Mass Spectrometry-Based Integration and Expansion of the Chemical Diversity Harbored Within a Marine Sponge

  • Thomas P. Cantrell
  • Christopher J. Freeman
  • Valerie J. Paul
  • Vinayak AgarwalEmail author
  • Neha GargEmail author
Focus: Emerging Investigators: Research Article


Marine sponges and their associated symbionts produce a structurally diverse and complex set of natural products including alkaloids, terpenoids, peptides, lipids, and steroids. A single sponge with its symbionts can produce all of the above-mentioned classes of molecules and their analogs. Most approaches to evaluating sponge chemical diversity have focused on major metabolites that can be isolated and characterized; therefore, a comprehensive evaluation of intra- (within a molecular family; analogs) and inter-chemical diversity within a single sponge remains incomplete. We use a combination of metabolomics tools, including a supervised approach via manual library search and literature search, and an unsupervised approach via molecular networking and MS2LDA analysis to describe the intra and inter-chemical diversity present in Smenospongia aurea. Furthermore, we use imaging mass spectrometry to link this chemical diversity to either the sponge or the associated cyanobacteria. Using these approaches, we identify seven more molecular features that represent analogs of four previously known peptide/polyketide smenamides and assign the biosynthesis of these molecules to the symbiotic cyanobacteria by imaging mass spectrometry. We extend this analysis to a wide diversity of molecular classes including indole alkaloids and meroterpenes.


Imaging mass spectrometry Marine sponge Molecular networking MS2LDA Untargeted metabolomics Chemical diversity 



This work was supported by US National Institutes of Health (R00-ES026620 to V.A.) and Alfred P. Sloan Foundation research fellowship (FG-2018-10920 to V.A.). The authors thank Ipsita Mohanty for sponge DNA barcoding and Andrew C. Mcavoy for collecting data for standards. We thank Erich Bartels (Mote Marine Laboratory) for field assistance. We wish to acknowledge the core facilities at the Parker H. Petit Institute for Bioengineering and Bioscience at the Georgia Institute of Technology for the use of their shared equipment, services and expertise: Andrew Shaw and Aaron Lifland for help with fluorescence microscopy and Aqua T. Asberry for help with cryosectioning of sponge samples. We would like to thank Prof. Facundo Fernandez (Georgia Institute of Technology) for use of their MALDI matrix sprayer. We would like to thank Ming Wang and Justin J. van der Hooft, University of California San Diego, for use of MS2LDA workflow.

Supplementary material

13361_2019_2207_MOESM1_ESM.pdf (1.5 mb)
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Copyright information

© American Society for Mass Spectrometry 2019

Authors and Affiliations

  1. 1.Engineered Biosystems Building, School of Chemistry and BiochemistryGeorgia Institute of TechnologyAtlantaUSA
  2. 2.Smithsonian Marine StationSmithsonian InstitutionFort PierceUSA
  3. 3.Department of BiologyCollege of CharlestonCharlestonUSA
  4. 4.School of Chemistry and BiochemistryGeorgia Institute of TechnologyAtlantaUSA
  5. 5.School of Biological SciencesGeorgia Institute of TechnologyAtlantaUSA
  6. 6.Center for Microbial Dynamics and InfectionSchool of Biological Sciences Georgia Institute of TechnologyAtlantaUSA

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