“Shine &amp; Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

The ability to modify biologically active molecules such as antibodies with drug molecules, fluorophores or radionuclides is crucial in drug discovery and target identification. Classic chemistry used for protein functionalisation relies almost exclusively on thermochemically mediated reactions. Our recent experiments have begun to explore the use of photochemistry to effect rapid and efficient protein functionalisation. This article introduces some of the principles and objectives of using photochemically activated reagents for protein ligation. The concept of simultaneous photoradiosynthesis of radiolabelled antibodies for use in molecular imaging is introduced as a working example. Notably, the goal of producing functionalised proteins in the absence of pre‐association (non‐covalent ligand‐protein binding) introduces requirements that are distinct from the more regular use of photoactive groups in photoaffinity labelling. With this in mind, the chemistry of thirteen different classes of photoactivatable reagents that react through the formation of intermediate carbenes, electrophiles, dienes, or radicals, is assessed.

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“…Luo et al. also developed a “Shine and Click” approach for functionalising the surface of bioactive nanoparticles …”

Section: Photoactive Reagents That Induce Cycloadditionsmentioning

confidence: 99%

Photochemical Reactions in the Synthesis of Protein–Drug Conjugates

Holland

Gut

Klingler

et al. 2019

Chemistry A European J

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“…A subsequent study showed that Caenorhabditis elegans and zebrafish embryos could also undergo in vivo labeling with cyclooctyne‐functionalized fluorophores, allowing for spatiotemporal imaging of cell surface glycosylation [33–37] . Since then, this reaction has been used for tissue engineering, [5] radiolabeling, [19] antibody–drug conjugates, [38] cell encapsulation, [39] the preparation of polymeric gels, [40, 41] and the development of nanomaterials [42, 43] …”

Section: Introductionmentioning

confidence: 99%

A Survey of Strain‐Promoted Azide–Alkyne Cycloaddition in Polymer Chemistry

Fong

Meichsner

et al. 2021

Chemistry A European J

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Highly efficient reactions that enable the assembly of molecules into complex structures have driven extensive progress in synthetic chemistry. In particular, reactions that occur under mild conditions and in benign solvents, while producing no by‐products and rapidly reach completion are attracting significant attention. Amongst these, the strain‐promoted azide–alkyne cycloaddition, involving various cyclooctyne derivatives reacting with azide‐bearing molecules, has gained extensive popularity in organic synthesis and bioorthogonal chemistry. This reaction has also recently gained momentum in polymer chemistry, where it has been used to decorate, link, crosslink, and even prepare polymer chains. This survey highlights key achievements in the use of this reaction to produce a variety of polymeric constructs for disparate applications.

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“…In particular, a thiolated strained cyclooctyne molecule, which represents the most obvious route towards functionalizing gold, cannot be stably obtained due to self-reactivity via thiol-yne addition. [20][21][22] To overcome this synthetic challenge, our group previously developed the use of cyclopropenones as photochemical alkyne precursors on gold nanoparticles (AuNPs) [23][24] , a chemical system adapted from Popik et al who first utilized cyclopropenone-masked dibenzocyclooctynes to label living cells, 25 and then to functionalize polymer brushes and immobilize azido molecules via SPAAC. 26 This method allowed us to synthesize a thiol precursor and assemble it onto AuNPs directly.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Au SAMs Photoclick Derivatization by PM-IRRAS

Workentin

Lagugné‐Labarthet²,

Legge³

2019

Preprint

Self Cite

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In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>

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“Shine & Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

Cited by 30 publications

References 54 publications

Photochemical Reactions in the Synthesis of Protein–Drug Conjugates

Photochemical Reactions in the Synthesis of Protein–Drug Conjugates

A Survey of Strain‐Promoted Azide–Alkyne Cycloaddition in Polymer Chemistry

Investigation of Au SAMs Photoclick Derivatization by PM-IRRAS

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