Zinc phthalocyanines(ZnPc)are widely recognized as efficient triplet photosensitizers in photodynamic therapy and photocatalysis,owing to their intense absorption in the visible range and long triplet-state lifetimes....Zinc phthalocyanines(ZnPc)are widely recognized as efficient triplet photosensitizers in photodynamic therapy and photocatalysis,owing to their intense absorption in the visible range and long triplet-state lifetimes.However,their application in triplet-triplet annihilation(TTA)upconversion is lacking to date.In this study,we synthesized a new ZnPc photosensitizer,4I-ZnPc,and composed a TTA upconversion system using rubrene as the energy acceptor.Upon photoexcitation at 663 nm,yellow fluorescence from rubrene was observed in deoxygenated dichloromethane,demonstrating TTA upconversion with an anti-Stokes shift of 0.331 eV and a quantum yield of 1.82%(out of the 50%maximum).Using nanosecond transient absorption spectroscopy,we determined the triplet lifetime of 4I-ZnPc,the triplet-triplet energy transfer efficiency,and the fluorescence quantum yield.These measurements provide critical insights into the photophysical processes governing the TTA upconversion system.Our results highlight the potential advantages and limitations of ZnPc as a triplet photosensitizer for TTA upconversion.展开更多
The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential...The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.展开更多
天冬氨酸(ASP)自身热缩聚产物聚琥珀酰亚胺(PSI)通过与氨基化聚乙二醇单甲醚(α-胺基-ω-甲氧基-聚乙二醇)和十二胺(DDA)进行连续两步开环反应,制备了双亲性蜈蚣形聚合物聚琥珀酰亚胺接枝聚乙二醇与十二胺(PSI-g-PEG-DDA).随着改变疏水...天冬氨酸(ASP)自身热缩聚产物聚琥珀酰亚胺(PSI)通过与氨基化聚乙二醇单甲醚(α-胺基-ω-甲氧基-聚乙二醇)和十二胺(DDA)进行连续两步开环反应,制备了双亲性蜈蚣形聚合物聚琥珀酰亚胺接枝聚乙二醇与十二胺(PSI-g-PEG-DDA).随着改变疏水链段DDA的接枝比例,通过胶束粒径的变化确定了最佳的接枝比例.核磁共振波谱(1H-NMR)及凝胶渗透色谱(GPC)对聚合物的性质进行了表征.通过相转移法,聚合物对油溶性超顺磁性氧化铁纳米粒子进行包覆,制备了新型的水溶性超顺磁性氧化铁纳米粒子(PSI-g-PEGDDA@IONPs).动态光散射(DLS)和透射电镜(TEM)对新型的水溶性氧化铁纳米粒子的粒径与形貌进行了表征.体外T2核磁造影成像(MRI in vitro)确定了制备的氧化铁纳米粒子的R2质子驰豫率.肝癌小鼠模型的体内核磁造影成像(MRI in vivo)结果表明新型氧化铁纳米粒子对肿瘤部位有明显的T2核磁造影增强效应,并有很长的体内循环半衰期.以上实验结果表明,新型的水溶性纳米氧化铁粒子可以作为一种潜在的用于肿瘤检测的核磁造影剂.展开更多
As a powerful noninvasive imaging technology,positron emission tomography(PET)has been playing an important role in disease theranostics and drug discovery.The successful application of PET relies on not only the biol...As a powerful noninvasive imaging technology,positron emission tomography(PET)has been playing an important role in disease theranostics and drug discovery.The successful application of PET relies on not only the biological properties of PET tracers but also the availability of facile and efficient radiochemical reactions to enable practical production and widespread use of PET tracers.Most recently,photochemistry is emerging as a novel,mild and efficient approach to generating PET agents.In this review,we focus on the recent advances in newly developed photocatalytic radiochemical reactions,innovation on automated photochemical radiosynthesis modules,as well as implementation in late-stage radiolabeling and radio-pharmaceutical synthesis for PET imaging.We believe that this review will inspire the development of more promising radiolabeling protocols for the preparation of clinically useful PET agents.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22473104 and 22403086)support of the China Postdoctoral Science Foundation(No.2023M733378).
文摘Zinc phthalocyanines(ZnPc)are widely recognized as efficient triplet photosensitizers in photodynamic therapy and photocatalysis,owing to their intense absorption in the visible range and long triplet-state lifetimes.However,their application in triplet-triplet annihilation(TTA)upconversion is lacking to date.In this study,we synthesized a new ZnPc photosensitizer,4I-ZnPc,and composed a TTA upconversion system using rubrene as the energy acceptor.Upon photoexcitation at 663 nm,yellow fluorescence from rubrene was observed in deoxygenated dichloromethane,demonstrating TTA upconversion with an anti-Stokes shift of 0.331 eV and a quantum yield of 1.82%(out of the 50%maximum).Using nanosecond transient absorption spectroscopy,we determined the triplet lifetime of 4I-ZnPc,the triplet-triplet energy transfer efficiency,and the fluorescence quantum yield.These measurements provide critical insights into the photophysical processes governing the TTA upconversion system.Our results highlight the potential advantages and limitations of ZnPc as a triplet photosensitizer for TTA upconversion.
基金Project supported by the National Natural Science Foundation of China(52062034)the National Key Research and Development Program of China(2019YFC0605002)。
文摘The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.
文摘天冬氨酸(ASP)自身热缩聚产物聚琥珀酰亚胺(PSI)通过与氨基化聚乙二醇单甲醚(α-胺基-ω-甲氧基-聚乙二醇)和十二胺(DDA)进行连续两步开环反应,制备了双亲性蜈蚣形聚合物聚琥珀酰亚胺接枝聚乙二醇与十二胺(PSI-g-PEG-DDA).随着改变疏水链段DDA的接枝比例,通过胶束粒径的变化确定了最佳的接枝比例.核磁共振波谱(1H-NMR)及凝胶渗透色谱(GPC)对聚合物的性质进行了表征.通过相转移法,聚合物对油溶性超顺磁性氧化铁纳米粒子进行包覆,制备了新型的水溶性超顺磁性氧化铁纳米粒子(PSI-g-PEGDDA@IONPs).动态光散射(DLS)和透射电镜(TEM)对新型的水溶性氧化铁纳米粒子的粒径与形貌进行了表征.体外T2核磁造影成像(MRI in vitro)确定了制备的氧化铁纳米粒子的R2质子驰豫率.肝癌小鼠模型的体内核磁造影成像(MRI in vivo)结果表明新型氧化铁纳米粒子对肿瘤部位有明显的T2核磁造影增强效应,并有很长的体内循环半衰期.以上实验结果表明,新型的水溶性纳米氧化铁粒子可以作为一种潜在的用于肿瘤检测的核磁造影剂.
基金the financial support from the Basic Research Program of Jiangsu Province(No.BK20220408).
文摘As a powerful noninvasive imaging technology,positron emission tomography(PET)has been playing an important role in disease theranostics and drug discovery.The successful application of PET relies on not only the biological properties of PET tracers but also the availability of facile and efficient radiochemical reactions to enable practical production and widespread use of PET tracers.Most recently,photochemistry is emerging as a novel,mild and efficient approach to generating PET agents.In this review,we focus on the recent advances in newly developed photocatalytic radiochemical reactions,innovation on automated photochemical radiosynthesis modules,as well as implementation in late-stage radiolabeling and radio-pharmaceutical synthesis for PET imaging.We believe that this review will inspire the development of more promising radiolabeling protocols for the preparation of clinically useful PET agents.
