Locating Methyl-Etherified and Methyl-Esterified Uronic Acids in the Plant Cell Wall Pectic Polysaccharide Rhamnogalacturonan II

O’Neill, Malcolm A.; Black, Ian; Urbanowicz, Breeanna; Bharadwaj, Vivek; Crowley, Mike; Koj, Sabina; Peña, Maria J.

doi:10.1177/2472630320923321

Title: Locating Methyl-Etherified and Methyl-Esterified Uronic Acids in the Plant Cell Wall Pectic Polysaccharide Rhamnogalacturonan II

Journal Article · Fri May 29 00:00:00 EDT 2020 · SLAS TECHNOLOGY: Translating Life Sciences Innovation

DOI:https://doi.org/10.1177/2472630320923321· OSTI ID:1631341

O’Neill, Malcolm A. ^[1]; Black, Ian ^[1]; Urbanowicz, Breeanna ^[1]; Bharadwaj, Vivek ^[2]; Crowley, Mike ^[2]; Koj, Sabina ^[1]; Peña, Maria J. ^[1]

Complex Carbohydrate Research Center, The University of Georgia, Athens, GA, USA
National Renewable Energy Laboratory, Golden, CO, USA

Rhamnogalacturonan II (RG-II) is a structurally complex pectic polysaccharide that exists as a borate ester cross-linked dimer in the cell walls of all vascular plants. The glycosyl sequence of RG-II is largely conserved, but there is evidence that galacturonic acid (GalA) methyl etherification and glucuronic acid (GlcA) methyl esterification vary in the A sidechain across plant species. Methyl esterification of the galacturonan backbone has also been reported but not confirmed. Here we describe a new procedure, utilizing aq. sodium borodeuteride (NaBD₄ )-reduced RG-II, to identify the methyl esterification status of backbone GalAs. Our data suggest that up to two different GalAs are esterified in the RG-II backbone. We also adapted a procedure based on methanolysis and NaBD₄ reduction to identify 3-, 4-, and 3,4- O-methyl GalA in RG-II. These data, together with matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF) MS analysis of sidechain A generated from selected RG-IIs and their NaBD₄-reduced counterparts, suggest that methyl etherification of the β-linked GalA and methyl esterification of the GlcA are widespread. Nevertheless, the extent of these modifications varies between plant species. Our analysis of the sidechain B glycoforms in RG-II from different dicots and nonpoalean monocots suggests that this sidechain has a minimum structure of an O-acetylated hexasaccharide (Ara-[MeFuc]-Gal-AceA-Rha-Api-). To complement these studies, we provide further evidence showing that dimer formation and stability in vitro is cation and borate dependent. Taken together, our data further refine the primary sequence and sequence variation of RG-II and provide additional insight into dimer stability and factors controlling dimer self-assembly.

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Research Organization:: Univ. of Georgia, Athens, GA (United States). Complex Carbohydrate Research Center

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008472; SC0015662

OSTI ID:: 1631341

Alternate ID(s):: OSTI ID: 1964020

Journal Information:: SLAS TECHNOLOGY: Translating Life Sciences Innovation, Journal Name: SLAS TECHNOLOGY: Translating Life Sciences Innovation Vol. 25 Journal Issue: 4; ISSN 2472-6303

Publisher:: Elsevier - Society for Laboratory Automation and ScreeningCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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