Photofragmentation of Isoleucine by Vacuum Ultraviolet Photoionization

Photofragmentation of Isoleucine by Vacuum Ultraviolet Photoionization
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真空紫外光电离异亮氨酸的光裂解

DOI:
10.1088/1674-0068/25/04/379-388
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发表时间:
2012-08
期刊:
Chin. J. Chem. Phys.
影响因子:
--
通讯作者:
Liu-si Sheng
Liu-si Sheng
中科院分区:
其他
文献类型:
--
作者:
Yang Xie;Lan-Lan Cao;Qiang Zhang;Jun Chen;Gen-bai Chu;Xiao-bin Shan;Fu-yi Liu;Liu-si Sheng

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用同步辐射光电离质谱和理论计算研究了异亮氨酸的真空紫外光诱导电离和解离。异亮氨酸在m/z=86、75、74、69、57、46、45、44、41、30、28和18处的主要碎片离子出现在13 eV的质谱图上。根据光致电离效率曲线,确定了主要碎片离子C5H12N+(m/z=86)、C2H5NO2+(m/z=75)、C5H9+(m/z=69)、C4H9+(m/z=57)和CH4N+(m/z=30)的出现能分别为8.84±0.07、9.25±0.06、10.20±0.12、9.25±0.10和11.05±0.07 eV,并在B3LYP/6-31+G(d,p)水平上建立了可能的形成途径。这些被提出的途径包括简单的键断裂反应以及涉及中间体和过渡结构的反应。实验和计算的表观能或势垒是一致的。
Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical calculations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions C5H12N+ (m/z=86), C2H5NO2+ (m/z=75), C5H9+ (m/z=69), C4H9+ (m/z=57), and CH4N+ (m/z=30) are determined to be 8.84±0.07, 9.25±0.06, 10.20±0.12, 9.25±0.10, and 11.05±0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.
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