Modified starches are used widely in the food industry but often have a low nutritional value, lacking minerals vital for the human body, such as magnesium. Magnesium addition to native starches has been shown to result in changes in pasting properties. However, little work has been done on the addition of magnesium and other divalent cations to highly oxidised starches. In this work, we used dibasic magnesium hypochlorite (DMH) to oxidise potato starch to an industrially relevant degree of oxidation while at the same time introducing magnesium into the starch structure. We found that magnesium incorporation changes the pasting properties of starch and increases the gelatinisation temperature significantly, possibly due to an ionic cross-linking effect. These properties resemble the properties found for heat-moisture-treated potato starches. This change in properties was found to be reversible by performing a straightforward exchange of metal cations, either from sodium to magnesium or from magnesium to sodium. We show in this work the potential of the addition of divalent cations to highly oxidised starches in modifying the rheological and pasting properties of these starches and at the same time adding possible health benefits to modified starches by introducing magnesium.
DOCUMENT
The catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules. These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.
DOCUMENT
The title uronates were prepared by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) catalysed sodium hypochlorite oxidation of α- and β-D-glucopyranosylphosphate (α-/β-Glc-1-P) and α-D-glucopyranosyl fluoride (α-Glc-1-F). Quantitative recovery of the TEMPO catalyst was achieved by azeotropic distillation of a small part of the reaction mixture. Also, a heterogeneous catalyst system was prepared by immobilisation of 4-oxo-tetramethyl-1-piperidinyloxy (OTEMPO) on amino-functionalized silica. The protected uronates were hydrolysed to yield D-glucuronate. Since α- and β-Glc-1-P and α-Glc-1-F can be obtained from starch in one step, D-glucuronic acid is now available from starch in a convenient three-step sequence.
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