Cargando…

Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity

[Image: see text] Polymeric assemblies, such as micelles, are gaining increasing attention due to their ability to serve as nanoreactors for the execution of organic reactions in aqueous media. The ability to conduct organic transformations, which have been traditionally limited to organic media, in...

Descripción completa

Detalles Bibliográficos
Autores principales: Tevet, Shahar, Wagle, Shreyas S., Slor, Gadi, Amir, Roey J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8717824/
https://www.ncbi.nlm.nih.gov/pubmed/34987270
http://dx.doi.org/10.1021/acs.macromol.1c01755
_version_ 1784624600896765952
author Tevet, Shahar
Wagle, Shreyas S.
Slor, Gadi
Amir, Roey J.
author_facet Tevet, Shahar
Wagle, Shreyas S.
Slor, Gadi
Amir, Roey J.
author_sort Tevet, Shahar
collection PubMed
description [Image: see text] Polymeric assemblies, such as micelles, are gaining increasing attention due to their ability to serve as nanoreactors for the execution of organic reactions in aqueous media. The ability to conduct organic transformations, which have been traditionally limited to organic media, in water is essential for the further development of important fields ranging from green catalysis to bioorthogonal chemistry. Considering the recent progress that has been made to expand the range of organometallic reactions conducted using nanoreactors, we aimed to gain a deeper understanding of the roles of the hydrophobicity of both the core of micellar nanoreactors and the substrates on the reaction rates in water. Toward this goal, we designed a set of five metal-loaded micelles composed of polyethylene glycol–dendron amphiphiles and studied their ability to serve as nanoreactors for a palladium-mediated depropargylation reaction of four substrates with different log P values. Using dendrons as the hydrophobic block, we could precisely tune the lipophilicity of the nanoreactors, which allowed us to reveal linear correlations between the rate constants and the hydrophobicity of the amphiphiles (estimated by the dendron’s cLog P). While exponential dependence was obtained for the lipophilicity of the substrates, a similar degree of rate acceleration was observed due to the increase in the hydrophobicity of the amphiphiles regardless of the effect of the substrate’s log P. Our results demonstrate that while increasing the hydrophobicity of the substrates may be used to accelerate reaction rates, tuning the hydrophobicity of the micellar nanoreactors can serve as a vital tool for further optimization of the reactivity and selectivity of nanoreactors.
format Online
Article
Text
id pubmed-8717824
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-87178242022-01-03 Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity Tevet, Shahar Wagle, Shreyas S. Slor, Gadi Amir, Roey J. Macromolecules [Image: see text] Polymeric assemblies, such as micelles, are gaining increasing attention due to their ability to serve as nanoreactors for the execution of organic reactions in aqueous media. The ability to conduct organic transformations, which have been traditionally limited to organic media, in water is essential for the further development of important fields ranging from green catalysis to bioorthogonal chemistry. Considering the recent progress that has been made to expand the range of organometallic reactions conducted using nanoreactors, we aimed to gain a deeper understanding of the roles of the hydrophobicity of both the core of micellar nanoreactors and the substrates on the reaction rates in water. Toward this goal, we designed a set of five metal-loaded micelles composed of polyethylene glycol–dendron amphiphiles and studied their ability to serve as nanoreactors for a palladium-mediated depropargylation reaction of four substrates with different log P values. Using dendrons as the hydrophobic block, we could precisely tune the lipophilicity of the nanoreactors, which allowed us to reveal linear correlations between the rate constants and the hydrophobicity of the amphiphiles (estimated by the dendron’s cLog P). While exponential dependence was obtained for the lipophilicity of the substrates, a similar degree of rate acceleration was observed due to the increase in the hydrophobicity of the amphiphiles regardless of the effect of the substrate’s log P. Our results demonstrate that while increasing the hydrophobicity of the substrates may be used to accelerate reaction rates, tuning the hydrophobicity of the micellar nanoreactors can serve as a vital tool for further optimization of the reactivity and selectivity of nanoreactors. American Chemical Society 2021-12-01 2021-12-28 /pmc/articles/PMC8717824/ /pubmed/34987270 http://dx.doi.org/10.1021/acs.macromol.1c01755 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Tevet, Shahar
Wagle, Shreyas S.
Slor, Gadi
Amir, Roey J.
Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity
title Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity
title_full Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity
title_fullStr Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity
title_full_unstemmed Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity
title_short Tuning the Reactivity of Micellar Nanoreactors by Precise Adjustments of the Amphiphile and Substrate Hydrophobicity
title_sort tuning the reactivity of micellar nanoreactors by precise adjustments of the amphiphile and substrate hydrophobicity
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8717824/
https://www.ncbi.nlm.nih.gov/pubmed/34987270
http://dx.doi.org/10.1021/acs.macromol.1c01755
work_keys_str_mv AT tevetshahar tuningthereactivityofmicellarnanoreactorsbypreciseadjustmentsoftheamphiphileandsubstratehydrophobicity
AT wagleshreyass tuningthereactivityofmicellarnanoreactorsbypreciseadjustmentsoftheamphiphileandsubstratehydrophobicity
AT slorgadi tuningthereactivityofmicellarnanoreactorsbypreciseadjustmentsoftheamphiphileandsubstratehydrophobicity
AT amirroeyj tuningthereactivityofmicellarnanoreactorsbypreciseadjustmentsoftheamphiphileandsubstratehydrophobicity