Department of Chemistry, Fudan University, Shanghai 200438, China.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China.
J Org Chem. 2021 Apr 2;86(7):5011-5015. doi: 10.1021/acs.joc.0c02942. Epub 2021 Mar 3.
We report the rapid oxidation of organic sulfides to sulfoxides by means of microdroplet chemistry at room temperature using a spray solution containing an organic sulfide dissolved in water/methanol, dilute (11%-14%) sodium hypochlorite (NaClO), and 5% chloroauric acid (HAuCl). Ultrasonic nebulization, easy ambient sonic-spray ionization, or electrosonic spray ionization serves as the microdroplet source. High-resolution mass spectrometry was used as an online detector, and nuclear magnetic resonance was used as an offline detector. We found that the sulfoxide yields vary between 66 and 95%, the highest rate of product formation is 195 mg/min for benzyl phenyl sulfoxide, and the time required is a few minutes, which is much less than that required for the conventional means of achieving this chemical transformation. We also applied this microdroplet method to protein fingerprinting. We found that protein sequences containing methionine can be quickly oxidized, providing useful information for protein structure determinations.
我们报告了一种在室温下通过微滴化学手段快速氧化有机硫化物为亚砜的方法，该方法使用的喷雾溶液包含溶解在水/甲醇中的有机硫化物、稀（11%-14%）次氯酸钠（NaClO）和 5%氯金酸（HAuCl）。超声雾化、常压超声喷雾电离或电声喷雾电离作为微滴源。高分辨率质谱用作在线检测器，核磁共振用作离线检测器。我们发现亚砜的产率在 66%至 95%之间变化，苯甲基苯基亚砜的产物形成速率最高可达 195mg/min，所需时间为数分钟，远少于常规方法实现这种化学转化所需的时间。我们还将这种微滴方法应用于蛋白质指纹图谱。我们发现含有蛋氨酸的蛋白质序列可以被快速氧化，为蛋白质结构测定提供了有用的信息。
