{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T00:27:19Z","timestamp":1791937639550,"version":"4.3.4"},"reference-count":55,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2025,5,27]],"date-time":"2025-05-27T00:00:00Z","timestamp":1748304000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Cocoa is a rich source of health-promoting polyphenols such as flavanols. These compounds can be separated from other matrix constituents using various adsorbents or resins. Seven different macroporous resins (Amberlite\u00ae XAD-2, XAD-4, XAD-7, XAD-7HP, XAD-16, SepabeadsTM SP207, and Diaion\u00ae HP2-MG) were evaluated for their adsorption and desorption properties for the enrichment of flavonoids from an aqueous cocoa (Theobroma cacao L.) extract. The influence of adsorption and desorption temperatures and the concentration of the desorption solvent (a hydroalcoholic solution) were investigated by static adsorption and desorption methods. The results of the resin comparison showed that the adsorbent XAD-7HP had the best adsorption characteristics, with an adsorption capacity of 39.8 mg ECE\/g. XAD-7HP was found to be the most suitable adsorbent, and 70% ethanol was the best desorbing solvent, based on static experiments. In addition, the optimal conditions for the adsorption of flavonoids were obtained at a temperature of 30 \u00b0C, where equilibrium was reached after 80 min. The static adsorption process was well-described by a pseudo-second-order kinetics model, while the adsorption isotherm data were fitted well by the Freundlich isotherm model. Further dynamic adsorption and desorption characteristics were evaluated on a packed glass column, and it was shown that XAD-7HP could enrich the flavanol content by 5.03-fold, with a dry matter content of 456.05 mg\/mL (as estimated by the degree of DP1\u2013DP7 procyanidin polymers using ultra-pressure liquid chromatography).<\/jats:p>","DOI":"10.3390\/molecules30112336","type":"journal-article","created":{"date-parts":[[2025,5,27]],"date-time":"2025-05-27T09:29:36Z","timestamp":1748338176000},"page":"2336","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Purification of Flavonoids from an Aqueous Cocoa (Theobroma cocoa L.) Extract Using Macroporous Adsorption Resins"],"prefix":"10.3390","volume":"30","author":[{"given":"Nicole","family":"Beeler","sequence":"first","affiliation":[{"name":"Food Process Development Research Group, Institute of Food and Beverage Innovation, School of Life Sciences and Facility Management, Zurich University of Applied Sciences, 8820 W\u00e4denswil, Switzerland"},{"name":"Department of Food Chemistry and Analysis, Institute of Food Technology and Food Chemistry, Technische Universit\u00e4t Berlin, 13355 Berlin, Germany"},{"name":"Oro de Cacao AG, Chocolate Manufacturer, 8807 Freienbach, Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tilo","family":"H\u00fchn","sequence":"additional","affiliation":[{"name":"Food Process Development Research Group, Institute of Food and Beverage Innovation, School of Life Sciences and Facility Management, Zurich University of Applied Sciences, 8820 W\u00e4denswil, Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5009-8830","authenticated-orcid":false,"given":"Sascha","family":"Rohn","sequence":"additional","affiliation":[{"name":"Department of Food Chemistry and Analysis, Institute of Food Technology and Food Chemistry, Technische Universit\u00e4t Berlin, 13355 Berlin, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Renato","family":"Colombi","sequence":"additional","affiliation":[{"name":"Oro de Cacao AG, Chocolate Manufacturer, 8807 Freienbach, Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,5,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1016\/j.ccr.2017.06.013","article-title":"Effect of Polyphenols-Membrane Interactions on the Performance of Membrane-Based Processes. A Review","volume":"351","author":"Cassano","year":"2017","journal-title":"Coord. Chem. Rev."},{"key":"ref_2","first-page":"906252","article-title":"Cocoa Polyphenols and Their Potential Benefits for Human Health","volume":"2012","author":"Recio","year":"2012","journal-title":"Oxid. Med. Cell Longev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"254","DOI":"10.1016\/j.foodchem.2016.01.130","article-title":"Determination of Antioxidant Capacity and Phenolic Content of Chocolate by Attenuated Total Reflectance-Fourier Transformed-Infrared Spectroscopy","volume":"202","author":"Hu","year":"2016","journal-title":"Food Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"116405","DOI":"10.1016\/j.lwt.2024.116405","article-title":"Purification of Phenolics from Plantago Depressa by Macroporous Resin: Adsorption\/Desorption Characteristics, Chromatographic Process Development and UPLC-TQ-MS\/MS Quantitative Analysis","volume":"203","author":"Cao","year":"2024","journal-title":"LWT"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"82","DOI":"10.1016\/j.trac.2017.12.018","article-title":"A Critical Analysis of Extraction Techniques Used for Botanicals: Trends, Priorities, Industrial Uses and Optimization Strategies","volume":"100","author":"Belwal","year":"2018","journal-title":"TrAc Trends Anal. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"538","DOI":"10.1016\/j.foodchem.2014.07.109","article-title":"Absorption and Desorption Behaviour of the Flavonoids from Glycyrrhiza glabra L. Leaf on Macroporous Adsorption Resins","volume":"168","author":"Dong","year":"2015","journal-title":"Food Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1965","DOI":"10.1021\/jf035220l","article-title":"Adsorption of Flavonoids on Resins: Cyanidin 3-Glucoside","volume":"52","author":"Scordino","year":"2004","journal-title":"J. Agric. Food Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"7349","DOI":"10.1021\/ie3004094","article-title":"Enrichment and Purification of Total Flavonoid C-Glycosides from Abrus mollis Extracts with Macroporous Resins","volume":"51","author":"Du","year":"2012","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"5070","DOI":"10.1002\/fsn3.2464","article-title":"Purification and Antioxidant Properties of Triterpenic Acids from Blackened Jujube (Ziziphus jujuba Mill.) by Macroporous Resins","volume":"9","author":"Fu","year":"2021","journal-title":"Food Sci. Nutr."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"127","DOI":"10.1016\/j.jfoodeng.2009.07.007","article-title":"Recovery of Antioxidants from Industrial Waste Liquors Using Membranes and Polymeric Resins","volume":"96","author":"Moure","year":"2010","journal-title":"J. Food Eng."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"2368","DOI":"10.1021\/jf205311v","article-title":"Adsorption and Desorption Properties of Macroporous Resins for Anthocyanins from the Calyx Extract of Roselle (Hibiscus sabdariffa L.)","volume":"60","author":"Chang","year":"2012","journal-title":"J. Agric. Food Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1079","DOI":"10.1016\/j.lwt.2010.10.008","article-title":"Enrichment and Fractionation of Major Apple Flavonoids, Phenolic Acids and Dihydrochalcones Using Anion Exchange Resins","volume":"44","author":"Kammerer","year":"2011","journal-title":"LWT\u2014Food Sci. Technol."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"431","DOI":"10.1007\/s00217-004-1078-z","article-title":"Recovery of Anthocyanins from Grape Pomace Extracts (Vitis vinifera L. Cv. Cabernet Mitos) Using a Polymeric Adsorber Resin","volume":"220","author":"Kammerer","year":"2005","journal-title":"Eur. Food Res. Technol."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"8421","DOI":"10.1021\/jf901840t","article-title":"Color and Polyphenolic Stability in Extracts Produced from Muscadine Grape (Vitis rotundifolia) Pomace","volume":"57","author":"Cardona","year":"2009","journal-title":"J. Agric. Food Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"3008","DOI":"10.3390\/molecules17033008","article-title":"Recovery and Concentration of Antioxidants from Winery Wastes","volume":"17","author":"Soto","year":"2012","journal-title":"Molecules"},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Che Zain, M.S., Lee, S.Y., Teo, C.Y., and Shaari, K. (2020). Adsorption and Desorption Properties of Total Flavonoids from Oil Palm (Elaeis guineensis Jacq.) Mature Leaf on Macroporous Adsorption Resins. Molecules, 25.","DOI":"10.3390\/molecules25040778"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"3987","DOI":"10.1021\/la990091h","article-title":"Correlation between Adsorption and Small Molecule Hydrogen Bonding","volume":"15","author":"Brune","year":"1999","journal-title":"Langmuir"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"9879","DOI":"10.1021\/jp991499q","article-title":"Differential Adsorption of Phenol Derivatives onto a Polymeric Sorbent: A Combined Molecular Modeling and Experimental Study","volume":"103","author":"Mardis","year":"1999","journal-title":"J. Phys. Chem. B"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"6689","DOI":"10.1039\/C8RA09319A","article-title":"Enrichment and Separation of Steroidal Saponins from the Fibrous Roots of Ophiopogon japonicus Using Macroporous Adsorption Resins","volume":"9","author":"Zhou","year":"2019","journal-title":"RSC Adv."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"579","DOI":"10.1016\/j.cej.2014.05.120","article-title":"Adsorption Kinetics, Isotherm and Thermodynamics Studies of Flavones from Vaccinium Bracteatum Thunb Leaves on NKA-2 Resin","volume":"254","author":"Chen","year":"2014","journal-title":"Chem. Eng. J."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"900","DOI":"10.1016\/j.foodchem.2015.08.070","article-title":"Adsorption and Desorption Characteristics of Adlay Bran Free Phenolics on Macroporous Resins","volume":"194","author":"Yang","year":"2016","journal-title":"Food Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1016\/j.seppur.2009.06.002","article-title":"Preparative Separation and Purification of Rosavin in Rhodiola Rosea by Macroporous Adsorption Resins","volume":"69","author":"Ma","year":"2009","journal-title":"Sep. Purif. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1016\/j.foodchem.2014.04.035","article-title":"Enrichment and Purification of Marine Polyphenol Phlorotannins Using Macroporous Adsorption Resins","volume":"162","author":"Kim","year":"2014","journal-title":"Food Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"417","DOI":"10.1016\/j.foodchem.2011.07.069","article-title":"Macroporous Resin Purification Behavior of Phenolics and Rosmarinic Acid from Rabdosia serra (MAXIM.) HARA Leaf","volume":"130","author":"Lin","year":"2012","journal-title":"Food Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"794","DOI":"10.1080\/01496390903566713","article-title":"Enrichment and Purification of Total Chlorogenic Acids from Tobacco Waste Extract with Macroporous Resins","volume":"45","author":"Hui","year":"2010","journal-title":"Sep. Sci. Technol."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"609","DOI":"10.1080\/01496390701787222","article-title":"Optimization of Sulforaphane Separation from Broccoli Seeds by Macroporous Resins","volume":"43","author":"Li","year":"2008","journal-title":"Sep. Sci. Technol."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"167","DOI":"10.1016\/j.jfoodeng.2013.12.029","article-title":"Adsorption\/Desorption Characteristics and Separation of Anthocyanins and Polyphenols from Blueberries Using Macroporous Adsorbent Resins","volume":"128","author":"Buran","year":"2014","journal-title":"J. Food Eng."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"6787","DOI":"10.1021\/jf1000869","article-title":"Pilot-Scale Resin Adsorption as a Means to Recover and Fractionate Apple Polyphenols","volume":"58","author":"Kammerer","year":"2010","journal-title":"J. Agric. Food Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"18","DOI":"10.1016\/j.chroma.2005.06.051","article-title":"The Application of Macroporous Resins in the Separation of Licorice Flavonoids and Glycyrrhizic Acid","volume":"1089","author":"Fu","year":"2005","journal-title":"J. Chromatogr. A"},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Zhang, X., Su, J., Chu, X., and Wang, X. (2022). A Green Method of Extracting and Recovering Flavonoids from Acanthopanax Senticosus Using Deep Eutectic Solvents. Molecules, 27.","DOI":"10.3390\/molecules27030923"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"434","DOI":"10.1021\/ie503590m","article-title":"Solvent Swing Adsorption for the Recovery of Polyphenols from Black Tea","volume":"54","author":"Monsanto","year":"2015","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"e14365","DOI":"10.1111\/jfpe.14365","article-title":"Separation Process Characteristics of Phenolic Compounds from Organic Purple-fleshed Sweet Potatoes (Ipomoea batatas L.) Leaves Using Macroporous Resins","volume":"46","author":"Mohammad","year":"2023","journal-title":"J. Food Process Eng."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"e12275","DOI":"10.1111\/jfpe.12275","article-title":"Recovery of Flavonoids from Walnuts De-Pellicle Wastewater with Macroporous Resins and Evaluation of Antioxidant Activities In Vitro","volume":"40","author":"Zhu","year":"2017","journal-title":"J. Food Process Eng."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"712","DOI":"10.1016\/j.foodchem.2015.08.084","article-title":"Adsorption Properties of Macroporous Adsorbent Resins for Separation of Anthocyanins from Mulberry","volume":"194","author":"Chen","year":"2016","journal-title":"Food Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"6998","DOI":"10.1021\/jf034496q","article-title":"Adsorption of Flavonoids on Resins: Hesperidin","volume":"51","author":"Scordino","year":"2003","journal-title":"J. Agric. Food Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"e12834","DOI":"10.1111\/jfpe.12834","article-title":"Adsorption\/Desorption, Diffusion, and Thermodynamic Properties of Anthocyanin from Purple Rice Bran Extract on Various Adsorbents","volume":"41","author":"Das","year":"2018","journal-title":"J. Food Process Eng."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"9270","DOI":"10.1021\/ie101721a","article-title":"Adsorption Thermodynamics and Kinetics of Uridine 5\u2032-Monophosphate on a Gel-Type Anion Exchange Resin","volume":"50","author":"Zhou","year":"2011","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"55","DOI":"10.1016\/j.foodchem.2014.07.038","article-title":"Preliminary Enrichment and Separation of Chlorogenic Acid from Helianthus tuberosus L. Leaves Extract by Macroporous Resins","volume":"168","author":"Sun","year":"2015","journal-title":"Food Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1244","DOI":"10.1111\/1750-3841.16028","article-title":"Purification of Polyphenols from Phyllanthus emblica L. Pomace Using Macroporous Resins: Antioxidant Activity and Potential Anti-Alzheimer\u2019s Effects","volume":"87","author":"Gan","year":"2022","journal-title":"J. Food Sci."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"293","DOI":"10.1016\/j.jhazmat.2007.12.102","article-title":"Adsorptive Removal of Phenol from Aqueous Phase by Using a Porous Acrylic Ester Polymer","volume":"157","author":"Pan","year":"2008","journal-title":"J. Hazard. Mater."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"2682","DOI":"10.1021\/ie201494k","article-title":"Synthesis of Functional Adsorption Resin and Its Adsorption Properties in Purification of Flavonoids from Hippophae rhamnoides L. Leaves","volume":"51","author":"Lou","year":"2012","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1985","DOI":"10.1002\/jssc.201200120","article-title":"Preparative Purification of Peoniflorin and Albiflorin from Peony Rhizome Using Macroporous Resin and Medium-pressure Liquid Chromatography","volume":"35","author":"Wang","year":"2012","journal-title":"J. Sep. Sci."},{"key":"ref_43","unstructured":"H\u00fchn, T. (2020). Cocoa Extraction Methods and Techniques. (Application EP3747275A1), European Patent."},{"key":"ref_44","unstructured":"H\u00fchn, T., and Laux, R. (2017). Cocoa Bean Processing Methods and Techniques. (Application EP2378892A2), European Patent."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"3991","DOI":"10.1021\/acs.jafc.8b06800","article-title":"Characterization of the Flavor Properties of Dark Chocolates Produced by a Novel Technological Approach and Comparison with Traditionally Produced Dark Chocolates","volume":"67","author":"Chetschik","year":"2019","journal-title":"J. Agric. Food Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"119486","DOI":"10.1016\/j.indcrop.2024.119486","article-title":"Enrichment of Polyphenols from Cinnamomum Camphora Seed Kernel by Macroporous Adsorption Resins and Evaluation of Its Antioxidant and Enzyme Inhibitory Activities","volume":"222","author":"Yang","year":"2024","journal-title":"Ind. Crops Prod."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"159","DOI":"10.1016\/j.molliq.2015.01.004","article-title":"Nanoadsorbents for Pollutants Removal: A Review","volume":"203","author":"Kyzas","year":"2015","journal-title":"J. Mol. Liq."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"117972","DOI":"10.1016\/j.molliq.2021.117972","article-title":"Adsorption of Low Molecular Weight Food Relevant Polyphenols on Cross-Linked Agarose Gel","volume":"347","author":"Escalona","year":"2022","journal-title":"J. Mol. Liq."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1016\/j.jhazmat.2008.09.106","article-title":"Methylene Blue Number as Useful Indicator to Evaluate the Adsorptive Capacity of Granular Activated Carbon in Batch Mode: Influence of Adsorbate\/Adsorbent Mass Ratio and Particle Size","volume":"165","author":"Raposo","year":"2009","journal-title":"J. Hazard. Mater."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"114980","DOI":"10.1016\/j.molliq.2020.114980","article-title":"Reasonable Calculation of the Thermodynamic Parameters from Adsorption Equilibrium Constant","volume":"322","author":"Chen","year":"2021","journal-title":"J. Mol. Liq."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"119610","DOI":"10.1016\/j.indcrop.2024.119610","article-title":"Development and Optimization of a Cocoa Extraction Treatment by Means of the Response Surface Methodology (RSM) and Artificial Neural Networks (ANN)","volume":"222","author":"Beeler","year":"2024","journal-title":"Ind. Crops Prod."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"248","DOI":"10.1016\/0003-2697(76)90527-3","article-title":"A Rapid and Sensitive Method for the Quantitation of Microgram Quantities of Protein Utilizing the Principle of Protein-Dye Binding","volume":"72","author":"Bradford","year":"1976","journal-title":"Anal. Biochem."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"1199","DOI":"10.1038\/1811199a0","article-title":"Antioxidant Determinations by the Use of a Stable Free Radical","volume":"181","author":"Blois","year":"1958","journal-title":"Nature"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"5905","DOI":"10.1007\/s00216-016-9705-7","article-title":"Extraction of Cocoa Proanthocyanidins and Their Fractionation by Sequential Centrifugal Partition Chromatography and Gel Permeation Chromatography","volume":"408","author":"Pedan","year":"2016","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"1932","DOI":"10.1111\/jfpp.12166","article-title":"Effect of Superheated Steam Roasting on the Phenolic Antioxidant Properties of Cocoa Beans","volume":"38","author":"Zzaman","year":"2014","journal-title":"J. Food Process Preserv."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/11\/2336\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T17:41:20Z","timestamp":1760031680000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/11\/2336"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,5,27]]},"references-count":55,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2025,6]]}},"alternative-id":["molecules30112336"],"URL":"https:\/\/doi.org\/10.3390\/molecules30112336","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,5,27]]}}}