MarinLit: Database and essential

tools for the marine natural

products community Serin Dabb, Royal Society of Chemistry

John Blunt & Murray Munro, University of

Canterbury

Literature Updating Services

Databases

• The Merck Index* Online

• Recently acquired MarinLit

Open Access

Open Data

Royal Society of Chemistry

Publishing

• Indexes all literature related to marine natural products (compounds found in marine environments)

• 26K articles (MARINe LITerature)

• Structure searchable compound database • 24K compounds

• Data (taxonomy, location, chemical)

• Dereplication tool

History

• Community developed database from University

of Canterbury, New Zealand

• Built by John Blunt and Murray Munro

Sep-2013

Apr-2014

Announcement Launch

Content selection

• No set source list

• Articles Biological activity, chemistry, culturing,

ecological, geography, pharmacology, synthesis

• Compounds Only indexed when: First isolated, new to marine,

structural revision

Bibliographic search

“Dereplication”

Dereplication in MarinLit

Can be achieved using

• 1H NMR features e.g. number of Me groups

• 13C and 1H chemical shifts

• Molecular formula (complete or partial)

• UV maxima

• Exact mass

OR a combination of any or all of the above.

Why is it important? “A conservative estimate would be that it takes an experienced NP chemist about three months to fully elucidate a structure…. We estimate these costs to be around $15 000 (personnel time, solvents, NMR/MS recharge, media, columns, etc.).

These estimates are for one structure, under the most ideal conditions. These costs can be easily lowered when dereplication can be accomplished or quickly raised for complex molecules with poor chromatographic properties produced in low overall titer. For some molecules the cost of complete structure elucidation can be over one million dollars.”

P. Dorrestein et al., Nat. Prod. Rep., 2014, 31, 718

Saves

time

New drugs

Advantages of 1H NMR

features

• Based on pattern recognition, so quickly

discriminatory

• Based only on the number of each type of feature

• Independent of NMR solvent, temperature and pH

• Can be combined with 2D NMR experiments to get

further information.

1H NMR Spectrum of Unknown. Is it a new compound

or is it known?

9 Me groups are obvious (from integrals)

Search of MarinLit: 9 Me gave 628 answers

4 Me singlets 4 Me doublets

1 OMe singlet

Aromatic protons

On examination these can be characterised as shown

On searching MarinLit for 9 total methyls: 4 singlets, 4 doublets, 1 OMe there

were 39 answers, but there are also aromatic protons that can be used

COSY spectrum

This implies a 1,2,4-trisubstituted

aromatic system

A broad singlet coupled/on-coupled to 2 doublets

4 Me singlets 4 Me doublets

1 OMe singlet

4 singlets, 4 doublets, 1 OMe, 1,2,4-trisubstituted aromatic 2

answers

Comparison of

NMR data

confirmed that the

unknown had this

structure

Due to be published early 2015

Modern NMR Approaches To The Structure Elucidation of Natural Products

Complete set ISBN 978-1-84973-459-2

Volume 1: Instrumentation and Software, ISBN 978-1-84973-518-6

Volume 2: Data Acquisition and Applications to Compound Classes,

ISBN 978-1-84973-393-9

Edited by Antony Williams,

Gary Martin, Merck, USA

David Rovnyak, Bucknell University, USA

www.rsc.org/books

New Book from the Royal Society

of Chemistry

Future plans

• Location

searching

?

Marine

Marine

Terrestrial

Microbial Animal

Plant

THE

MERCK INDEX

NEW

15th

Edition

*The name THE MERCK INDEX is owned by Merck Sharp & Dohme Corp., a subsidiary of Merck & Co., Inc., Whitehouse Station, N.J., U.S.A., and is licensed to The Royal Society of Chemistry for use in the U.S.A. and Canada.

Questions?

dabbs@rsc.org

@SerinDabb

marinlit@rsc.org

Pioneering Series

New Developments in NMR Editor in Chief: William S Price, University of Western Sydney

Series Editors: Bruce Balcom, University of New Brunswick

István Furó, KTH Royal Institute of Technology, Sweden

Maili Liu, Chinese Academy of Sciences

Masatsune Kainosho, Nagoya University, Japan

Focus is on novel aspects of method and instrumentation

development, applications in emerging fields and new techniques

and technologies.

http://rsc.li/nmr