Department of Chemical and Biochemical Engineering, University of Western Ontario , London, Ontario, N6A 5B9, Canada.
Langmuir. 2014 Feb 25;30(7):1893-9. doi: 10.1021/la403914k. Epub 2014 Feb 7.
In this study, biocompatible and proton-resistant CdSe quantum dots (QDs) assembled on gelatin nanospheres (GNs) have been synthesized by combining the two-step desolvation method with the layer-by-layer assembly technique. The core-shell fluorescent gelatin nanosphere consists of a gelatin core and a four-layer shell of hydrophilic CdSe QDs assembled through polyelectrolytes (PE). The morphology, microstructures, and photostability of the hybrid spheres were further investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fluorospectrometery, and confocal fluorescent microscopy (CFM), respectively. The average diameter of the hybrid QDs-gelatin nanospheres (QDs-GNs) is estimated at 484 ± 40 nm. Our results indicate that the 20 ± 5 nm of the shell is attributed to the four-layer of CdSe QDs assembled through the PE. QD-GNs show a strong photoluminescence with the maximum emission (λ(em)) at 613 nm at the excitation wavelength of 470 nm. The core-shell QDs-GNs are able to resist quenching in acidic solution (pH < 4). Furthermore, core-shell QDs-GNs show a longer lifetime in a broad range of pH values, from 9 to 1. The calculated average lifetime (τ(ave)) of QDs-GNs is about 889 ± 23 ps, which is 3-fold longer than that of MUA-QDs (263 ± 10 ps) at pH 7.0. The enhanced lifetime of QDs-GNs is almost 9 times of that of CdSe QDs when pH value is 1. Meanwhile, the cell viability study shows that no significant toxic effect is imposed on the NIH/3T3 mouse fibroblast cell line when the concentration of QD-GNs is below 5 mg/mL. It is expected that this new biocompatible fluorescent nanospheres could be an excellent alternative fluorescent imaging agent for cell labeling, especially in acidic conditions.
在这项研究中,通过两步去溶剂法与层层组装技术相结合,合成了在明胶纳米球(GNs)上组装的生物相容性和质子抗性 CdSe 量子点(QDs)。核壳荧光明胶纳米球由明胶核和通过聚电解质(PE)组装的四层亲水性 CdSe QD 壳组成。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、荧光光谱仪和共聚焦荧光显微镜(CFM)分别进一步研究了混合球的形态、微观结构和光稳定性。混合 QDs-明胶纳米球(QDs-GNs)的平均直径约为 484±40nm。我们的结果表明,壳的 20±5nm 归因于通过 PE 组装的四层 CdSe QDs。QD-GNs 表现出很强的光致发光,在 470nm 激发波长下最大发射(λ(em))为 613nm。核壳 QDs-GNs 能够抵抗酸性溶液(pH<4)的猝灭。此外,核壳 QDs-GNs 在从 9 到 1 的宽 pH 值范围内显示出更长的寿命。QD-GNs 的平均寿命(τ(ave))约为 889±23ps,在 pH7.0 时比 MUA-QDs(263±10ps)长 3 倍。当 pH 值为 1 时,QD-GNs 的增强寿命是 CdSe QDs 的近 9 倍。同时,细胞活力研究表明,当 QD-GNs 的浓度低于 5mg/mL 时,对 NIH/3T3 小鼠成纤维细胞系没有显著的毒性作用。预计这种新的生物相容性荧光纳米球可以成为细胞标记的优秀替代荧光成像剂,特别是在酸性条件下。