Analytical pyrolysis-based study on intra-skeletal organic matrices from Mediterranean corals

Off-line analytical pyrolysis combined with gas chromatography–mass spectroscopy (GC–MS), directly or after trimethylsilylation, along with infrared spectroscopy and amino acid analysis was applied for the first time to the characterization of the intra-skeletal organic matrix (OM) extracted from four Mediterranean hard corals. They were diverse in growth form and trophic strategy namely Balanophyllia europaea and Leptopsammia pruvoti—solitary corals, only the first having zooxanthelle—and Cladocora caespitosa and Astroides calycularis—colonial corals, only the first with zooxanthelle. Pyrolysis products evolved from OM could be assigned to lipid (e.g. fatty acids, fatty alcohols, monoacylglicerols), protein (e.g. 2,5-diketopiperazines, DKPs) and polysaccharide (e.g. anhydrosugars) precursors. Their quantitative distribution showed for all the species a low protein content with respect to lipids and polysaccharides. A chemometric approach using principal component analysis (PCA) and clustering analysis was applied on OM mean amino acidic compositions. The small compositional diversity across coral species was tentatively related with coral growth form. The presence of N-acetyl glucosamine markers suggested a functional link with other calcified tissues containing chitin. The protein fraction was further investigated using novel DKP markers tentatively identified from analytical pyrolysis of model polar linear dipeptides. Again, no correlation was observed in relation to coral ecology. These analytical results revealed that the bulk structure and composition of OMs among studied corals are similar, as it is the textural organization of the skeletonmineralized units. Therefore, they suggest that coral’s biomineralization is governed by similar macromolecules, and probably mechanisms, independently from their ecology.