Structure of Algal‐Born Phenolic Polymeric Adhesives

Abstract

Adhesive materials extracted from the brown alga Fucus serratus are composed of phenolic polymer, alginate, and CaCl2. The phenolic polymer undergoes an oxidation reaction in the presence of bromoperoxidase, KI, and H2O2. The nanostructure of the adhesive was investigated using small angle X-ray scattering, light scattering, and cryo- transmission electron microscopy experiments. These have shown that the phenolic polymer undergoes self-assembly and forms flexible chain-like objects. Oxidation or adding alginate does not alter this structure. However, once calcium ions are added, a rigid network is formed. Presumably, this network is responsible for the cohesive strength of the glue.

Dynamics of cell wall assembly during early embryogenesis in the brown algaFucus

“…Additionally, the genomic information recently released from marine bacteria and brown algae allows for the characterization of recombinant enzymes involved in cell wall degradation [i.e. alginate lyases (Thomas et al , 2013), fucanase (Colin et al , 2006)] and alginate synthesis [i.e. GDP-mannose dehydrogenase (Tenhaken et al , 2011), ManC5-E (Fischl et al , 2016; Inoue et al , 2016)].…”

“…Another possibility is that the MAbs bind to single alginate chains and that their binding abilities are challenged in complex composites where calcium and GG-block regions mediate self-association of the polymers. Another explanation could be that the cross-linking of alginates by phenols (Bitton et al , 2006; Deniaud-Bouët et al , 2014) would impair MAb accessibility to epitopes. This is consistent with the view that phenols are first incorporated at the rhizoid pole at these later stages (Schoenwaelder and Wiencke, 2000).…”

Experimental and computational analysis of a novel flow channel to assess the adhesion strength of sessile marine organisms

“…Bearing in mind that this may be the result of uncontrolled variability in forces generated when transferring substrates to the flow channel, it is also worth noting the possibility that this is the result of rapid interactions between the polyphenolic adhesive secretion, the polyanionic moieties of the substrate and positive divalent ions present in seawater, namely Ca 2þ and Mg 2þ [3]. Alternatively, increased settlement on Agar may lie in haloperoxidase-mediated cross-linking reactions involving polyphenolic adhesive compounds and the agarose chains of the substrate [8,9,46], though it is unlikely that these processes will have taken place by 6 h settlement. At the other end of the spectrum, initial settlement density after 6 h is lowest on the XLGel-Lip surface.…”

Peroxidase-catalysed interfacial adhesion of aquatic caddisworm silk

“…Haloperoxidases catalyse two electron oxidation of halides (Cl -, Br -, I -) using H 2 O 2 to produce hypohalites (OCl -, OBr -, OI -), which react non-specifically with nearby nucleophiles [40,41]. The ability of vanadium bromoperoxidases to cross-link phenolic compounds and polysaccharides derived from brown alga was demonstrated in vitro [26,42,43], providing a basis for developing biomimetic algal adhesives [44][45][46]. The paucity of evidence for enzyme-catalysed natural adhesion is odd considering the myriad examples of enzyme-catalysed oxidative cross-linking of extracellular structural materials.…”