Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate.

0550044 - ÚCHP 2022 RIV GB eng J - Journal Article
Guselnikova, O. - Váňa, J. - Phuong, L.T. - Panov, Illia - Rulíšek, Lubomír - Trelin, A. - Postnikov, P. - Švorčík, V. - Andris, Erik - Lyutakov, O.
Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate.
Chemical Science. Roč. 12, č. 15 (2021), s. 5591-5598. ISSN 2041-6520. E-ISSN 2041-6539
R&D Projects: GA MŠMT(CZ) LTAUSA19148
Institutional support: RVO:67985858 ; RVO:61388963
Keywords : activation energy * cycloaddition * efficiency
OECD category: Physical chemistry; Physical chemistry (UOCHB-X)
Impact factor: 9.969, year: 2021
Method of publishing: Open access
https://pubs.rsc.org/en/content/articlepdf/2021/sc/d0sc05898j

Plasmon assistance promotes a range of chemical transformations by decreasing their activation energies. In a common case, thermal and plasmon assistance work synergistically: higher temperature results in higher plasmon-enhanced catalysis efficiency. Herein, we report an unexpected tenfold increase in the reaction efficiency of surface plasmon-assisted Huisgen dipolar azide-alkyne cycloaddition (AAC) when the reaction mixture is cooled from room temperature to35 degrees C. We attribute the observed increase in the reaction efficiency to complete plasmon-induced annihilation of the reaction barrier, prolongation of plasmon lifetime, and decreased relaxation of plasmon-excited-states under cooling. Furthermore, control quenching experiments supported by theoretical calculations indicate that plasmon-mediated substrate excitation to an electronic triplet state may play the key role in plasmon-assisted chemical transformation. Last but not least, we demonstrated the possible applicability of plasmon assistance to biological systems by AAC coupling of biotin to gold nanoparticles performed at35 degrees C.
Permanent Link: http://hdl.handle.net/11104/0325897