Shackleton C H, Chuang H, Kim J, de la Torre X, Segura J
Children's Hospital Oakland Research Institute, CA 94609, USA.
Steroids. 1997 Jul;62(7):523-9. doi: 10.1016/s0039-128x(97)00004-4.
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 but 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 were separated by microbore C4 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 detecting the steroids in plasma. Using this methodology, testosterone enanthate and undecanoate could be detected after intramuscular injection or oral 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.
所述研究涉及在给予此类药物后试图鉴定血浆中17种睾酮的β-脂肪酸酯。这些药物具有治疗作用，但运动员越来越多地滥用它们以试图提高运动成绩。描述了电喷雾电离下睾酮酯的质谱特性。这些酯（睾酮乙酸酯、丙酸酯、异己酸酯、苯甲酸酯、庚酸酯、环戊丙酸酯、苯丙酸酯、癸酸酯和十一酸酯）在“最佳灵敏度”质谱条件下基本上只给出质子化分子离子（MH+），但可在三重四极杆质谱仪的源或碰撞池中诱导裂解。未衍生化的类固醇酯通过直接进样进行分析，因为对于这些非极性化合物，尚未开发出与高效液相色谱（HPLC）兼容的溶剂系统。当类固醇转化为极性、水溶性的吉拉德腙时，HPLC/MS（质谱）是可行的，并且几乎所有化合物都通过使用水、乙腈、三氟乙酸梯度的微径C4 HPLC进行分离。最佳电离条件下的质谱基本上仅包含分子离子（M+），但源裂解对所有化合物产生了m/z为M - 59和M - 87的主要离子。在为检测血浆中类固醇而开发的选择离子记录（SIR）方法中监测分子离子和这些碎片离子。使用该方法，在肌肉注射或口服这些药物后可以检测到庚酸睾酮和十一酸睾酮。该技术的进一步发展可以形成确认体育界滥用睾酮的方案基础，特别是如果灵敏度能够提高的话。
