Direct Observation of Amide Bond Formation in a Plasmonic Nanocavity Triggered by Single Nanoparticle Collisions
Direct Observation of Amide Bond Formation in a Plasmonic Nanocavity Triggered by Single Nanoparticle Collisions
复制标题
单纳米粒子碰撞触发的等离子体纳米腔中酰胺键形成的直接观测
DOI：
10.1021/jacs.1c02426
复制
发表时间：
2021-06-24
影响因子：
15
通讯作者：
Yang, Wenrong
中科院分区：
文献类型：
--
作者：
Kong, Na;Guo, Jing;Yang, Wenrong
在单分子水平上实时观察化学键的形成是有机化学和生物分子化学领域的重大挑战之一。可以收集使用总体平均测量无法获得的有价值的信息。尽管已经开发出非常复杂的监测化学反应的技术，但在单分子水平上原位检测化学键的特定形成的能力仍然是一个难以捉摸的目标。酰胺键通常由N-羟基琥珀酰亚胺（NHS）酯通过伯胺的氨解形成，并且该方案广泛用于肽和蛋白质的合成、交联和标记。在本文中，等离子体纳米腔被应用于研究酰胺键形成的氨解反应，其由适当官能化的自由移动的金纳米颗粒和金纳米电极在水性缓冲液中的单个纳米颗粒碰撞事件引发。通过同步表面增强拉曼光谱（Sers）和单实体电化学（EC）测量，我们以10 s的毫秒时间分辨率探测了氨解反应中酰胺键形成的动态演化。因此，我们表明，单实体EC-SERS是一种有价值的和敏感的技术，通过它可以在单分子水平上研究化学反应。
The real-time observation of chemical bond formation at the single-molecule level is one of the great challenges in the fields of organic and biomolecular chemistry. Valuable information can be gleaned that is not accessible using ensemble-average measurements. Although remarkably sophisticated techniques for monitoring chemical reactions have been developed, the ability to detect the specific formation of a chemical bond in situ at the single-molecule level has remained an elusive goal. Amide bonds are routinely formed from the aminolysis of N-hydroxysuccinimide (NHS) esters by primary amines, and the protocol is widely used for the synthesis, cross-linking, and labeling of peptides and proteins. Herein, a plasmonic nanocavity was applied to study aminolysis reaction for amide bond formation, which was initiated by single nanoparticle collision events between suitably functionalized free-moving gold nanoparticles and a gold nanoelectrode in an aqueous buffer. By means of simultaneous surface enhanced Raman spectroscopy (SERS) and single-entity electrochemistry (EC) measurements, we have probed the dynamic evolution of amide bond formation in the aminolysis reaction with 10 s of millisecond time resolution. Hence, we demonstrate that single-entity EC-SERS is a valuable and sensitive technique by which chemical reactions can be studied at the single-molecule level.