Small-Molecule-Selective Organosilica Nanoreactors for Copper-Catalyzed Azide-Alkyne Cycloaddition Reactions in Cellular and Living Systems.
We reported the synthesis of a tris(triazolylmethyl)amine (TTA)-bridged organosilane, functioning as Cu(I)-stabilizing ligands, and the installation of this building block into the backbone of mesoporous organosilica nanoparticles (TTASi) by a sol-gel way. Upon coordinating with Cu(I), the mesoporous CuI-TTASi, with a restricted metal active center inside the pore, functions as a molecular-sieve-typed nanoreactor to efficiently perform Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reactions on small-molecule substrates but fails to work on macromolecules larger than the pore diameter. As a proof of concept, we witnessed the advantages of selective nanoreactors in screening protein substrates for small molecules. Also, the robust CuI-TTASi could be implanted into the body of animal models including zebrafish and mice as biorthogonal catalysts without apparent toxicity, extending its utilization in vivo ranging from fluorescent labeling to in situ drug synthesis.
['Gao|Zhiguo|Z|0000-0002-6091-618X', 'Li|Yaojia|Y|', 'Liu|Zhikun|Z|', 'Zhang|Yu|Y|', 'Chen|Fanghui|F|', 'An|Peijing|P|', 'Lu|Wenjun|W|', 'Hu|Jinzhong|J|', 'You|Chaoqun|C|0000-0003-4529-077X', 'Xu|Jun|J|', 'Zhang|Xiangyang|X|', 'Sun|Baiwang|B|0000-0001-8724-0055']
D000480:Alkynes D000818:Animals D001386:Azides D002384:Catalysis D003300:Copper D061565:Cycloaddition Reaction D051379:Mice D036103:Nanotechnology D015027:Zebrafish
In Situ Drug Synthesis Bioorthogonal Catalysis Copper Mesoporous Organosilicon Molecular Sieve