RATIONALE Successful coupling of a multi-ionization automated platform with commercially available mass spectrometers provides improved coverage of compounds in complex mixtures through implementation of new and traditional ionization methods. The versatility of the automated platform is demonstrated through coupling with mass spectrometers from two different vendors. Standards and complex biological samples were acquired using electrospray ionization (ESI), solvent-assisted ionization (SAI) and matrix-assisted ionization (MAI). METHODS The MS™ prototype automated platform samples from 96- or 384-well plates as well as surfaces. The platform interfaces with Thermo Fisher Scientific mass spectrometers by replacement of the IonMax source, and on Waters mass spectrometers with additional minor source inlet modifications. The sample is transferred to the ionization region using a fused-silica or metal capillary which is cleaned between acquisitions using solvents. For ESI and SAI, typically 1 μL of sample solution is drawn into the capillary tube and for ESI slowly dispensed near the inlet of the mass spectrometer with voltage placed on the delivering syringe barrel to which the tubing is attached, while for SAI the sample delivery tubing inserts into the inlet without the need for high voltage. For MAI, typically, 0.2 μL of matrix solution is drawn into the syringe before drawing 0.1 μL of the sample solution and dispensing to dry before insertion into the inlet. RESULTS A comparison study of a mixture of angiotensin I, verapamil, crystal violet, and atrazine representative of peptides, drugs, dyes, and herbicides using SAI, MAI, and ESI shows large differences in ionization efficiency of the various components. Solutions of a mixture of erythromycin and azithromycin in wells of a 384-microtiter well plate were mass analyzed at the rate of ca 1 min per sample using MAI and ESI. In addition, we report the analysis of bacterial extracts using automated MAI and ESI methods. Finally, the ability to perform surface analysis with the automated platform is also demonstrated by directly analyzing dyes separated on a thin-layer chromatography (TLC) plate and compounds extracted from the surface of a beef liver tissue section. CONCLUSIONS The prototype multi-ionization automated platform offers solid matrix introduction used with MAI, as well as solution introduction using either ESI or SAI. The combination of ionization methods extends the types of compounds which are efficiently ionized and is especially valuable with complex mixtures as demonstrated for bacterial extracts. While coupling of the automated multi-ionization platform to Thermo and Waters mass spectrometers is demonstrated, it should be possible to interface it with most commercial mass spectrometers.

中文翻译：

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用于自动多电离质谱的机器人平台的开发。

理性的多电离自动化平台与市售质谱仪的成功结合，通过实施新的和传统的电离方法，可以改善复杂混合物中化合物的覆盖率。通过与来自两个不同供应商的质谱仪结合使用，展示了自动化平台的多功能性。使用电喷雾电离（ESI），溶剂辅助电离（SAI）和基质辅助电离（MAI）获得标准品和复杂的生物样品。方法MS™原型自动平台可从96或384孔板以及表面取样。该平台通过替换IonMax离子源与Thermo Fisher Scientific质谱仪连接，并在沃特斯质谱仪上进行了其他较小的离子源进样口修改。使用熔融石英或金属毛细管将样品转移到电离区域，在两次采集之间使用溶剂对其进行清洁。对于ESI和SAI，通常将1μL样品溶液抽入毛细管中，而对于ESI，将电压缓慢分配到质谱仪入口附近，并在连接有管道的输送注射器针筒上施加电压，而对于SAI，则进行样品输送无需高压即可将软管插入进样口。对于MAI，通常先将0.2μL的基质溶液吸入注射器，然后再吸入0.1μL的样品溶液，然后在插入进样口之前分配干燥。结果使用SAI，MAI对代表肽，药物，染料和除草剂的血管紧张素I，维拉帕米，结晶紫和阿特拉津的混合物进行了比较研究，ESI显示各种组分的电离效率差异很大。使用MAI和ESI以每份样品约1分钟的速度对384孔微量滴定板的孔中红霉素和阿奇霉素的混合物溶液进行质量分析。此外，我们报告了使用自动化MAI和ESI方法进行细菌提取物的分析。最后，通过直接分析在薄层色谱（TLC）板上分离的染料和从牛肉肝组织切片表面提取的化合物，也证明了使用自动化平台执行表面分析的能力。结论原型多电离自动化平台提供了与MAI一起使用的固体基质引入，以及使用ESI或SAI进行的溶液引入。电离方法的组合扩展了有效电离的化合物的类型，对于细菌提取物所证明的复杂混合物特别有价值。在演示了自动多电离平台与Thermo和Waters质谱仪的耦合后，应该可以将其与大多数商用质谱仪连接。