Naturally occurring esterification reactions with bryostatin

Abstract

Bryostatin structures share a commonality of a central bryophan ring, but each differs due to two groups (R ₁ and R ₂) that are attached to the bryophan ring via ester bonds. This research examines the impact that conditions such as UV light, acidic and basic conditions can have on the bryostatin structure in the presence of octanoic acid and water. Mass spectrometry (MS) measurements suggest that bryostatin can easily rearrange into various structures under natural conditions by reacting with carboxylates that are ubiquitous in nature. A second set of measurements suggest bryostatin can be hydrolyzed by water, a reaction that has significant implications in both medicinal applications and extraction procedures.

Keywords:

• Esterification
• Bryostatin
• Mass spectrometry
• Fe⁺³
• Siderophore
• Hydrolysis
• Bugula neritina
• Ferric
• Genetics
• Marine natural products
• Bryozoa

Acknowledgements

The authors would like to thank administrators at Valdosta State University and the University of Sunderland for making this research possible, including grants from the VSU faculty development program and the Applied Research Center. Some initial measurements made by the FT-ICR facility at the National High Field Magnet Lab (Dr Tu Lam, Prof. Alan Marshall) were important in forming some of the practical experience needed for this work. Jack Rudloe of the Gulf Specimen Marine Lab has been helpful with this work by enlightening us on many aspects of the marine environment and the Bugula ecosystem. Dr Dave Newman of the National Cancer Institute (Md, USA) has allowed us to bounce ideas off him over the years and is gratefully acknowledged. Shanda Sermons, Tiffany Stoney, and Sheena Roberts are all gratefully acknowledged for the help with the UV/Vis measurements.