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Effects of Modulated Differential Scanning Calorimetry (MDSC) Variables on Thermodynamic and Kinetic Characteristics During Gelatinization of Waxy Rice Starch

Vivian M.‐F. Lai, Cheng‐yi Lii

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Abstract

ABSTRACT The total, reversing, and nonreversing thermal properties during gelatinization of waxy rice starch (starch‐to‐water ratio = 1:2, w/w) were examined by modulated differential scanning calorimetry (MDSC). The effect of MDSC operating variables (i.e., the amplitude and frequency of temperature modulation and the underlying heating rate) on these thermal properties was determined by response surface methodology (RSM) and statistical analysis. The frequency of temperature modulation and the underlying heating rate significantly influenced the gelatinization temperatures and enthalpy changes in total and nonreversing endotherms. In addition, the combination of 0.025Hz and 4–8°C/min with a properly low degree of oscillation was suitable for characterization of starch gelatinization by MDSC. The enthalpy changes in the reversing (thermodynamic) endotherms increased, but those in the nonreversing (kinetic) endotherms decreased with increasing periods (i.e., decreasing frequencies) and underlying heating rates. However, the total enthalpy changes were only slightly influenced by the MDSC variables studied. In addition, the activation energies for the total and nonreversing events were 281.8–417.3 and 386.3–739.7 kJ/mol, respectively, depending on the MDSC conditions. From the compensation relationship between the activation energy and frequency factor, we concluded that the total and nonreversing endotherms were linked to the same single transition.

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ABSTRACT The total, reversing, and nonreversing thermal properties during gelatinization of waxy rice starch (starch‐to‐water ratio = 1:2, w/w) were examined by modulated differential scanning calorimetry (MDSC). The effect of MDSC operating variables (i.e., the amplitude and frequency of temperature modulation and the underlying heating rate) on these thermal properties was determined by response surface methodology (RSM) and statistical analysis. The frequency of temperature modulation and the underlying heating rate significantly influenced the gelatinization temperatures and enthalpy changes in total and nonreversing endotherms. In addition, the combination of 0.025Hz and 4–8°C/min with a properly low degree of oscillation was suitable for characterization of starch gelatinization by MDSC. The enthalpy changes in the reversing (thermodynamic) endotherms increased, but those in the nonreversing (kinetic) endotherms decreased with increasing periods (i.e., decreasing frequencies) and underlying heating rates. However, the total enthalpy changes were only slightly influenced by the MDSC variables studied. In addition, the activation energies for the total and nonreversing events were 281.8–417.3 and 386.3–739.7 kJ/mol, respectively, depending on the MDSC conditions. From the compensation relationship between the activation energy and frequency factor, we concluded that the total and nonreversing endotherms were linked to the same single transition.

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Available abstract

ABSTRACT The total, reversing, and nonreversing thermal properties during gelatinization of waxy rice starch (starch‐to‐water ratio = 1:2, w/w) were examined by modulated differential scanning calorimetry (MDSC). The effect of MDSC operating variables (i.e., the amplitude and frequency of temperature modulation and the underlying heating rate) on these thermal properties was determined by response surface methodology (RSM) and statistical analysis. The frequency of temperature modulation and the underlying heating rate significantly influenced the gelatinization temperatures and enthalpy changes in total and nonreversing endotherms. In addition, the combination of 0.025Hz and 4–8°C/min with a properly low degree of oscillation was suitable for characterization of starch gelatinization by MDSC. The enthalpy changes in the reversing (thermodynamic) endotherms increased, but those in the nonreversing (kinetic) endotherms decreased with increasing periods (i.e., decreasing frequencies) and underlying heating rates. However, the total enthalpy changes were only slightly influenced by the MDSC variables studied. In addition, the activation energies for the total and nonreversing events were 281.8–417.3 and 386.3–739.7 kJ/mol, respectively, depending on the MDSC conditions. From the compensation relationship between the activation energy and frequency factor, we concluded that the total and nonreversing endotherms were linked to the same single transition.

Key concepts: Chemistry, Enthalpy, Differential scanning calorimetry, Starch gelatinization, Starch, Thermodynamics, Kinetic energy, Kinetics

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