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Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry

机译:超声辅助喷雾电离质谱法实时监测加速化学反应

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Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions.
机译:超声已用于加速化学反应。如果可以通过合适的检测工具(例如质谱)实时监测超声辅助化学反应,那将是理想的。阐明反应中间体/产物并更好地了解反应机理将是有帮助的。在这项工作中,我们开发了一种超声辅助喷雾电离质谱(UASI-MS)系统,该系统具有〜1.7 MHz超声换能器,可实时监控化学反应。我们证明,只需将样品溶液沉积在基于MHz的超声换能器上即可,该超声换能器位于质谱仪孔口的前面,可以轻松地通过质谱仪检测分析物信号。可以在UASI质谱图中观察到分别来自小分子和大分子的单电荷和多电荷离子。此外,在通过UASI-MS进行监控的同时,用于UASI设置的超声换能器可加速化学反应。证明了使用这种方法进行化学反应的实时加速/监测的可行性。将吉拉德T试剂和羟胺与类固醇的反应用作模型反应。当反应物溶液沉积在超声换能器上时,很容易生成中间离子/产物离子,并在1 s内使用MS进行即时监测。此外,我们还显示了使用这种反应性UASI-MS方法通过监测产物离子的生成来帮助从复杂尿液样品中确认痕量类固醇的可能性。

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