Near-Infrared Photoinduced Coupling Reactions Assisted by Upconversion Nanoparticles

Paul Lederhose; Zhijun Chen; Rouven Müller; James P Blinco; Si Wu; Christopher Barner-Kowollik

doi:10.1002/anie.201606425

Near-Infrared Photoinduced Coupling Reactions Assisted by Upconversion Nanoparticles

Angew Chem Int Ed Engl. 2016 Sep 26;55(40):12195-9. doi: 10.1002/anie.201606425. Epub 2016 Aug 25.

Authors

Paul Lederhose^{1

2

3}, Zhijun Chen⁴, Rouven Müller^{2

3}, James P Blinco⁵, Si Wu⁶, Christopher Barner-Kowollik^{7

8

9}

Affiliations

¹ School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), 2 George St, Brisbane, QLD, 4001, Australia.
² Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131, Karlsruhe, Germany.
³ Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
⁴ Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128, Mainz, Germany.
⁵ School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), 2 George St, Brisbane, QLD, 4001, Australia. [email protected].
⁶ Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128, Mainz, Germany. [email protected].
⁷ School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), 2 George St, Brisbane, QLD, 4001, Australia. [email protected], [email protected].
⁸ Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131, Karlsruhe, Germany. [email protected], [email protected].
⁹ Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany. [email protected], [email protected].

PMID: 27560097
DOI: 10.1002/anie.201606425

Abstract

We introduce nitrile imine-mediated tetrazole-ene cycloadditions (NITEC) in the presence of upconversion nanoparticles (UCNPs) as a powerful covalent coupling tool. When a pyrene aryl tetrazole derivative (λabs, max =346 nm) and UCNPs are irradiated with near-infrared light at 974 nm, rapid conversion of the tetrazole into a reactive nitrile imine occurs. In the presence of an electron-deficient double bond, quantitative conversion into a pyrazoline cycloadduct is observed under ambient conditions. The combination of NITEC and UCNP technology is used for small-molecule cycloadditions, polymer end-group modification, and the formation of block copolymers from functional macromolecular precursors, constituting the first example of a NIR-induced cycloaddition. To show the potential for in vivo applications, through-tissue experiments with a biologically relevant biotin species were carried out. Quantitative cycloadditions and retention of the biological activity of the biotin units are possible at 974 nm irradiation.

Keywords: NITEC; near infrared; photoinduced cycloaddition; polymer coupling; upconversion.

Publication types

Research Support, Non-U.S. Gov't