2-Hydroxychalcone-β-Cyclodextrin Conjugate with pH-Modulated Photoresponsive Binding Properties

Micael Paulino; Ignacio Pérez-Juste; María Magdalena Cid; José P. Da Silva; M. Manuela A. Pereira; Nuno Basílio

doi:10.1021/acs.joc.2c01875

2-Hydroxychalcone-β-Cyclodextrin Conjugate with pH-Modulated Photoresponsive Binding Properties

Micael Paulino, Ignacio Pérez-Juste, María Magdalena Cid, José P. Da Silva, M. Manuela A. Pereira, Nuno Basílio

Research output: Contribution to journal › Article › peer-review

Abstract

Stimuli-responsive supramolecular receptors are important building blocks for the construction of self-assembled functional materials. We report the design and synthesis of a pH- and light-responsive 2-hydroxychalcone-β-cyclodextrin conjugate (1-Ct) and its characterization by spectroscopic and computational methods. 1-Ct follows the typical reaction network of trans-chalcone-flavylium photoswitches. Upon light irradiation, 1-Ct can be photochemically converted into the cis-chalcone/hemiketal forms (1-Cc/1-B) under neutral pH conditions or to the flavylium cation (1-AH⁺) at acidic pH values. This stimuli-responsive β-cyclodextrin host, 1-Ct, was found to form stronger intramolecular self-inclusion complexes (K_intra= 14) than 1-AH⁺(K_intra= 3) and weaker than 1-Cc/1-B (overall K_intra= 179), allowing control over their stability and binding properties by combinations of pH and light stimuli.

Original language	English
Pages (from-to)	14422-14432
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	87
Issue number	21
DOIs	https://doi.org/10.1021/acs.joc.2c01875
Publication status	Published - 4 Nov 2022

Keywords

Binding energy
Functional materials
pH
Binding properties
Building blockes
Chalcones
Flavylium
Hemiketals
Light irradiations
Photo-responsive
Photoswitch
Reaction network
Stimuli-responsive
Cyclodextrins

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10.1021/acs.joc.2c01875

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@article{ff8acb0eb3a7419988fca14ea0a73d4a,

title = "2-Hydroxychalcone-β-Cyclodextrin Conjugate with pH-Modulated Photoresponsive Binding Properties",

abstract = "Stimuli-responsive supramolecular receptors are important building blocks for the construction of self-assembled functional materials. We report the design and synthesis of a pH- and light-responsive 2-hydroxychalcone-β-cyclodextrin conjugate (1-Ct) and its characterization by spectroscopic and computational methods. 1-Ct follows the typical reaction network of trans-chalcone-flavylium photoswitches. Upon light irradiation, 1-Ct can be photochemically converted into the cis-chalcone/hemiketal forms (1-Cc/1-B) under neutral pH conditions or to the flavylium cation (1-AH+) at acidic pH values. This stimuli-responsive β-cyclodextrin host, 1-Ct, was found to form stronger intramolecular self-inclusion complexes (Kintra= 14) than 1-AH+(Kintra= 3) and weaker than 1-Cc/1-B (overall Kintra= 179), allowing control over their stability and binding properties by combinations of pH and light stimuli.",

keywords = "Binding energy, Functional materials, pH, Binding properties, Building blockes, Chalcones, Flavylium, Hemiketals, Light irradiations, Photo-responsive, Photoswitch, Reaction network, Stimuli-responsive, Cyclodextrins",

author = "Micael Paulino and Ignacio P{\'e}rez-Juste and Cid, {Mar{\'i}a Magdalena} and {Da Silva}, {Jos{\'e} P.} and Pereira, {M. Manuela A.} and Nuno Bas{\'i}lio",

note = "Funding Information: This work was supported by the Associate Laboratory for Green Chemistry─LAQV (projects UIDB/50006/2020 and UIDP/50006/2020), which is financed by national funds from FCT/MCTES. FCT/MCTES is also acknowledged for supporting the National Portuguese NMR Network (ROTEIRO/0031/2013-PINFRA/22161/2016, cofinanced by FEDER through COMPETE 2020, POCI, PORL, and FCT through PIDDAC) and for the projects UIDB/04326/2020 and PTDC/QUI-COL/32351/2017 and the CEECIND/00466/2017 research contract (N.B.). This study also received Portuguese national funds from the operational programs CRESC Algarve 2020 and COMPETE 2020 through project EMBRC.PT ALG-01-0145-FEDER-022121. Publisher Copyright: {\textcopyright} 2022 Authors. All rights reserved.",

year = "2022",

month = nov,

day = "4",

doi = "10.1021/acs.joc.2c01875",

language = "English",

volume = "87",

pages = "14422--14432",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "ACS - American Chemical Society",

number = "21",

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TY - JOUR

T1 - 2-Hydroxychalcone-β-Cyclodextrin Conjugate with pH-Modulated Photoresponsive Binding Properties

AU - Paulino, Micael

AU - Pérez-Juste, Ignacio

AU - Cid, María Magdalena

AU - Da Silva, José P.

AU - Pereira, M. Manuela A.

AU - Basílio, Nuno

N1 - Funding Information: This work was supported by the Associate Laboratory for Green Chemistry─LAQV (projects UIDB/50006/2020 and UIDP/50006/2020), which is financed by national funds from FCT/MCTES. FCT/MCTES is also acknowledged for supporting the National Portuguese NMR Network (ROTEIRO/0031/2013-PINFRA/22161/2016, cofinanced by FEDER through COMPETE 2020, POCI, PORL, and FCT through PIDDAC) and for the projects UIDB/04326/2020 and PTDC/QUI-COL/32351/2017 and the CEECIND/00466/2017 research contract (N.B.). This study also received Portuguese national funds from the operational programs CRESC Algarve 2020 and COMPETE 2020 through project EMBRC.PT ALG-01-0145-FEDER-022121. Publisher Copyright: © 2022 Authors. All rights reserved.

PY - 2022/11/4

Y1 - 2022/11/4

N2 - Stimuli-responsive supramolecular receptors are important building blocks for the construction of self-assembled functional materials. We report the design and synthesis of a pH- and light-responsive 2-hydroxychalcone-β-cyclodextrin conjugate (1-Ct) and its characterization by spectroscopic and computational methods. 1-Ct follows the typical reaction network of trans-chalcone-flavylium photoswitches. Upon light irradiation, 1-Ct can be photochemically converted into the cis-chalcone/hemiketal forms (1-Cc/1-B) under neutral pH conditions or to the flavylium cation (1-AH+) at acidic pH values. This stimuli-responsive β-cyclodextrin host, 1-Ct, was found to form stronger intramolecular self-inclusion complexes (Kintra= 14) than 1-AH+(Kintra= 3) and weaker than 1-Cc/1-B (overall Kintra= 179), allowing control over their stability and binding properties by combinations of pH and light stimuli.

AB - Stimuli-responsive supramolecular receptors are important building blocks for the construction of self-assembled functional materials. We report the design and synthesis of a pH- and light-responsive 2-hydroxychalcone-β-cyclodextrin conjugate (1-Ct) and its characterization by spectroscopic and computational methods. 1-Ct follows the typical reaction network of trans-chalcone-flavylium photoswitches. Upon light irradiation, 1-Ct can be photochemically converted into the cis-chalcone/hemiketal forms (1-Cc/1-B) under neutral pH conditions or to the flavylium cation (1-AH+) at acidic pH values. This stimuli-responsive β-cyclodextrin host, 1-Ct, was found to form stronger intramolecular self-inclusion complexes (Kintra= 14) than 1-AH+(Kintra= 3) and weaker than 1-Cc/1-B (overall Kintra= 179), allowing control over their stability and binding properties by combinations of pH and light stimuli.

KW - Binding energy

KW - Functional materials

KW - pH

KW - Binding properties

KW - Building blockes

KW - Chalcones

KW - Flavylium

KW - Hemiketals

KW - Light irradiations

KW - Photo-responsive

KW - Photoswitch

KW - Reaction network

KW - Stimuli-responsive

KW - Cyclodextrins

UR - http://www.scopus.com/inward/record.url?scp=85140337312&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.2c01875

DO - 10.1021/acs.joc.2c01875

M3 - Article

C2 - 36242558

AN - SCOPUS:85140337312

VL - 87

SP - 14422

EP - 14432

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 21

ER -

2-Hydroxychalcone-β-Cyclodextrin Conjugate with pH-Modulated Photoresponsive Binding Properties

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Keywords

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