Key Laboratory of Photochemical Biomaterials and Energy Storage Materials and College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025, China.
NHC and CAMS Key Laboratory of Molecular Probe and Targeted Theranostics, Molecular Imaging Research Center (MIRC), Harbin Medical University and TOF-PET/CT/MR Center, The Fourth Hospital of Harbin Medical University, Heilongjiang 150025, China.
ACS Appl Mater Interfaces. 2021 Mar 3;13(8):9604-9619. doi: 10.1021/acsami.0c21284. Epub 2021 Feb 19.
Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, NiS/CuS nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron-hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide HO into O, directly. Meanwhile, the photostimulated electrons can capture the dissolved O to form a toxic reactive oxygen species (ROS). Moreover, NiS/CuS nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous HO into ·OH and O, which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for NiS/CuS. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and NiS/CuS@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.
肿瘤微环境中的缺氧抑制了光动力疗法（PDT）的疗效。在这里，合成了 NiS/CuS 纳米异质结构作为一种新的光敏剂，它还实现了细胞内光催化 O 释放，以缓解 TME 中的缺氧，并增强 PDT。由于具有较窄的带隙（低于 1.5 eV），近红外（NIR）（808nm）可以刺激它们的电子-空穴分离。通过实验数据和密度泛函理论（DFT）计算证实的新型 Z 型纳米异质结构具有更高的氧化还原能力，赋予光激发空穴足够的势能，直接将 HO 氧化成 O。同时，光激发的电子可以捕获溶解的 O 形成毒性活性氧（ROS）。此外，NiS/CuS 纳米复合材料还具有类过氧化物酶/过氧化氢酶的活性，可以将内源性 HO 转化为·OH 和 O，不仅引起化学动力学治疗（CDT），还可以缓解缺氧，从而辅助 PDT。此外，由于较窄的带隙，它们具有较高的近红外吸收和出色的光热转换效率（49.5%）。值得注意的是，纳米复合材料还表现出新型的生物降解性，并可在 2 周内通过粪便和尿液代谢和消除。Ni/Cu 离子中的单电子诱导磁共振成像（MRI）能力用于 NiS/CuS。为了确保癌细胞被特异性靶向，将透明质酸（HA）接枝到外部，并且 NiS/CuS@HA 集成了光动力疗法（PDT）、化学动力学疗法（CDT）和光热疗法（PTT），以表现出针对缺氧肿瘤消除的出色抗癌效率。
