Abstract
Understanding native aroma of chocolate is important for development of food science and food industry. However, isolation of volatile compounds from chocolate is difficult due to matrix effects of cocoa butter and, so far, done using evaporation, vaporization, and distillation techniques with losing volatile compounds. The aim of this study is to develop an effective method for isolation of the volatile compounds from chocolate under mild conditions and conditions with less matrix effects. In the model study, a big gap among partition coefficients (log Pow value) of cocoa butter and volatile compounds was focused to separate volatile compounds from the matrix. Charging deodorized cocoa butter to a hexane-methanol bilayer solution enabled to perform liquid-liquid extraction and thereby push out volatile compounds into methanol layer. We named this phenomenon, the “oiling-out effect.” As a typical application, volatile compounds in dark chocolate containing 35.3% cocoa butter were extracted using liquid-liquid extraction based on the oiling-out effect. The chocolate extract was prepared under room temperature conditions and then analyzed using gas chromatography-mass spectrometry (GC-MS). Fifty-four volatile compounds from 5 g dark chocolate were identified, comprising acids, alcohols, aldehydes, esters, ketones, lactones, furans, hydrocarbons, pyrazines, pyrroles, sulfur compounds, and thiazoles. Compared with solvent extraction and headspace solid-phase micro extraction (HS-SPME), the present method, named the oiling-out assisted liquid-liquid extraction, enabled the isolation of a wide range of volatile compounds from dark chocolate. In this paper, we demonstrated the oiling-out effect as an efficient extraction method for volatile compounds in high-fat foods.
Similar content being viewed by others
References
Acierno V, Yener S, Alewijn M, Biasioli F, van Ruth S (2016) Factors contributing to the variation in the volatile composition of chocolate: botanical and geographical origins of the cocoa beans, and brand-related formulation and processing. Food Res Int 84:86–95. https://doi.org/10.1016/j.foodres.2016.03.022
Afoakwa EO, Paterson A, Fowler M, Ryan A (2009) Matrix effects on flavor volatiles release in dark chocolates varying in particle size distribution and fat content using GC-mass spectrometry and GC-olfactometry. Food Chem 113:208–215. https://doi.org/10.1016/j.foodchem.2008.07.088
Balasubramanian S, Panigrahi S (2011) Solid-phase microextraction (SPME) techniques for quality characterization of food products: a review. Food Bioprocess Technol 4:1–26. https://doi.org/10.1007/s11947-009-0299-3
Braga SCGN, Oliveira LF, Hashimoto JC, Gama MR, Efraim P, Poppi RJ, Augusto F (2018) Study of volatile profile in cocoa nibs, cocoa liquor and chocolate on production process using GC × GC-QMS. Microchem J 141:353–361. https://doi.org/10.1016/j.microc.2018.05.042
Bureau SM, Baumes RL, Razungles AJ (2000) Effects of vine or bunch shading on the glycosylated flavor precursors in grapes of Vitis vinifera L. cv. Syrah. J Agric Food Chem 48:1290–1297. https://doi.org/10.1021/jf990507x
Chetschik I, Pedan V, Chatelain K, Kneubühl M, Hühn T (2019) Characterization of the flavor properties of dark chocolates produced by a novel technological approach and comparison with traditionally produced dark chocolates. J Agric Food Chem 67:3991–4001. https://doi.org/10.1021/acs.jafc.8b06800
Counet C, Callemien D, Ouwerx C, Collin S (2002) Use of gas chromatography-olfactometry to identify key odorant compounds in dark chocolate. Comparison of samples before and after conching. J Agric Food Chem 50:2385–2391. https://doi.org/10.1021/jf0114177
Ducki S, Miralles-Garcia J, Zumbé A, Tornero A, Storey DM (2008) Evaluation of solid-phase micro-extraction coupled to gas chromatography-mass spectrometry for the headspace analysis of volatile compounds in cocoa products. Talanta 74:1166–1174. https://doi.org/10.1016/j.talanta.2007.08.034
Endo S, Pfennigsdorff A, Goss KU (2012) Salting-out effect in aqueous NaCl solutions increases with size and decreases with polarities of solute molecule. Environ Sci Technol 46:1496–1503. https://doi.org/10.1021/es203183z
Frauendorfer F, Schieberle P (2006) Identification of the key aroma compounds in cocoa powder based on molecular sensory correlations. J Agric Food Chem 54:5521–5529. https://doi.org/10.1021/jf060728k
Frauendorfer F, Schieberle P (2008) Changes in key aroma compounds of Criollo cocoa beans during roasting. J Agric Food Chem 56:10244–10251. https://doi.org/10.1021/jf802098f
Gill MS, Macleod AJ, Moreau M (1984) Volatile components of cocoa with particular reference to glucosinolate products. Phytochemistry 23:1937–1942. https://doi.org/10.1016/S0031-9422(00)84945-6
Howard KL, Mike JH, Riesen R (2005) Validation of a solid-phase microextraction method for headspace analysis of wine aroma components. Am J Enol Vitic 56:37–45 http://www.ajevonline.org/content/56/1/37
Li Y, Feng Y, Zhu S, Luo C, Ma J, Zhong F (2012) The effect of alkalization on the bioactive and flavor related components in commercial cocoa powder. J Food Compos Anal 25:17–23. https://doi.org/10.1016/j.jfca.2011.04.010
Liu J, Liu M, He C, Song H, Guo J, Wang Y, Yang H, Su X (2015) A comparative study of aroma-active compounds between dark and milk chocolate: relationship to sensory perception. J Sci Food Agric 95:1362–1372. https://doi.org/10.1002/jsfa.6831
Magalhães VMI, de Figueiredo LV, Santos C, Lima N, Schwan RF (2018) Volatile compounds and protein profiles analyses of fermented cocoa beans and chocolates from different hybrids cultivated in Brazil. Food Res Int 109:196–203. https://doi.org/10.1016/j.foodres.2018.04.012
Magi E, Bono L, Di Carro M (2012) Characterization of cocoa liquors by GC-MS and LC-MS/MS: focus on alkylpyrazines and flavanols. J Mass Spectrom 47:1191–1197. https://doi.org/10.1002/jms.3034
Mayuoni-kirshinbaum L, Tietel Z, Porat R, Ulrich D (2012) Identification of aroma-active compounds in ‘wonderful’ pomegranate fruit using solvent-assisted flavour evaporation and headspace solid-phase micro-extraction methods. Eur Food Res Technol 235:277–283. https://doi.org/10.1007/s00217-012-1757-0
Misnawi, Ariza BTS (2011) Use of gas chromatography-olfactometry in combination with solid phase micro extraction for cocoa liquor aroma analysis. Int Food Res J 18:829–835 http://www.ifrj.upm.edu.my/volume-18-2011.html
Mustakas GC (1987) Recovery of oil from soybean. In: Ericson DR, Prycle EH, Brekke OL, Mounts TL, Falb RA (eds) Handbook of soy oil processing and utilization. American Soybean Association, St. Louis, pp 49–65
Noguerol-Pato R, González-Barreiro C, Cancho-Grande B, Santiago JL, Martínez MC, Simal-Gándara J (2012a) Aroma potential of Brancellao grapes from different cluster positions. Food Chem 132:112–124. https://doi.org/10.1016/j.foodchem.2011.10.042
Noguerol-Pato R, González-Álvarez M, González-Barreiro C, Cancho-Grande B, Simal-Gándara J (2012b) Aroma profile of Garnacha Tintorera-based sweet wines by chromatographic and sensorial analyses. Food Chem 134:2313–2325. https://doi.org/10.1016/j.foodchem.2012.03.105
Ong S, Liu H, Pidgeon C (1996) Immobilized-artificial-membrane chromatography: measurements of membrane partition coefficient and predicting drug membrane permeability. J Chromatogr A 728:113–128. https://doi.org/10.1016/0021-9673(95)00837-3
Pini GF, de Brito ES, Garcia NHP, Valente ALP, Augusto F (2004) A headspace solid phase microextraction (HS-SPME) method for the chromatographic determination of alkylpyrazines in cocoa samples. J Braz Chem Soc 15:267–271 https://doi.org/10.1590/S0103-50532004000200017
PubChem Open Chemical Database (n.d.) https://pubchem.ncbi.nlm.nih.gov/. Accessed 21 Jan 2019
Ramli N, Hassan O, Said M, Samsudin W, Idris NA (2006) Influence of roasting conditions on volatile flavor of roasted Malaysian cocoa beans. J Food Process Preserv 30:280–298. https://doi.org/10.1111/j.1745-4549.2006.00065.x
Rodriguez-Campos J, Escalona-Buendía HB, Contreras-Ramos SM, Orozco-Avila I, Jaramillo-Flores E, Lugo-Cervantes E (2012) Effect of fermentation time and drying temperature on volatile compounds in cocoa. Food Chem 132:277–288. https://doi.org/10.1016/j.foodchem.2011.10.078
Schnermann P, Schieberle P (1997) Evaluation of key odorants in milk chocolate and cocoa mass by aroma extract dilution analyses. J Agric Food Chem 45:867–872. https://doi.org/10.1021/jf960670h
Segall SD, Artz WE, Raslan DS, Ferraz VP, Takahashi JA (2004) Analysis of triacylglycerol isomers in Malaysian cocoa butter using HPLC-mass spectrometry. Food Res Int 38:167–174. https://doi.org/10.1016/j.foodres.2004.09.008
Serrato AG (1981) Extraction of oil from soybeans. J Am Oil Chem Soc 58:157–159. https://doi.org/10.1007/BF02582327
Seyfried C, Granvogl M (2019) Characterization of the key aroma compounds in two commercial dark chocolates with high cocoa contents by means of the sensomics approach. J Agric Food Chem 67:5827–5837. https://doi.org/10.1021/acs.jafc.8b06183
Simoneau C, Hannaert P, Anklam E (1999) Detection and quantification of cocoa butter equivalents in chocolate model systems: analysis of triglycerides profiles by high-resolution GC. Food Chem 65:111–116. https://doi.org/10.1016/S0308-8146(98)00106-X
Tran PD, Van de Walle D, De Clercq N, De Winne A, Kadow D, Lieberei R, Messens K, Tran DN, Dewettinck K, Van Durme J (2015) Assessing cocoa aroma quality by multiple analytical approaches. Food Res Int 77:657–669. https://doi.org/10.1016/j.foodres.2015.09.019
van der Wal B, Kettenes DK, Stoffelsma J, Sipma G, Semper A (1971) New volatile components of roasted cocoa. J Agric Food Chem 19:276–280. https://doi.org/10.1021/jf60174a005
van Praag M, Stein H, Tibbetts S (1968) Steam volatile aroma constituents of roasted cocoa beans. J Agric Food Chem 16:1005–1008. https://doi.org/10.1021/jf60160a011
Ziegleder G (1991) Composition of flavor extracts of raw and roasted cocoas. Z Lebensm Unters Forsch 192:521–525. https://doi.org/10.1007/BF01202506
Ziegleder G (2009) Flavour development in cocoa and chocolate. In: Beckett ST (ed) Industrial chocolate manufacture and use, 4th edn. Blackwell Publishing Ltd, Oxford, pp 169–191
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of Interest
Daisuke Suzuki declares that he has no conflict of interest. Yuko Sato declares that she has no conflict of interest. Hiromi Nishiura declares that she has no conflict of interest. Risa Harada declares that she has no conflict of interest. Hiroshi Kamasaka declares that he has no conflict of interest. Takashi Kuriki declares that he has no conflict of interest. Hirotoshi Tamura declares that he has no conflict of interest.
Ethical Approval
This article does not contain any studies on human or animal subjects performed by any of the authors.
Informed Consent
Not applicable.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Suzuki, D., Sato, Y., Nishiura, H. et al. A Novel Extraction Method for Aroma Isolation from Dark Chocolate Based on the Oiling-Out Effect. Food Anal. Methods 12, 2857–2869 (2019). https://doi.org/10.1007/s12161-019-01642-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-019-01642-0