Chen Zhigang, Chen Huili, Hu He, Yu Mengxiao, Li Fuyou, Zhang Qiang, Zhou Zhiguo, Yi Tao, Huang Chunhui
Department of Chemistry & Laboratory of Advanced Materials, Fudan University, 220 Handan Road, Shanghai 200433, People's Republic of China.
J Am Chem Soc. 2008 Mar 12;130(10):3023-9. doi: 10.1021/ja076151k. Epub 2008 Feb 16.
Up-converting rare-earth nanophosphors (UCNPs) have great potential to revolutionize biological luminescent labels, but their use has been limited by difficulties in obtaining UCNPs that are biocompatible. To address this problem, we have developed a simple and versatile strategy for converting hydrophobic UCNPs into water-soluble and carboxylic acid-functionalized analogues by directly oxidizing oleic acid ligands with the Lemieux-von Rudloff reagent. This oxidation process has no obvious adverse effects on the morphologies, phases, compositions and luminescent capabilities of UCNPs. Furthermore, as revealed by Fourier transform infrared (FTIR) and NMR results, oleic acid ligands on the surface of UCNPs can be oxidized into azelaic acids (HOOC(CH2)7COOH), which results in the generation of free carboxylic acid groups on the surface. The presence of free carboxylic acid groups not only confers high solubility in water, but also allows further conjugation with biomolecules such as streptavidin. A highly sensitive DNA sensor based on such streptavidin-coupled UCNPs have been prepared, and the demonstrated results suggest that these biocompatible UCNPs have great superiority as luminescent labeling materials for biological applications.
上转换稀土纳米磷光体(UCNPs)在革新生物发光标记方面具有巨大潜力,但其应用因难以获得具有生物相容性的UCNPs而受到限制。为解决这一问题,我们开发了一种简单通用的策略,通过用Lemieux-von Rudloff试剂直接氧化油酸配体,将疏水性UCNPs转化为水溶性且带有羧酸官能团的类似物。该氧化过程对UCNPs的形态、相、组成和发光能力没有明显的不利影响。此外,傅里叶变换红外光谱(FTIR)和核磁共振(NMR)结果表明,UCNPs表面的油酸配体可被氧化成壬二酸(HOOC(CH2)7COOH),从而在表面产生游离羧酸基团。游离羧酸基团的存在不仅赋予其在水中的高溶解度,还能使其进一步与生物分子如链霉亲和素结合。基于这种链霉亲和素偶联的UCNPs制备了一种高灵敏度的DNA传感器,结果表明这些具有生物相容性的UCNPs作为生物应用中的发光标记材料具有很大优势。