Versatile synthesis strategy for carboxylic acid-functionalized upconverting nanophosphors as biological labels

Versatile synthesis strategy for carboxylic acid-functionalized upconverting nanophosphors as biological labels
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DOI:
10.1021/ja076151k
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发表时间:
2008-03-12
影响因子:
15
通讯作者:
Huang, Chunhui
Huang, Chunhui
中科院分区:
化学1区
文献类型:
--
作者:
Chen, Zhigang;Chen, Huili;Huang, Chunhui

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上转换稀土纳米磷光体(UCNP)具有彻底改变生物发光标记的巨大潜力,但由于难以获得生物相容性的UCNP,其使用受到限制。为了解决这个问题,我们开发了一种简单而通用的策略,通过用 Lemieux-von Rudloff 试剂直接氧化油酸配体,将疏水性 UCNP 转化为水溶性和羧酸功能化的类似物。该氧化过程对UCNPs的形貌、物相、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(FTIR)和核磁共振结果表明,UCNPs表面的油酸配体可以被氧化成壬二酸(HOOC(CH2)(7)COOH),从而导致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,而且还允许与生物分子(例如链霉亲和素)进一步缀合。基于这种链霉亲和素偶联的 UCNP 的高灵敏度 DNA 传感器已经被制备出来,并且证明的结果表明这些生物相容性 UCNP 作为生物应用的发光标记材料具有巨大的优越性。
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)(7)COOH), 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.