A unique structural distribution pattern discovered for the cerebrosides from starfish Asterias amurensis

Abstract

Cerebroside is an important family of the mono-glycosylated ceramides involved in the larger family of glycosphingolipid and sulfatide. Cerebroside is synthesized from ceramide by the transfer of glucose from UDP-glucose, and degraded back to ceramide, which plays an important role at the epidermis protecting interior of the body as a barrier. Because cerebroside is regarded as the source molecule of ceramide and is amphiphilic in nature, cerebroside is considered valuable as the ingredient of cosmetic lotion.Various sources can be considered as raw material of cerebrosides. Starfish is considered as one of such potent source. However, the structure of the ceramide part of cerebroside is not fully investigated. Therefore, the individual structures of cerebroside molecules need to be identified including sphingosine and fatty acyl group composition to assess the potential of the molecule.We investigated and determined the structures of cerebrosides in starfish Asterias amurensis using LC-MS, GC-MS, tandem mass spectrometry (MS/MS), and 1H NMR. We also discovered a characteristic structure distribution that was divided into three major groups: 1) a group composed of a relatively long sphingosine (C22) and a short length of fatty acyl group (less than C16), 2) a group composed of a typical C18 sphingosine and long fatty acyl groups (greater than C23), and 3) a group composed of C18 sphingosine and fatty acyl groups with their length less than C18. The calculated Log P values of cerebrosides ranging from 9 to 11 covered about 80% of the molecules that were in the range of those used in cosmetics, thus showing the potential usefulness of starfish Asterias amurensis as a source of raw material for cerebrosides.