Supramolecular architectures of natural organic matter

A new conceptual model for supramolecular aggregation of natural organic matter (OM) is proposed. Scientific awareness of OM as natural hydrogels is slowly increasing although in the literature they are primarily categorized as physical hydrogels stabilized only by weak interactions. The supramolecular view of OM is here expanded, based on insight from comprehensive hydrogen bond theory, to include three-center-four-electron near-covalent linkages and introduce a new category of metachemical hydrogels that are neither chemical nor physical hydrogels. Hydrogels are typically classified into chemical (permanent, covalently bonded) or physical (reversible, ionic, hydrophobic, or hydrogen bonded) classes based on crosslinking. However, augmented by contemporary advances in hydrogen bonding theory purporting that not all hydrogen bonds are weak and that some hydrogen bonding motifs result in moderate and strong interactions, the popular supramolecular view of OM is extended to include all types of hydrogen bonds. We propose a new category of hydrogels exists-metachemical hydrogels-as a fundamental component of OM. Strong, near covalent, equally shared hydrogel cross-linkages in the metachemical hydrogel can outcompete water. Here, metachemical (<= 1 mu m diameter) and physical (>1 mu m diameter) hydrogels are described as two primary forms of aggregates observed for OM in a hierarchical 'supramolecular within supramolecular' self-assembling architecture with new information about shear. The metachemical hydrogels are postulated to be encapsulated within a dispersible physical hydrogel scaffold which can form, dissipate, and spontaneously reform over turbulent/quiescent cycles indicating reversible abiotic self-assembly. The significance of this investigation is to understand the form OM evolved in nature to provide essential functions. The potential for strong intermolecular forces to form a metachemical hydrogel in OM and the concept of a dynamic dual metachemical/physical hydrogel structure was not previously introduced. The metachemical hydrogel construct should inform hydrogen bonded systems in other chemical and biochemical disciplines. (C) 2019 Elsevier B.V. All rights reserved.