Previous research on the binding and gelation of calcium/alginate in aqueous solution were mostly conducted in the (semi-)concentrated regime, and it did not provide details of the binding process and the formation of egg-box junctions. In the present investigation, the binding of calcium to alginate, of low and high molecular weight and different guluronate/mannuronate ratios, was investigated in dilute solutions using isothermal titration calorimetry (ITC), Ca2+-selective potentiometry, and viscometry techniques. The results reveal three distinct and successive steps in the binding of calcium to alginate with increased concentration of Ca ions. They were assigned to (i) interaction of Ca2+ with a single guluronate unit forming monocomplexes; (ii) propagation and formation of egg-box dimers via pairing of these monocomplexes; and (iii) lateral association of the egg-box dimers, generating multimers. The third step has different association modes depending on the molecular weight of alginate. The boundaries between these steps are reasonably critical, and they closely correlate with the Ca/guluronate stoichiometry expected for egg-box dimers and multimers with 2/1 helical chains. The formation of egg-box dimers and their subsequent association are thermodynamically equivalent processes and can be fitted by a model of independent binding sites. The binding of Ca to alginates of different guluronate contents is controlled by a balance between enthalpy and entropy.
The physico-chemical characteristics of various sago starch samples from South East Asia were determined and compared to starches from other sources. X-ray diffraction studies showed that all the sago starches exhibited a C-type diffraction pattern. Scanning electron microscopy showed that they consist of oval granules with an average diameter around 30 mm. Proximate composition studies showed that the moisture content in the sago samples varied between 10.6% and 20.0%, ash between 0.06% and 0.43%, crude fat between 0.10% and 0.13%, fiber between 0.26% and 0.32% and crude protein between 0.19% and 0.25%. The amylose content varied between 24% and 31%. The percentage of amylose obtained by colourimetric determination agreed well with the values obtained by fractionation procedures and potentiometric titration. Intrinsic viscosities and weight average molecular weight were determined in 1M KOH. Intrinsic viscosity for amylose from sago starches varied between 310 and 460 ml/g while for amylopectin the values varied between 210 and 250 ml/g. The molecular weight for amylose was found to be in the range of 1.41 × 10 6 to 2.23 × 10 6 while for amylopectin it was in the range of 6.70 × 10 6 to 9.23 × 10 6 . The gelatinisation temperature for the sago starches studied varied between 69.4ЊC and 70.1ЊC. The exponent 'a' in the Mark-Houwink equation and the exponent 'a ' in the equation R g kM a was found to be 0.80 and 0.58, respectively for amylose separated from sago starch and these are indicative of a random coil conformation. Two types of pasting properties were observed. The first was characterised by a maximum consistency immediately followed by sharp decrease in consistency while the second type was characterised by a plateau when the maximum consistency was reached. ᭧
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