Wang Shuo, Wei Zhongyu, Xu Qi, Yu Long, Xiao Yuxiu
Department of Thyroid and Breast Surgery, Zhongnan Hospital of Wuhan University, School of Pharmaceutical Sciences, Wuhan University, Wuhan 430071, China.
Key Laboratory of Combinatorial Biosynthesis and Drug Discovery (Ministry of Education), School of Pharmaceutical Sciences, Wuhan University, Wuhan 430071, China.
ACS Nano. 2024 Jan 9;18(1):1084-1097. doi: 10.1021/acsnano.3c10548. Epub 2023 Dec 27.
Water instability and sensing homogeneity are the Achilles' heel of CsPbX NPs in biological fluids application. This work reports the preparation of Mn:CsPbCl@SiO yolk-shell nanoparticles (YSNPs) in aqueous solutions created through the integration of ligand, surface, and crystal engineering strategies. The S2 reaction between 4-chlorobutyric acid (CBA) and oleylamine (OAm) yields a zwitterionic ligand that facilitates the dispersion of YSNPs in water, while the robust SiO shell enhances their overall stability. Besides, Mn doping in YSNPs not only introduces a second emission center but also enables potential postsynthetic designability, leading to the switching from YSNPs to MnO@YSNPs with excellent oxidase (OXD)-like activity. Theoretical calculations reveal that electron transfer from CsPbCl to MnO and the adsorption-desorption process of 3,3',5,5'-tetramethylbenzidine (TMB) synergistically amplify the OXD-like activity. In the presence of ascorbic acid (AA), Mn in MnO@YSNPs (fluorescent nanozyme) is reduced to Mn and dissociated, thereby inhibiting the OXD-like activity and triggering fluorescence "turn-on/off", i.e., dual-mode recognition. Finally, a biomarker reporting platform based on MnO@YSNPs fluorescent nanozyme is constructed with AA as the reporter molecule, and the accurate detection of human serum alkaline phosphatase (ALP) is realized, demonstrating the vast potential of perovskites in biosensing.
水不稳定性和传感均匀性是CsPbX纳米颗粒在生物流体应用中的致命弱点。这项工作报道了通过整合配体、表面和晶体工程策略,在水溶液中制备Mn:CsPbCl@SiO核壳纳米颗粒(YSNPs)。4-氯丁酸(CBA)与油胺(OAm)之间的S2反应产生一种两性离子配体,有助于YSNPs在水中的分散,而坚固的SiO壳增强了它们的整体稳定性。此外,在YSNPs中掺杂Mn不仅引入了第二个发射中心,还实现了潜在的合成后可设计性,从而实现了从YSNPs到具有优异氧化酶(OXD)样活性的MnO@YSNPs的转变。理论计算表明,电子从CsPbCl转移到MnO以及3,3',5,5'-四甲基联苯胺(TMB)的吸附-解吸过程协同放大了OXD样活性。在抗坏血酸(AA)存在下,MnO@YSNPs(荧光纳米酶)中的Mn被还原为Mn并解离,从而抑制OXD样活性并触发荧光“开启/关闭”,即双模式识别。最后,以AA为报告分子构建了基于MnO@YSNPs荧光纳米酶的生物标志物报告平台,实现了对人血清碱性磷酸酶(ALP)的准确检测,证明了钙钛矿在生物传感中的巨大潜力。