Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials
The useful concepts of reticular chemistry, rigid and predictable metal nodes together with strong and manageable covalent interactions between metal centers and organic linkers, have made the so-called metal–organic frameworks (MOFs) a flourishing area of enormous applicability. In this work, the e...
| Autores: | , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Universidad del País Vasco |
| Repositorio: | Addi. Archivo Digital para la Docencia y la Investigación |
| OAI Identifier: | oai:addi.ehu.eus:10810/64546 |
| Acceso en línea: | http://hdl.handle.net/10810/64546 |
| Access Level: | acceso abierto |
| Palabra clave: | metal-organic frameworks crystal-structures separation isoreticular opper-adenine |
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Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materialsMena Gutiérrez, SandraPascual Colino, JonBeobide Pacheco, GarikoitzCastillo García, OscarCastellanos Rubio, AinaraLuque Arrebola, AntonioMaiza Razkin, EkainMentxaka Salgado, JonPérez Yáñez, Soniametal-organic frameworkscrystal-structuresseparationisoreticularopper-adenineThe useful concepts of reticular chemistry, rigid and predictable metal nodes together with strong and manageable covalent interactions between metal centers and organic linkers, have made the so-called metal–organic frameworks (MOFs) a flourishing area of enormous applicability. In this work, the extension of similar strategies to supramolecularly assembled metal–organic materials has allowed us to obtain a family of isoreticular compounds of the general formula [Cu7(μ-adeninato-κN3:κN9)6(μ3-OH)6(μ-OH2)6](OOC-R-COO)·nH2O (R: ethylene-, acetylene-, naphthalene-, or biphenyl-group) in which the rigid copper–adeninato entities and the organic dicarboxylate anions are held together not by covalent interactions but by a robust and flexible network of synergic hydrogen bonds and π–π stacking interactions based on well-known supramolecular synthons (SMOFs). All compounds are isoreticular, highly insoluble, and water-stable and show a porous crystalline structure with a pcu topology containing a two-dimensional (2D) network of channels, whose dimensions and degree of porosity of the supramolecular network are tailored by the length of the dicarboxylate anion. The partial loss of the crystallization water molecules upon removal from the mother liquor produces a shrinkage of the unit cell and porosity, which leads to a color change of the compounds (from blue to olive green) if complete dehydration is achieved by means of gentle heating or vacuuming. However, the supramolecular network of noncovalent interactions is robust and flexible enough to reverse to the expanded unit cell and color after exposure to a humid atmosphere. This humidity-driven breathing behavior has been used to design a sensor in which the electrical resistance varies reversibly with the degree of humidity, very similar to the water vapor adsorption isotherm of the SMOF. The in-solution adsorption properties were explored for the uptake and release of the widely employed 5-fluorouracil, 4-aminosalycilic acid, 5-aminosalycilic acid, and allopurinol drugs. In addition, cytotoxicity activity assays were completed for the pristine and 5-fluorouracil-loaded samples.Basque Goverment (IT1722-22 and ELKARTEK KK-2022/00032) . Spanish Ministry of Science and Innovation (TED2021-129810B-C22 financed by MCIN/AEI/10.13039/501100011033 and by the European Union Next Generation EU/PRTR, and the PID2019-108028GB-C21 project funded by MCIN/AEI/10.13039/501100011033). Basque Government and the European Union Next GenerationEU (Investigo Program 2022-46).American Chemical Society202420242023info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/64546reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoEspañolinfo:eu-repo/grantAgreement/MICIN/TED2021-129810B-C22/info:eu-repo/grantAgreement/MICIN/PID2019-108028GB-C21/https://doi.org/10.1021/acs.inorgchem.3c02708info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/3.0/es© 2023 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0.oai:addi.ehu.eus:10810/645462026-06-18T09:23:17Z |
| dc.title.none.fl_str_mv |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| title |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| spellingShingle |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials Mena Gutiérrez, Sandra metal-organic frameworks crystal-structures separation isoreticular opper-adenine |
| title_short |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| title_full |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| title_fullStr |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| title_full_unstemmed |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| title_sort |
Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials |
| dc.creator.none.fl_str_mv |
Mena Gutiérrez, Sandra Pascual Colino, Jon Beobide Pacheco, Garikoitz Castillo García, Oscar Castellanos Rubio, Ainara Luque Arrebola, Antonio Maiza Razkin, Ekain Mentxaka Salgado, Jon Pérez Yáñez, Sonia |
| author |
Mena Gutiérrez, Sandra |
| author_facet |
Mena Gutiérrez, Sandra Pascual Colino, Jon Beobide Pacheco, Garikoitz Castillo García, Oscar Castellanos Rubio, Ainara Luque Arrebola, Antonio Maiza Razkin, Ekain Mentxaka Salgado, Jon Pérez Yáñez, Sonia |
| author_role |
author |
| author2 |
Pascual Colino, Jon Beobide Pacheco, Garikoitz Castillo García, Oscar Castellanos Rubio, Ainara Luque Arrebola, Antonio Maiza Razkin, Ekain Mentxaka Salgado, Jon Pérez Yáñez, Sonia |
| author2_role |
author author author author author author author author |
| dc.subject.none.fl_str_mv |
metal-organic frameworks crystal-structures separation isoreticular opper-adenine |
| topic |
metal-organic frameworks crystal-structures separation isoreticular opper-adenine |
| description |
The useful concepts of reticular chemistry, rigid and predictable metal nodes together with strong and manageable covalent interactions between metal centers and organic linkers, have made the so-called metal–organic frameworks (MOFs) a flourishing area of enormous applicability. In this work, the extension of similar strategies to supramolecularly assembled metal–organic materials has allowed us to obtain a family of isoreticular compounds of the general formula [Cu7(μ-adeninato-κN3:κN9)6(μ3-OH)6(μ-OH2)6](OOC-R-COO)·nH2O (R: ethylene-, acetylene-, naphthalene-, or biphenyl-group) in which the rigid copper–adeninato entities and the organic dicarboxylate anions are held together not by covalent interactions but by a robust and flexible network of synergic hydrogen bonds and π–π stacking interactions based on well-known supramolecular synthons (SMOFs). All compounds are isoreticular, highly insoluble, and water-stable and show a porous crystalline structure with a pcu topology containing a two-dimensional (2D) network of channels, whose dimensions and degree of porosity of the supramolecular network are tailored by the length of the dicarboxylate anion. The partial loss of the crystallization water molecules upon removal from the mother liquor produces a shrinkage of the unit cell and porosity, which leads to a color change of the compounds (from blue to olive green) if complete dehydration is achieved by means of gentle heating or vacuuming. However, the supramolecular network of noncovalent interactions is robust and flexible enough to reverse to the expanded unit cell and color after exposure to a humid atmosphere. This humidity-driven breathing behavior has been used to design a sensor in which the electrical resistance varies reversibly with the degree of humidity, very similar to the water vapor adsorption isotherm of the SMOF. The in-solution adsorption properties were explored for the uptake and release of the widely employed 5-fluorouracil, 4-aminosalycilic acid, 5-aminosalycilic acid, and allopurinol drugs. In addition, cytotoxicity activity assays were completed for the pristine and 5-fluorouracil-loaded samples. |
| publishDate |
2023 |
| dc.date.none.fl_str_mv |
2023 2024 2024 |
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info:eu-repo/semantics/article |
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article |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10810/64546 |
| url |
http://hdl.handle.net/10810/64546 |
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Español |
| language_invalid_str_mv |
Español |
| dc.relation.none.fl_str_mv |
info:eu-repo/grantAgreement/MICIN/TED2021-129810B-C22/ info:eu-repo/grantAgreement/MICIN/PID2019-108028GB-C21/ https://doi.org/10.1021/acs.inorgchem.3c02708 |
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info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/3.0/es |
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openAccess |
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http://creativecommons.org/licenses/by/3.0/es |
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application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
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American Chemical Society |
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