Martin Sjögren

Recruitment in the field of Balanus improvisus and Mytilus edulis in response to the antifouling cyclopeptides barettin and 8,9-dihydrobarettin from the marine sponge Geodia barretti.

In this field investigation the two cyclopeptides, isolated from the marine sponge Geodia barretti Bowerbank (Geodiidae, Astrophorida), are shown to be very efficient in preventing recruitment of the barnacle Balanus improvisus (Cirripedia, Crustacea) and the blue mussel Mytilis edulis (Protobranchia, Lamellibranchia) when included in different marine paints. These brominated cyclopeptides, named barettin and 8,9-dihydrobarettin were incorporated in different non-toxic coatings. The substances were used in the concentrations 0.1 and 0.01% in all treatments. The most efficient paint was a SPC polymer. This paint, in combination with barettin and 8,9-dihydrobarettin, reduced the recruitment of B. improvisus by 89% (barettin, 0.1%) and by 67% (8,9-dihydrobarettin, 0.1%) as compared to control panels. For M. edulis, the reduction of recruitment was 81% with barettin (0.1%) and 72% with 8,9-dihydrobarettin (0.1%) included in the SPC paint. This indicates that the two compounds from G. barretti could provide non-toxic alternatives as additives in antifouling paints, since the heavy metal-based marine paints are to be replaced.

Antifouling activity of synthesized peptide analogs of the sponge metabolite barettin

Barettin (cyclo [(6-bromo-8-en-tryptophan) arginine]), a diketopiperazine isolated from the marine sponge Geodia barretti, is a potent inhibitor of barnacle larvae settlement with an EC50-value of 0.9 microM. In the present study, 14 analogs of barettin and its structural congener dipodazine were synthezised and tested for their ability to inhibit larval settlement. Two of the analogs have an intact barettin skeleton. The remaining analogs have a dipodazine skeleton (a diketopiperazine where arginine is replaced with glycine). Six of the tested synthetic analogs displayed significant settlement inhibition with the most potent inhibitor being benzo[g]dipodazine, which displayed even stronger activity than barettin (EC50-value 0.034 microM). The effect of benzo[g]dipodazine was also shown to be readily reversible, when cyprids were transferred to filtered seawater (FSW).

Antifouling Activity of a Dibrominated Cyclopeptide from the Marine Sponge Geodia barretti

Many sessile suspension-feeding marine organisms rely on chemical defense to keep their surfaces free from fouling organisms. The brominated cyclopeptides barettin (cyclo[(6-bromo-8-entryptophan)arginine]) ( 1) and 8,9-dihydrobarettin (cyclo[(6-bromotryptophan)arginine]) ( 2) from the cold-water sponge Geodia barretti have previously displayed settlement inhibition of barnacle larvae in a dose-dependent manner. In this paper, we describe a novel dibrominated cyclopeptide, bromobenzisoxazolone barettin (cyclo[(6-bromo-8-(6-bromobenzioxazol-3(1 H)-one)-8-hydroxy)tryptophan)]arginine) ( 3), which we have isolated from G. barretti and which displays settlement inhibition of barnacle larvae ( Balanus improvisus) with an EC 50 value of 15 nM. The chemical structure was determined using MS and 2D-NMR.

Two Brominated Cyclic Dipeptides Released by the Coldwater Marine Sponge Geodia barretti Act in Synergy As Chemical Defense

The current work shows that two structurally similar cyclodipeptides, barettin (1) and 8,9-dihydrobarettin (2), produced by the coldwater marine sponge Geodia barretti Bowerbank act in synergy to deter larvae of surface settlers and may also be involved in defense against grazers. Previously, 1 and 2 were demonstrated to bind specifically to serotonergic 5-HT receptors. It may be suggested that chemical defense in G. barretti involves a synergistic action where one of the molecular targets is a 5-HT receptor. A mixture of 1 and 2 lowered the EC(50) of larval settlement as compared to the calculated theoretical additive effect of the two compounds. Moreover, an in situ sampling at 120 m depth using a remotely operated vehicle revealed that the sponge releases these two compounds to the ambient water. Thus, it is suggested that the synergistic action of 1 and 2 may benefit the sponge by reducing the expenditure of continuous production and release of its chemical defense substances. Furthermore, a synergistic action between structurally closely related compounds produced by the same bioenzymatic machinery ought to be the most energy effective for the organism and, thus, is more common than synergy between structurally indistinct compounds.

Affinity states of biocides determine bioavailability and release rates in marine paints

A challenge for the next generation marine antifouling (AF) paints is to deliver minimum amounts of biocides to the environment. The candidate AF compound medetomidine is here shown to be released at very low concentrations, ie ng ml−1 day−1. Moreover, the release rate of medetomidine differs substantially depending on the formulation of the paint, while inhibition of barnacle settlement is independent of release to the ambient water, ie the paint with the lowest release rate was the most effective in impeding barnacle colonisation. This highlights the critical role of chemical interactions between biocide, paint carrier and the solid/aqueous interface for release rate and AF performance. The results are discussed in the light of differential affinity states of the biocide, predicting AF activity in terms of a high surface affinity and preserved bioavailability. This may offer a general framework for the design of low-release paint systems using biocides for protection against biofouling on marine surfaces.