School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P.R.China.
Anal Chem. 2022 Apr 5;94(13):5415-5424. doi: 10.1021/acs.analchem.2c00235. Epub 2022 Mar 24.
The weak interfacial binding affinities of the inorganic perovskite core with ligands and high density of surface defect states induce the facile detachment of surface ligands from nanocrystals (NCs), resulting in their poor colloidal stability and fluorescence in aqueous. In this work, a powerful ligand engineering strategy was proposed for eliminating the surface defects and aggregation of the NCs. Using an amphiphilic polymer octylamine-modified polyacrylic acid (OPA) as a capping ligand, the as-synthesized CsPbBr NCs retain high photoluminescence intensity and stability by the modified ligand-assisted reprecipitation method. The increase in the fluorescence lifetime and NC size could also be observed, and how the NC particle size influences fluorescence lifetime was further studied. In addition, the water stability, photostability, and thermal stability were significantly improved, and the fluorescence of NCs can maintain 80.13% of the original value in water for 15 d. We further validated that the strong binding affinity of OPA and oleylamine ligands with CsPbBr NCs leads to a reduction in surface trap states, and a large amount of carboxyl groups of the OPA made the NCs preserve good water solubility. In addition, the OPA has the ability of adjusting the particle size of NCs. Furthermore, a wavelength-shifted colorimetric sensor based on these NCs was constructed for detection of Cl in sweat, which enables the rapid and visual detection of Cl with high accuracy and stability. Overall, these CsPbBr NCs synthesized by the ligand engineering strategy validated their wide applications in biomedical sensing fields.
无机钙钛矿核与配体的弱界面结合亲和力和高密度的表面缺陷态促使表面配体从纳米晶体(NCs)上轻易脱离,从而导致其在水相中的胶体稳定性和荧光强度差。在这项工作中,提出了一种强大的配体工程策略,用于消除 NCs 的表面缺陷和聚集。通过使用两亲性聚合物辛胺改性聚丙烯酸(OPA)作为封端配体,通过改性配体辅助再沉淀法合成的 CsPbBr NCs 保留了高的光致发光强度和稳定性。还可以观察到荧光寿命和 NC 尺寸的增加,并且进一步研究了 NC 颗粒尺寸如何影响荧光寿命。此外,水稳定性、光稳定性和热稳定性得到了显著提高,NCs 的荧光在水中 15 天内可保持原始值的 80.13%。我们进一步验证了 OPA 和油胺配体与 CsPbBr NCs 之间的强结合亲和力导致表面陷阶态减少,并且大量的 OPA 羧基基团使 NCs 保持良好的水溶性。此外,OPA 具有调节 NCs 颗粒尺寸的能力。此外,基于这些 NCs 构建了一种波长移动比色传感器,用于检测汗液中的 Cl,其可以实现高精度和高稳定性的 Cl 的快速和可视化检测。总的来说,通过配体工程策略合成的这些 CsPbBr NCs 验证了它们在生物医学传感领域的广泛应用。