Near-infrared excited cooperative upconversion in luminescent Ytterbium(III) bioprobes as light-responsive theranostic agents
Near-infrared excited cooperative upconversion in luminescent Ytterbium(III) bioprobes as light-responsive theranostic agents
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DOI：
10.1016/j.ejmech.2018.12.010
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发表时间：
2019-02-01
影响因子：
6.7
通讯作者：
Patra, Ashis K.
中科院分区：
文献类型：
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作者：
Dasari, Srikanth;Singh, Swati;Patra, Ashis K.
基于光敏天线的近红外镱（III）配合物[Yb(dpq)(DMF)(2)Cl-3](1)、[Yb(dppz)(DME)(2)Cl-3](2)、[Yb(dpq)(ttfa)(3)](3)]和[Yb(dppz)(ttfa)（3)](4)）利用Yb（III）的协同上转换发光（CUCL）设计了[Yb(dpq) -[3,2-d:2',3'-f]喹诺啉（dpq）、[dipyrido-[3,2-a:2',3'-c]-吩那嗪（dppz）和4,4,4-三氟-1-（2-噻吩基）-1,3-丁二酮（Httfa）作为近红外生物显像剂。研究了它们的结构、详细的光物理特性、生物相互作用、光诱导DNA切割、近红外光细胞毒性、细胞内化和生物成像特性。离散单核配合物采用七配位(LnN(2)O（2)Cl(3)）单帽八面体（1,2）和八配位(LnN（2)O(6)）畸变方形反棱镜几何（3,4），具有双齿N， N给体dpq， dppz和O，O给体ttfa配体。所设计的Yb（III）探针（3,4）具有双增敏天线（dpq/dppz和Httfa）的优点，可以在近红外区域调制所需的光学特性，用于生物透明窗口的生物成像和光响应细胞内损伤，并具有时空控制。球内水的缺乏（q = 0），显著的光稳定性，大的斯托克斯位移，能量正确平衡的配体T-3态的存在，允许有效的能量转移（ET）到Yb（III）的发射态F-2（5/2）。在980 nm近红外激发下，Yb（III）在1-4可见蓝区（λ (em) = 490 nm）具有独特的协同上转换发光（CUCL），使其成为近红外-可见或近红外-近红外细胞成像探针的特殊候选物。研究了Yb（III）在固态和溶液中离散单核配合物的CUCL性质。据我们所知，我们首次优雅地利用了Yb（III）的这一显著特性进行细胞成像应用，包括在CUC/多光子激发显微镜中的潜在用途。该复合物对DNA、HSA和BSA具有明显的结合倾向（K与10(5)M-1相似）。它们通过光氧化还原途径在365 nm处有效地将超螺旋（SC） DNA切割成其缺口圆（NC）形式。细胞摄取研究明显显示复合物的胞质和核定位。最后，Yb（III）配合物在980 nm连续激光下的近红外光细胞毒性证明了其用于PDT的能力。这里描述的结果为开发光响应高光稳定性的Yb（III）探针提供了一种智能策略，用于近红外治疗在生物透明光疗窗口中的应用。(C) 2018 Elsevier Masson SAS。版权所有。
Near-infrared (NIR) Ytterbium(III) complexes namely [Yb(dpq)(DMF)(2)Cl-3] (1), [Yb(dppz)(DME)(2)Cl-3] (2), [Yb(dpq)(ttfa)(3)] (3) and [Yb(dppz)(ttfa)(3)] (4) based on photosensitizing antenna: dipyrido-[3,2-d:2',3'-f]quinoxaline (dpq), dipyrido-[3,2-a:2',3'-c]-phenazine (dppz) and 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Httfa), were designed as NIR bioimaging agents utilizing cooperative upconversion luminescence (CUCL) of Yb(III). Their structures, detailed photophysical properties, biological interactions, photo-induced DNA cleavage, NIR photocytotoxicity and cellular internalization and bioimaging properties were examined. Discrete mononuclear complexes adopt a seven-coordinated (LnN(2)O(2)Cl(3)) mono capped octahedron (1, 2) and eight-coordinated (LnN(2)O(6)) distorted square antiprism geometry (3, 4) with bidentate N, N-donor dpq, dppz and O,O-donor ttfa ligands. The designed Yb(III) probes (3, 4) having advantages of dual sensitizing antennae (dpq/dppz and Httfa) to modulate the desirable optical properties in NIR region for bioimaging in biologically transparent window and light-responsive intracellular damage with spatiotemporal control. The lack of inner-sphere water (q = 0), remarkable photostability, large Stokes' shifts, presence of energetically rightly poised ligand T-3 states allows efficient energy transfer (ET) to the emissive F-2(5/2) state of Yb(III). The unique cooperative upconversion luminescence (CUCL) of Yb(III) was observed in 1-4 in the visible blue region (lambda(em) = 490 nm) upon NIR excitation at 980 nm, makes them special candidates for NIR-to-visible or NIR-to-NIR cellular imaging probes. The CUCL property of Yb(III) were observed in the discrete mononuclear complexes both in solid state and solution. We elegantly utilized this remarkable property of Yb(III) for cellular imaging application for the first time to the our knowledge including potential uses in CUC/multiphoton excitation microscopy. The complexes exhibit significant binding propensity to DNA, HSA and BSA (K similar to 10(5) M-1). They effectively cleave supercoiled (SC) DNA to its nicked circular (NC) form at 365 nm via photoredox pathways. The cellular uptake studies evidently displayed cytosolic and nuclear localization of the complexes. Finally, the capability of Yb(III) complexes usage for PDT were demonstrated through significant near-IR photocytotoxicity at 980 nm CW laser. The results depicted here offers an intelligent strategy towards developing light-responsive highly photostable Yb(III) probes for NIR theranostic application in the biologically transparent phototherapeutic window. (C) 2018 Elsevier Masson SAS. All rights reserved.