According to the Avrami equation, the resultant kinetic parameters for AP retrogradation were obtained in relation to structural factors. Generally, the AP systems ...
Molecular Characteristics Influencing Retrogradation Kinetics of Rice Amylopectins Vivian M.-F. Lai,1 Shin Lu,2 and Cheng-yi Lii3 ABSTRACT
Cereal Chem. 77(3):272–278
The enthalpy changes (∆H) for melting of crystallites formed during retrogradation of 60% (w/w) amylopectins (AP) aged at 4°C were investigated using AP from 13 rice cultivars with well-known structural properties. According to the Avrami equation, the resultant kinetic parameters for AP retrogradation were obtained in relation to structural factors. Generally, the AP systems studied showed two stages of retrogradation behavior during early (≤7 days) and late (≥7 days) storage. The Avrami exponent for early-stage kinetics (n1, 1.04–5.54) was greater than the corresponding value for late-stage kinetics (n2, 0.28−1.52). While the Avrami K constant of the early-stage kinetics (K1, 1.0×10–5 to 2.3×10–1 day–n) was lower than the corresponding value of late-stage kinetics (K2, 4.4×10–2 to 1.4 day–n). The ∆H values for late and infinite retrogradation
stages showed a significantly positive correlation with the proportions of short chain (chain length [CL] ≤ 15 glucose units) and long chain (CL = 16–100 glucose units) fractions, respectively. Retrogradation of AP with a higher number-average degree of polymerization, greater proportion of short chain fractions, and shorter average chain lengths revealed significantly greater n1 values and smaller K1 values. Values for n2 and K2 showed little influence from the molecular properties except for the proportion of extra long (CL >100 glucose units) and long chain fractions on K2. The negatively linear relationships between log K and n suggest the importance of some nonstructural factors for AP retrogradation mechanisms in various starch systems.
Extensive association of starch molecules occurs during storage of gelatinized starch materials at below the melting temperature of starch crystallites, resulting in viscosity increase, gel firming, and textural staling of predominantly starch-containing systems. This phenomenon is called retrogradation and is of considerable importance to the food industry (Atwell et al 1988). It is generally regarded as a crystallization or recrystallization (i.e., formation and subsequent aggregation of double helices) process of amylopectin (AP) and amylose (AM) molecules (Miles et al 1985, Atwell et al 1988). Because the amount of AP in most starches is greater than AM, most of the crystallites formed during starch retrogradation are related to the association of AP chains (Miles et al 1985). The melting of these crystallites is thermoreversible ( TCN1, TCS10, TS1 (6.7×10–3 to 2.4×10–2 day–n) > five japonica cultivars and TCSW1 (1.0×10–5 to 4.4×10–3 day–n). These K1 values were lower than the corresponding K2 values of late-stage kinetics and those for HKW and TCW70 (4.4×10–2 to 1.4 day–n), contrary to the tendency of increasing rate of ∆H. The kinetic equations accounted for 97.5−99.9% and 88.5− 99.9% of the data deviations for early and late retrogradation stages (R2 = 0.975−0.999 and 0.885−0.999, respectively). A higher n value accompanied by lower K value was reported for 20% corn AP (Mua and Jackson 1998), 40−50% wheat starches (Longton and LeGrys 1981, Zhang and Jackson 1992), 60-80% corn starches
(Jouppila et al 1998), and 28.6% rice flour (Fan and Marks 1998). The n value for each AP system decreased as the crystallization proceeded, which is in agreement with the findings for two-stage spherulitic crystallization (Wunderlich 1976, Sperling 1993). Correlation Between Retrogradation and Molecular Properties In our previous studies (Lu et al 1997b), the number-average degree of polymerization (DPn) was 2,743−7,850, 7,327−11,931, and 7,721-9,101 glucose units (gu), respectively, for indica, japonica, and waxy AP. The average numbers of chain (NC) of these AP were 128−424, 424−760, and 389−517, respectively; the average chain lengths (CL) were 18.5−22.1, 15.4−17.5, and 17.6−19.8 gu, respectively; the average exterior chain lengths (ECL), were 13.2− 15.8, 11.3−12.6, and 12.2−13.2 gu, respectively; and the average interior chain lengths (ICL) were 4.2−5.3, 3.2−4.1, and 4.4−5.7 gu, respectively. The weight percentages of short chains (s) (CL ≤ 15 gu) were 58.5−65.1, 64.6−65.7, and 64.3−65.8%, respectively, for the indica, japonica, and waxy cultivars. The weight percentages of long chains (l) (CL = 16−100 gu) were 29.2−36.2, 34.3− 35.4, and 34.2−35.7%, respectively. Only the AP of indica TCN1, TCS17, and KSS7 possessed 3.7−10.9% of extra-long chains (el) (CL > 100 gu). Generally, the higher the DPn, the lower the chain length and the greater the s value (Lu et al 1997b). Correlation coefficients between the retrogradation characteristics in Table I and the molecular properties of AP were investigated and listed in Table II. The induction time tind was significantly (P < 0.05) correlated positively with DPn and s values. The ∆H1 showed no significant
TABLE I Retrogradation Properties and Kinetic Parameters During Early (≤7 days) and Late (≥7 days) Storage Stages of Amylopectins from Taiwan Rice Cultivars (60%, w/w, at 4°C) Retrogradation Properties (J/g) Cultivar KSS7 TCS17 TCN1 TCS10 TS1 KS142 TC189 TN9 TNu67 TNu70 TCSW1 HKW TCW70
∆H1b
tinda (days) 3 3 3 3 3 4 3 5 5 5 3 6 6
9.5 6.6 5.4 6.0 6.1 6.8 7.9 3.3 5.0 6.3 6.6 2.0 3.8
∆H2c 1.0 1.4 3.0 3.5 3.2 3.1 2.0 5.8 4.1 3.3 2.7 5.7 4.9
∆H∞ 10.5 8.0 8.4 9.5 9.3 9.9 9.9 9.1 9.1 9.6 9.3 7.7 8.7
Early n1 1.32 1.04 1.96 2.58 2.55 5.54 3.52 5.49 2.98 4.78 2.91 . . .d ...
Late
K1 (day–n) 10 –1
1.7 × 2.3 × 10 –1 2.4 × 10 –2 6.7 × 10 –3 7.9 × 10 –3 2.3 × 10 –3 1.5 × 10 –3 1.0 × 10 –3 2.4 × 10 –3 9.6 × 10 –3 4.4 × 10 –3 ... ...
R2
n2
0.980 0.998 0.983 0.999 0.988 0.996 0.975 0.999 0.999 0.999 0.999 ... ...
0.98 0.28 0.96 1.23 1.18 1.08 0.93 1.22 1.52 0.61 0.40 0.96 0.78
K2 (day–n) 10 –1
3.5 × 1.4 1.6 × 10 –1 9.1 × 10 –2 1.1 × 10 –1 1.3 × 10 –1 2.5 × 10 –1 6.6 × 10 –2 4.4 × 10 –2 5.1 × 10 –1 6.5 × 10 –1 6.8 × 10 –2 1.8 × 10 –1
R2 0.999 0.990 0.997 0.999 0.996 0.944 0.947 0.973 0.999 0.885 0.999 0.989 0.972
a
Induction time (tind) during which no detectable enthalpy changes (∆H) were obtained. Subscripts 1 and 2 represent early and late retrogradation stages. c ∆H = ∆H – ∆H . 2 ∞ 1 d Insufficient data. b
TABLE II Correlation Coefficients Between Retrogradation Characteristics and Molecular Properties of Amylopectins from Taiwan Rice Cultivars (60%, w/w, at 4°C) a Molecular Propertyb DPn NC CL ECL ICL el l s a b
c
tind 0.55* c 0.52 –0.44 –0.48 –0.31 –0.43 0.13 0.58*
∆H1 –0.34 –0.26 0.10 0.18 –0.02 0.20 0.06 –0.37
∆H2
∆H∞
n1
K1
0.53 0.46 –0.37 –0.43 –0.22 –0.48 0.24 0.59*
0.15 0.21 –0.43 –0.37 –0.45 –0.40 0.61* 0.18
0.75** 0.76** –0.79** –0.82** –0.64* –0.64* 0.41 0.72*
–0.72* –0.67* 0.61* 0.66* 0.44 0.70* –0.58 –0.68*
n2 0.16 0.16 –0.32 –0.24 –0.45 –0.40 0.46 0.29
K2 –0.36 –0.33 0.42 0.40 0.40 0.59* –0.65* –0.44
Retrogradation characteristics as in Table I. DPn, NC, CL, ECL, and ICL are number-average degree of polymerization, average numbers of chain, average chain length, average exterior chain length, and average interior chain length in glucose units (gu), respectively; el, l and s are wt% of extra long (>100 gu), long (16−100 gu), and short (≤15 gu) chain fractions, respectively. * , ** = P ≤ 0.05 and ≤ 0.01, respectively.
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correlation with any of the molecular properties; the ∆H2 and ∆H∞ exhibited significantly positive correlation with s and l values (P < 0.05), respectively. For early-stage retrogradation kinetics, the n1 significantly increased with increasing DPn, NC (P < 0.01), and s value (P < 0.05), and with decreasing CL, ECL (P < 0.01), ICL, and el (P < 0.05). These molecular parameters, except ICL, also appeared to significantly affect K1 (P
