MASS SPECTROMETRY IN ORGANIC AND BIOCHEMISTRY

各种质谱学技术在结构中的应用 三类具有生物重要性的天然产物的解析 将会被研究。第一类包括新的海洋甾醇，它 主要与陆地类固醇的不同之处在于其不寻常的性质 (细长的或分支的)侧链。此功能似乎是 细胞膜功能的重要性和对质量的详细了解 需要这种类型的甾醇的光谱碎裂模式 新型海洋甾醇化合物的结构解析 有机体。这项工作的大部分需要合成必需的甾醇。 参考化合物或假定结构的合成验证。这个 第二类天然产物涉及不寻常的磷脂 从海洋生物中分离出来的。对质量的了解要少得多 这类具有重要生物学意义的天然生物的光谱行为 产品与甾醇的比较，我们打算在 通过比较不同的电离技术(电子碰撞与 场解吸VS化学电离VS快原子轰击) 每一项都可能提供特定的特定结构信息 磷脂分子的一部分。因为小说《海洋奇兵》 磷脂在其背景下尤其不寻常 史无前例的脂肪酸成分(通常是多不饱和的)，工作也 设想中这种双键的质谱学位置 长链脂肪酸。最后，我们打算开发质谱学 程序(特别是通过使用化学电离质量 氢气光谱分析)在卟啉领域，目的是 实现一个尚未基本实现的目标，即 卟啉四种不同吡咯环上的化学取代基 分子仅通过使用质谱学。如果成功，这将是 不仅应该对卟啉化学做出重要贡献，而且 对涉及细胞色素的药物新陈代谢研究也有很大帮助 P-450。

The application of various mass spectrometric techniques to structure elucidation of three classes of biologically important natural products will be studied. The first group encompasses novel marine sterols, which differ primarily from terrestrial sterols in the nature of their unusual (elongated or branched) side chains. This feature appears to be of importance in cell membrane function and a detailed knowledge of the mass spectral fragmentation pattern of such sterol types is needed for structural elucidation of novel and as yet unidentified sterols of marine organisms. Much of this work requires synthesis of requisite sterol reference compounds or synthetic verification of postulated structure. The second group of natural products deals with the unusual phospholipids isolated from marine organisms. Much less is known about the mass spectrometric behavior of this biologically important class of natural products as compared to sterols, and we intend to explore this field in detail by comparing different ionization techniques (electron impact vs. field desorption vs. chemical ionization vs. fast atom bombardment) since each is likely to provide special structural information on specific portions of the phospholipid molecule. Since the novel marine phospholipids are particularly unusual in the context of their unprecedented fatty acid components (usually polyunsaturated), work is also envisaged on the mass spectrometric location of such double bonds in long-chain fatty acids. Finally, we intend to develop mass spectral procedures (notably through the use of chemical ionization mass spectrometry with hydrogen gas) in the porphyrin field with the aim of accomplishing an as yet largely unrealized goal, namely the location of chemical substituents in the four different pyrrole rings of the prophyrin molecule solely through the use of mass spectrometry. If successful, this should not only make an important contribution to porphyrin chemistry, but should also help greatly in drug metabolism studies involving cytochrome P-450.