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[Chem. Eur. J.] Chemoselective Phototransformation of C-H Bond on Polymer Surface via a Novel Photoinduced Cerium Recycling Redox
作者:Zhenhua Huang, Zhengfang Wu, Peng Yang* and Wantai Yang*
關鍵字:Surface modification, Cerium, Photooxidation, C-H activation, Carbohydrate Microarray
論文來源:期刊
具體來源:Chemistry A European Journal
發(fā)表時間:2014年
It is generally accepted that Ce4+ is unable to directly oxidize inert alkyl C-H bond without the assistance of adjacent polar groups. Herein we demonstrated in our newly developed confined photochemical reaction system, this recognition might be challenged. As we found, when a thin layer of CeCl3/HCl aqueous solution was applied onto polymeric substrate, and under UV irradiation, Ce3+ was firstly photooxidized into Ce4+ in the presence of H+, and then in situ formed Ce4+ could perform oxidation reaction on C-H bonds of polymer surface to form active surface carbon radical for further radical graft polymerization as well as functional group transformation, meanwhile reduced itself to Ce3+ status with releasing H+. This photoinduced cerium recycling redox (PCRR) actually behaved as a biomimetic system towards an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bond on polymer surfaces to small molecular group and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer surface modification.
關鍵字:Surface modification, Cerium, Photooxidation, C-H activation, Carbohydrate Microarray
論文來源:期刊
具體來源:Chemistry A European Journal
發(fā)表時間:2014年
It is generally accepted that Ce4+ is unable to directly oxidize inert alkyl C-H bond without the assistance of adjacent polar groups. Herein we demonstrated in our newly developed confined photochemical reaction system, this recognition might be challenged. As we found, when a thin layer of CeCl3/HCl aqueous solution was applied onto polymeric substrate, and under UV irradiation, Ce3+ was firstly photooxidized into Ce4+ in the presence of H+, and then in situ formed Ce4+ could perform oxidation reaction on C-H bonds of polymer surface to form active surface carbon radical for further radical graft polymerization as well as functional group transformation, meanwhile reduced itself to Ce3+ status with releasing H+. This photoinduced cerium recycling redox (PCRR) actually behaved as a biomimetic system towards an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bond on polymer surfaces to small molecular group and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer surface modification.