Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, P. R. China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, P. R. China.
Anal Chem. 2016 Jun 21;88(12):6115-9. doi: 10.1021/acs.analchem.6b01374. Epub 2016 May 27.
The alkyne tags possess unique interference-free Raman emissions but are still hindered for further application in the field of biochemical labels due to its extremely weak spontaneous Raman scattering. With the aid of computational chemistry, herein, an alkyne-modulated surface-enhanced Raman scattering (SERS) palette is constructed based on rationally designed 4-ethynylbenzenethiol derivatives for spectroscopic signature, Au@Ag core for optical enhancement and an encapsulating polyallylamine shell for protection and conjugation. Even for the pigment rich plant cell (e.g., pollen), the alkyne-coded SERS tag can be highly discerned on two-dimension distribution impervious to strong organic interferences originating from resonance-enhanced Raman scattering or autofluorescence. In addition, the alkynyl-containing Raman reporters contribute especially narrow emission, band shift-tunable (2100-2300 cm(-1)) and tremendously enhanced Raman signals when the alkynyl group locates at para position of mercaptobenzene ring. Depending on only single Raman band, the suggested alkyne-modulated SERS-palette potentially provides a more effective solution for multiplex cellular imaging with vibrant colors, when the hyperspectral and fairly intense optical noises originating from lower wavenumber region (<1800 cm(-1)) are inevitable under complex ambient conditions.
炔基标签具有独特的无干扰拉曼发射,但由于其自发拉曼散射极其微弱,仍阻碍其在生化标记领域的进一步应用。在此,借助计算化学,我们基于合理设计的 4-乙炔基苯硫醇衍生物构建了一个炔基调控的表面增强拉曼散射(SERS)谱板,用于光谱特征,Au@Ag 核用于光学增强,以及聚烯丙胺壳用于保护和连接。即使对于富含色素的植物细胞(例如花粉),也可以在二维分布上高度分辨炔基编码的 SERS 标签,不受源自共振增强拉曼散射或自发荧光的强有机干扰。此外,当炔基位于巯基苯环的对位时,含炔基的拉曼报告分子会贡献出特别窄的发射、带位移可调谐(2100-2300cm-1)和极大增强的拉曼信号。仅依靠单个拉曼带,所提出的炔基调控 SERS 谱板在复杂环境条件下,由于来自较低波数区域(<1800cm-1)的高光谱和相当强的光学噪声不可避免时,为具有鲜艳颜色的多路细胞成像提供了更有效的解决方案。