Dataset Information

Biomimetic Enzymatic Oxidative Coupling of Barley Phenolamides: Hydroxycinnamoylagmatines.

ABSTRACT: Oxidative coupling of hydroxycinnamoylagmatines in barley (Hordeum vulgare) and related Hordeum species is part of the plant defense mechanism. Three linkage types have been reported for hydroxycinnamoylagmatine dimers, but knowledge on oxidative coupling reactions underlying their formation is limited. In this study, the monomers coumaroylagmatine, feruloylagmatine, and sinapoylagmatine were each incubated with horseradish peroxidase. Their coupling reactivity was in line with the order of peak potentials measured: sinapoylagmatine (245 mV) > feruloylagmatine (341 mV) > coumaroylagmatine (506 mV). Structure elucidation of fourteen in vitro coupling products by NMR and MS revealed that the three main linkage types were identical to those naturally present in Hordeum species, namely, 4-O-7'/3-8', 2-7'/8-8', and 8-8'/9-N-7'. Furthermore, we identified two linkage types that were not previously reported for hydroxycinnamoylagmatine dimers, namely, 8-8' and 4-O-8'. We conclude that oxidative coupling by horseradish peroxidase can be used for biomimetic formation of natural antifungal hydroxycinnamoylagmatine dimers from barley.

SUBMITTER: van Zadelhoff A

PROVIDER: S-EPMC9801423 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Biomimetic Enzymatic Oxidative Coupling of Barley Phenolamides: Hydroxycinnamoylagmatines.

van Zadelhoff Annemiek A Meijvogel Lieke L Seelen Anna-Marie AM de Bruijn Wouter J C WJC Vincken Jean-Paul JP

Journal of agricultural and food chemistry 20221214 51

Oxidative coupling of hydroxycinnamoylagmatines in barley (<i>Hordeum vulgare</i>) and related <i>Hordeum</i> species is part of the plant defense mechanism. Three linkage types have been reported for hydroxycinnamoylagmatine dimers, but knowledge on oxidative coupling reactions underlying their formation is limited. In this study, the monomers coumaroylagmatine, feruloylagmatine, and sinapoylagmatine were each incubated with horseradish peroxidase. Their coupling reactivity was in line with the ...[more]

PMID: 36516832

Similar Datasets

Project description:BACKGROUND:A two-stage chemical pretreatment of corn stover is investigated comprising an NaOH pre-extraction followed by an alkaline hydrogen peroxide (AHP) post-treatment. We propose that conventional one-stage AHP pretreatment can be improved using alkaline pre-extraction, which requires significantly less H2O2 and NaOH. To better understand the potential of this approach, this study investigates several components of this process including alkaline pre-extraction, alkaline and alkaline-oxidative post-treatment, fermentation, and the composition of alkali extracts. RESULTS:Mild NaOH pre-extraction of corn stover uses less than 0.1 g NaOH per g corn stover at 80°C. The resulting substrates were highly digestible by cellulolytic enzymes at relatively low enzyme loadings and had a strong susceptibility to drying-induced hydrolysis yield losses. Alkaline pre-extraction was highly selective for lignin removal over xylan removal; xylan removal was relatively minimal (~20%). During alkaline pre-extraction, up to 0.10 g of alkali was consumed per g of corn stover. AHP post-treatment at low oxidant loading (25 mg H2O2 per g pre-extracted biomass) increased glucose hydrolysis yields by 5%, which approached near-theoretical yields. ELISA screening of alkali pre-extraction liquors and the AHP post-treatment liquors demonstrated that xyloglucan and ?-glucans likely remained tightly bound in the biomass whereas the majority of the soluble polymeric xylans were glucurono (arabino) xylans and potentially homoxylans. Pectic polysaccharides were depleted in the AHP post-treatment liquor relative to the alkaline pre-extraction liquor. Because the already-low inhibitor content was further decreased in the alkaline pre-extraction, the hydrolysates generated by this two-stage pretreatment were highly fermentable by Saccharomyces cerevisiae strains that were metabolically engineered and evolved for xylose fermentation. CONCLUSIONS:This work demonstrates that this two-stage pretreatment process is well suited for converting lignocellulose to fermentable sugars and biofuels, such as ethanol. This approach achieved high enzymatic sugars yields from pretreated corn stover using substantially lower oxidant loadings than have been reported previously in the literature. This pretreatment approach allows for many possible process configurations involving novel alkali recovery approaches and novel uses of alkaline pre-extraction liquors. Further work is required to identify the most economical configuration, including process designs using techno-economic analysis and investigating processing strategies that economize water use.

Dataset Information

Biomimetic Enzymatic Oxidative Coupling of Barley Phenolamides: Hydroxycinnamoylagmatines.

Publications

Biomimetic Enzymatic Oxidative Coupling of Barley Phenolamides: Hydroxycinnamoylagmatines.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets