Assessment of freeze damage in tuber starch with electrical impedance spectroscopy and thermodynamic, rheological, spectrographic techniques.

In this study, we aimed to use electrical impedance spectroscopy (EIS) to assess the freeze-damage level of starches from potato tubers treated with multiple freezing-thawing (FT) cycles. The results showed that the relationship between the physicochemical properties of starches and the impedance characteristics of starch paste is temperature-dependent. As the temperature rises to 70-90 °C, the impedance modules show a significant correlation with the amylose and mineral contents, gelatinization and pasting properties, short-range ordered structure, relative crystallinity, and damage level within the range of 10-1 MHz (p < 0.01). This could be because FT leads to a reduction in amylose and ion content. Compared to a high level of freeze-damaged starch (FDS), a low level of FDS has less amylopectin and more amylose. Additionally, the ions could be typically evenly distributed throughout the unbranched linear amylose structure in starch paste. At the peak gelatinization temperature, the starch paste made from a low level of FDS exhibits a weakened network structure, allowing more unbound water for ion movement and enhancing electric conduction. In conclusion, EIS can predict the damage level and properties of FDS, which can benefit the frozen starchy food industry.

Modelling and assessment of plasticizer migration and structure changes in hydrophobic starch-based films.

The structures of starch and starch-based materials determine additives migration from material matrix. Propionylated starch derived from waxy, normal, G50 and G80 starch were selected as the matrix, the amylose effect on plasticizer (triacetin) migration as well as structural changes in hydrophobic starch-based films were discussed. The constant (k1) of first-order rate and initial release rate (V0) of triacetin migration were consistent with the increment of amylose content. Meanwhile, diffusion model disclosed that Fick's second law was apposite to characterize the short-term migration of triacetin, and larger diffusion coefficient (D) values of short- and long-term migration were also found in films with higher amylose content, indicating that amylose-formed structures were in favor of triacetin migration. In comparison of propionylated amylopectin, Van der Waals's interactions between propionylated amylose and triacetin were easier to be weakened with the migration of triacetin, which promoted the decrease of wavenumber of C-O-C, and enlarged the inter-planner spacing of crystalline structures, promoting the formation of amorphous structures and wrinkles and embossments in films with higher amylose content. This work confirmed that regulating the structures of starch were effective to control the migration behavior of additives from starch-based films.

Starch hydrolysis modeling: application to fuel ethanol production.

Efficiency of the starch hydrolysis in the dry grind corn process is a determining factor for overall conversion of starch to ethanol. A model, based on a molecular approach, was developed to simulate structure and hydrolysis of starch. Starch structure was modeled based on a cluster model of amylopectin. Enzymatic hydrolysis of amylose and amylopectin was modeled using a Monte Carlo simulation method. The model included the effects of process variables such as temperature, pH, enzyme activity and enzyme dose. Pure starches from wet milled waxy and high-amylose corn hybrids and ground yellow dent corn were hydrolyzed to validate the model. Standard deviations in the model predictions for glucose concentration and DE values after saccharification were less than ± 0.15% (w/v) and ± 0.35%, respectively. Correlation coefficients for model predictions and experimental values were 0.60 and 0.91 for liquefaction and 0.84 and 0.71 for saccharification of amylose and amylopectin, respectively. Model predictions for glucose (R2 = 0.69-0.79) and DP4+ (R2 = 0.8-0.68) were more accurate than the maltotriose and maltose for hydrolysis of high-amylose and waxy corn starch. For yellow dent corn, simulation predictions for glucose were accurate (R2 > 0.73) indicating that the model can be used to predict the glucose concentrations during starch hydrolysis.

Monte Carlo simulation of the alpha-amylolysis of amylopectin potato starch. 2. alpha-amylolysis of amylopectin.

A model is presented that describes all the saccharides that are produced during the hydrolysis of starch by an alpha-amylase. Potato amylopectin, the substrate of the hydrolysis reaction, was modeled in a computer matrix. The four different subsite maps presented in literature for alpha-amylase originating from Bacillus amyloliquefaciens were used to describe the hydrolysis reaction in a Monte Carlo simulation. The saccharide composition predicted by the model was evaluated with experimental values. Overall, the model predictions were acceptable, but no single subsite map gave the best predictions for all saccharides produced. The influence of an alpha(1-->6) linkage on the rate of hydrolysis of nearby alpha(1-->4) linkages by the alpha-amylase was evaluated using various inhibition constants. For all the subsites considered the use of inhibition constants led to an improvement in the predictions (a decrease of residual sum of squares), indicating the validity of inhibition constants as such. As without inhibition constants, no single subsite map gave the best fit for all saccharides. The possibility of generating a hypothetical subsite map by fitting was therefore investigated. With a genetic algorithm it was possible to construct hypothetical subsite maps (with inhibition constants) that gave further improvements in the average prediction for all saccharides. The advantage of this type of modeling over a regular fit is the additional information about all the saccharides produced during hydrolysis, including the ones that are difficult to measure experimentally.

Monte Carlo simulation of multiple attack mechanism of alpha-amylase.

Porcine pancreatic alpha-amylase (EC 3.2.1.1) produces short maltooligosaccharides from a single enzyme-substrate complex without dissociation by multiple or repetitive attack. Multiple attack is caused by relative sliding of the enzyme along the product chain of the enzyme-product complex without dissociation to form another productive complex. The Monte Carlo method was applied to the multiple attack mechanism to predict product distribution from amylose and amylopectin molecules of arbitrary sizes. The position of the initial attack to make the enzyme-substrate complex and branched reaction paths from the enzyme-product complex were selected by random numbers and probabilities. A simulated product distribution from 100,000 samples of amylose of chain length greater than 80 agreed completely with experimental data at the early stage of hydrolysis of amylose of mean chain length 90. On the other hand, the simulated product distribution from amylopectin agreed with experimental data of potato amylopectin when the effective chain length of the A chain was 9. Since the mean chain length of the A chain of potato amylopectin is 15, it is possible that amylopectin is partially compact in solution, so that the enzyme can recognize and act only on the outer side of the A chain at the early stage of digestion.