-Fariña, Effect of choline chloride-based deep eutectic solvents on polyphenols extraction from cocoa (Theobroma cacao L.) bean shells and antioxidant activity of extracts, Curr. Res. Food Sci. 7 (2023) 100614.
M. Vilková, J. P?otka-Wasylka, and V. Andruch, The role of water in deep eutectic solvent-base extraction, J. Mol. Liq. 304 (2020) 112747.
F. Ramos-Escudero, A. Rojas-García, M. de la L. Cádiz-Gurrea, and A. Segura-Carretero, High potential extracts from cocoa byproducts through sonotrode optimal extraction and a comprehensive characterization, Ultrason. Sonochem. 106 (2024) 106887.
Z. Lu, Y. Chen, X. Tang, J. Gao, F. He, X. Zhang, H. He, P. Dramou, and D. Xiao, Simultaneous and selective extraction of different polarity bioactive substances from Ligustri Lucidi Fructus based on a designable biphasic deep eutectic solvent, J. Clean Prod. 449 (2024) 141791.
L. A. da Silva, M. R. da Silva Scapim, J. F. da Silva, A. P. Stafussa, A. C. R. Aranha, L. M. de M. Jorge, R. O. Defendi, O. de O. Santos Júnior, and G. S. Madrona, Modeling the extraction of bioactive compounds of green and red camu-camu peel and identification using UPLC-MS/MS, Chem. Eng. Res. Des. 196 (2023) 1–12.
C. H. Lau, L. S. Chua, C. T. Lee, and R. Aziz, Optimization and Kinetic Modeling of Rosmarinic Acid Extraction from Orthosiphon stamineus, Curr. Bioact. Compd. 10(4) (2014) 271-285.
W. Pereira da Silva, J. S. Nunes, J. P. Gomes, and C. M. D. P. da Silva e Silva, Obtaining anthocyanin from jambolan fruit: Kinetics, extraction rate, and prediction of process time for different agitation frequencies, Food Sci. Nutr. 6 (2018) 1664–1669.
P. L. Kiew, M. D. Mashitah, and Z. Ahmad, Kinetics and modeling of pepsin soluble collagen (PSC) extraction from the skin of malaysian catfish (Hybrid Clarias sp.), J. Korean Soc. Appl. Biol. Chem. 57 (2014) 53–66.
K. V. Kumar, H. K. S. Souza, and V. K. Gupta, On the initial reaction rate of Peleg’s model for rehydration kinetics, J. Taiwan Inst. Chem. Eng. 42 (2011) 278–280.
H. S. Kusuma, P. D. Amelia, C. Admiralia, and M. Mahfud. Kinetics study of oil extraction from Citrus aurantium L. by solvent-free microwave extraction. Commun. Sci. Technol. 1 (2016) 15–18.
N. N. M. Phuong, T. T. Le, M. Q. Dang, J. Van Camp, and K. Raes, Selection of extraction conditions of phenolic compounds from rambutan (Nephelium lappaceum L.) peel, Food Bioprod. Process. 122 (2020) 222-229.
M. Irakli, P. Chatzopoulou, and L. Ekateriniadou, Optimization of ultrasound-assisted extraction of phenolic compounds: Oleuropein, phenolic acids, phenolic alcohols and flavonoids from olive leaves and evaluation of its antioxidant activities, Ind. Crops. Prod. 124 (2018) 382-388.
C. S. Dzah, Y. Duan, H. Zhang, C. Wen, J. Zhang, G. Chen, and H. Ma, The effects of ultrasound assisted extraction on yield, antioxidant, anticancer and antimicrobial activity of polyphenol extracts: A review, Food Biosci. 35 (2020) 100547.
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