{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,2]],"date-time":"2025-11-02T08:48:53Z","timestamp":1762073333798,"version":"build-2065373602"},"reference-count":37,"publisher":"MDPI AG","issue":"21","license":[{"start":{"date-parts":[[2022,10,29]],"date-time":"2022-10-29T00:00:00Z","timestamp":1667001600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100008530","name":"AgriFood XXI I&amp;D&amp;I","doi-asserted-by":"publisher","award":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"],"award-info":[{"award-number":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"]}],"id":[{"id":"10.13039\/501100008530","id-type":"DOI","asserted-by":"publisher"}]},{"name":"European Regional Development Fund","award":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"],"award-info":[{"award-number":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"]}]},{"name":"Associated Laboratory for Sustainable Chemistry, Clean Processes, and Technologies LAQV","award":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"],"award-info":[{"award-number":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"]}]},{"name":"European Union","award":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"],"award-info":[{"award-number":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"]}]},{"DOI":"10.13039\/501100001871","name":"FCT","doi-asserted-by":"publisher","award":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"],"award-info":[{"award-number":["NORTE-01-0145-FEDER-000041","Norte 2014\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","NORTE-01-0145-FEDER-000052","SFRH\/BD\/146549\/2019"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>This work reports the functionalization of pyranoflavyliums pigment using 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride coupling chemistry. Four cinnamic acids were used to establish an ester bond with the hydroxyl group of the pyranoflavylium, namely 4-dimethylamino-, 4-amino-, 4-bromo-, and trans-cinnamic acids. The experimental condition, namely the molar ratios, solvent, and reaction time, were adjusted to obtain higher reaction yields in a reduced period. Excellent reaction yields of 68%, 85%, 94%, and 99% were achieved for 4-amino, trans-, 4-bromo, and 4-dimethylamino pyranoflavylium cinnamates, respectively. The structure of the functionalized pigments was fully clarified using one-dimensional (1H) and two-dimensional (COSY, HSQC, and HMBC) NMR experiments and HRSM analysis. Regardless of the type of functionalization, the UV-Visible spectrum showed a bathochromic shift (red region) on the maximum absorption wavelength and the absence of acid-base reactions throughout a broad pH range in comparison to the pyranoflavylium precursor. This work offers a valuable environmentally friendly, quick, and straightforward alternative to flavylium compounds\u2019 challenging and labor-intensive functionalization, resulting in novel dyes with higher stability and dissimilar chromatic features.<\/jats:p>","DOI":"10.3390\/molecules27217351","type":"journal-article","created":{"date-parts":[[2022,10,30]],"date-time":"2022-10-30T09:01:42Z","timestamp":1667120502000},"page":"7351","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Functionalization of 7-Hydroxy-pyranoflavylium: Synthesis of New Dyes with Extended Chromatic Stability"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9779-2678","authenticated-orcid":false,"given":"Ana Rita","family":"Pereira","sequence":"first","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde\u2014REQUIMTE, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal"}]},{"given":"Victor de","family":"Freitas","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde\u2014REQUIMTE, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9318-9732","authenticated-orcid":false,"given":"Nuno","family":"Mateus","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde\u2014REQUIMTE, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9996-1463","authenticated-orcid":false,"given":"Joana","family":"Oliveira","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde\u2014REQUIMTE, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2022,10,29]]},"reference":[{"key":"ref_1","unstructured":"Oyvind, A.M., and Kenneth, M.R. (2005). Flavonoids: Chemistry, Biochemistry and Applications, CRC Press. [1st ed.]."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Wallace, T.C., and Giusti, M.M. (2019). Anthocyanins\u2014Nature\u2019s Bold, Beautiful, and Health-Promoting Colors. Foods, 8.","DOI":"10.3390\/foods8110550"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"4388","DOI":"10.1021\/jf049653f","article-title":"Properties of 3-Deoxyanthocyanins from Sorghum","volume":"52","author":"Awika","year":"2004","journal-title":"J. Agric. Food Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"127494","DOI":"10.1016\/j.foodchem.2020.127494","article-title":"Stability of 3-deoxyanthocyanin pigment structure relative to anthocyanins from grains under microwave assisted extraction","volume":"333","author":"Herrman","year":"2020","journal-title":"Food Chem."},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Ara\u00fajo, P., Fernandes, A., de Freitas, V., and Oliveira, J. (2017). A New Chemical Pathway Yielding A-Type Vitisins in Red Wines. Int. J. Mol. Sci., 18.","DOI":"10.3390\/ijms18040762"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3933","DOI":"10.1016\/j.tetlet.2009.04.072","article-title":"A novel synthetic pathway to vitisin B compounds","volume":"50","author":"Oliveira","year":"2009","journal-title":"Tetrahedron Lett."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1401","DOI":"10.1016\/S0031-9422(97)00772-3","article-title":"A new class of wine pigments generated by reaction between pyruvic acid and grape anthocyanins","volume":"47","author":"Fulcrand","year":"1998","journal-title":"Phytochemistry"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"9598","DOI":"10.1021\/jf062325q","article-title":"Isolation and Structural Characterization of New Anthocyanin-Derived Yellow Pigments in Aged Red Wines","volume":"54","author":"He","year":"2006","journal-title":"J. Agric. Food Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"8814","DOI":"10.1021\/jf101408q","article-title":"Oxovitisins: A new class of neutral pyranone-anthocyanin derivatives in red wines","volume":"58","author":"He","year":"2010","journal-title":"J Agric Food Chem"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"479","DOI":"10.1016\/j.dyepig.2017.03.005","article-title":"Influence of the structural features of amino-based pyranoanthocyanins on their acid-base equilibria in aqueous solutions","volume":"141","author":"Oliveira","year":"2017","journal-title":"Dye. Pigment."},{"key":"ref_11","first-page":"299","article-title":"New Family of Bluish Pyranoanthocyanins","volume":"2004","author":"Mateus","year":"2004","journal-title":"J. Biomed. Biotechnol."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"190","DOI":"10.1016\/j.dyepig.2013.09.009","article-title":"Previous and recent advances in pyranoanthocyanins equilibria in aqueous solution","volume":"100","author":"Oliveira","year":"2014","journal-title":"Dye. Pigment."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1416","DOI":"10.1021\/acs.chemrev.1c00399","article-title":"Natural and Synthetic Flavylium-Based Dyes: The Chemistry Behind the Color","volume":"122","author":"Cruz","year":"2022","journal-title":"Chem. Rev."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"3066","DOI":"10.1016\/j.tet.2014.10.058","article-title":"Aged red wine pigments as a source of inspiration for organic synthesis\u2014The cases of the color-stable pyranoflavylium and flavylium-(4\u21928)-flavan chromophores","volume":"71","author":"Chassaing","year":"2015","journal-title":"Tetrahedron"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"884","DOI":"10.1039\/b800165k","article-title":"Blue flower color development by anthocyanins: From chemical structure to cell physiology","volume":"26","author":"Yoshida","year":"2009","journal-title":"Nat. Prod. Rep."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"4937","DOI":"10.1021\/acs.chemrev.5b00507","article-title":"Stabilizing and modulating color by copigmentation: Insights from theory and experiment","volume":"116","author":"Trouillas","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"153487","DOI":"10.1016\/j.tetlet.2021.153487","article-title":"Synthesis, structural characterization and chromatic features of new 2-phenyl-1-benzopyrylium and 2-phenyl-styryl-1-benzopyrylium amino-based blue dyes","volume":"85","author":"Mateus","year":"2021","journal-title":"Tetrahedron Lett."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1016\/j.jphotochem.2012.06.013","article-title":"Synthesis, characterization and photochromism of 3\u2032-butoxyflavylium derivatives","volume":"244","author":"Gago","year":"2012","journal-title":"J. Photochem. Photobiol. A Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"69","DOI":"10.1016\/j.dyepig.2008.09.007","article-title":"The synthesis and reaction network of 2-styryl-1-benzopyrylium salts: An unexploited class of potential colorants","volume":"81","author":"Gomes","year":"2009","journal-title":"Dye. Pigment."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1390","DOI":"10.1055\/s-0036-1591978","article-title":"Synthesis and Structural Characterization of a Novel Symmetrical 2,10-Bis-Styryl-1-Benzopyrylium Dye","volume":"29","author":"Gomes","year":"2018","journal-title":"Synlett"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"480","DOI":"10.1016\/j.foodchem.2014.11.062","article-title":"Synthesis, characterisation and antioxidant features of procyanidin B4 and malvidin-3-glucoside stearic acid derivatives","volume":"174","author":"Cruz","year":"2015","journal-title":"Food Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"6513","DOI":"10.1021\/acs.jafc.6b05461","article-title":"Malvidin 3-Glucoside\u2013Fatty Acid Conjugates: From Hydrophilic toward Novel Lipophilic Derivatives","volume":"65","author":"Cruz","year":"2017","journal-title":"J. Agric. Food Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/j.foodchem.2017.02.140","article-title":"Lipophilization and MS characterization of the main anthocyanins purified from hibiscus flowers","volume":"230","author":"Salas","year":"2017","journal-title":"Food Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2909","DOI":"10.1021\/acs.jafc.7b05924","article-title":"Enzymatic Acylation of Anthocyanins Isolated from Alpine Bearberry (Arctostaphylos alpina) and Lipophilic Properties, Thermostability, and Antioxidant Capacity of the Derivatives","volume":"66","author":"Yang","year":"2018","journal-title":"J. Agric. Food Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"125167","DOI":"10.1016\/j.foodchem.2019.125167","article-title":"An efficient method for anthocyanins lipophilization based on enzyme retention in membrane systems","volume":"300","author":"Mateus","year":"2019","journal-title":"Food Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"7387","DOI":"10.1021\/acs.jafc.0c02599","article-title":"Microwave-Assisted Synthesis and Ionic Liquids: Green and Sustainable Alternatives toward Enzymatic Lipophilization of Anthocyanin Monoglucosides","volume":"68","author":"Mateus","year":"2020","journal-title":"J. Agric. Food Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"6359","DOI":"10.1002\/chem.201003726","article-title":"Synthesis and characterization of a symmetric bis(7-hydroxyflavylium) containing a methyl viologen bridge","volume":"17","author":"Diniz","year":"2011","journal-title":"Chemistry"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"69698","DOI":"10.1039\/C6RA12017B","article-title":"Synthesis and multistate characterization of bis-flavylium dications\u2014symmetric resorcinol- and phloroglucinol-type derivatives as stochastic systems","volume":"6","author":"Garnier","year":"2016","journal-title":"RSC Adv."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"236","DOI":"10.1002\/open.201500210","article-title":"Extending the Study of the 6,8 Rearrangement in Flavylium Compounds to Higher pH Values: Interconversion between 6-Bromo and 8-Bromo-apigeninidin","volume":"5","author":"Cruz","year":"2016","journal-title":"ChemistryOpen"},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Ruwizhi, N., and Aderibigbe, B.A. (2020). Cinnamic Acid Derivatives and Their Biological Efficacy. Int. J. Mol. Sci., 21.","DOI":"10.3390\/ijms21165712"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2754","DOI":"10.1039\/C6FO00466K","article-title":"Enzymatic synthesis, structural characterization and antioxidant capacity assessment of a new lipophilic malvidin-3-glucoside-oleic acid conjugate","volume":"7","author":"Cruz","year":"2016","journal-title":"Food Funct."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"128482","DOI":"10.1016\/j.foodchem.2020.128482","article-title":"Enzymatic acylation of cyanidin-3-glucoside with fatty acid methyl esters improves stability and antioxidant activity","volume":"343","author":"Zhang","year":"2021","journal-title":"Food Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"371","DOI":"10.1136\/jcp.17.4.371","article-title":"Fluorescence of Solutions: A Review","volume":"17","author":"Williams","year":"1964","journal-title":"J. Clin. Pathol."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"356","DOI":"10.1016\/j.saa.2019.01.023","article-title":"Solvent effects on the absorption and fluorescence spectra of Zaleplon: Determination of ground and excited state dipole moments","volume":"212","author":"Divac","year":"2019","journal-title":"Spectrochim. Acta A Mol. Biomol. Spectrosc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"17853","DOI":"10.1021\/acsomega.8b02745","article-title":"Achieving Complexity at the Bottom. 2,6-Bis(arylidene)cyclohexanones and Anthocyanins: The Same General Multistate of Species","volume":"3","author":"Corici","year":"2018","journal-title":"ACS Omega"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"8920","DOI":"10.1039\/C6CP00890A","article-title":"A blue 4\u2032,7-diaminoflavylium cation showing an extended pH range stability","volume":"18","author":"Tron","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"7583","DOI":"10.1016\/j.tetlet.2003.08.065","article-title":"A novel synthetic route to substituted pyranoanthocyanins with unique colour properties","volume":"44","author":"Schwarz","year":"2003","journal-title":"Tetrahedron Lett."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/21\/7351\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:05:31Z","timestamp":1760144731000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/21\/7351"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,10,29]]},"references-count":37,"journal-issue":{"issue":"21","published-online":{"date-parts":[[2022,11]]}},"alternative-id":["molecules27217351"],"URL":"https:\/\/doi.org\/10.3390\/molecules27217351","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2022,10,29]]}}}