On the biosynthetic origin of carminic acid

Silas A Rasmussen; Kenneth T Kongstad; Paiman Khorsand-Jamal; Rubini Maya Kannangara; Majse Nafisi; Alex Van Dam; Mads Bennedsen; Bjørn Madsen; Finn Okkels; Charlotte H Gotfredsen; Dan Staerk; Ulf Thrane; Uffe H Mortensen; Thomas O Larsen; Rasmus J N Frandsen

doi:10.1016/j.ibmb.2018.03.002

On the biosynthetic origin of carminic acid

Insect Biochem Mol Biol. 2018 May:96:51-61. doi: 10.1016/j.ibmb.2018.03.002. Epub 2018 Mar 16.

Authors

Affiliations

¹ Department of Bioengineering and Biomedicine, Technical University of Denmark, Søltofts Plads, Building 221 and 223, 2800 Kongens Lyngby, Denmark.
² Department of Drug Design and Pharmacology, University of Copenhagen, Universitetsparken 2, 2100 Copenhagen, Denmark.
³ Department of Bioengineering and Biomedicine, Technical University of Denmark, Søltofts Plads, Building 221 and 223, 2800 Kongens Lyngby, Denmark; Chr. Hansen A/S, Boege Alle 10-12, 2970 Hoersholm, Denmark.
⁴ Chr. Hansen A/S, Boege Alle 10-12, 2970 Hoersholm, Denmark; Plant Biochemistry Laboratory, Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, 1871 Frederiksberg, Denmark.
⁵ Chr. Hansen A/S, Boege Alle 10-12, 2970 Hoersholm, Denmark.
⁶ Department of Chemistry, Technical University of Denmark, Kemitorvet, Building 207, 2800 Kongens Lyngby, Denmark.
⁷ Department of Bioengineering and Biomedicine, Technical University of Denmark, Søltofts Plads, Building 221 and 223, 2800 Kongens Lyngby, Denmark. Electronic address: tol@bio.dtu.dk.
⁸ Department of Bioengineering and Biomedicine, Technical University of Denmark, Søltofts Plads, Building 221 and 223, 2800 Kongens Lyngby, Denmark. Electronic address: rasf@bio.dtu.dk.

PMID: 29551461
DOI: 10.1016/j.ibmb.2018.03.002

Abstract

The chemical composition of the scale insect Dactylopius coccus was analyzed with the aim to discover new possible intermediates in the biosynthesis of carminic acid. UPLC-DAD/HRMS analyses of fresh and dried insects resulted in the identification of three novel carminic acid analogues and the verification of several previously described intermediates. Structural elucidation revealed that the three novel compounds were desoxyerythrolaccin-O-glucosyl (DE-O-Glcp), 5,6-didehydroxyerythrolaccin 3-O-β-D-glucopyranoside (DDE-3-O-Glcp), and flavokermesic acid anthrone (FKA). The finding of FKA in D. coccus provides solid evidence of a polyketide, rather than a shikimate, origin of coccid pigments. Based on the newly identified compounds, we present a detailed biosynthetic scheme that accounts for the formation of carminic acid (CA) in D. coccus and all described coccid pigments which share a flavokermesic acid (FK) core. Detection of coccid pigment intermediates in members of the Planococcus (mealybugs) and Pseudaulacaspis genera shows that the ability to form these pigments is taxonomically more widely spread than previously documented. The shared core-FK-biosynthetic pathway and wider taxonomic distribution suggests a common evolutionary origin for the trait in all coccid dye producing insect species.

Keywords: Anthraquinones; Biosynthesis; Carmine; Carminic acid; Coccid pigment; Dactylopius coccus; Insects; Polyketide.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Animals
Carmine / metabolism*
Hemiptera / genetics
Hemiptera / metabolism*
Pigmentation / physiology*

Substances

Carmine