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In this paper, a detailed characterization of the mechanisms at the origin of the shape-memory effect in amorphous potato starch is presented. Using different treatments (annealing) and preparation methods (hot casting and extrusion), the local structures responsible for the shape-memory were disrupted, as evidenced in the first part of the article detailing the macroscopic properties: mechanical, calorimetric and shape-memory. In the second part the macromolecular scale is investigated using X-rays diffraction and CP-MAS NMR, and thus allows making the link between the structural differences and the macroscopic properties. Finally we discuss the origin of shape-memory in amorphous starch., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The many studies about amylolysis have collected considerable information regarding the contribution of the starch physico-chemical properties. But the inherent elaborate and variable structure of granular starch and, consequently, the multifactorial condition of the system hinders the interpretation of the experimental results. The immediate benefit of multivariate statistical analysis approaches with that regard is twofold: considering the factors, possibly interrelated, all together and not independently, providing a first estimation of the magnitude and confidence level of the relations between factors and amylolysis kinetic parameters. Based on data of amylolysis of 13 starch samples from wild type, single and double mutants of maize by porcine pancreatic α-amylase (PPA), a multivariate analysis is proposed. Amylolysis progress-curves were fitted by a Weibull function, as proposed in a previous work, to extract three kinetic parameters: the reaction rate coefficient during the first time-unit, k, the reaction rate retardation over time, h, and the final hydrolysis extent, X∞. Multivariate models relate the macromolecular composition and the fractions of crystalline polymorphic types to the kinetic parameters. h and X∞ are found to be highly related to the measured properties. Thus the amylose content appears to be significantly correlated to the hydrolysis rate retardation, which sheds some light on the probable contribution of the amylose molecules contained in the granules. The multivariate models give correct prediction performances except for k whose a part of variability remains unexplained. A further analysis points out the extent of the characterisation effort of the granule structure needed to extend the fraction of explained variability., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Two empirical models, a conventional first-order kinetics and a fractal-like first-order kinetic model were tested for analysing the hydrolysis of 13 wild type, single and double mutants of maize starch by porcine pancreatic α-amylase (PPA). The major difference between the two models is an additional parameter, the fractal kinetics exponent h, which enables to characterise a decrease of the reaction rate coefficient over time. The fractal-like kinetic model should be preferred to characterise the amylolysis for 10 mutants out of 13 as sugary-2 and amylose-extender curves exhibit clear reaction rate retardation, unlike normal maize and waxy maize. Analysis of the model parameter values reveals two groups of kinetics for the maize mutants: amylose-extender, normal and waxy on one hand, sugary-2 on the other hand. Possible relations between the parameters of the model and granule composition and structure are discussed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The effects of chain distribution, concentration, temperature and hydrothermal treatments on the recrystallization behavior and formation of resistant starch (RS) were investigated. Waxy and normal rice starches were debranched at 10 and 21% w/w solid concentrations, incubated at 25 or 50 °C, and further subjected to annealing or heat moisture treatment (HMT) to enhance RS formation. The crystallization at 25 °C favored the formation of the B-type structure, whereas crystallization at 50 °C led to the A-type structure with a higher melting temperature (100-120 °C) and a higher RS content (52%). All incubated samples showed an increase in RS content after subsequent hydrothermal treatments. The sample incubated at a high temperature contained the highest RS content (74.5%) after HMT with larger/perfect crystallites. These results suggested that the RS formation could be manipulated by crystallization conditions and improved by hydrothermal treatments which are dependent on the initial crystalline perfection., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

1-10% starch/clay bionanocomposites with shape memory properties were obtained by melt processing. X-ray diffraction (XRD) and TEM evidenced the presence of a major fraction of clay tactoids, consisting of 4-5 stacked crystalline layers, with a thickness of 6.8 nm. A significant orientation of the nanoparticles induced by extrusion was also observed. Tensile tests performed above the glass transition of the materials showed that the presence of clay nanoparticles leads to higher elastic modulus and maximum stress, without significant loss in elongation at break which typically reached 100%. Samples submitted to a 50% elongation and cooled below the glass transition showed shape memory behavior. Like unreinforced starch, the bionanocomposites showed complete shape recovery in unconstrained conditions. In mechanically constrained conditions, the maximum recovered stress was significantly improved for the bionanocomposites compared to unreinforced starch, opening promising perspectives for the design of sensors and actuators., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The aim of this work was to characterize the amylopectin of low amylose content cassava starches obtained from transgenesis comparatively with a natural waxy cassava starch (WXN) discovered recently in CIAT (International Center for Tropical Agriculture). Macromolecular features, starch granule morphology, crystallinity and thermal properties of these starches were determined. M¯(w) of amylopectin from the transgenic varieties are lower than WXN. Branched and debranched chain distributions analyses revealed slight differences in the branching degree and structure of these amylopectins, principally on DP 6-9 and DP>37. For the first time, a deep structural characterization of a series of transgenic lines of waxy cassava was carried out and the link between structural features and the mutated gene expression approached. The transgenesis allows to silenced partially or totally the GBSSI, without changing deeply the starch granule ultrastructure and allows to produce clones with similar amylopectin as parental cassava clone., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

A new α-amylase from Anoxybacillus flavothermus (AFA) was found to be effective in hydrolyzing raw starch in production of glucose syrup at temperatures below the starch gelatinization temperature. AFA is very efficient, leading to 77% hydrolysis of a 31% raw starch suspension. The final hydrolysis degree is reached in 2-3h at starch concentrations lower than 15% and 8-24h at higher concentrations. AFA is also very efficient in hydrolyzing the crystalline domains in the starch granule. The major A-type crystalline structure is more rapidly degraded than amorphous domains in agreement with the observed preferential hydrolysis of amylopectin. Amylose-lipid complexes are degraded in a second step, yielding amylose fragments which then re-associate into B-type crystalline structures forming the final α-amylase resistant fraction. The mode of action of AFA and the factors limiting complete hydrolysis are discussed in details., (Copyright © 2011 Elsevier Ltd. All rights reserved.)