Photoclick reactions combine the advantages offered by light-driven processes, that is, non-invasive and high spatiotemporal control, with classical click chemistry and have found applications ranging from surface functionalization, polymer conjugation, photocrosslinking, protein labelling and bioimaging. Despite these advances, most photoclick reactions typically require near-ultraviolet (UV) and mid-UV light to proceed. UV light can trigger undesirable responses, including cellular apoptosis, and therefore, visible and near-infrared light-induced photoclick reaction systems are highly desirable. Shifting to a longer wavelength can also reduce degradation of the photoclick reagents and products. Several strategies have been used to induce a bathochromic shift in the wavelength of irradiation-initiating photoclick reactions. For instance, the extension of the conjugated π-system, triplet-triplet energy transfer, multi-photon excitation, upconversion technology, photocatalytic and photoinitiation approaches, and designs involving photocages have all been used to achieve this goal. Current design strategies, recent advances and the outlook for long wavelength-driven photoclick reactions are presented.
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http://dx.doi.org/10.1038/s41570-024-00633-y | DOI Listing |
Chemistry
December 2024
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu, 610064, P. R. China.
Trifluoromethylarenes (ArCF) are crucial bioisosteres in medicinal chemistry, but catalyst-free and controlled photo-activation of the ArC(sp)-F bond remains a significant challenge. The photo-induced defluorination acyl fluoride exchange (photo-DAFEx) of m-trifluoromethylaniline, induced by ultraviolet light, emerges as a promising novel photo-click reaction for photoaffinity drug discovery. However, the photophysical properties of NMePhFC(sp)-F derivatives and factors affecting ArC(sp)-F bond activation in photo-DAFEx are not yet fully understood, hindering the development of new photo-defluorination reagents with longer absorption wavelength for the photo-DAFEx.
View Article and Find Full Text PDFJ Colloid Interface Sci
March 2025
School of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK. Electronic address:
Controllable surface modification of nanoparticulate drug delivery vectors is key to enhancing specific desirable properties such as colloidal stability, targeting, and stimuli-responsive cargo release. Metal-organic frameworks (MOFs) have been proposed as potential delivery devices, with surface modification achieved by various bioconjugate "click" reactions, including copper-catalysed and strain-promoted azide-alkyne cycloaddition. Herein, we show that photo-induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) can be used to surface-modify tetrazole-appended Zr MOFs with maleimides, and vice versa, with the extent of this traceless surface functionalisation controlled by the length of photoirradiation.
View Article and Find Full Text PDFOrg Lett
December 2024
School of Chemistry, University College Dublin, O'Brien Centre for Science, Belfield, Dublin 4, Ireland.
Continuous flow technology was exploited for the effective generation of nitrile imines via photolysis of substituted aryl tetrazoles. The resulting photo-click process rapidly affords advanced nitrogen-rich scaffolds upon the subsequent trapping of the reactive dipole with alkenes, alkynes, and benzylic amines. Crucially, this approach uncovers the differential reactivity for ether vs amine tethers, thus providing facile and scalable access to underexplored medicinally relevant heterocyclic entities.
View Article and Find Full Text PDFBiomacromolecules
December 2024
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China.
Four biobased phosphate-containing aryl monomers with methoxy, allyl, and vinyl groups as substituents have been successfully synthesized. Copolymerizing these monomers with thiophenol or mercaptans via the photoclick thiol-ene reaction gives the polymers with refractive indices () of 1.63-1.
View Article and Find Full Text PDFNat Rev Chem
September 2024
Centre for Systems Chemistry, Stratingh Institute for Chemistry, Faculty for Science and Engineering, University of Groningen, Groningen, The Netherlands.
Photoclick reactions combine the advantages offered by light-driven processes, that is, non-invasive and high spatiotemporal control, with classical click chemistry and have found applications ranging from surface functionalization, polymer conjugation, photocrosslinking, protein labelling and bioimaging. Despite these advances, most photoclick reactions typically require near-ultraviolet (UV) and mid-UV light to proceed. UV light can trigger undesirable responses, including cellular apoptosis, and therefore, visible and near-infrared light-induced photoclick reaction systems are highly desirable.
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