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具有四光子吸收活性、溶酶体特异性和精确癌症治疗功能的铂(II)配合物。

Functional Platinum(II) Complexes with Four-Photon Absorption Activity, Lysosome Specificity, and Precise Cancer Therapy.

机构信息

Department of Chemistry, Key Laboratory of Functional Inorganic Material Chemistry of Anhui Province, Anhui University, Hefei 230601, P. R. China.

School of Life Science, Anhui University, Hefei 230601, P. R. China.

出版信息

Inorg Chem. 2021 Feb 15;60(4):2362-2371. doi: 10.1021/acs.inorgchem.0c03245. Epub 2021 Jan 25.

Abstract

Multiphoton materials are in special demand in the field of photodynamic therapy and multiphoton fluorescence imaging. However, rational design methodology for these brands of materials is still nascent. This is despite transition-metal complexes favoring optimized nonlinear-optical (NLO) activity and heavy-atom-effected phosphorescent emission. Here, three four-photon absorption (4PA) platinum(II) complexes (-) are achieved by the incorporation of varied functionalized C^N^C ligands with high yields. - exhibit triplet metal-to-ligand charge-transfer transitions at ∼460 nm, which are verified multiple times by transient absorption spectra, time-dependent density functional theory calculations, and low-temperature emission spectra. Further, - undergo 4PA. Notably, one of the complexes, , has maximum 4PA cross-sectional values of up to 15.2 × 10 cm s photon under excitation of a 1600 nm femtosecond laser (near-IR II window). The 4PA cross sections vary when is binding to lecithin and when it displays its lysosome-specific targeting behavior. On the basis of the excellent 4PA property of , we believe that those 4PA platinum(II) complexes have great potential applications in cancer theranostics.

摘要

多光子材料在光动力治疗和多光子荧光成像领域有特殊需求。然而,这些材料的合理设计方法仍处于起步阶段。尽管过渡金属配合物有利于优化非线性光学(NLO)活性和重原子效应磷光发射。在这里,通过引入不同功能化的 C^N^C 配体,以高产率得到了三种四光子吸收(4PA)铂(II)配合物(-)。-在约 460nm 处表现出三重态金属-配体电荷转移跃迁,这多次通过瞬态吸收光谱、时间相关密度泛函理论计算和低温发射光谱得到验证。此外,-还经历了 4PA。值得注意的是,其中一种配合物,[Pt(tpy)(L1)],在 1600nm 飞秒激光(近红外 II 窗口)激发下,最大 4PA 横截面值高达 15.2×10cm s 光子。当与卵磷脂结合时,以及当它表现出溶酶体特异性靶向行为时,4PA 横截面会发生变化。基于[Pt(tpy)(L1)]优异的 4PA 性能,我们相信这些 4PA 铂(II)配合物在癌症治疗中有很大的应用潜力。

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