The synthesis of three isomers based on Michael addition mechanism for the detection of sulfurcontaining species in aqueous solution is described. These compounds are constructed by conjugating an enone to a coumarin ...The synthesis of three isomers based on Michael addition mechanism for the detection of sulfurcontaining species in aqueous solution is described. These compounds are constructed by conjugating an enone to a coumarin fluorophore. A substituted-phenyl（o, m, or p-） was appended at the carbonyl carbon to adjust the reactivity. The experimental results showed that（E）-7-（diethylamino）-3-（3-（3-hydroxyphenyl）-3-oxoprop-1-en-1-yl）-2H-chromen-2-one（m-QPS） and（E）-7-（diethylamino）-3-（3-（4-hydroxyphenyl）-3-oxoprop-1-en-1-yl）-2H-chromen-2-one（p-QPS） barely react with sulfur-containing nucleophiles, while（E）-7-（diethylamino）-3-（3-（2-hydroxyphenyl）-3-oxoprop-1-en-1-yl）-2H-chromen-2-one（o-QPS） exhibited a fast response toward sulfite, sulfide and thiols in DMSO/phosphate buffer（2：1）. The above results are probably due to the intramolecular H-bonding activated Michael addition.More interestingly, cysteine triggered unusual photophysical responses of o-QPS： the original absorption（488 nm） and emission peaks（573 nm） underwent significant blue shifts initially and then recovered,which might be caused by the Michael addition and elimination reaction, respectively.展开更多
基金supported by National 973 Program (No. 2011CB910403)Shanghai Municipal Natural Science Foundation (No. 15ZR1409000)the open fund of Shanghai Key Laboratory of Chemical Biology (No. SKLCB-2013-03)
文摘The synthesis of three isomers based on Michael addition mechanism for the detection of sulfurcontaining species in aqueous solution is described. These compounds are constructed by conjugating an enone to a coumarin fluorophore. A substituted-phenyl（o, m, or p-） was appended at the carbonyl carbon to adjust the reactivity. The experimental results showed that（E）-7-（diethylamino）-3-（3-（3-hydroxyphenyl）-3-oxoprop-1-en-1-yl）-2H-chromen-2-one（m-QPS） and（E）-7-（diethylamino）-3-（3-（4-hydroxyphenyl）-3-oxoprop-1-en-1-yl）-2H-chromen-2-one（p-QPS） barely react with sulfur-containing nucleophiles, while（E）-7-（diethylamino）-3-（3-（2-hydroxyphenyl）-3-oxoprop-1-en-1-yl）-2H-chromen-2-one（o-QPS） exhibited a fast response toward sulfite, sulfide and thiols in DMSO/phosphate buffer（2：1）. The above results are probably due to the intramolecular H-bonding activated Michael addition.More interestingly, cysteine triggered unusual photophysical responses of o-QPS： the original absorption（488 nm） and emission peaks（573 nm） underwent significant blue shifts initially and then recovered,which might be caused by the Michael addition and elimination reaction, respectively.
