Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan, Republic of China.
Department of Chemistry, Universitas Airlangga, Surabaya 60115, Indonesia.
ACS Appl Mater Interfaces. 2022 Jan 12;14(1):278-296. doi: 10.1021/acsami.1c19644. Epub 2021 Dec 28.
In this study, for the first time, red-emitting CsMgPbI quantum dots (QDs) are prepared by doping with magnesium (Mg) ions via the one-pot microwave pyrolysis technique. The X-ray diffraction and X-ray photoelectron spectroscopy results have confirmed partial substitution of Pb by Mg inside the CsPbI framework. The as-synthesized CsMgPbI QDs have exhibited excellent morphology, higher quantum yield (upto ∼89%), better photostability and storage stability than undoped CsPbI. Next, the bioavailability of as-synthesized hydrophobic CsMgPbI QDs is improved by encapsulating them into gadolinium-conjugated pluronic 127 (PF127-Gd) micelles through hydrophobic interactions (PQD@Gd). The optical properties of perovskite quantum dots (PQDs) and the presence of Gd could endow the PQD@Gd with fluorescence imaging, magnetic resonance imaging (MRI), and phototherapeutic properties. Accordingly, the MRI contrasting effects of PQD@Gd nanoagents are demonstrated by employing and studies, which validated that PQD@Gd nanoagents had superior MR contrasting effect with a / ratio of 1.38. In vitro MRI and fluorescence imaging analyses have shown that the PQD@Gd nanoagents are internalized into the cancer cells via a caveolae-mediated endocytosis pathway. The PQD@Gd nanoagents have exhibited excellent biocompatibility even at concentrations as high as 450 ppm. Interestingly, the as-prepared PQD@Gd nanoagents have efficiently produced cytotoxic reactive oxygen species in the cancer cells under 671 nm laser illumination and thereby induced cell death. Moreover, the PQD@Gd nanoagent also demonstrated excellent photocatalytic activity toward organic pollutants under visible light irradiation. The organic pollutants rhodamine b, methyl orange, and methylene blue were degraded by 92.11, 89.21, and 76.21%, respectively, under 60, 80, and 100 min, respectively, irradiation time. The plausible mechanism for the photocatalytic activity is also elucidated. Overall, this work proposes a novel strategy to enhance the optical properties, stability, and bioapplicability of PQDs. The multifunctional PQD@Gd nanoagents developed in this study could be the potential choice of components not only for cancer therapy due to dual-modal imaging and photodynamic therapeutic properties but also for organic pollutant or bacterial removal due to excellent photocatalytic properties.
在这项研究中，首次通过一锅微波热解技术，通过掺杂镁（Mg）离子制备了红色发光的 CsMgPbI 量子点（QDs）。X 射线衍射和 X 射线光电子能谱结果证实了 CsPbI 框架内 Pb 的部分被 Mg 取代。所合成的 CsMgPbI QD 具有优异的形态、更高的量子产率（高达约 89%）、更好的光稳定性和存储稳定性，优于未掺杂的 CsPbI。接下来，通过疏水相互作用（PQD@Gd）将合成的疏水性 CsMgPbI QD 封装到钆共轭的泊洛沙姆 127（PF127-Gd）胶束中，提高了其生物利用度。钙钛矿量子点（PQD）的光学性质和 Gd 的存在赋予 PQD@Gd 荧光成像、磁共振成像（MRI）和光疗特性。因此，通过 T1 和 T2 研究证明了 PQD@Gd 纳米剂的 MRI 对比效应，验证了 PQD@Gd 纳米剂具有更高的 MRI 对比效应，/ 比值为 1.38。体外 MRI 和荧光成像分析表明，PQD@Gd 纳米剂通过胞吞作用途径被内化到癌细胞中。即使在高达 450ppm 的浓度下，PQD@Gd 纳米剂也表现出优异的生物相容性。有趣的是，在 671nm 激光照射下，制备的 PQD@Gd 纳米剂能够有效地在癌细胞中产生细胞毒性活性氧物质，从而诱导细胞死亡。此外，PQD@Gd 纳米剂在可见光照射下对有机污染物也表现出优异的光催化活性。在 60、80 和 100min 的照射时间下，罗丹明 B、甲基橙和亚甲基蓝分别降解了 92.11%、89.21%和 76.21%。还阐明了光催化活性的可能机制。总体而言，本工作提出了一种增强 PQD 光学性质、稳定性和生物适用性的新策略。本研究中开发的多功能 PQD@Gd 纳米剂不仅由于双模态成像和光动力治疗特性，而且由于出色的光催化性能，对于癌症治疗而言，也可能是一种理想的选择，也可用于去除有机污染物或细菌。
