Gladchuk Alexey S, Krasnov Konstantin A, Keltsieva Olga A, Kalninia Yana K, Alexandrova Marina L, Ivanov Nikita S, Muradymov Marat Z, Krasnov Nikolai V, Reynyuk Vladimir L, Sukhodolov Nikolai G, Podolskaya Ekaterina P
Golikov Research Center of Toxicology, St. Petersburg, 192019, Russia.
Institute of Chemistry, St. Petersburg State University, St. Petersburg, 198504, Russia.
Rapid Commun Mass Spectrom. 2021 Nov 15;35(21):e9185. doi: 10.1002/rcm.9185.
The polyprenols are involved in some essential biosynthetic pathways and serve as ubiquitous components of cellular membranes, so their fingerprinting in natural samples is of great interest. Previous studies indicate that due to the high hydrophobicity of polyprenols their direct analysis by mass spectrometry with soft ionization techniques may be difficult and require preliminary off-line derivatization. Hence, a method for rapid and sensitive screening of polyprenols is required.
A combination of thin-film chemical deposition and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for analysis of the polyprenol profile of Abies sibirica L. extract. Polyprenol-based monolayers were formed at the interphase of aqueous barium acetate solution, supplemented with 2,5-dihydroxybenzoic acid, and an n-hexane solution of polyprenols directly on a MALDI target plate.
Peaks corresponding to [M - H + Ba] ions were observed in the MALDI-TOF mass spectra of polyprenols. A total of nine polyprenol homologues were identified with a polyprenol of 16 isoprene units dominating. The limit of detection was established at the level of 6 pg. Possible mechanisms of formation of [M - H + Ba] ions of polyprenols were discussed.
The proposed approach can be suitable for high-throughput screening of polyprenols in biological samples of different origin due to easy sample preparation and high sensitivity.
聚戊烯醇参与一些重要的生物合成途径,是细胞膜中普遍存在的成分,因此对其在天然样品中的指纹图谱分析具有重要意义。先前的研究表明,由于聚戊烯醇具有高疏水性,采用软电离技术通过质谱对其进行直接分析可能存在困难,需要进行初步的离线衍生化。因此,需要一种快速灵敏的聚戊烯醇筛选方法。
采用薄膜化学沉积与基质辅助激光解吸/电离飞行时间质谱(MALDI-TOFMS)相结合的方法,分析西伯利亚冷杉提取物中的聚戊烯醇谱。在含有2,5-二羟基苯甲酸的乙酸钡水溶液与聚戊烯醇正己烷溶液的界面上,直接在MALDI靶板上形成基于聚戊烯醇的单分子层。
在聚戊烯醇的MALDI-TOF质谱中观察到对应于[M - H + Ba]离子的峰。共鉴定出9种聚戊烯醇同系物,其中以16个异戊二烯单元的聚戊烯醇为主。检测限确定为6 pg。讨论了聚戊烯醇[M - H + Ba]离子形成的可能机制。
由于样品制备简便且灵敏度高,所提出的方法适用于高通量筛选不同来源生物样品中的聚戊烯醇。