Department of Chemistry, Stanford University, Stanford, CA 94305.
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070 Wuhan, China.
Proc Natl Acad Sci U S A. 2018 Jun 26;115(26):6590-6595. doi: 10.1073/pnas.1806153115. Epub 2018 Jun 11.
With suppressed photon scattering and diminished autofluorescence, in vivo fluorescence imaging in the 1,500- to 1,700-nm range of the near-IR (NIR) spectrum (NIR-IIb window) can afford high clarity and deep tissue penetration. However, there has been a lack of NIR-IIb fluorescent probes with sufficient brightness and aqueous stability. Here, we present a bright fluorescent probe emitting at ∼1,600 nm based on core/shell lead sulfide/cadmium sulfide (CdS) quantum dots (CSQDs) synthesized in organic phase. The CdS shell plays a critical role of protecting the lead sulfide (PbS) core from oxidation and retaining its bright fluorescence through the process of amphiphilic polymer coating and transferring to water needed for imparting aqueous stability and compatibility. The resulting CSQDs with a branched PEG outer layer exhibited a long blood circulation half-life of 7 hours and enabled through-skin, real-time imaging of blood flows in mouse vasculatures at an unprecedented 60 frames per second (fps) speed by detecting ∼1,600-nm fluorescence under 808-nm excitation. It also allowed through-skin in vivo confocal 3D imaging of tumor vasculatures in mice with an imaging depth of ∼1.2 mm. The PEG-CSQDs accumulated in tumor effectively through the enhanced permeation and retention effect, affording a high tumor-to-normal tissue ratio up to ∼32 owing to the bright ∼1,600-nm emission and nearly zero autofluorescence background resulting from a large ∼800-nm Stoke's shift. The aqueous-compatible CSQDs are excreted through the biliary pathway without causing obvious toxicity effects, suggesting a useful class of ∼1,600-nm emitting probes for biomedical research.
在 1500-1700nm 近红外(NIR)光谱(NIR-IIb 窗口)范围内,抑制光子散射和减少自发荧光,活体荧光成像是可以提供高清晰度和深层组织穿透的。然而,目前缺乏具有足够亮度和水分稳定性的 NIR-IIb 荧光探针。在这里,我们提出了一种基于核/壳型 lead sulfide/cadmium sulfide(CdS)量子点(CSQDs)的亮荧光探针,其发射波长约为 1600nm,这些量子点是在有机相中合成的。CdS 壳在保护 lead sulfide(PbS)核免受氧化方面起着关键作用,并通过两亲聚合物涂层和转移到赋予水分稳定性和相容性所需的水中的过程保留其明亮的荧光。具有支化 PEG 外层的所得 CSQDs 表现出 7 小时的长血液循环半衰期,并能够通过检测 808nm 激发下约 1600nm 的荧光,以每秒 60 帧(fps)的速度实现前所未有的速度实时成像小鼠血管中的血流。它还允许通过皮肤对小鼠肿瘤血管进行体内共聚焦 3D 成像,成像深度约为 1.2mm。PEG-CSQDs 通过增强的渗透和保留效应有效地积聚在肿瘤中,由于明亮的约 1600nm 发射和几乎为零的自发荧光背景,由于大的约 800nm Stoke 位移,实现高达约 32 的高肿瘤与正常组织比。水分相容的 CSQDs 通过胆道途径排出,不会引起明显的毒性作用,这表明一类具有约 1600nm 发射的有用探针可用于生物医学研究。