Abstract
The action of sodium hydroxide on the rate and extent of loss of wall polysaccharides from wheat and barley straws incubated in the rumen of the sheep was studied using a nylon bag technique. Cellulose loss reached a maximum in straws treated with 10 g NaOH 100 g^−1^ straw. Further increase in amounts of alkali applied resulted in additional solubilisation of straw constituents, particularly xylan, but did not further enhance cellulose degradation. Rates of degradation of isolated straw, cotton and wood celluloses correlated with three of four measures of cellulose crystallinity obtained by X‐ray diffraction and infrared analysis. Treatment of cellulose samples with 20 g NaOH 100 g^−1^ cellulose did not affect rates of loss or produce detectable changes to cellulose morphology. Loss of acetic acid esters, which accompanied alkali treatment, did not relate to improvements to digestibility. The rate of loss of cellulose from delignified neutral detergent fibre (NDF) was that shown by the isolated straw cellulose, despite the presence of acetylated hemicellulose. Deacetylation of delignified NDF with NaOH or sodium methoxide did not enhance rates of xylose or cellulose loss. In lignified wall material (NDF) the molar ratio acetyl:xylose (approximately 1:3.5) and proportion of the major phenolic acids (p‐coumaric and ferulic acids) remained essentially constant throughout the course of degradation in the rumen. It is suggested that loss of phenolic acids, while not directly contributing to digestibility enhancement, may model the susceptibility of ester linkages formed between polysaccharide and polyphenolic material to alkali. The extent of solubilisation of p‐coumaric acid produced by NaOH showed a linear relationship with cellulose digestibility. An upper limit of 40% acid detergent lignin and 55% of total phenolics were released by NaOH, the extent of release closely paralleling cellulose digestibility. Phenolic material resistant to alkali remained associated with wall polysaccharides and was not released from nylon bags until over 50% of cellulose (and hemicellulose) had been degraded.