MASS SPECTROMETRY IN ORGANIC AND BIOCHEMISTRY

各种质谱技术在结构分析中的应用 三种生物学上重要的天然产物的阐明 将被研究。 第一类包括新的海洋甾醇， 主要区别于地球甾醇的性质， （伸长的或分支的）侧链。 这一特点似乎是 细胞膜功能的重要性和质量的详细知识 需要这些甾醇类型的光谱碎裂模式， 新海洋甾醇的结构鉴定 有机体 这项工作的大部分需要合成所需的甾醇 参考化合物或假定结构的合成验证。 的 第二类天然产物处理不寻常的磷脂 分离自海洋生物。 对质量的了解要少得多 这种生物学上重要的天然产物的光谱行为 产品相比，甾醇，我们打算探索这一领域， 通过比较不同的电离技术（电子碰撞与 场解吸对化学电离对快原子轰击），因为 每一个都可能提供关于特定的 磷脂分子的一部分。 自从小说《海军陆战队》 磷脂在它们的环境中是特别不寻常的， 前所未有的脂肪酸成分（通常是多不饱和的），工作也是 设想在质谱中这种双键的位置， 长链脂肪酸 最后，我们打算开发质谱 程序（特别是通过使用化学电离质量 用氢气的光谱法）在卟啉领域的目的是 完成一个尚未实现的目标，即 藜芦素四个不同吡咯环中的化学取代基 分子仅仅通过使用质谱。 如果成功，这 不仅对卟啉化学做出了重要贡献， 这也将极大地有助于涉及细胞色素的药物代谢研究 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.