Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril
The incorporation of a guest, with different basic sites, into an organized system (host), such as macrocycles, could stabilize, detect, or promote the formation of a certain protomer. In this context, this work aimed to study the influence of cucurbit[7]uril (CB7) on dyes such as 7-(dimethylamino)-...
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Frontiers Media S.A.
2022-04-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/articles/10.3389/fchem.2022.870137/full |
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| author | Jackson J. Alcázar Edgar Márquez Luis García-Río Agustín Robles-Muñoz Angélica Fierro José G. Santos Margarita E. Aliaga |
| author_facet | Jackson J. Alcázar Edgar Márquez Luis García-Río Agustín Robles-Muñoz Angélica Fierro José G. Santos Margarita E. Aliaga |
| author_sort | Jackson J. Alcázar |
| collection | DOAJ |
| description | The incorporation of a guest, with different basic sites, into an organized system (host), such as macrocycles, could stabilize, detect, or promote the formation of a certain protomer. In this context, this work aimed to study the influence of cucurbit[7]uril (CB7) on dyes such as 7-(dimethylamino)-aza-coumarins, which have more than one basic site along their molecular structure. For this, three 3-styryl derivatives of 7-(dialkylamino)-aza-coumarin dyes (SAC1-3) were synthesized and characterized by NMR, ESI-HRMS and IR. The spectral behaviour of the SACs in the absence and presence of CB7 was studied. The results showed large shifts in the UV-vis spectrum in acid medium: a hypsochromic shift of ≈5400 cm−1 (SAC1-2) and ≈3500 cm−1 (SAC3) in the absence of CB7 and a bathochromic shift of ≈4500 cm−1 (SAC1-3) in the presence of CB7. The new absorptions at long and short wavelengths were assigned to the corresponding protomers by computational calculations at the density functional theory (DFT) level. Additionally, the binding mode was corroborated by molecular dynamics simulations. Findings revealed that in the presence of CB7 the heterocyclic nitrogen was preferably protonated instead of the dialkylamino group. Namely, CB7 induces a change in the protonation preference at the basic sites of the SACs, as consequence of the molecular recognition by the macrocycle. |
| first_indexed | 2024-12-10T04:05:44Z |
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| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-12-10T04:05:44Z |
| publishDate | 2022-04-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-31e661f0ad1a46d4a09a40b35cf4bfa72022-12-22T02:02:51ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462022-04-011010.3389/fchem.2022.870137870137Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]urilJackson J. Alcázar0Edgar Márquez1Luis García-Río2Agustín Robles-Muñoz3Angélica Fierro4José G. Santos5Margarita E. Aliaga6Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, ChileDepartamento de Química y Biología, Facultad de Ciencias Exactas, Grupo de Investigaciones en Química y Biología, Universidad Del Norte, Barranquilla, ColombiaDepartamento de Química Física, Centro de Investigación en Química Biológica y Materiales Moleculares (CIQUS), Universidad de Santiago, Santiago, SpainFacultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, ChileFacultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, ChileFacultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, ChileFacultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, ChileThe incorporation of a guest, with different basic sites, into an organized system (host), such as macrocycles, could stabilize, detect, or promote the formation of a certain protomer. In this context, this work aimed to study the influence of cucurbit[7]uril (CB7) on dyes such as 7-(dimethylamino)-aza-coumarins, which have more than one basic site along their molecular structure. For this, three 3-styryl derivatives of 7-(dialkylamino)-aza-coumarin dyes (SAC1-3) were synthesized and characterized by NMR, ESI-HRMS and IR. The spectral behaviour of the SACs in the absence and presence of CB7 was studied. The results showed large shifts in the UV-vis spectrum in acid medium: a hypsochromic shift of ≈5400 cm−1 (SAC1-2) and ≈3500 cm−1 (SAC3) in the absence of CB7 and a bathochromic shift of ≈4500 cm−1 (SAC1-3) in the presence of CB7. The new absorptions at long and short wavelengths were assigned to the corresponding protomers by computational calculations at the density functional theory (DFT) level. Additionally, the binding mode was corroborated by molecular dynamics simulations. Findings revealed that in the presence of CB7 the heterocyclic nitrogen was preferably protonated instead of the dialkylamino group. Namely, CB7 induces a change in the protonation preference at the basic sites of the SACs, as consequence of the molecular recognition by the macrocycle.https://www.frontiersin.org/articles/10.3389/fchem.2022.870137/fullheterocyclic nitrogen protonation7-dialkylamino-aza-coumarin dyesprotonation induced by cucurbit[7]urilmolecular recognition by cucurbit[7]urilspectral behaviour of protomers |
| spellingShingle | Jackson J. Alcázar Edgar Márquez Luis García-Río Agustín Robles-Muñoz Angélica Fierro José G. Santos Margarita E. Aliaga Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril Frontiers in Chemistry heterocyclic nitrogen protonation 7-dialkylamino-aza-coumarin dyes protonation induced by cucurbit[7]uril molecular recognition by cucurbit[7]uril spectral behaviour of protomers |
| title | Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril |
| title_full | Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril |
| title_fullStr | Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril |
| title_full_unstemmed | Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril |
| title_short | Changes in Protonation Sites of 3-Styryl Derivatives of 7-(dialkylamino)-aza-coumarin Dyes Induced by Cucurbit[7]uril |
| title_sort | changes in protonation sites of 3 styryl derivatives of 7 dialkylamino aza coumarin dyes induced by cucurbit 7 uril |
| topic | heterocyclic nitrogen protonation 7-dialkylamino-aza-coumarin dyes protonation induced by cucurbit[7]uril molecular recognition by cucurbit[7]uril spectral behaviour of protomers |
| url | https://www.frontiersin.org/articles/10.3389/fchem.2022.870137/full |
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