Ma Yunfei, Li Yan, Ma Shijian, Zhong Xinhua
Shanghai Key Laboratory of Functional Materials Chemistry, Institute of Applied Chemistry, East China University of Science and Technology, Shanghai 200237, China.
J Mater Chem B. 2014 Aug 21;2(31):5043-5051. doi: 10.1039/c4tb00458b. Epub 2014 Jun 30.
Silica coating via a Stöber method is an effective route to render luminescent quantum dots (QDs) with great biocompatibility, low toxicity and water-solubility for bioapplications. However, the bottleneck in this route is the access of highly luminescent, colloidally stable QD dispersion in alcoholic solution. Herein, we report a facile route based on the Stöber method for the synthesis of isolated silica coated QDs (QD@SiO) with high emission efficiencies, tunable small size (less than 30 nm) and excellent stability. Prior to silica coating, the initial oil-soluble QDs were made dispersible in alcohol-water media by replacing the native hydrophobic ligands with adenosine 5'-monophosphate (AMP). Then, 3-mercaptopropyl-trimethoxysilane (MPS) was introduced to serve as silane nucleation primers. Finally, a silica shell with controllable thickness was obtained on the QD surface by hydrolysis/condensation of tetraethyl orthosilicate (TEOS). Remarkably, the resultant QD@SiO had nearly the same high luminescent efficiency (50-65%) as that of initial oil-soluble QDs and exhibited excellent long-term photo and colloidal stability in harsh environments (pH range of 3-13, saturated NaCl solution and thermal treatment at 100 °C). It was demonstrated that the cytotoxicity of the resultant QD@SiO was significantly diminished. Moreover, the QD@SiO conjugated with folic acid exhibits high specific binding toward receptor-positive Hela cells over receptor-negative A549 cells, indicating the potential of our obtained QD@SiO as robust biomarkers in cells due to their chemical processibility and low cytotoxicity.
通过施托伯方法进行二氧化硅包覆是一种有效的途径,可使发光量子点(QDs)具有良好的生物相容性、低毒性和水溶性,适用于生物应用。然而,该途径的瓶颈在于在醇溶液中获得高发光、胶体稳定的量子点分散体。在此,我们报道了一种基于施托伯方法的简便途径,用于合成具有高发射效率、可调谐小尺寸(小于30 nm)和优异稳定性的孤立二氧化硅包覆量子点(QD@SiO)。在二氧化硅包覆之前,通过用5'-单磷酸腺苷(AMP)取代天然疏水配体,使初始油溶性量子点可分散在醇水介质中。然后,引入3-巯基丙基三甲氧基硅烷(MPS)作为硅烷成核引物。最后,通过原硅酸四乙酯(TEOS)的水解/缩合在量子点表面获得了厚度可控的二氧化硅壳。值得注意的是,所得的QD@SiO具有与初始油溶性量子点几乎相同的高发光效率(50-65%),并在恶劣环境(pH范围为3-13、饱和NaCl溶液和100°C热处理)中表现出优异的长期光稳定性和胶体稳定性。结果表明,所得QD@SiO的细胞毒性显著降低。此外,与叶酸缀合的QD@SiO对受体阳性的Hela细胞比对受体阴性的A549细胞表现出更高的特异性结合,这表明我们获得的QD@SiO由于其化学可加工性和低细胞毒性而具有作为细胞中强大生物标志物的潜力。