Boggs Ashley S P, Schock Tracey B, Schwacke Lori H, Galligan Thomas M, Morey Jeanine S, McFee Wayne E, Kucklick John R
National Institute of Standards and Technology, Hollings Marine Laboratory, 331 Fort Johnson Road, Charleston, SC, 29412, USA.
National Oceanic and Atmospheric Administration, National Centers for Coastal Ocean Science, 219 Fort Johnson Rd, Charleston, SC, 29412, USA.
Anal Bioanal Chem. 2017 Aug;409(21):5019-5029. doi: 10.1007/s00216-017-0446-z. Epub 2017 Jun 19.
Monitoring of marine mammal steroid hormone status using matrices alternative to blood is desirable due to the ability to remotely collect samples, which minimizes stress to the animal. However, measurement techniques in alternative matrices such as blubber described to date are limited in the number and types of hormones measured. Therefore, a new method using bead homogenization to QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction, C18 post extraction cleanup and analysis by liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed and applied to the measurement of hormone suites in bottlenose dolphin blubber. Validations were conducted in blubber from fresh dead stranded bottlenose dolphin. The final method consisting of two LC separations and garnet bead homogenization was tested for extraction efficiencies. Steroids were separated using a biphenyl column for reproductive hormones and C18 column for corticosteroids. Three hormones previously noted in blubber, testosterone, progesterone, and cortisol, were quantified in addition to previously unmeasured androstenedione, 17-hydroxyprogesterone, 11-deoxycortisol, 11-deoxycorticosterone, and cortisone in a single sample (0.4 g blubber). Extraction efficiencies of all hormones from blubber ranged from 84% to 112% and all RSDs were comparable to those reported using immunoassay methods (< 15%). The method was successfully applied to remote biopsied blubber samples to measure baseline hormone concentrations. Through this method, increased coverage of steroid hormone pathways from a single remotely collected sample potentially enhances the ability to interpret biological phenomena such as reproduction and stress in wild dolphin populations. Graphical abstract The steroid hormone profile is quantifiable from a single sample of bottlenose dolphin blubber using liquid chromatography tandem mass spectrometry. This profile can be applied to remotely collected dart biopsies and be used to determine reproductive or stress status of a wild-living dolphin.
由于能够远程采集样本,从而将对动物的应激降至最低,因此使用血液以外的基质监测海洋哺乳动物的类固醇激素状态是很有必要的。然而,迄今为止所描述的在诸如鲸脂等替代基质中的测量技术,在所测量激素的数量和类型方面存在局限性。因此,开发了一种新方法,该方法采用磁珠匀浆结合QuEChERS(快速、简便、廉价、有效、耐用且安全)提取、C18萃取后净化以及液相色谱串联质谱(LC-MS/MS)分析,并将其应用于宽吻海豚鲸脂中激素组的测量。在新鲜死亡搁浅的宽吻海豚的鲸脂中进行了验证。对由两次LC分离和石榴石磁珠匀浆组成的最终方法进行了提取效率测试。使用联苯柱分离生殖激素,使用C18柱分离皮质类固醇。除了之前未测量的雄烯二酮、17-羟孕酮、11-脱氧皮质醇、11-脱氧皮质酮和可的松外,还对鲸脂中先前已记录的三种激素睾酮、孕酮和皮质醇在单个样本(0.4 g鲸脂)中进行了定量。从鲸脂中提取所有激素的效率范围为84%至112%,所有相对标准偏差(RSD)与使用免疫分析方法报告的结果相当(<15%)。该方法成功应用于远程活检的鲸脂样本,以测量基线激素浓度。通过这种方法,从单个远程采集的样本中增加类固醇激素途径的覆盖范围,有可能增强解释野生海豚种群中繁殖和应激等生物学现象的能力。图形摘要 使用液相色谱串联质谱法可从单个宽吻海豚鲸脂样本中定量类固醇激素谱。该谱可应用于远程采集的镖活检样本,并用于确定野生海豚的生殖或应激状态。