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Chemical cross-linking of starch is an important modification used in the industry for granule stabilization. It has been demonstrated that treatment with branching enzyme (BE) can stabilize the granular structure of starch and such treatment thereby provides a potential clean alternative for chemical modification. This study demonstrates that such BE-assisted stabilization of starch granules led to partial protection from BE catalysis of both amylose (AM) and amylopectin (AP) in their native state as assessed by triiodide complexation, X-ray diffractometry (XRD) and differential scanning calorimetry (DSC). The granule stabilizing effects were inversely linked to hydration of the starch granules, which was increased by the presence of starch-phosphate esters and suppressed by extreme substrate concentration. The data support that the granule stabilization is due to the intermolecular transglycosylation occurring in the initial stages of the reaction prior to AM-AP phase separation. The enzyme activity needed to obtain granule stabilization was therefore dependent on the hydration capability of the starch used., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

This study investigated the influence of the internal structure of amylopectin on annealing (3h, 24h) of starches from four different types of amylopectin (Bertoft, Koch, & Aman, 2012; Bertoft, Piyachomkwan, Chatakanonda, & Sriroth, 2008). Regardless of the starch source and incubation time, annealing significantly increased the onset gelatinization temperature (To) and narrowed and deepened the amylopectin endotherm. However, the extent of the change in the melting temperature (Tm) and the enthalpy of gelatinization (ΔH) differed among the types. In terms of the To and Tm, starches from type 1 (oat, rye, barley, and waxy barley) showed the most significant response to annealing. The Tm of starches belonging to type 2 (waxy maize, rice, waxy rice, and sago) remained unchanged after 3h of annealing. Type 1 and type 2 starches with the lowest gelatinization temperatures showed the greatest increase in melting temperature after annealing. However, type 3 (tapioca, mung bean, and arrowroot) and type 4 (potato, waxy potato, canna, and yam) starches were not in line with these observations. Instead, starches from type 3 and type 4 showed a pronounced increase in the ΔH. The inter-block chain length (IB-CL) (distance between tightly branched units within a cluster) correlated positively (r=0.93, p<0.01) with the change in enthalpy after 24h of annealing. These data indicate that a short IB-CL affects the optimum registration of double helices within the crystalline lamellae. The relationship between the gelatinization parameters before and after annealing suggests that type 1 and 2 starches might possess a high number of unpacked double helices (type 1>type 2) compared to other types. Longer IB-CLs, which facilitate the parallel packing of splayed double helices, and the lengthening of double helices likely increased the ΔH in type 3 and type 4 starches. It is concluded that annealing can be used as a probe for visualizing the organization of glucan chains (alignment of double helices/degree of perfection) within crystalline lamellae., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The relationship between the internal structure of amylopectin from diverse plants and thermal properties of the starch granules has been investigated. Correlations were found between structural parameters, such as number of building blocks in clusters, interblock chain length and length of external chains, and gelatinization parameters. Onset gelatinization temperature negatively correlated with number of building blocks (r=-0.952, p<0.01) and positively correlated with inter-block chain length (r=0.905, p<0.01). Enthalpy of gelatinization positively correlated with external chain length (r=0.854, p<0.01). These data showed that the internal structure is predictive of trends in thermal properties. A model is proposed based on the backbone concept of amylopectin structure that explains how the organization of chains in the semicrystalline lamellae of starch granules relates to the thermal properties., (Copyright © 2012 Elsevier Ltd. All rights reserved.)