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作 者:Erting Feng Fangyuan Lv Shanliang Tang Jianjun Du Shibo Lv Yingnan Wu Dapeng Liu Panwang Zhou Fengling Song Xiaojun Peng 冯二厅;吕方圆;汤善亮;杜健军;吕世博;吴蓥男;刘大鹏;周潘旺;宋锋玲;彭孝军(State Key Laboratory of Fine Chemicals,Frontiers Science Center for Smart Materials Oriented Chemical Engineering,Dalian University of Technology,Dalian,116024,China;Institute of Frontier Chemistry,School of Chemistry and Chemical Engineering,Shandong University,Qingdao,266237,China;Institute Shenzhen Research Institute of Shandong University,Shenzhen,518057,China)
机构地区:[1]State Key Laboratory of Fine Chemicals,Frontiers Science Center for Smart Materials Oriented Chemical Engineering,Dalian University of Technology,Dalian,116024,China [2]Institute of Frontier Chemistry,School of Chemistry and Chemical Engineering,Shandong University,Qingdao,266237,China [3]Institute Shenzhen Research Institute of Shandong University,Shenzhen,518057,China
出 处:《Science China Materials》2024年第9期3003-3011,共9页中国科学(材料科学)(英文版)
基 金:supported financially by Guangdong Basic and Applied Basic Research Foundation(2019A1515110441);the Natural Science Foundation of Shandong Province(ZR2020QB001);the National Key Research and Development Program of China(2023YFC3403000);the National Natural Science Foundation of China(22378231 and 22001148)。
摘 要:J-aggregates of cyanine have shown great merits in tumor photothermal therapy(PTT)due to their distinct redshift absorption as well as superior photothermal conversion efficiency(PCE).However,due to the complexity of intermolecular interactions,especially the impact of steric hindrance on aggregation,exploring effective strategies to regulate the aggregation modes of organic materials remains challenging.Herein,steric hindrance-regulated J-aggregation of near-infrared(NIR)cyanine was reported based on Pt-coordinated cyanine self-assembly with unexpected“butterfly effect”.Two Pt-coordinated cyanine dimers CyR-Pt(R=Me and Et)were synthesized and spontaneously self-assembled into aggregates in aqueous solution.CyEt-Pt aggregates were loose and amorphous stacking.By replacing ethyl with methyl to reduce steric hindrance,a tiny change resulted in the generation of tightly stacked cyanine J-aggregates(thickness less than 3 nm)observed in CyMe-Pt self-assembly.Significantly,this unexpected“butterfly effect”enabled CyMe-Pt J-aggregates to effectively inhibit reactive oxygen species and greatly improve its photostability.Besides,CyMe-Pt J-aggregates with NIR-II absorption exhibited outstanding photothermal stability and higher PCE(η=37%)than CyEt-Pt disordered aggregates(η=20%).Evident tumor suppression performance of CyMe-Pt J-aggregates was validated under 980 nm laser irradiation,demonstrating its great potential in tumor PTT.花菁染料的J-聚集体因其独特的红移吸收和优异的光热转换效率(PCE)而在肿瘤光热治疗(PTT)中显示出巨大的优势.然而,由于分子间相互作用的复杂性,探索新的策略来调控有机材料的聚集模式仍然具有挑战性.在本文中,我们设计了两个金属Pt配位的花菁二聚体CyRPt(R=Me,Et),并在水溶液中自发自组装成聚集体.CyEt-Pt聚集体为疏松和无定形堆积.通过用甲基取代乙基以减少空间位阻,这一微小的变化导致在CyMe-Pt自组装中出现了紧密有序的J-聚集体.这种意外的“蝴蝶效应”使CyMe-Pt J-聚集体表现出NIR-Ⅱ吸收、优异的光稳定性以及突出的光热性能(PCE=37%).在980 nm激光以安全功率(0.5W cm^(-2))照射下,CyMe-Pt J-聚集体显著抑制肿瘤生长,证明了其在肿瘤PTT中的巨大潜力.
关 键 词:near-infrared cyanine metal coordination steric hindrance J-AGGREGATION photothermal therapy
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