Schüler Jördis-Ann, Kramell Annemarie E, Schmidt Antonia, Walesch Pauline D, Csuk René
Institute of Computer Science, Martin Luther University Halle-Wittenberg, Halle (Saale), Germany.
Department of Organic Chemistry, Martin Luther University Halle-Wittenberg, Halle (Saale), Germany.
J Mass Spectrom. 2025 May;60(5):e5129. doi: 10.1002/jms.5129.
Because the manual interpretation of ESI-MS fragmentation spectra is time-consuming and usually requires expert knowledge, automated annotation is often sought. The fragmentation software ChemFrag enables the annotation of MS spectra by combining a rule-based fragmentation and a semiempirical quantum chemical approach. In this study, the rule set was extended by 31 cleavage rules and 12 rearrangement rules and used for the interpretation of ESI(+)-MS spectra of antibiotics, pesticides, and natural products as well as their structural analogs. The fragmentation pathways predicted by ChemFrag for compounds such as 17β-estradiol were confirmed by a comparison with pathways published in other studies. In addition, the annotations were compared with those of the programs MetFrag and CFM-ID, for example, with regard to the number and intensity of annotated fragment ions. Our experiments show that ChemFrag provides reliable and in some cases chemically more realistic annotations for the fragment ions of the investigated compounds. Thus, ChemFrag is a helpful addition to the established in silico methods for the interpretation of ESI(+)-MS spectra.
由于手动解读电喷雾电离质谱（ESI-MS）碎裂谱既耗时又通常需要专业知识，因此人们常常寻求自动化注释方法。碎裂软件ChemFrag通过结合基于规则的碎裂和半经验量子化学方法，实现了对质谱的注释。在本研究中，规则集扩展了31条裂解规则和12条重排规则，并用于解释抗生素、农药、天然产物及其结构类似物的电喷雾电离正离子模式质谱（ESI(+)-MS）谱。通过与其他研究中公布的碎裂途径进行比较，证实了ChemFrag预测的如17β-雌二醇等化合物的碎裂途径。此外，还将这些注释与MetFrag和CFM-ID等程序的注释进行了比较，例如在注释碎片离子的数量和强度方面。我们的实验表明，ChemFrag为所研究化合物的碎片离子提供了可靠的注释，在某些情况下在化学上更符合实际情况。因此，ChemFrag是对现有用于解释ESI(+)-MS谱的计算机模拟方法的一个有益补充。
