The slow digestion property of native cereal starches, represented by normal maize starch, was investigated. The in vitro Englyst test showed that 53.0% of the maize starch is slowly digestible starch (SDS), and scanning electron microscopy (SEM) revealed that SDS starts from an increase of pore size until almost complete fragmentation of starch granules. However, similar amounts of SDS ( approximately 50%) were shown for partially digested fragmented starch residuals, which would normally be considered resistant to digestion based on the Englyst assay. Molecularly, both amylopectin (AP) and amylose (AM) contributed to the amount of SDS as evidenced by a similar ratio of AP to AM at different digestion times. Consistently, similar degrees of crystallinity, comparable gelatinization behavior, and similar debranched profiles of starch residuals following different digestion times indicated that the crystalline and amorphous regions of starch granules were evenly digested through a mechanism of side-by-side digestion of concentric layers of semicrystalline shells of native starch granules.
The hypothesis of increasing the branch density of starch to reduce its digestion rate through partial shortening of amylopectin exterior chains and the length of amylose was investigated. Starch products prepared using -amylase, -amylase and transglucosidase, maltogenic R-amylase, and maltogenic R-amylase and transglucosidase showed significant reduction of rapidly digested starch by 14.5%, 29.0%, 19.8%, and 31.0% with a concomitant increase of slowly digested starch by 9.0%, 19.7%, 5.7%, and 11.0%, respectively. The resistant starch content increased from 5.1% to 13.5% in treated starches. The total contents of the prebiotics isomaltose, isomaltotriose, and panose (Isomaltooligosaccharides) were 2.3% and 5.5%, respectively, for -amylase/transglucosidase-and maltogenic R-amylase/transglucosidase-treated starches. The molecular weight distribution of enzyme-treated starches and their debranched chain length distributions, analyzed using high-performance sizeexclusion chromatography with multiangle laser light scattering and refractive index detection (HPSEC-MALLS-RI) and HPSEC-RI, showed distinctly different patterns among starches with different enzyme treatments. A larger proportion of low molecular weight fractions appeared in starches treated additionally with transglucosidase. All enzyme-treated starches showed a mixture of B-and V-type X-ray diffraction patterns, and 1 H NMR spectra showed a significant increase of R-1,6 linkages. Both the increase of the starch branch density and the crystalline structure in the treated starches likely contribute to their slow digestion property.
Physical and structural characteristics of rice flour and starch obtained from gammairradiated white rice were determined. Pasting viscosities of the rice flour and starch, analyzed by using a Rapid Visco Analyser, decreased continuously with the increase in irradiation dosage. Differential scanning calorimetry showed that gelatinization onset, peak and conclusion temperatures of rice flour and starch changed slightly but the enthalpy change decreased significantly with increase of irradiation dosage. All irradiated starch displayed an A-type X-ray diffraction pattern like the native starch. Gel permeation chromatography showed that the blue value ratio of the first peak (amylopectin) to the second one (amylose) decreased with the increase of the irradiation dosage. The weight-average molecular weight (M w ) and gyration radius (R z ) of amylopectin analyzed by using HPSEC-MALLS-RI (high-performance size-exclusion chromatography equipped with multiangle laser-light scattering and refractive index detector) decreased gradually from 1.48610 9 (M w ) and 384.1 nm (R z ) of native rice starch to 2.36610 8 (M w ) and 236.8 nm of 9 kGy-irradiated starch. The branch chainlength distribution of amylopectins determined by HPAEC-ENZ-PAD (high-performance anion-exchange chromatography with amyloglucosidase post-column on-line reactor and pulsed amperometric detector) showed that gamma irradiation had no significant effect on the amylopectin branch chains with 13DP24 and 37DP, but produced more branch chains with 6DP12 when the irradiation dosage was less than 9 kGy. It might be deduced that gamma irradiation caused the breakage of the amylopectin chains at the amorphous regions, but had little effects on the crystalline regions of starch granules, especially at low dosage irradiation.
The relationship between the slow digestion property of cooked maize starch and its molecular fine structure was investigated. Results of the in vitro Englyst assay showed a range of rapidly digestible starch (RDS) (70.1-98.9%), slowly digestible starch (SDS) (0.2-20.3%), and resistant starch (RS) (0.0-13.7%) among the tested maize mutant flour samples. Further analysis showed that amylose content was significantly correlated ( R = 0.763, P < 0.001) with RS amount but not with that of SDS, indicating that amylopectin is the starch molecule associated with SDS. Total starch debranching analysis revealed a parabolic relationship between SDS content and the weight ratio of amylopectin short chains (DP < 13, named SF) to long chains (DP >/= 13, named LF), which means amylopectin with a higher amount of either short chains or long chains can produce relatively high amounts of SDS. Furthermore, debranching analysis of the SDS materials from samples with the highest and lowest weight ratios of SF/LF (both had a high amount SDS) showed significantly different profiles, indicating there is not a uniform molecular structure for SDS. Thus, genetic mutants of maize samples have a good potential to provide raw starch materials of high nutritional quality. An additional finding showed that a simple and comparably high-throughput technique of Rapid Visco-Analyzer (RVA) can be used to screen genetic mutants on the basis of their RVA profiles.
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