Analytical characteristics of contained electrospray ionization (ESI) are summarized in terms of its potential to modify the analyte solution during the stages of droplet formation to provide opportunities to generate native versus denatured biomolecular gas-phase ions, without the need for bulk-phase analyte modifications. The real-time modification of the charged microdroplets occurs in a cavity that is included in the outlet of the contained-ESI ion source. Close examination of the inside of the cavity using a high-speed camera revealed the formation of discrete droplets as well as thin liquid films in the droplets wake. When operated at 20 psi N2 pressure, the droplets were observed to move at an average speed of 8 mm/s providing ∼1 s mixing time in a 10 mm cavity length. Evidence is provided for the presence of highly reactive charged droplets based on myoglobin charge state distribution, apo-myoglobin contents, and ion mobility drift time profiles under different spray conditions. Mechanistic insights for the capture of vapor-phase reagents and droplet dynamics as influenced by different operational modes are also described.

中文翻译：

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包含电喷雾电离的喷雾机理。

总结了所包含的电喷雾电离（ESI）的分析特性，因为它具有在液滴形成阶段修改分析物溶液的潜力，从而提供了生成天然或变性生物分子气相离子的机会，而无需进行本体相分析物修改。带电的微滴的实时修改发生在所包含的ESI离子源出口中包含的空腔中。使用高速摄影机仔细检查空腔内部，发现了离散液滴的形成以及液滴尾流中的薄液膜。当在20 psi N2压力下运行时，观察到液滴以8 mm / s的平均速度移动，在10 mm的腔长中提供了约1 s的混合时间。根据肌红蛋白的电荷状态分布，脱辅基-肌红蛋白含量和离子迁移率在不同喷雾条件下的迁移时间曲线，提供了高反应性带电液滴的存在证据。还介绍了如何捕获气相试剂和受不同操作模式影响的液滴动力学的机械原理。