B-type Crystallites Research Articles

Impact of crystalline structure on the digestibility of amylopectin-based starch-lipid complexes

In this study, chain-elongated waxy corn starch (mWCS) was complexed with lauric acid (LA) to produce starch-lipid complexes (mWCS@LA) with a mixture of B- and V-type crystalline structures. Results from in vitro digestion showed that mWCS@LA had higher digestibility than mWCS, and the logarithm of slope plots of mWCS@LA revealed a two-stage digestion pattern, with digestion rate of the first stage (k1 = 0.038 min−1) being much higher than that of the following stage (k2 = 0.0116 min−1). The complexation between the long branch chains of mWCS and LA formed amylopectin-based V-type crystallites that were rapidly hydrolyzed during the first stage. The digesta isolated from the second stage of digestion had a B-type crystallinity of 52.6 %, and starch chains with degree of polymerization of 24–28 mainly contributed to the formation of the B-type crystalline structure. The results from the present study reveal that the B-type crystallites were more resistant to amylolytic hydrolysis than the amylopectin-based V-type crystallites.

Microwave reheating enriches resistant starch in cold-chain cooked rice: A view of structural alterations during digestion

Cold-chain cooked rice is an instant food consumed worldwide. Through inspecting rice structural alterations during digestion, this work discloses how microwave reheating tailors the starch digestibility of cooked rice following cold storage. The cold storage allowed approximately 2% of B-type (not V-type) starch crystallites, more nanoscale and short-range orders, and smaller pores in the rice matrix. These changes retarded the hydrolysis of structural domains (e.g., amorphous regions and short-range orders) during digestion, which increased the content of slowly digestible starch to about 38.16%. Then, microwave reheating partially disrupted the B-type crystallites and nanoscale orders, but unaffected the contents of V-type crystallites and short-range orders. Even with such structural disruptions, the resistant starch content was apparently increased to approximately 30.06%, as the structural domains became less susceptible to the digestion. Additionally, for the rice samples, the percentage of V-type crystallites could be largely increased from ca. 3% to 13%–14% during digestion.

Crystal structure transformations in extruded starch plasticized with glycerol and urea

Cornstarch was processed on an extruder with glycerol and different contents of urea giving rise to samples named as SGU-0, SGU-1, SGU-5, and SGU-10. The gelatinization enthalpy ΔHgel, calculated by DSC, indicated that the mixture of glycerol and urea seems to better plasticize the starch than glycerol alone. XRD was used to identify the changes in the crystal structure of native starch after extrusion processing. XRD diffractograms indicated the presence of both residual native crystallinity and processing-induced crystallinity. The morphology observed by SEM was compatible with the presence of residual crystals and recrystallization, as suggested by XRD analysis. SAXS experiments pointed out the minute amount of B-type crystallites in the samples with urea, probably due to the hydrophilic character of urea, which contributes to starch hydration.

Hydration-induced crystalline transformation of starch polymer under ambient conditions

With synchrotron small/wide-angle X-ray scattering (SAXS/WAXS), we revealed that post-harvest hydration at ambient conditions can further alter the starch crystalline structure. The hydration process induced the alignment of starch helices into crystalline lamellae, irrespective of the starch type (A- or B-). In this process, non-crystalline helices were probably packed with water molecules to form new crystal units, thereby enhancing the overall concentration of starch crystallinity. In particular, a fraction of the monoclinic crystal units of the A-type starches encapsulated water molecules during hydration, leading to the outward movement of starch helices. Such movement resulted in the transformation of monoclinic units into hexagonal units, which was associated with the B-type crystallites. Hence, the hydration under ambient conditions could enhance the B-polymorphic features for both A-type and B-type starches. The new knowledge obtained here may guide the design of biopolymer-based liquid crystal materials with controlled lattice regularity and demanded features.

Digestibility of retrograded starches with A- and B-type crystalline structures

This study investigated whether the crystalline structure of the retrograded starch affects the contents of slowly digestible starch (SDS) and resistant starch (RS). When the relative crystallinities were similar, there was no difference in RS content between the retrograded starches with A- and B-type crystallites. However, the SDS content in A-type crystalline structure was constantly higher than B-type, contradicting the observation that the granular starches with B-type crystallites were more enzyme resistant. Therefore, the primary factor that accounts for the digestibility of granular starch is not the crystalline structure, but the granular properties, including the surface pores and the size.

Preparation, structure, and digestibility of crystalline A- and B-type aggregates from debranched waxy starches

Highly crystalline A- and B-type aggregates were prepared from short linear α-1,4 glucans generated from completely debranched waxy maize and waxy potato starches by manipulating the chain length and crystallization conditions including starch solids concentration and crystallization temperature. The A-type crystalline products were more resistant to enzyme digestion than the B-type crystalline products, and the digestibility of the A- and B-type allomorphs was not correlated with the size of the aggregates formed. Annealing increased the peak melting temperature of the B-type crystallites, making it similar to that of the A-type crystallites, but did not improve the enzyme resistance of the B-type crystalline products. The possible reason for these results was due to the compact morphology as well as the denser packing pattern of double helices in A-type crystallites. Our observations counter the fact that most B-type native starches are more enzyme-resistant than A-type native starches. Crystalline type per se does not seem to be the key factor that controls the digestibility of native starch granules; the resistance of native starches with a B-type X-ray diffraction pattern is probably attributed to the other structural features in starch granules.

Starch chain interactions within the amorphous and crystalline domains of pulse starches during heat-moisture treatment at different temperatures and their impact on physicochemical properties

Pulse (faba bean [FB], black bean [BB] and pinto bean [PB]) starches were heat-moisture treated (HMT) at 80, 100 and 120°C for 12h at a moisture content of ∼23%. Structural changes on HMT were monitored by microscopy, HPAEC-PAD, ATR-FTIR, WAXS, DSC and susceptibility towards acid and enzyme hydrolysis. Amylopectin chain length distribution remained unchanged in all starches on HMT. In all starches, HMT increased crystallinity and gelatinisation temperatures. The gelatinization enthalpy remained unchanged in some starches, whereas it decreased slightly in other starches on HMT. Slowly digestible starch content decreased at all temperatures of HMT, whereas resistant starch content increased at HMT80 and HMT100 (HMT80>HMT100), but decreased at HMT120. Birefringence, B-type crystallites and acid hydrolysis decreased on HMT. The extent of the above changes varied amongst starch sources and genotypes. HMT altered the X-ray pattern from A+B→A. The results of this study showed that structural reorganisation of starch chains during HMT temperature was influenced by starch chain flexibility, starch chain interactions and crystalline stability of the native granules.

Impact of structural changes due to heat-moisture treatment at different temperatures on the susceptibility of normal and waxy potato starches towards hydrolysis by porcine pancreatic alpha amylase

The objectives of this study were to determine the impact of structural changes within the amorphous and crystalline domains of normal potato (NP) and waxy potato (WP) starches subjected to heat-moisture treatment (HMT) at 80, 100, 120 and 130 °C for 16 h at a moisture content of 27% and to determine the impact of structural changes at each of the above temperatures on the susceptibility on hydrolysis by porcine pancreatic α-amylase (PPA). The results showed that structural changes due to HMT were influenced by differences in starch chain mobility at the different temperatures of HMT. Starch chain mobility in turn was influenced by the interplay between the extent to which B-type crystallites were transformed into A + B-type crystallites, kinetic energy imparted to starch chains and amylose content. The main type of structural changes influencing physicochemical properties at the different temperatures of HMT was starch chain interactions (at 80 and 100 °C), disruption of hydrogen bonds between amylose (AM)–amylopectin (AMP) and AMP–AMP chains (at 120 and 130 °C), disorganization of AMP chains near the vicinity of the hilum (at 100, 120 and 130 °C) and formation of interrupted helices (at 130 °C). The susceptibility of NP and WP starches towards α-amylase decreased at 80 °C, but increased in the range of 100 to 130 °C. This suggested that α-amylase hydrolysis of HMT starches was influenced by the interplay of: 1) amount of A-type crystallites, 2) starch chain interactions and 3) changes to double helical conformation. Differences in granule morphology in PPA hydrolyzed NP and WP starches were largely influenced by the higher granular swelling in the latter. NP and WP starches exhibited heterogeneity in degradation (NP > WP) in both their native and HMT states.

Structural and functional properties of starches from field peas

Starch was isolated from seven varieties of field peas (Pisumsativum L.) and characterised using a combination of physical, chemical and functional tests. The total starch content of the peas ranged between 34% and 42.7% of dry matter, and the amylose content of the starch was between 35% and 38%. Average particle diameter of the seven starches varied between 21.4 and 26.1μm. All of the pea starches gave a typical C-type X-ray diffraction pattern, with relative crystallinity ranging between 36% and 55% and the proportion of B-type crystallites between 3.8% and 30.4%. Although there were only small differences between the starches in amylose content, they displayed significant variability in functional properties, including swelling power, pasting characteristics, thermal transition temperatures in the differential scanning calorimeter, and in susceptibility to invitro attack by α-amylase. The results indicate the importance of structural characteristics of starch molecules, particularly amylopectin, as determinants of the properties of native starch granules.

Amylose involvement in the amylopectin clusters of potato starch granules

The granular organization of common corn and potato starch is characteristically different. The objective of this study was to investigate iodine complex formation with starch lintners from common corn starch (CCS) and potato starch (PS) litners as a function of water content. Starches were subjected to mild acid hydrolysis (lintnerization). Size exclusion chromatography of the lintners indicated that the linear chains remaining after lintnerization had smaller degree of polymerization in PS lintners than in the corresponding CCS lintners. For both CCS and PS, the absorbance intensity and the wavelength of maximum absorption ( λ max) of molecularly dispersed starches, in diluted iodine solution, decreased with increasing lintnerization extent. When the granular lintners were exposed to iodine vapor, following equilibration to different moisture contents, the reduction in the iodine binding was evident in PS lintners but not in CCS lintners. Furthermore, the iodination partially destroyed the crystallinity of native PS granules but not that of CCS granules. However, B-type crystallinity was still evident in PS lintners. This behavior was attributed to different location of amylose within starch granules, supporting the involvement of amylose in the B-type crystallites of PS, and the independence of amylose from the A-type crystallites of CCS.

Dynamics of starch granule biogenesis – the role of redox-regulated enzymes and low-affinity carbohydrate-binding modules

The deposition and degradation of starch in plants is subject to extensive post-translational regulation. To permit degradation of B-type crystallites present in tuberous and leaf starch these starch types are phosphorylated by glucan, water dikinase (GWD). At the level of post-translational redox regulation, ADPglucose pyrophosphorylase, β-amylase (BAM1), limit dextrinase (LD), the starch phosphorylator GWD and the glucan phosphatase dual-specificity phosphatase 4 (DSP4), also named starch excess 4 (SEX4), are reductively activated in vitro. Redox screens now suggest the presence of a substantially more extensive and coordinated redox regulation involving a larger number of enzymes. Noticeably several of these enzymes contain a new type of low-affinity carbohydrate-binding module that we term a low-affinity starch-binding domain or LA-SBD. These are present in the CBM20, CBM45 and CBM53 families and can enable diurnal dynamics of starch–enzyme recognition. Such diurnal changes in starch binding have been indicated for the redox-regulated GWD and SEX4.

A Genetic Approach to Studying the Morphology, Structure and Function of Starch Granules using Pea as a Model

A series of near-isogenic lines have been developed for mutations induced and identified at six independent loci controlling steps in starch biosynthesis of pea (Pisum sativum) seeds. The review describes the methodology associated with the development of these lines and with the characterisation of the starches produced, in particular the effects that the mutations have on the morphology, structure and properties of the starch granules. The shape of starch granules from lines containing mutations at either the r or rug5 loci, encoding a starch branching enzyme and a soluble starch synthase, differ significantly from granules found in the non-mutant parental line. Mutations at each of the six loci result in characteristic changes in granular structure, which has been studied using polarised light microscopy, wide angle X-ray diffraction, solid state NMR and differential scanning calorimetry. Relatively small but significant changes were found in the proportion of crystalline material within the granules and much greater differences in the spatial distribution of the crystals within the granules. In particular, granules from rand rugs mutants do not show the characteristic 'Maltese cross' pattern when viewed under polarised light. Large differences were found between the mutants in the proportion of A- and B-type crystallites within the granules, ranging from about 60% A-type in rug3 mutants to 100% B-type in rmutant lines. It is suggested that the pea lines are an invaluable resource for answering fundamental questions on the genetic control of starch granule structure and function.

A Multi-stages Biosynthetic Pathway in Starch Granules Revealed by the Ultrastructure of Maize Mutant Starches

Our previous work indicated that starches containing B-type crystallites show low susceptibility to amylolysis and suggested that B-type crystallites have an effect on starch granule organisation. To elucidate granular ultrastructure, double wxae and aedu maize mutant starches containing A- (30 and 50% respectively) and B-type (70 and 50% respectively) crystallites were treated with porcine pancreatic alpha -amylase. The surface structure of the native and degraded starches was studied by scanning electron microscopy, and the internal ultrastructure by transmission electron microscopy after staining with PATAg reagents. The results confirm the influence of B-type crystallites on granule organisation and indicate that starches containing B-type crystallites show an amylolysis attack pattern with minor exocorrosion and major endocorrosion. The granule organisation of A- and B-type starches proposed is not consistent with an onion ring model1and may account for the different behaviour of these starches to amylolysis. Transmission electron microscopy showed that most native wxae and aedu starch granules are composed of a core with a classical alternating structure and a peripheral ring. The peripheral ring in wxae starch was ordered and resistant to amylolysis, whereas that of aedu was disordered and degradable. It is proposed that these two specific forms of granule organisation are attributable to variations in the enzymatic activities of specific starch synthesising enzymes during the course of starch biosynthesis.

ION CHANNELING STUDIES OF HETEROEPITAXIAL STRUCTURES FORMED BY MOLECULAR BEAM

Epitaxial growth of CaF 2 films onto Si(111)substrates and the subsequent growth of si or Ge films onto the CaF 2 /Si(111) structure have been conducted with heteroepitaxial structures of Si/CaF 2 /Si(111) or Ge/CaF 2 /Si(111), and then investigated by the Rutherford backscattering and ion channeling measurements. It is found that the Si film deposited on the CaF 2 layer consists of the crystallites of two kinds: one with the orientation either the same as that of silicon substrate (A type) or rotating 180°to the normal of the substrate surface (B type), indicating the mixture of A-and B-type crystallites in the top Si film. In the case of Si/CaF 2 /Si (111) structure the minimum yields of channeling along all directions are much higher than those in CaF 2 /Si (111) because the top silicon film are formed by A-and B-type crystallites and twinned. The misalignment of off-normal axes CaF 2 (110) (or ) relative to the substrate Si (or ) indicates the existence of strain at the CaF 2 -interface region. When Ge film was epitaxially grown onto the CaF 2 /Si(111), the above-mentioned A-and B-type mixture also exists in the top germanium film but the majority are the B-type component. Therefore, good quality of the hetero-structure Ge/CaF 2 /Si(111) can be prepared. However, since the mismatch of lattice constants between germanium and calcium fluoride is much larger than that between silicon and calcium fluoride, thus serious disorder exists within the Ge region at the interface between Ge and CaF 2 films.