The preparation and susceptibility to hydrolysis of novel O-galacturonoyl derivatives of carbohydrates

Brown, J. A.; Fry, Stephen C.

doi:10.1016/0008-6215(93)84175-6

Cited by 21 publications

(20 citation statements)

References 28 publications

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“…The kinetics of production of GalA3 at pH 11 indicated a half-life for the ester bond of compound 17 of 7.2 min (Fig. 5), which is comparable to that of 6-O-polygalacturonoy1-~-Glc (Brown and Fry, 1993) and indicates a much greater alkalilability than, for example, an 0-feroloyl-disaccharide ester bond (Fry, 1982a). In contrast, the gradual alkaline hydrolysis of compound 12 at pH 11 and 25OC resulted in the transient formation of an intermediate-Rip radioactive product before the end product [I4C]GalA3 appeared (Fig.…”

Section: Partial Characterization Of Selected Esters By Their Hydrolymentioning

confidence: 73%

“…G~c, but did hydrolyze the glycosidic bonds of the galacturonan chain except for two glycosidic bonds in the immediate vicinity of the [3H]Glc group; thus, a major product of Driselase digestion was the esterified trisaccharide Brown and Fry, 1993). These observations suggested that Driselase digestion of plant cell walls could generate small pectic oligosaccharides still bearing the hypothesized (nonmethyl) ester-linked substituent(s).…”

Section: -O-polygalact~ironoyl-~-[~h]mentioning

confidence: 75%

“…Authentic GalA3 was not converted into material with the RF in EAW of compound 17 under any of the conditions used in our work, including prolonged treatment with PAW. GalA3 did not yield compound 17 after incubation in an aqueous solution containing 5% EDC and 5% pyridine, conditions designed for the synthesis of O-Dgalacturonoyl esters (Brown and Fry, 1993). In addition, the drying in vacuo of authentic GalA3 from a solution containing 1 M TFA (conditions that will lactonize glucuronic acid) yielded no compound 17 (data not shown).…”

Section: Evidence Against Methyl Esters Phenolic Conjugates and Lacmentioning

confidence: 97%

“…The RF of compound 17 in EAW was considerably higher than that of GalA3, indicating that the GalA3 moiety was esterified to a relatively nonpolar substituent (R). The 0-D-galacturonoyl esters of all the common monosaccharides possess lower R F values in EAW than free galacturonic acid (Brown and Fry, 1993); thus, R must be substantially less polar than any common monosaccharide. Upon alkaline hydrolysis, compound 17 yielded a-( 1-4)-~-['4C]GalA3 as the sole 14C-labeled product, indicating that R did not contain a uronate moiety.…”

Section: Discussionmentioning

confidence: 99%

“…One such model compound was 6-0-polygalacturonoyl-D-[ l-3H]Glc-that is, an a-(1+4)-~-galacturonan in which a small proportion of the galacturonate residues are esterified to 0 -6 of [3H]Glc (Brown and Fry, 1993). At 25OC, the ester bonds in this model compound were relatively stable to 1 M TFA and to PAW (an excellent protein extractant [Selvendran and O'Neill, 1987]), but were very alkali labile, exhibiting a half-life of about 4 min at Abbreviations: BPW, butan-1-…”

mentioning

confidence: 99%

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Novel O-D-Galacturonoyl Esters in the Pectic Polysaccharides of Suspension-Cultured Plant Cells

Brown

Fry

1993

Plant Physiol.

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(50% yield of CalA3 in 7.2 min at p H 11 and 25°C). One of the three galacturonate residues i n compound 17 was reducible to a galactose residue with sodium borohydride, indicating that that CalA residue was esterified, via its -COOH group, to a putative alcohol. Compound 17 had a higher mobility than CalA3 on paper chromatography, indicating that the putative alcohol was relatively nonpolar. The putative alcohol could not have been methanol because Driselase readily hydrolyzed mono-, di-, and trimethyl esters of CalA3 to yield free galacturonic acid. Another Driselase digestion product (compound 12) was a derivative of CalA3 that apparently possessed two nonpolar esterified substituents: one about as labile as i n compound 17, and the other approximately 10 times more stable. Compounds 12 and 17 could not be labeled by in vivo feeding of [U-'4C]cinnamate, suggesting that they were not phenolic conjugates. Similar but chromatographically distinguishable ~ronate-'~C-labeled esters were obtained by Driselase digestion of walls of cultured carrot (Daucus carota L.), Paul's Scarlet rose (Rosa sp.), and tall fescue (festuca arundinacea Schreber) cells. In spinach, the novel compounds constituted about 5% of the total galacturonate residues of the cell wall. The observations suggest that pectic polysaccharides are linked, via 0-D-galacturonoyl ester bonds, to relatively hydrophobic constituents of the primary cell wall. Their possible role in wall architecture is discussed.Pectic polysaccharides (pectins) usually make up about one-third of the dry weight of the primary cell walls of dicots; smaller amounts are present in the Gramineae. Pectins are rich in (1+4)-linked a-D-galacturonate residues and also contain a-L-arabinose, 0-D-galactose, a-L-rhamnose, and numerous minor sugar residues (O'Neill et al., 1990). Several noncarbohydrate substituents are linked to pectins via ester bonds involving both carboxy and hydroxy groups of the polysaccharide. For example, many of the galacturonate residues are carboxy-esterified to methanol (Deuel and Stutz, 1958), a variable proportion of the galacturonate residues are 0-acetylated (Komalavilas and Mort, 1989), and (especially in the Chenopodiaceae) a few of the Ara and Gal residues are 0-feruloylated and 0-p-coumaroylated (Fry, 1982a). 993Several observations are consistent with the hypothesis that some pectins are cross-linked within the wall matrix via ester bonds (Fry, 1986). For example, a proportion of the CDTA-and endopolygalacturonase-inextractable pectin can be extracted from the cell wall in cold aqueous Na2C03 (e.g. 0.5 M; Selvendran and O'Neill, 1987;Ishii et al., 1989;Renard et al., 1990), a reagent that would break many types of ester bond. Also, suspension-cultured tomato cells that had been adapted to growth in the presence of 2,6-dichlorobenzonitrile possessed abnormal cell walls almost lacking cellulose and xyloglucan but composed largely of pectins, which became water soluble after treatment with alkali (Shedletzky et al., 1990). However, this type of eviden...

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Section: Partial Characterization Of Selected Esters By Their Hydrolymentioning

confidence: 73%

Section: -O-polygalact~ironoyl-~-[~h]mentioning

confidence: 75%

Section: Evidence Against Methyl Esters Phenolic Conjugates and Lacmentioning

confidence: 97%

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

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Novel O-D-Galacturonoyl Esters in the Pectic Polysaccharides of Suspension-Cultured Plant Cells

Brown

Fry

1993

Plant Physiol.

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Cell Wall Polysaccharide Composition and Covalent Crosslinking

Fry

2018

Annual Plant Reviews Online

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Genetics now potentially lets us modify the production, crosslinking and degradation of cell wall polysaccharides. There remains, however, the need to test experimentally whether intended modifications of polysaccharide metabolism have successfully been effected in vivo . Simple methods for this are described, including in‐vivo radiolabelling, enzymic dissection (e.g. with Driselase) and chromatographic/electrophoretic fractionation of dissection products. After an overview of polysaccharide chemistry, I discuss the structures and taxonomic distribution of wall polysaccharides in charophytes and land plants. Primary and secondary walls are compared. The major wall polysaccharides are cellulose [microfibrillar β‐(1→4)‐ d ‐glucan], pectins (α‐ d ‐galacturonate‐rich) and hemicelluloses (lacking galacturonate; hydrogen‐bonding to cellulose; extractable by 6 M NaOH at 37 °C). Land‐plant pectins are anionic polymers built of about four glycosidically interconnected domains (homogalacturonan, rhamnogalacturonans I and II, xylogalacturonan). Hemicelluloses occurring in most/all land plants are α‐xylo‐β‐glucans, β‐xylans (including α‐arabino‐β‐xylans, α‐glucurono‐β‐xylans, etc.) and β‐mannans (including α‐galacto‐β‐mannans, β‐gluco‐β‐mannans, etc.). Another hemicellulose [mixed‐linkage β‐(1→3)(1→4)‐ d ‐glucan) is confined to Equisetum and some Poales. Other taxonomically restricted features of angiosperm primary walls occur in Poales (xylose‐poor xyloglucans; feruloylated arabinoxylans); Solanales and Lamiales (characteristic xyloglucans); Caryophyllales (feruloylated pectins); and Alismatales (apiogalacturonan). I also summarize characteristic wall features of charophytes, bryophytes, lycopodiophytes, fern‐allies and gymnosperms. The making or breaking of a ‘crosslink’ (defined as an individual chemical bond, not a whole ‘tethering’ chain) may cause wall tightening/loosening. Covalent crosslinks include phenolic coupling products, uronoyl esters and amides, and borate diesters.

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Cell Wall Polysaccharide Composition and Covalent Crosslinking

Fry¹

2010

Annual Plant Reviews

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Genetics now potentially lets us modify the production, crosslinking and degradation of cell wall polysaccharides. There remains, however, the need to test experimentally whether intended modifi cations of polysaccharide metabolism have successfully been effected in vivo . Simple methods for this are described, including in -vivo radiolabelling, enzymic dissection (e.g. with Driselase) and chromatographic/electrophoretic fractionation of dissection products.After an overview of polysaccharide chemistry, I discuss the structures and taxonomic distribution of wall polysaccharides in charophytes and land plants. Primary and secondary walls are compared.The major wall polysaccharides are cellulose [microfi brillar β -(1 → 4) -d -glucan], pectins ( α -d -galacturonate -rich) and hemicelluloses (lacking galacturonate; hydrogen -bonding to cellulose; extractable by 6 M NaOH at 37 ° C). Land -plant pectins are anionic polymers built of about four glycosidically interconnected domains (homogalacturonan, rhamnogalacturonans I and II, xylogalacturonan). Hemicelluloses occurring in most/all land plants are α -xylo -β -glucans, β -xylans (including α -arabino -β -xylans, α -glucurono -β -xylans, etc.) and β -mannans (including α -galacto -β -mannans, β -gluco -β -mannans, etc.). Another hemicellulose [mixed -linkage β -(1 → 3)(1 → 4) -d -glucan) is confi ned to Equisetum and some Poales.Other taxonomically restricted features of angiosperm primary walls occur in Poales (xylose -poor xyloglucans; feruloylated arabinoxylans); Solanales and Lamiales (characteristic xyloglucans); Caryophyllales (feruloylated pectins); and Alismatales (apiogalacturonan). I also summarize characteristic wall features of charophytes, bryophytes, lycopodiophytes, fern -allies and gymnosperms.

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The preparation and susceptibility to hydrolysis of novel O-galacturonoyl derivatives of carbohydrates

Cited by 21 publications

References 28 publications

Novel O-D-Galacturonoyl Esters in the Pectic Polysaccharides of Suspension-Cultured Plant Cells

Novel O-D-Galacturonoyl Esters in the Pectic Polysaccharides of Suspension-Cultured Plant Cells

Cell Wall Polysaccharide Composition and Covalent Crosslinking

Cell Wall Polysaccharide Composition and Covalent Crosslinking

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