Call number: LD2668 .T4 1949 H62 / Master of Science

The role of hydrophobic substituents on the gelation mechanism of highly esterified pectin and the cellulose derivatives methylcellulose and hydroxypropylmethylcellulose (HPMC) has been explored by monitoring the behaviour of the amphiphilic polysaccharides in varying combinations of an ethylene glycoVwater solvent. The gelling ability (mechanical spectroscopy, visual observation) of very highly esterified (- 100%) pectin in high concentrations of ethylene glycol (>60%) is greatly reduced, however, the polymer still undergoes conformational ordering (CD, OR). A model for gel formation involving a two stage process has been proposed, comprising adoption of the ordered structure stabilised by hydrogen bonding between OH groups of contiguous polysaccharide chains, followed by (or coincident with) aggregation of the ordered sequences by 'hydrophobic' clustering of the fundamental structural subunits to form the three dimensional gel network. It has been found that ethylene glycol promotes the fIrst stage (ordering) but is antagonistic to the second (aggregation). The reversibility (mechanical spectroscopy) of the thermo-gelling cellulose derivatives can be largely abolished in the presence of ethylene glycol (40% for methylcellulose, 10% for HPMC), attributed to solubilisation of the proposed ordered 'bundle' structure at low temperatures removing the enthalpic advantage (DSC) of gel melting. The increased sensitivity of HPMC to modification of the solvent environment is due to the presence of the polar hydroxypropyl substituent causing an inceptive destabilisation of the 'bundle' structure. It is suggested that gelation is driven by the entropic advantage of melting-out 'cages' of structured water surrounding the hydrophobic groups giving rise to intermolecular 'hydrophobic' aggregation.

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Rice is an important dietary grain but may be difficult to fortify with water-soluble vitamins due to the losses incurred during processing and preparation. Edible coatings can offer reasonable protection against folate processing losses in fortified rice, in particular pectin (Shrestha, 2003). However, pectin, an indigestible fibre, may entrap or bind added folate, decreasing its absorption efficiency. Healthy volunteers (n=26, 18-39 yrs) received oral 400??g [13C5]PteGlu doses in three separate test meals in randomized cross-over trials as follows: 1) aqueous 2) 200g white rice and 3) 200g of pectin-coated rice premix. A plasma AUC0-8 was conducted (0, 1, 2, 5 and 8 hrs postprandial). Subjects followed a low folate basal diet (112??12 ??g/day) - verified using L.casei microbiological assay - during the AUC and for 24 hours prior. Optimisation of the pectin-coated rice premix gave folic acid coating and cooking losses of 33.5% and 15.5% respectively. The mean test dose error per 400??g folic acid was ?? 26 ??g. Single- or tri- enzyme extraction of fortified rice extracts did not significantly increase the mean assayable folate content compared to the mean folic acid content. The levels of plasma [13C5]5-methyl-THF, [13C5]PteGlu and 5-methyl-THF were quantified using a validated HPLC-tandem MS method. The calibration curves indicated good response linearity in the 0-100 ng/mL range (R2&gt0.9978). Inter- and intra-assay variation of 5-methyl-THF (100 ng/mL) was 6.9% (n=6) and 5.2% (n=4) respectively. The mean recovery of 5, 20 and 50 ng/mL 5-methyl-THF in spiked plasma extracts was 98.6 ?? 8.7%, 89.3 ?? 2.8% and 92.6 ?? 3.7% (n=3) respectively. Standard Reference Material-1846, infant formula (129??28 ??g/100g) was measured at 110 ?? 15 ??g folic acid/100g. The relative bioavailability of the folic acid in meals 2 and 3 was measured by comparing their [13C5]5-methyl-THF AUC???s relative to meal 1. The relative bioavailabilities (Mean % ?? CI) of meals 2 and 3 were 86.5 ?? 4.6 % and 68.7 ?? 5.4 % respectively. It appears the pectin coat moderately reduces short-term folic acid bioavailability. These studies define the basis for calculating the amount of folic acid to be added to rice so that an adequate amount can be absorbed after coating and cooking losses. Pectin coatings may be a useful means of increasing the folate status of populations that rely heavily on rice as a staple.

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