Substituent distribution within cross-linked and hydroxypropylated sweet potato starch and potato starch

Revealing the substituents distribution within starch can help to understand the changes of starch properties after modification. The distribution of substituents over cross-linked and hydroxypropylated sweet potato starch was investigated and compared with modified potato starch. The starches were cross-linked with sodium trimetaphosphate and/or hydroxypropylated with propylene oxide. The native and modified starches were gelatinized and hydrolysed by pullulanase, β-amylase, α-amylase and a combination of pullulanase, α-amylase and amyloglucosidase. The hydrolysates were analysed by HPSEC, HPAEC and MALDI-TOF mass spectrometry. Cross-linking had only a slight effect on the enzymatic hydrolysis, where hydroxypropylation evidently limited the enzymatic hydrolysis. The results obtained suggest that the hydroxypropyl substituents are not distributed regularly over the starch chains. Although the average substitution was around 2 hydroxypropyl groups per 10 glucose units, in the enzyme digests of hydroxypropylated starches, oligomer fragments of 10–15 glucose units, carrying 5–8 hydroxypropyl groups, were identified. It is hypothesised that higher levels of substituents are present in the amorphous regions and periphery of clusters of starch granules. This is the first time that the location of hydroxypropyl groups within sweet potato starch has been examined in this detail. Despite significant differences in granule architecture between starches from potato and sweet potato, similar patterns of hydroxypropylation have been found.