Macromolecules in brachiopod shells: characterization and diagenesis

An immunological investigation was conducted of soluble intra-crystalline macromolecules isolated from living and fossil brachiopod shells, which had previously been used for an immunologically based study of phylogeny (serotaxonomy). The soluble intra-crystalline macromolecules comprised 0.03% by weight of the extant shell material. Bulk analysis and gel electrophoresis indicated that the organic material is predominantly glycoprotein, and contains up to 30% by weight carbohydrate. Treatment of the macromolecules with periodate and proteinase K revealed that antibodies were raised predominantly against the carbohydrate moieties. Using a specially adapted dot blot immunobinding assay (DIBA) the decay in immunological signal over geological time was determined. Pleistocene shells have lost between 99 and 99.9% of immunological reactivity, and original antigenic determinants form a declining proportion of total organic matter. It is suggested that condensation reactions between amino acids and sugars account for the rapid destruction of determinants; this has important implications for the direction of future studies on fossil macromolecules. □ Serotaxonomy, biomolecular palaeontology, glycoproteins, melanoidins, brachiopods.