RESUMO
We introduce a mild and efficient avenue to induce the folding of single chain polymer nanoparticles (SCNPs) using visible light. The versatility of the method is based on three folding mechanisms exploiting tetrazole chemistry, i.e., nitrile imine-mediated tetrazole-ene cycloaddition (NITEC), nitrile imine carboxylic acid ligation (NICAL) as well as nitrile imine self-dimerization. To our knowledge, this visible light driven approach is the to-date mildest avenue to fold single polymer chains into compact particles using light.
RESUMO
We pioneer the synthesis of fluorescent single chain nanoparticles (SCNPs) via UV-light induced folding based on tetrazole chemistry directly in pure water. Water-soluble photoreactive precursor polymers based on poly(acrylic acid) (PAA) bearing tetrazole, alkene and tetraethylene glycol monomethyl ether moieties, (PAAn(Tet/p-Mal/TEG)), or simply tetrazoles moieties, PAAn(Tet), were generated via RAFT polymerization. While tetrazole, ene, and acrylic acid containing polymers fold via dual nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) as well as nitrile imine-carboxylic acid ligation (NICAL), tetrazole and acrylic acid only functional prepolymers fold exclusively via NICAL. A detailed study of the underpinning photochemistry of NITEC and NICAL is also included. The resulting water-soluble SCNPs were carefully characterized via analytical techniques such as NMR, UV-vis, and fluorescence spectroscopy, as well as SEC and DLS.
RESUMO
We introduce the facile synthesis of fluorescent single-chain nanoparticles (SCNPs) based on chain-shattering acyclic diene metathesis (ADMET) polymers featuring self-immolative azobenzene motifs. An electrophilic alkoxyetherification is utilized to introduce the photoreactive moieties required for the subsequent chain collapse via UV-induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC).
