Behaviour of xyloisosaccharinic acid and xyloisosaccharino-1,4-lactone in aqueous solutions at varying pHs

Michael Almond, Paul B. Shaw, Paul N. Humphreys, Marcus J. Chadha, Klaus Niemelä, Andrew P. Laws

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Xyloisosaccharinic acid is one of the major degradation products formed during the alkali catalysed hydrolysis of hemicelluloses. In acidic solution xyloisosaccharinic acid undergoes an acid catalysed lactonisation to generate xyloisosaccharino-1,4-lactone. We report here the solution phase properties of xyloisosaccharinic including measurement of its aqueous pKa (3.00 ± 0.05) using 13C NMR methods. We also report rate constants for the acid catalysed lactonisation, klact(D20), of xyloisosaccharinic acid and the results of our investigations of the kinetics of hydrolysis of xyloisosaccharino-1,4-lactone at acidic and basic pHs. The second-order rate constants for the hydrolysis reactions kHO- (25 M-1 s-1) and kD+ (4.13 E-4 M-1 s-1).

LanguageEnglish
Pages51-57
Number of pages7
JournalCarbohydrate Research
Volume363
Early online date10 Oct 2012
DOIs
Publication statusPublished - 1 Dec 2012

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Lactones
Acids
Hydrolysis
Rate constants
Alkalies
Nuclear magnetic resonance
Degradation
Kinetics

Cite this

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title = "Behaviour of xyloisosaccharinic acid and xyloisosaccharino-1,4-lactone in aqueous solutions at varying pHs",
abstract = "Xyloisosaccharinic acid is one of the major degradation products formed during the alkali catalysed hydrolysis of hemicelluloses. In acidic solution xyloisosaccharinic acid undergoes an acid catalysed lactonisation to generate xyloisosaccharino-1,4-lactone. We report here the solution phase properties of xyloisosaccharinic including measurement of its aqueous pKa (3.00 ± 0.05) using 13C NMR methods. We also report rate constants for the acid catalysed lactonisation, klact(D20), of xyloisosaccharinic acid and the results of our investigations of the kinetics of hydrolysis of xyloisosaccharino-1,4-lactone at acidic and basic pHs. The second-order rate constants for the hydrolysis reactions kHO- (25 M-1 s-1) and kD+ (4.13 E-4 M-1 s-1).",
keywords = "2,4-Dihydroxy-2-hydroxymethylbutanoic acid, 3-Deoxy-2-C-hydroxymethyl-d,l-tetronic acid, pK measurement, Xyloisosaccharinic acid, Xyloisosaccharino-1,4-lactone",
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Behaviour of xyloisosaccharinic acid and xyloisosaccharino-1,4-lactone in aqueous solutions at varying pHs. / Almond, Michael; Shaw, Paul B.; Humphreys, Paul N.; Chadha, Marcus J.; Niemelä, Klaus; Laws, Andrew P.

In: Carbohydrate Research, Vol. 363, 01.12.2012, p. 51-57.

Research output: Contribution to journalArticle

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AU - Shaw, Paul B.

AU - Humphreys, Paul N.

AU - Chadha, Marcus J.

AU - Niemelä, Klaus

AU - Laws, Andrew P.

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AB - Xyloisosaccharinic acid is one of the major degradation products formed during the alkali catalysed hydrolysis of hemicelluloses. In acidic solution xyloisosaccharinic acid undergoes an acid catalysed lactonisation to generate xyloisosaccharino-1,4-lactone. We report here the solution phase properties of xyloisosaccharinic including measurement of its aqueous pKa (3.00 ± 0.05) using 13C NMR methods. We also report rate constants for the acid catalysed lactonisation, klact(D20), of xyloisosaccharinic acid and the results of our investigations of the kinetics of hydrolysis of xyloisosaccharino-1,4-lactone at acidic and basic pHs. The second-order rate constants for the hydrolysis reactions kHO- (25 M-1 s-1) and kD+ (4.13 E-4 M-1 s-1).

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