期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 14, 页码 4860-4868出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b00126
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资金
- NIH [R01GM085092]
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM085092] Funding Source: NIH RePORTER
In pursuit of fast bioorthogonal reactions, reactive moieties have been increasingly employed for selective labeling of biomolecules in living systems, posing a challenge in attaining reactivity without sacrificing selectivity. To address this challenge, here we report a bioinspired strategy in which molecular shape controls the selectivity of a transient, highly reactive nitrile imine dipole. By tuning the shape of structural pendants attached to the ortho position of the N-aryl ring of diaryltetrazoles precursors of nitrile imines, we discovered a sterically shielded nitrile imine that favors the 1,3-dipolar cycloaddition over the competing nucleophilic addition. The photogenerated nitrile imine exhibits an extraordinarily long half-life of 102 s in aqueous medium, owing to its unique molecular shape that hinders the approach of a nucleophile as shown by DFT calculations. The utility of this sterically shielded nitrile imine in rapid (similar to 1 min) bioorthogonal labeling of glucagon receptor in live mammalian cells was demonstrated.
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