Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis
Silica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activit...
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-07-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/13/2490 |
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| author | Katia Martina Federica Calsolaro Alessio Zuliani Gloria Berlier Fernando Chávez-Rivas Maria Jesus Moran Rafael Luque Giancarlo Cravotto |
| author_facet | Katia Martina Federica Calsolaro Alessio Zuliani Gloria Berlier Fernando Chávez-Rivas Maria Jesus Moran Rafael Luque Giancarlo Cravotto |
| author_sort | Katia Martina |
| collection | DOAJ |
| description | Silica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activity. The present work presents a detailed investigation of an ultrasound-promoted synthetic protocol for the grafting of β-cyclodextrin (β-CD) onto silica. Truly, ultrasound irradiation has emerged as a fast technique for promoting efficient derivatization of a silica surface with organic moieties at low temperature. Three different β-CD silica-grafted derivatives have been obtained, and the ability of β-CD to direct and bind Cu when CD is bonded to silica has been studied. A detailed characterization has been performed using TGA, phenolphthalein titration, FT-IR, diffuse reflectance (DR), DR UV-Vis, as well as the inductively-coupled plasma (ICP) of the β-CD silica-grafted systems and the relative Cu-supported catalysts. Spectroscopic characterization monitored the different steps of the reaction, highlighting qualitative differences in the properties of amino-derivatized precursors and final products. In order to ensure that the Cu-β-CD silica catalyst is efficient and robust, its applicability in Cu(II)-catalyzed alkyne azide reactions in the absence of a reducing agent has been explored. The presence of β-CD and an amino spacer has been shown to be crucial for the reactivity of Cu(II), when supported. |
| first_indexed | 2024-12-11T19:38:34Z |
| format | Article |
| id | doaj.art-6414a89fa30b4c6fa37b9c0324ffaffb |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-11T19:38:34Z |
| publishDate | 2019-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-6414a89fa30b4c6fa37b9c0324ffaffb2022-12-22T00:53:05ZengMDPI AGMolecules1420-30492019-07-012413249010.3390/molecules24132490molecules24132490Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper CatalysisKatia Martina0Federica Calsolaro1Alessio Zuliani2Gloria Berlier3Fernando Chávez-Rivas4Maria Jesus Moran5Rafael Luque6Giancarlo Cravotto7Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via Pietro Giuria 9, 10125 Turin, ItalyDipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via Pietro Giuria 9, 10125 Turin, ItalyDepartamento de Quimica Organica, Universidad de Cordoba, Edificio Marie-Curie (C-3), Ctra Nnal IV-A, Km 396 Cordoba, SpainDipartimento di Chimica, Università di Torino, Via Pietro Giuria 7, 10125 Turin, ItalyDipartimento di Chimica, Università di Torino, Via Pietro Giuria 7, 10125 Turin, ItalyDipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via Pietro Giuria 9, 10125 Turin, ItalyDepartamento de Quimica Organica, Universidad de Cordoba, Edificio Marie-Curie (C-3), Ctra Nnal IV-A, Km 396 Cordoba, SpainDipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via Pietro Giuria 9, 10125 Turin, ItalySilica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activity. The present work presents a detailed investigation of an ultrasound-promoted synthetic protocol for the grafting of β-cyclodextrin (β-CD) onto silica. Truly, ultrasound irradiation has emerged as a fast technique for promoting efficient derivatization of a silica surface with organic moieties at low temperature. Three different β-CD silica-grafted derivatives have been obtained, and the ability of β-CD to direct and bind Cu when CD is bonded to silica has been studied. A detailed characterization has been performed using TGA, phenolphthalein titration, FT-IR, diffuse reflectance (DR), DR UV-Vis, as well as the inductively-coupled plasma (ICP) of the β-CD silica-grafted systems and the relative Cu-supported catalysts. Spectroscopic characterization monitored the different steps of the reaction, highlighting qualitative differences in the properties of amino-derivatized precursors and final products. In order to ensure that the Cu-β-CD silica catalyst is efficient and robust, its applicability in Cu(II)-catalyzed alkyne azide reactions in the absence of a reducing agent has been explored. The presence of β-CD and an amino spacer has been shown to be crucial for the reactivity of Cu(II), when supported.https://www.mdpi.com/1420-3049/24/13/2490sonochemistrycopper-catalysisβ-cyclodextrinsilicagreen chemistryorganic-inorganic hybrid materialsinfrared spectroscopydiffuse reflectanceUV-visible |
| spellingShingle | Katia Martina Federica Calsolaro Alessio Zuliani Gloria Berlier Fernando Chávez-Rivas Maria Jesus Moran Rafael Luque Giancarlo Cravotto Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis Molecules sonochemistry copper-catalysis β-cyclodextrin silica green chemistry organic-inorganic hybrid materials infrared spectroscopy diffuse reflectance UV-visible |
| title | Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis |
| title_full | Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis |
| title_fullStr | Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis |
| title_full_unstemmed | Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis |
| title_short | Sonochemically-Promoted Preparation of Silica-Anchored Cyclodextrin Derivatives for Efficient Copper Catalysis |
| title_sort | sonochemically promoted preparation of silica anchored cyclodextrin derivatives for efficient copper catalysis |
| topic | sonochemistry copper-catalysis β-cyclodextrin silica green chemistry organic-inorganic hybrid materials infrared spectroscopy diffuse reflectance UV-visible |
| url | https://www.mdpi.com/1420-3049/24/13/2490 |
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