摘要
With the blossom of DNA encoded library(DEL)and nucleic acid aptamer techniques,DNA-compatible reactions draw increasing attention in both the pharmaceutical industry and academia.In this regard,the incorporation of organosulfur scaffolds on DNA via the Csp2-S bond exhibits advantages but remains underrepresented.Herein,we report a mild and efficient photoredox atom transfer radical addition(ATRA)to terminal and internal alkynes with thiosulfonates catalyzed by organic photocatalyst,furnishing a wide array of E-β-arylthiol-vinyl sulfones with excellent regio-and stereoselectivity.Mechanistic investigations demonstrate that sulfonyl radical likely served as the key intermediate in this transformation.Leveraging the broad functional group tolerance and the mild and biofriendly conditions,this protocol could be adapted to simultaneously install sulfones and sulfides on DNA.More importantly,a redox-responsive fluorescent probe(10-ethyl-2-sulfonate-acridone,ESAC)could be conveniently introduced on two commonly used aptamers(AS1411 and Sgc8c),allowing their subsequent imaging studies across a series of human tumor cell lines.Remarkably,the process of ESAC-aptamers entering the cells was captured by both confocal microscopy and flow cytometry techniques,whereby most of the ESAC-aptamers exhibited green fluorescence after their cellular uptake,with the small portion remaining in the outer membrane emitting blue fluorescence.
基金
the following institutions for their financial support:T.J.thanks Guangdong Basic and Applied Basic Research Foundation,China(grant nos.2021B1515120046 and 2022B1515120075)
the Science and Technology Innovation Commission of Shenzhen Municipality,China(grant nos.JCYJ20220818101404010 and 20220815113214003)
High-Level of Special Funds,China(grant no.G03050K003)
the National Natural Science Foundation of China(grant no.22078263)
the National Key R&D Program of China(grant no.2022YFC2106100)
the Hunan Provincial Science Foundation for Distinguished Young Scholars,China(grant no.2022JJ10005)
the Key Science and Technology project of Hunan Province,China(grant no.2021SK1020).
