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Ultrafast Deep-Ultraviolet Laser Ionization Mass Spectrometry Applicable To Identify Phenylenediamine Isomers
Analytical Chemistry ( IF 6.7 ) Pub Date : 2018-07-30 00:00:00 , DOI: 10.1021/acs.analchem.8b03167 Haiming Wu 1 , Chengqian Yuan 1 , Hanyu Zhang 1 , Guanhua Yang 1 , Chaonan Cui 1 , Mengzhou Yang 1 , Wensheng Bian 1 , Hongbing Fu 2 , Zhixun Luo 1 , Jiannian Yao 1
Analytical Chemistry ( IF 6.7 ) Pub Date : 2018-07-30 00:00:00 , DOI: 10.1021/acs.analchem.8b03167 Haiming Wu 1 , Chengqian Yuan 1 , Hanyu Zhang 1 , Guanhua Yang 1 , Chaonan Cui 1 , Mengzhou Yang 1 , Wensheng Bian 1 , Hongbing Fu 2 , Zhixun Luo 1 , Jiannian Yao 1
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The application of low-fragmentation mass spectrometry to identify chemicals has been recognized to be of particular importance in chemistry, biomedicine, and materials science. Utilizing a customized all-solid-state picosecond-pulsed deep-ultraviolet (DUV) laser, here we present new advances into photoionization mass spectrometry. The DUV laser ionization mass spectrometry (DUV-LIMS) results in very clean spectra pertaining to minimized structure relaxation and fragmentation under the ultrafast ionization process. Typical DUV-LIMS applications are illustrated not only for small organic molecules but also for long-chain unsaturated hydrocarbons and clusters of benzene. The unique advantages of DUV-LIMS enable us to detect and analyze confusing organic compound mixtures, indicating promising applications. DUV-LIMS is also found to be applicable in the identification of phenylenediamine isomers. An in-depth analysis of reaction dynamics is provided showing how hydrogen-atom-transfer (HAT) initiates the distinguishable photodissociation of phenylenediamines under near-resonant excitation. In particular, ortho-phenylenediamine (OPD) finds a remarkable dehydrogenation product with comparable intensity to the molecular ion peak, which is associated with the quantum tunnelling tautomers, providing new subjects for studying intramolecular noncovalent interactions.
中文翻译：
超快速深紫外激光电离质谱法可用于鉴定苯二胺异构体
在化学，生物医学和材料科学中，应用低碎片质谱法鉴定化学物质尤为重要。利用定制的全固态皮秒脉冲深紫外（DUV）激光器，在这里，我们介绍了光电离质谱的新进展。DUV激光电离质谱（DUV-LIMS）产生非常干净的光谱，该光谱与超快电离过程中结构弛豫和碎片的最小化有关。DUV-LIMS的典型应用不仅针对有机小分子，而且还针对长链不饱和烃和苯簇进行了说明。DUV-LIMS的独特优势使我们能够检测和分析令人困惑的有机化合物混合物，从而显示出广阔的应用前景。还发现DUV-LIMS可用于鉴定苯二胺异构体。提供了对反应动力学的深入分析，显示了氢原子转移（HAT）如何在近共振激发下引发苯二胺的独特光解离。尤其是，邻苯二胺（OPD）发现了一种显着的脱氢产物，其强度可与分子离子峰相媲美，这与量子隧穿互变异构体有关，为研究分子内非共价相互作用提供了新的课题。
更新日期：2018-07-30
中文翻译：
超快速深紫外激光电离质谱法可用于鉴定苯二胺异构体
在化学，生物医学和材料科学中，应用低碎片质谱法鉴定化学物质尤为重要。利用定制的全固态皮秒脉冲深紫外（DUV）激光器，在这里，我们介绍了光电离质谱的新进展。DUV激光电离质谱（DUV-LIMS）产生非常干净的光谱，该光谱与超快电离过程中结构弛豫和碎片的最小化有关。DUV-LIMS的典型应用不仅针对有机小分子，而且还针对长链不饱和烃和苯簇进行了说明。DUV-LIMS的独特优势使我们能够检测和分析令人困惑的有机化合物混合物，从而显示出广阔的应用前景。还发现DUV-LIMS可用于鉴定苯二胺异构体。提供了对反应动力学的深入分析，显示了氢原子转移（HAT）如何在近共振激发下引发苯二胺的独特光解离。尤其是，邻苯二胺（OPD）发现了一种显着的脱氢产物，其强度可与分子离子峰相媲美，这与量子隧穿互变异构体有关，为研究分子内非共价相互作用提供了新的课题。
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