基于FT-ICR质谱仪的光解离光谱自动化谱图采集程序的开发与应用

光解离光谱在气相离子结构及动力学研究中发挥着重要的作用。这种方法非常灵活，可在实验室中利用不同种类的激光器及质谱仪的结合来开展相应的研究。但也存在一些问题，例如，自动化水平低，费时，长时间的操作容易引入人为错误，使实验结果的可信度降低。为解决此类问题，该工作开发了一套可用于光谱自动采集和分析的程序AutoMS。该程序包含：(1)AutoSpecMS用于在无需改变原仪器配套的商业化操作软件的前提下，实现多台商业激光器及一台商业高分辨FT-ICR质谱仪的集成，只需要预设参数即可自动获取action光谱；(2)AutoDataMS用于实验数据的分析，可以通过一维、二维或三维图示的方法来展示光解离质谱和光谱等。为验证改程序的可行性，针对tetraphenylpyrrin(四苯基卟啉，TPP)，tetra(4-carboxypyryl)porphyrin(四对羧基苯基卟啉，TCPP)以及tetra(4-aminophenyl)porphyrin(四对氨基苯基卟啉，TCPP)三种卟啉衍生物分别开展了相应的实验。使用光解离光谱自动采集程序采集了TPP, TCPP和TAPP在210~700 nm波段的紫外-可见光解离光谱。同时获得了相关光解离碎片离子的单通道光谱，有利于用户对所研究体系的解离机理及解离动力学等方面开展深入的分析探讨。光解离质谱可观察到目标离子在特定波长激光照射下的具体解离碎片，与光解离光谱相结合，可以更好地帮助研究者理解离子在特定波段内的光解离行为。使用AutoDataMS可分别获得样品的2D及3D光解离质谱-光谱，增强了结果的可视化，使研究者更方便地获得光谱中的相关信息。对数据进行进一步分析可看出，不同的取代基对紫外可见光谱的吸收产生了差异明显的影响。此外通过AutoDataMS程序的功能扩展，还实现了对质子化TPP在500～650 nm波段内各离子的相关度分析，加深了对实验数据的理解。由此可见该方法及程序具有较好的扩展性和实用性，并可以为其他相关的工作提供很好的参考。

Development and Application of an Automated Program for Photodissociation Spectroscopy Study Based on a FT ICR Mass Spectrometer

Photodissociation spectroscopy plays a significant role in studying the structure and kinetics of species in the gas phase. This method is very flexible and can be realized by combining different kinds of lasers and mass spectrometers in the laboratory. However, the method also brings some problems, such as time-consuming, mainly relying on manual operation, low degree of automation and prone to artificial errors. To solve the problem, we design a program named AutoMS, which can collect and analyze data automatically. The program consists of two parts. The first part AutoSpecMS integrates multiple commercial lasers and one commercial high-resolution FT ICR mass spectrometer. It can realize automatic scanning of the action spectrum through user setting parameters, reducing labor intensity and avoiding human error. The second part AutoDataMS is used for the analysis of obtained experimental data. It can be applied for displaying photodissociation mass spectra and action spectra in the forms of one-dimensional, two-dimensional or three-dimensional graphics. The feasibility of this program has been experimentally verified by the selected examples of tetraphenylpyrrin (TPP), tetra (4-carboxypyryl) porphyrin (TCPP) and tetra (4-aminophenyl) porphyrin (TAPP). The UV-Vis action spectra of TPP, TCPP and TAPP in the 210~700 nm band were collected automatically using the program. Yield spectra of some photofragment ions have also been obtained, whichare helpful for users to analyze the dissociation mechanism and dynamics of the system. More valuable information can be obtained by considering the corresponding photodissociation mass spectra and photodissociation spectrum simultaneously. 2D and 3D spectra can also be obtained by the program of AutoDataMS, enhancing the visualization of the experimental data. Further data analysis about the three samples studied here showed that the UV-Vis action spectra of the molecules have obvious substituent effects. In addition, the correlation analysis of ions was fulfilled through the program, providing more information relative to the dissociation process. It is believed that the method and procedure described in this paper have good expansibility and applicability and can be applied as a good reference for many related works.