Electrospray mass spectrometry of testosterone esters: Potential for use in doping control
Electrospray mass spectrometry of testosterone esters: Potential for use in doping control
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DOI：
10.1016/s0039-128x(97)00004-4
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发表时间：
1997-07-01
期刊：
影响因子：
2.7
通讯作者：
Segura, J
中科院分区：
文献类型：
--
作者：
Shackleton, CHL;Chuang, H;Segura, J
所描述的研究涉及在施用此类药剂后在血浆中鉴定睾酮的17 β-脂肪酸酯的尝试。这些药物是治疗性的，但越来越多的运动员为了提高运动成绩而滥用这些药物。描述了睾酮酯类化合物在电喷雾电离下的质谱特性。这些酯（醋酸睾酮、丙酸睾酮、异己酸睾酮、苯甲酸睾酮、庚酸睾酮、环戊丙酸睾酮、苯丙酸睾酮、癸酸睾酮和十一酸睾酮）在“最佳灵敏度”质谱条件下基本上仅产生质子化分子离子（MH+），但在三重四极杆质谱仪的源或碰撞池中可能被诱导产生碎片。未衍生化的类固醇酯通过直接输注进行分析，因为这些非极性化合物未开发出与高效液相色谱法（HPLC）兼容的溶剂系统。当类固醇转化为极性时，HPLC/MS（质谱法）是可能的;水溶性吉拉德腙，并且几乎所有化合物都通过微孔C-4 HPLC使用水乙腈，TFA梯度分离。在最佳电离条件下的质谱基本上只包含一个分子离子（M+），但所有化合物的源裂解产生的主要离子为M-59和M-87。分子离子和这些碎片离子监测在选择离子记录（SIR）的方法开发的检测等离子体中的类固醇。用这种方法，庚酸睾酮和十一酸睾酮可以在肌肉注射或给药后检测。该技术的进一步发展可以形成一个协议的基础，用于确认在运动中滥用睾酮，特别是如果灵敏度可以提高。(C)Elsevier Science Inc.出版。
The study described involves an attempt to identify 17 beta-fatty acid esters of testosterone in blood plasma following administration of such agents. These drugs are therapeutic bur are increasingly misused by athletes in an attempt to improve sports performance. The mass spectral properties of testosterone esters under electrospray ionization are described. These esters (testosterone acetate, propionate, isocaproate, benzoate, enanthate, cypionate, phenylpropionate, decanoate, and undecanoate) essentially give only a protonated molecular ion (MH+) under ''optimum sensitivity'' mass spectrometric conditions but could be induced to fragment in the source or collision cell of a triple quadrupole mass spectrometer. The underivatized steroid esters were analyzed by direct infusion because development of solvent systems compatible with high-performance liquid chromatography (HPLC) was not achieved for these nonpolar compounds. HPLC/MS (mass spectrometry) was possible when the steroids were converted to polar; water soluble, Girard hydrazones, and almost all compounds were separated by microbore C-4 HPLC using a water acetonitrile, TFA gradient. The mass spectra under optimal ionization conditions essentially comprised only a molecular ion (M+), but source fragmentation gave major ions at M-59 and M-87 for all compounds. The molecular ion and these fragment ions were monitored in a selected-ion-recording (SIR) method developed for defecting the steroids in plasma. Using this methodology, testosterone enanthate and undecanoate could be detected after intramuscular injection or or al administration of the drugs. Further development of the technique could form the basis of a protocol for confirming the misuse of testosterone in sport, especially if sensitivity could be improved. (C) 1997 by Elsevier Science Inc.