Uhlig Silvio, Vikøren Turid, Ivanova Lada, Handeland Kjell
National Veterinary Institute, P.O. Box 8156 Dep., 0033 Oslo, Norway.
Rapid Commun Mass Spectrom. 2007;21(10):1651-60. doi: 10.1002/rcm.3005.
Ergot alkaloids are mycotoxins which are produced among fungi in the family Clavicipitaceae. Poisoning with ergot alkaloids is an important veterinary problem in animal husbandry and has recently also been recognised in wild animals. While the poisoning syndrome observed in domestic animals such as cattle, horses and sheep is usually caused by endophyte-infected grass, the recently observed ergotism among Norwegian cervids is probably due to infection of wild grasses with Claviceps. Mass spectrometry is today the method of choice for the rapid qualitative and quantitative determination of many natural compounds. This study uses tandem quadrupole mass spectrometry as well as ion trap mass spectrometry in connection with electrospray(+) ionisation for the quantification, screening and fragmentation of ergot alkaloids in extracts from Claviceps sclerotia that had been picked from wild grasses from several locations in Norway. Ergotamine, ergovaline, ergonovine and ergocryptine were available as standards and were quantified in the extracts, while ergocrystine, ergocornine, ergonine/ergosine, lysergic acid and lysergol were identified on the basis of their molecular weights and semi-quantified. Ergocrystine dominated the alkaloid spectrum of most extracts. Levels of the quantified alkaloids were in the range 0.2-9300 microg/g. Several unknown ergot alkaloids were found in the extracts. MS(n) experiments identified some as simple lysergic acid amide derivatives, while othes are probably related to ergocrystine and ergocryptine by dehydration, dehydrogenation and/or amino acid substitution at R(1) of the peptide moiety.
麦角生物碱是由麦角菌科真菌产生的霉菌毒素。麦角生物碱中毒是畜牧业中一个重要的兽医问题，最近在野生动物中也得到了认识。虽然在牛、马和羊等家畜中观察到的中毒综合征通常是由内生菌感染的草引起的，但最近在挪威鹿类中观察到的麦角中毒可能是由于麦角菌感染了野草。质谱分析是目前快速定性和定量测定许多天然化合物的首选方法。本研究使用串联四极杆质谱以及离子阱质谱，并结合电喷雾（+）电离，对从挪威多个地点的野草中采集的麦角菌菌核提取物中的麦角生物碱进行定量、筛选和裂解。麦角胺、麦角新碱、麦角克碱和麦角隐亭作为标准品，在提取物中进行了定量，而麦角晶碱、麦角柯宁碱、麦角异胺/麦角胺、麦角酸和麦角醇则根据其分子量进行了鉴定并半定量。麦角晶碱在大多数提取物的生物碱谱中占主导地位。定量生物碱的含量在0.2 - 9300微克/克范围内。提取物中发现了几种未知的麦角生物碱。MS(n)实验确定其中一些是简单的麦角酸酰胺衍生物，而其他一些可能通过肽部分R(1)处的脱水、脱氢和/或氨基酸取代与麦角晶碱和麦角隐亭有关。
