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Conceptual similarities between zeolites and artificial enzymes
By using a Diels–Alder (DA) reaction as a base case, we show that a pure silica zeolite acting as an entropy-trapping scaffold can be synthesized with an organic structure directing agent (OSDA) analogue of the transition state (TS) of the DA reaction. A cavity stabilization of the TS is observed wi...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6837030/ https://www.ncbi.nlm.nih.gov/pubmed/31853356 http://dx.doi.org/10.1039/c9sc02477h |
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author | Gallego, Eva M. Paris, Cecilia Cantín, Ángel Moliner, Manuel Corma, Avelino |
author_facet | Gallego, Eva M. Paris, Cecilia Cantín, Ángel Moliner, Manuel Corma, Avelino |
author_sort | Gallego, Eva M. |
collection | PubMed |
description | By using a Diels–Alder (DA) reaction as a base case, we show that a pure silica zeolite acting as an entropy-trapping scaffold can be synthesized with an organic structure directing agent (OSDA) analogue of the transition state (TS) of the DA reaction. A cavity stabilization of the TS is observed with the corresponding decrease in the activation energy of the reaction. A lower enthalpy of activation and a larger decrease in entropy are obtained with the zeolite synthesized with the analogue of the DA TS when compared with other zeolitic structures. Those differences are maintained, while catalytic activity is increased, when active sites are introduced in the zeolite. The catalytic zeolitic system synthesized with the OSDA analogue of the TS shows conceptual similarities with “de novo design” of an artificial enzyme to perform DA reactions, in where a suitable scaffold of existing proteins is chosen, and computationally designed active sites able to catalyze the cycloaddition reaction are introduced. |
format | Online Article Text |
id | pubmed-6837030 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-68370302019-12-18 Conceptual similarities between zeolites and artificial enzymes Gallego, Eva M. Paris, Cecilia Cantín, Ángel Moliner, Manuel Corma, Avelino Chem Sci Chemistry By using a Diels–Alder (DA) reaction as a base case, we show that a pure silica zeolite acting as an entropy-trapping scaffold can be synthesized with an organic structure directing agent (OSDA) analogue of the transition state (TS) of the DA reaction. A cavity stabilization of the TS is observed with the corresponding decrease in the activation energy of the reaction. A lower enthalpy of activation and a larger decrease in entropy are obtained with the zeolite synthesized with the analogue of the DA TS when compared with other zeolitic structures. Those differences are maintained, while catalytic activity is increased, when active sites are introduced in the zeolite. The catalytic zeolitic system synthesized with the OSDA analogue of the TS shows conceptual similarities with “de novo design” of an artificial enzyme to perform DA reactions, in where a suitable scaffold of existing proteins is chosen, and computationally designed active sites able to catalyze the cycloaddition reaction are introduced. Royal Society of Chemistry 2019-07-17 /pmc/articles/PMC6837030/ /pubmed/31853356 http://dx.doi.org/10.1039/c9sc02477h Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Gallego, Eva M. Paris, Cecilia Cantín, Ángel Moliner, Manuel Corma, Avelino Conceptual similarities between zeolites and artificial enzymes |
title | Conceptual similarities between zeolites and artificial enzymes
|
title_full | Conceptual similarities between zeolites and artificial enzymes
|
title_fullStr | Conceptual similarities between zeolites and artificial enzymes
|
title_full_unstemmed | Conceptual similarities between zeolites and artificial enzymes
|
title_short | Conceptual similarities between zeolites and artificial enzymes
|
title_sort | conceptual similarities between zeolites and artificial enzymes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6837030/ https://www.ncbi.nlm.nih.gov/pubmed/31853356 http://dx.doi.org/10.1039/c9sc02477h |
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