Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed Bifurcaria bifurcata

Brown alga Bifurcaria bifurcata is an extraordinarily rich source of linear (acylic) diterpenes with enormous structural diversity. As part of our interest into secondary metabolites of the Irish seaweeds, here we report four new acyclic diterpenes (1–4...

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Main Authors:	Vangelis Smyrniotopoulos, Daria Firsova, Howard Fearnhead, Laura Grauso, Alfonso Mangoni, Deniz Tasdemir
Format:	Article
Language:	English
Published:	MDPI AG 2021-01-01
Series:	Marine Drugs
Subjects:	<i>Bifurcaria bifurcata</i> brown alga seaweed linear diterpene DFT anticancer activity
Online Access:	https://www.mdpi.com/1660-3397/19/1/42

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spelling	doaj-41ec223ff0f44c4fa3940574a6ff77022021-01-20T00:00:27ZengMDPI AGMarine Drugs1660-33972021-01-0119424210.3390/md19010042Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>Vangelis Smyrniotopoulos0Daria Firsova1Howard Fearnhead2Laura Grauso3Alfonso Mangoni4Deniz Tasdemir5School of Chemistry, National University of Ireland Galway, University Road, H91 TK33 Galway, IrelandSchool of Chemistry, National University of Ireland Galway, University Road, H91 TK33 Galway, IrelandPharmacology and Therapeutics, School of Medicine, National University of Ireland Galway, University Road, H91 W2TY Galway, IrelandDipartimento di Agraria, Università degli Studi di Napoli Federico II, 80055 Portici (NA), ItalyDipartimento di Farmacia, Università degli Studi di Napoli Federico II, 80131 Napoli, ItalySchool of Chemistry, National University of Ireland Galway, University Road, H91 TK33 Galway, IrelandBrown alga <i>Bifurcaria bifurcata</i> is an extraordinarily rich source of linear (acylic) diterpenes with enormous structural diversity. As part of our interest into secondary metabolites of the Irish seaweeds, here we report four new acyclic diterpenes (<b>1</b>–<b>4</b>) and seven known terpenoids (<b>5</b>–<b>11</b>) from the CHCl<sub>3</sub> extract of <i>B. bifurcata</i>. The planar structures of the new metabolites were elucidated by means of 1D and 2D NMR, HRMS, and FT-IR spectroscopy. Since linear diterpenes are highly flexible compounds, the assignment of their stereochemistry by conventional methods, e.g., NOESY NMR, is difficult. Therefore, we employed extensive quantum-mechanical prediction of NMR chemical shifts and optical rotation analyses to identify the relative and absolute configurations of the new compounds <b>1</b>–<b>4</b>. Several compounds moderately inhibited the human breast cancer cell line (MDA-MB-231) with IC<sub>50</sub> values ranging from 10.0 to 33.5 μg/mL. This study not only demonstrates the vast capacity of the Irish <i>B. bifurcata</i> to produce highly oxygenated linear diterpenoids, but also highlights the potential of new methodologies for assignment of their stereogenic centers.https://www.mdpi.com/1660-3397/19/1/42<i>Bifurcaria bifurcata</i>brown algaseaweedlinear diterpeneDFTanticancer activity
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Vangelis Smyrniotopoulos Daria Firsova Howard Fearnhead Laura Grauso Alfonso Mangoni Deniz Tasdemir
spellingShingle	Vangelis Smyrniotopoulos Daria Firsova Howard Fearnhead Laura Grauso Alfonso Mangoni Deniz Tasdemir Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i> Marine Drugs <i>Bifurcaria bifurcata</i> brown alga seaweed linear diterpene DFT anticancer activity
author_facet	Vangelis Smyrniotopoulos Daria Firsova Howard Fearnhead Laura Grauso Alfonso Mangoni Deniz Tasdemir
author_sort	Vangelis Smyrniotopoulos
title	Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>
title_short	Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>
title_full	Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>
title_fullStr	Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>
title_full_unstemmed	Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>
title_sort	density functional theory (dft)-aided structure elucidation of linear diterpenes from the irish brown seaweed <i>bifurcaria bifurcata</i>
publisher	MDPI AG
series	Marine Drugs
issn	1660-3397
publishDate	2021-01-01
description	Brown alga <i>Bifurcaria bifurcata</i> is an extraordinarily rich source of linear (acylic) diterpenes with enormous structural diversity. As part of our interest into secondary metabolites of the Irish seaweeds, here we report four new acyclic diterpenes (<b>1</b>–<b>4</b>) and seven known terpenoids (<b>5</b>–<b>11</b>) from the CHCl<sub>3</sub> extract of <i>B. bifurcata</i>. The planar structures of the new metabolites were elucidated by means of 1D and 2D NMR, HRMS, and FT-IR spectroscopy. Since linear diterpenes are highly flexible compounds, the assignment of their stereochemistry by conventional methods, e.g., NOESY NMR, is difficult. Therefore, we employed extensive quantum-mechanical prediction of NMR chemical shifts and optical rotation analyses to identify the relative and absolute configurations of the new compounds <b>1</b>–<b>4</b>. Several compounds moderately inhibited the human breast cancer cell line (MDA-MB-231) with IC<sub>50</sub> values ranging from 10.0 to 33.5 μg/mL. This study not only demonstrates the vast capacity of the Irish <i>B. bifurcata</i> to produce highly oxygenated linear diterpenoids, but also highlights the potential of new methodologies for assignment of their stereogenic centers.
topic	<i>Bifurcaria bifurcata</i> brown alga seaweed linear diterpene DFT anticancer activity
url	https://www.mdpi.com/1660-3397/19/1/42
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Density Functional Theory (DFT)-Aided Structure Elucidation of Linear Diterpenes from the Irish Brown Seaweed <i>Bifurcaria bifurcata</i>

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