Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation

The acylation of flavonoids serves as a means to alter their physicochemical properties, enhance their stability, and improve their bioactivity. Compared with natural flavonoid glycosides, the acylation of nonglycosylated flavonoids presents greater challenges since they contain fewer reactive sites...

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Detalhes bibliográficos
Autores: González-Alfonso, José L., Alonso, Cristina, Poveda, Ana, Ubiparip, Zorica, Ballesteros Olmo, Antonio, Desmet, Tom, Jiménez-Barbero, Jesús, Coderch Negra, M. Luisa, Plou, Francisco J.
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/349019
Acesso em linha:http://hdl.handle.net/10261/349019
https://api.elsevier.com/content/abstract/scopus_id/85185604907
Access Level:acceso abierto
Palavra-chave:Hydrophile–lipophile balance (HLB)
Acylation
Antioxidants
Dihydrochalcones
Flavonoids
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
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spelling Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-GlucosylationGonzález-Alfonso, José L.Alonso, CristinaPoveda, AnaUbiparip, ZoricaBallesteros Olmo, Antonio Desmet, TomJiménez-Barbero, JesúsCoderch Negra, M. LuisaPlou, Francisco J.Hydrophile–lipophile balance (HLB)AcylationAntioxidantsDihydrochalconesFlavonoidshttp://metadata.un.org/sdg/3Ensure healthy lives and promote well-being for all at all agesThe acylation of flavonoids serves as a means to alter their physicochemical properties, enhance their stability, and improve their bioactivity. Compared with natural flavonoid glycosides, the acylation of nonglycosylated flavonoids presents greater challenges since they contain fewer reactive sites. In this work, we propose an efficient strategy to solve this problem based on a first α-glucosylation step catalyzed by a sucrose phosphorylase, followed by acylation using a lipase. The method was applied to phloretin, a bioactive dihydrochalcone mainly present in apples. Phloretin underwent initial glucosylation at the 4'-OH position, followed by subsequent (and quantitative) acylation with C8, C12, and C16 acyl chains employing an immobilized lipase from Thermomyces lanuginosus. Electrospray ionization-mass spectrometry (ESI-MS) and two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) confirmed that the acylation took place at 6-OH of glucose. The water solubility of C8 acyl glucoside closely resembled that of aglycone, but for C12 and C16 derivatives, it was approximately 3 times lower. Compared with phloretin, the radical scavenging capacity of the new derivatives slightly decreased with 2,2-diphenyl-1-picrylhydrazyl (DPPH) and was similar to 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+). Interestingly, C12 acyl-α-glucoside displayed an enhanced (3-fold) transdermal absorption (using pig skin biopsies) compared to phloretin and its α-glucoside.This work was supported by (1) Grant PDC2022-133134-C21 “ACYLGLUFLAV_APP” funded by MCIN/AEI/10.13039/501100011033 by the “European Union NextGenerationEU/PRTR”; (2) Grant PID2019-105838RB-C31 “GLYCOENZ-PHARMA” funded by MCIN/AEI/10.13039/501100011033; (3) Grant PID2022-136367OB-C31 “GLYCOENZ-GREEN” funded by MCIN/AEI/10.13039/501100011033 and through FEDER, a Way of Making Europe; and (4) Grant CM_5779 “Programa Investigo” (Madrid Region, Call 2022, European Union NextGenerationEU). The authors thank the support of the scholarship of Jose Luis Gonzalez from the Spanish Ministry of Education, Culture and Sport through the National Program FPU (FPU17/00044).Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia e Innovación (España)0000-0002-3396-79850000-0001-5060-23070000-0002-1967-20560000-0002-5788-30220000-0001-5421-85130000-0003-0831-893XConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articleartículoPublisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/349019https://api.elsevier.com/content/abstract/scopus_id/85185604907reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MCIN/AEI/10.13039Journal of agricultural and food chemistryhttps://doi.org/10.1021/acs.jafc.3c09261Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3490192026-05-22T06:33:51Z
dc.title.none.fl_str_mv Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
title Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
spellingShingle Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
González-Alfonso, José L.
Hydrophile–lipophile balance (HLB)
Acylation
Antioxidants
Dihydrochalcones
Flavonoids
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
title_short Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
title_full Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
title_fullStr Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
title_full_unstemmed Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
title_sort Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation
dc.creator.none.fl_str_mv González-Alfonso, José L.
Alonso, Cristina
Poveda, Ana
Ubiparip, Zorica
Ballesteros Olmo, Antonio
Desmet, Tom
Jiménez-Barbero, Jesús
Coderch Negra, M. Luisa
Plou, Francisco J.
author González-Alfonso, José L.
author_facet González-Alfonso, José L.
Alonso, Cristina
Poveda, Ana
Ubiparip, Zorica
Ballesteros Olmo, Antonio
Desmet, Tom
Jiménez-Barbero, Jesús
Coderch Negra, M. Luisa
Plou, Francisco J.
author_role author
author2 Alonso, Cristina
Poveda, Ana
Ubiparip, Zorica
Ballesteros Olmo, Antonio
Desmet, Tom
Jiménez-Barbero, Jesús
Coderch Negra, M. Luisa
Plou, Francisco J.
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
0000-0002-3396-7985
0000-0001-5060-2307
0000-0002-1967-2056
0000-0002-5788-3022
0000-0001-5421-8513
0000-0003-0831-893X
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Hydrophile–lipophile balance (HLB)
Acylation
Antioxidants
Dihydrochalcones
Flavonoids
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
topic Hydrophile–lipophile balance (HLB)
Acylation
Antioxidants
Dihydrochalcones
Flavonoids
http://metadata.un.org/sdg/3
Ensure healthy lives and promote well-being for all at all ages
description The acylation of flavonoids serves as a means to alter their physicochemical properties, enhance their stability, and improve their bioactivity. Compared with natural flavonoid glycosides, the acylation of nonglycosylated flavonoids presents greater challenges since they contain fewer reactive sites. In this work, we propose an efficient strategy to solve this problem based on a first α-glucosylation step catalyzed by a sucrose phosphorylase, followed by acylation using a lipase. The method was applied to phloretin, a bioactive dihydrochalcone mainly present in apples. Phloretin underwent initial glucosylation at the 4'-OH position, followed by subsequent (and quantitative) acylation with C8, C12, and C16 acyl chains employing an immobilized lipase from Thermomyces lanuginosus. Electrospray ionization-mass spectrometry (ESI-MS) and two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) confirmed that the acylation took place at 6-OH of glucose. The water solubility of C8 acyl glucoside closely resembled that of aglycone, but for C12 and C16 derivatives, it was approximately 3 times lower. Compared with phloretin, the radical scavenging capacity of the new derivatives slightly decreased with 2,2-diphenyl-1-picrylhydrazyl (DPPH) and was similar to 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+). Interestingly, C12 acyl-α-glucoside displayed an enhanced (3-fold) transdermal absorption (using pig skin biopsies) compared to phloretin and its α-glucoside.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
artículo
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/349019
https://api.elsevier.com/content/abstract/scopus_id/85185604907
url http://hdl.handle.net/10261/349019
https://api.elsevier.com/content/abstract/scopus_id/85185604907
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MCIN/AEI/10.13039
Journal of agricultural and food chemistry
https://doi.org/10.1021/acs.jafc.3c09261
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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