摘要
Diketopyrrolopyrrole(DPP)derivatived photosensitizers(PSs)with near infrared(NIR)absorption and good photophysical properties have drawn tremendous attention in cancer phototherapy.However,current DPP derivatives present unsatisfactory quantum yield of singlet oxygen(1O2)due to the large energy gap between the excited singlet and triplet states.To tackle this challenge,herein the DPP core is functionalized with triphenylphosphine-Au(I)group(Th DPP-Au),leading to a high1O2 quantum yield of 0.65.Theoretical calculation attributes the enhancement to spin-orbit coupling and population of the triplet excition upon photoexcitation.The hydrophilic Th DPP-Au nanoparticals(NPs)are prepared via nano-reprecipitation,which displays homogeneous size and excellent light absorption ability(ε=4.382×104 M-1cm-1).And the Th DPP-Au NPs exhibit low dark toxicity and high phototoxicity,which can effectively kill tumor cells via 1O2 induced mitochondrial apoptotic pathway upon irradiation.Furthermore,in vivo experiments demonstrate that Th DPP-Au NPs can selective accumulation in tumor and present excellent synergistic photodynamic/photothermal therapy guided by fluorescence and photothermal dual imaging.
Diketopyrrolopyrrole（DPP） derivatived photosensitizers（PSs） with near infrared（NIR） absorption and good photophysical properties have drawn tremendous attention in cancer phototherapy. However, current DPP derivatives present unsatisfactory quantum yield of singlet oxygen（1O2） due to the large energy gap between the excited singlet and triplet states. To tackle this challenge, herein the DPP core is functionalized with triphenylphosphine-Au（I） group（Th DPP-Au）, leading to a high1O2 quantum yield of 0.65. Theoretical calculation attributes the enhancement to spin-orbit coupling and population of the triplet excition upon photoexcitation. The hydrophilic Th DPP-Au nanoparticals（NPs） are prepared via nano-reprecipitation, which displays homogeneous size and excellent light absorption ability(ε=4.382×104 M-1cm-1). And the Th DPP-Au NPs exhibit low dark toxicity and high phototoxicity, which can effectively kill tumor cells via 1O2 induced mitochondrial apoptotic pathway upon irradiation. Furthermore, in vivo experiments demonstrate that Th DPP-Au NPs can selective accumulation in tumor and present excellent synergistic photodynamic/photothermal therapy guided by fluorescence and photothermal dual imaging.
基金
supported by the National Natural Science of Foundation of China(61525402,61775095,21704043)
Jiangsu Provincial Key Research and Development Plan(BE2017741)
the Natural Science Foundation of Jiangsu Province(BK20170990,17KJB150020)
the Six talent peak innovation team in Jiangsu Province(TD-SWYY-009)
