Occurrence of non-hydrolysable amides in the macromolecular constituent of Scenedesmus quadricauda cell wall as revealed by 15N NMR: Origin of n-alkylnitriles in pyrolysates of ultralaminae-containing kerogens

Abstract

New structures, termed ultralaminae, were recently shown to occur in kerogens from numerous oil shales and source rocks. Morphological and chemical studies revealed that ultralaminae originate from the selective preservation of the non-hydrolysable biomacromolecules (algaenans) building up the thin outer walls of several Chlorophyceae (green microalgae) including the cosmopolitan genera Scenedesmus and Chlorella. The chemical correlation between such algaenans and fossil ultralaminae was mainly based on the production, on pyrolysis, of nitrogen compounds, n-alkylnitriles, with specific distributions depending on the lacustrine or marine origin of the considered samples. In addition, these bioand geopolymers were characterized by quite high N levels. Solid-state 15N NMR was carried out on 15N-enriched algaenan (isolated from Scenesdesmus quadricauda grown with 15NO 3 − as sole nitrogen source) and revealed that amides are the most abundant nitrogen groups in this material. Minor amounts of two other nitrogen groups, amines and probably Nalkyl substituted pyrroles (indoles, carbazoles), are also observed. Amines are unlikely to contribute to the macromolecular structure but could simply correspond to trapped compounds. A part of the tentatively identified N-alkyl substituted pyrroles is released during pyrolysis, but a large fraction of these moieties is retained in the insoluble residue while their N-alkyl substituents are eliminated. The predominant amide groups associated with long polymethylenic chains, occurring in S. quadricauda algaenan, are eliminated during pyrolysis and lead, after a fast dehydration, to the formation of n-alkylnitriles. This study provides, to our knowledge, the first example of non-hydrolysable amide moieties in a biomacromolecule. This unusual resistance is probably due to steric protection within the macromolecular network. Such a protection also allows amide groups in chlorophycean algaenans to survive diagenesis and accounts for the production of n-alkylnitriles with typical distributions on pyrolysis of ultralaminae-containing kerogens.