Laboratoire Réactions et Génie des Procédés, UPR 3349, Nancy-University, CNRS, 1 Rue Grandville, 54001 Nancy Cedex, France.
Acta Biomater. 2011 Mar;7(3):1327-38. doi: 10.1016/j.actbio.2010.10.012. Epub 2010 Oct 18.
This work presents a novel approach to producing water soluble manganese-doped core/shell ZnS/ZnS quantum dots (ZnS:Mn/ZnS). The Mn-doped ZnS core was prepared through a nucleation doping strategy and a ZnS shell was grown on ZnS:Mn d-dots by decomposition of Zn(2+)-3-mercaptopropionic acid (MPA) complexes at 100 °C. It was found that the Mn2+(4)T1→6A1 fluorescence emission at ∼590 nm significantly increased after growth of the shell when the Mn2+ doping content was 4.0 at.%. A photoluminescence quantum yield of ∼22% was obtained for core/shell nanocrystals. The nanoparticles were structurally and compositionally characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and dynamic light scattering. The surface MPA molecules favor the dispersion of ZnS:Mn/ZnS QDs in aqueous media and make possible conjugation with targeting folic acid molecules. The folate receptor-mediated delivery of folic acid-conjugated ZnS:Mn/ZnS QDs was demonstrated using confocal microscopy with biphotonic excitation. Bare and folate-conjugated QDs exhibit only weak cytotoxicity towards folate receptor-positive T47D cancer cells and MCF-7 cells, used as a reference, at high concentrations (mmolar range) after 72h incubation.
本工作提出了一种制备水溶性锰掺杂核/壳型 ZnS/ZnS 量子点(ZnS:Mn/ZnS)的新方法。Mn 掺杂的 ZnS 核通过成核掺杂策略制备,然后在 100°C 下通过 Zn(2+)-3-巯基丙酸(MPA)配合物的分解在 ZnS:Mn d-点上生长 ZnS 壳。研究发现,当 Mn2+掺杂含量为 4.0 at.%时,在壳生长后,约 590nm 的 Mn2+(4)T1→6A1 荧光发射显著增强。核/壳纳米晶体的光致发光量子产率约为 22%。通过透射电子显微镜、X 射线衍射、X 射线光电子能谱和动态光散射对纳米粒子进行了结构和组成表征。表面 MPA 分子有利于 ZnS:Mn/ZnS QDs 在水介质中的分散,并使与靶向叶酸分子的缀合成为可能。使用双光子激发共聚焦显微镜证明了叶酸偶联的 ZnS:Mn/ZnS QDs 通过叶酸受体介导的递释。裸 QDs 和叶酸偶联 QDs 在 72h 孵育后,在高浓度(毫摩尔级)下对叶酸受体阳性 T47D 癌细胞和 MCF-7 细胞(用作对照)表现出仅较弱的细胞毒性。