(-)-rhizochalin is a dimeric enantiomorphic (2R)-sphingolipid:: Absolute configuration of pseudo-C2y-symmetric bis-2-amino-3-alkanols by CD
(-)-rhizochalin is a dimeric enantiomorphic (2R)-sphingolipid:: Absolute configuration of pseudo-C2y-symmetric bis-2-amino-3-alkanols by CD
复制标题
DOI：
10.1002/1521-3773(20001117)39:22
复制
发表时间：
2000-01-01
影响因子：
16.6
通讯作者：
Stonik, VA
中科院分区：
文献类型：
--
作者：
Molinski, TF;Makarieva, TN;Stonik, VA
鞘脂是所有高等真核生物中众所周知的细胞成分，随着红-d-鞘磷脂1a及其衍生物（如神经酰胺n -脂肪酰基鞘磷脂）和鞘磷脂1- o-磷酸)在高等哺乳动物中作为第一信使发挥重要作用的发现，鞘脂引起了人们新的兴趣高度修饰的鞘脂，如鞘脂菌素，[2]存在于低等无脊椎动物和微生物中，也可能作为哺乳动物鞘脂生物合成的各种途径的抑制剂。-根霉碱2)是一种抗菌半乳糖氨基假二聚体α， ω-双极性鞘脂，从马达加斯加附近采集的钙质海绵中分离得到。虽然通过光谱和降解分析确定了2的组成结构，但其立体结构仍未确定。用圆二色法对鞘氨醇消旋体进行了构型分析。[4,5]我们先前设计了一种α， ω-双鞘碱的CD方法，利用相应的四苯甲酰衍生物[6]的CD光谱中的重叠激子偶联的反volution，并将其应用于抗真菌剂oceanapiside 3),[7]（从温带海水海绵Oceanapia phillipensis Dendy 1895 Haplosclerida， Phloeodictyidae）中分离的相关α， ω-鞘脂。该技术值得注意的是其简单性，特别是二聚氨基醇，灵敏度（50 nmol）充足，并且与其他神经鞘脂结构分析的CD方法具有互补性。[4,5,8]而3中的链末端具有不同的取代，2的伪对称结构呈现添加
Sphingolipids are well-known cellular components of all higher eukaryotes and have attracted renewed interest with the finding that erythro-d-sphingosine 1a) and its derivatives, such as ceramides N-fatty acyl sphingosines) and sphinosine 1-O-phosphate, have important roles in higher mammals as™ first messengers∫.[1] Highly modified sphingolipids, such as the sphingofungins,[2] occur in lower invertebrates and microbes and may also function as inhibitors of various pathways in mammalian sphingolipid biosynthesis.¿)-Rhizochalin 2), an antimicrobial galactopyranosyl pseudodimeric α, ω-bipolar sphingolipid, was isolated from the calcareous sponge Rhizochalina incrustata,[3] collected near Madagascar. Although the constitutional structure of 2 was established from spectroscopic and degradative analysis, the stereostructure remained undefined.Configurational analysis of sphingosine diasteromers by circular dichroism CD) has been reported.[4, 5] We have previously devised a CD method for α, ω-bis-sphingoid bases that exploits deconvolution of superposed exciton couplings in the CD spectrum of the corresponding tetrabenzoyl derivatives [6] and we applied this to the antifungal agent oceanapiside 3),[7] a related α, ω-sphingolipid isolated from a temperate-water marine sponge, Oceanapia phillipensis Dendy 1895 Haplosclerida, Phloeodictyidae). The technique is noteworthy for simplicity, particularly with respect to dimeric amino alkanols, ample sensitivity% 50 nmol), and complementarity with other CD methods for the configurational analysis of sphingolipids.[4, 5, 8] Whereas the chain termini in 3 have dissimilar substitution, the pseudosymmetric structure of 2 presents the added