Cao Yue, Li Da-Wei, Zhao Li-Jun, Liu Xiao-Yuan, Cao Xiao-Ming, Long Yi-Tao
Key Laboratory for Advanced Materials & Department of Chemistry, East China University of Science and Technology , 130 Meilong Road, Shanghai, 200237, P. R. China.
Anal Chem. 2015 Oct 6;87(19):9696-701. doi: 10.1021/acs.analchem.5b01793. Epub 2015 Sep 8.
A novel nanosensor was explored for the highly selective detection of intracellular carbon monoxide (CO) by surface enhanced Raman spectroscopy (SERS) on the basis of palladacycle carbonylation. By assembling new synthesized palladacycles (PC) on the surface of gold nanoparticles (AuNPs), SERS nanosensors (AuNP/PC) were prepared with good SERS activity and reactivity with CO. When the AuNP/PC nanosensors were incubated with a CO-containing system, carbonylation of the PC assembled on AuNPs was initiated, and the corresponding SERS spectra of AuNP/PC changed significantly, which allowed the carbonylation reaction to be directly observed in situ. Upon SERS observation of CO-dependent carbonylation, this SERS nanosensor was used for the detection of CO under physiological conditions. Moreover, benefiting from the specificity of the reaction coupled with the fingerprinting feature of SERS, the developed nanosensor demonstrated high selectivity over other biologically relevant species. In vivo studies further indicated that CO in normal human liver cells and HeLa cells at concentrations as low as 0.5 μM were successfully detected with the proposed SERS strategy, demonstrating its great promise for the analytical requirements in studies of physiopathological events involved with CO.
基于钯环羰基化反应,利用表面增强拉曼光谱(SERS)开发了一种新型纳米传感器,用于高选择性检测细胞内一氧化碳(CO)。通过将新合成的钯环(PC)组装在金纳米颗粒(AuNPs)表面,制备了具有良好SERS活性且能与CO发生反应的SERS纳米传感器(AuNP/PC)。当AuNP/PC纳米传感器与含CO体系孵育时,引发了组装在AuNPs上的PC的羰基化反应,AuNP/PC相应的SERS光谱发生显著变化,从而能够直接原位观察羰基化反应。通过SERS观察CO依赖性羰基化反应,该SERS纳米传感器用于生理条件下CO的检测。此外,得益于该反应的特异性以及SERS的指纹特征,所开发的纳米传感器对其他生物相关物质具有高选择性。体内研究进一步表明,采用所提出的SERS策略成功检测到正常人类肝细胞和HeLa细胞中低至0.5 μM浓度的CO,证明了其在涉及CO的生理病理事件研究中的分析需求方面具有巨大潜力。