Electrospray ionization mass spectrometry adduct formation by mobile phase additives: A case study using nitrile functional groups containing selective androgen receptor modulators

• Published in: Rapid communications in mass spectrometry Vol. 37; no. 14; pp. e9530 - n/a
• Main Authors: Karatt, Tajudheen Kunhamu, Muhammed Ajeebsanu, Meleparappil, Karakka Kal, Abdul Khader, Subhahar, Michael Benedict, Sathiq, Mohamedkhani Anwar, Laya, Saraswathy
• Format: Journal Article
• Language: English
• Published: England Wiley Subscription Services, Inc 30.07.2023
• Subjects: Additives; Adducts; Androgens; Animals; Chromatography, High Pressure Liquid - methods; Electrospraying; Functional groups; Horses; Indicators and Reagents; Ionization; Ions; Mass spectrometry; Modulators; Receptors; Receptors, Androgen; Scientific imaging; Spectrometry, Mass, Electrospray Ionization - methods
• ISSN: 0951-4198; 1097-0231
• DOI: 10.1002/rcm.9530

Rationale The formation of mass adducts is common during electrospray ionization mass spectrometry (ESI‐MS). However, the mechanism that leads to adduct formation is poorly understood and difficult to control. Multiplication of mass adducts at once will adversely impact the sensitivity of mass analysis and cause misinterpretation of the level of detection. Prior studies on selective androgen receptor modulators (SARMs) revealed an immense mass adduct formation in both positive and negative ESI modes. Methods In this study, additives in the mobile phases are investigated as a potential means of controlling mass adduct formation in various SARMs. Results The first evidence of chloride adduct formation when SARMs are detected via ESI‐MS has been reported in this research. A series of mobile phase combinations were tested to achieve the optimal condition for HPLC–MS. A comparison was also made between adduct formation on various grades of water used for preparing the mobile phase. A validation study using equine urine and plasma was also conducted to assess the suitability of the developed method. Conclusion The results of this study will allow for a more accurate identification of SARMs, which will make it easier to investigate their illicit use in horse racing.