Periodate oxidation of crystalline cellulose

Conversion of 1,2-dihydroxyl groups to dialdehyde by periodate oxidation is a useful method of derivatizing polysaccharides but has not been extensively utilized in derivatization of cellulose because of complicacy due to the crystalline nature of cellulose. To understand the influence of cellulose crystallinity on this reaction, we investigated how the periodate oxidation proceeds with a highly crystalline cellulose of the marine alga Cladophora sp. The crystallinity of the oxidized cellulose, determined by X-ray diffraction, decreased according to the oxidation level. The half-height widths of equatorial diffraction peaks were nearly unchanged. The solid-state 13C NMR spectra did not show peaks corresponding to aldehyde groups, but solution 13C NMR spectra showed the presence of dicarboxylic groups after subsequent oxidation by sodium chlorite. Transmission electron microscopy showed that microfibrils of Cladophora tended to be bent and more flexible than the original sample. Gold labeling of the aldehyde groups, mediated by thiosemicarbazide derivatization, revealed a highly uneven distribution of dialdehyde groups. When treated by 50% (w/v) sulfuric acid, partially oxidized Cladophora cellulose gave many short fragments of microfibril. These features indicate that the periodate oxidation proceeds by forming dialdehyde groups in longitudinally spaced, bandlike domains.