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Anionic derivatives of xyloglucan function as acceptor but not donor substrates for xyloglucan endotransglucosylase activity

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Abstract

Tamarind xyloglucan was oxidised by reaction with sodium hypochlorite in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO). Galactose residues and non-xylosylated glucose residues were thus converted into galacturonic and glucuronic acid residues, respectively, producing an anionic polysaccharide. Acid hydrolysis of oxidised xyloglucan yielded two aldobiouronic acids, deduced to be β-d-GalpA-(1→2)-d-Xyl and β-d-GlcpA-(1→4)-d-Glc. Anionic xyloglucan had a decreased ability to hydrogen-bond to cellulose and to complex with iodine. It was almost totally resistant to digestion by cellulase [endo-(1→4)-β-glucanase] and did not serve as a donor substrate for xyloglucan endotransglucosylase (XET) activity. Like several other anionic polysaccharides, it promoted XET activity when unmodified (non-ionic) xyloglucan was used as donor substrate. Anionic xyloglucan may mimic polyanions whose presence in the plant cell wall promotes the action of endogenous XTH proteins. NaOCl with TEMPO oxidised the heptasaccharide, XXXG, to form XXX-glucarate, which did serve as an acceptor substrate although at a rate approximately fourfold less than XXXG itself. Anionic derivatives of xyloglucan, acting as acceptor but not donor substrates, may be valuable tools for exploring the biological roles of XTHs in the integration versus the re-structuring of xyloglucan in the plant cell wall.

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Abbreviations

CMC:

Carboxymethylcellulose

DP:

Degree of polymerisation

GPC:

Gel-permeation chromatography

HEC:

Hydroxyethylcellulose

MLG:

Mixed-linkage (1→3), (1→4)-β-d-glucan

PyAW:

Pyridine/acetic acid/water (1:1:98, by vol., pH 4.7) containing 0.5% chlorobutanol

TEMPO:

2,2,6,6-Tetramethyl-1-piperidinyloxy

TFA:

Trifluoroacetic acid

TLC:

Thin-layer chromatography

XEH:

Xyloglucan endohydrolase (activity)

XET:

Xyloglucan endotransglucosylase (activity)

XGO:

Xyloglucan-derived oligosaccharide

XTH:

Xyloglucan endotransglucosylase/hydrolase (protein)

XXXGol, XLLG, etc.:

Oligosaccharides of xyloglucan (for abbreviated nomenclature see ref. Fry et al. 1993)

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Acknowledgements

We are very grateful to Dr Janet Braam (Rice University, Houston, Texas) for providing the XTH24 preparation. T.T. thanks the Japan Society for Promotion of Science (JSPS) for the award of a Fellowship. We thank the Biotechnology and Biological Sciences Research Council (UK) for financial support.

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  1. Takumi Takeda

    Present address: Iwate Biotechnology Research Center, 22-174-4 Narita, Kitakami, Iwate, 024-0003, Japan

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  1. The Edinburgh Cell Wall Group, Institute of Molecular Plant Sciences, School of Biological Sciences, The University of Edinburgh, The King’s Buildings, Mayfield Road, Edinburgh, EH9 3JH, UK

    Takumi Takeda, Janice G. Miller & Stephen C. Fry

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  1. Takumi Takeda
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Correspondence to Stephen C. Fry.

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Takeda, T., Miller, J.G. & Fry, S.C. Anionic derivatives of xyloglucan function as acceptor but not donor substrates for xyloglucan endotransglucosylase activity. Planta 227, 893–905 (2008). https://doi.org/10.1007/s00425-007-0665-1

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