Investigation of the link between first-order kinetic models of the in vitro digestion of native starches and the accompanying changes in their crystallinity and structure.

Starch is the main source of dietary energy for humans. In order to understand the mechanisms governing native starch in vitro digestion, digestion data for six starches [wheat, maize, (waxy) maize, rice, potato and pea] of different botanical sources were fitted with the most common first-order kinetic models, i.e. the single, sequential, parallel and combined models. Parallel and combined models provided the most accurate fits and showed that all starches studied except potato starch followed a biphasic in vitro digestion pattern. The biological relevance of the kinetic parameters was explored by determining changes in crystallinity and molecular structure of the undigested starch residues during in vitro digestion. While the crystallinity of the undigested potato starch residues did not change substantially, a respectively small and large decrease in their amylose content and chain length during in vitro digestion was observed, indicating that amylose was digested slightly preferentially over amylopectin in native starch. However, the molecular structure of the starch residues changed too slowly and/or only to an insufficient extent to relate it to the kinetic parameters of the digested fractions predicted by the models. Such parameters thus need to be interpreted with caution, as their biological relevance still needs to be proven.

Changes in overall digital structure, starch properties and moisture distribution reveal how the hardness of wheat noodles evolves under different cooking status.

To elucidate the relationship between the structural evolution of starch within noodles during cooking and the hardness, the panoramic and local microstructure of cooked noodles were quantitatively analyzed, and the structure of starch in noodles were measured. We found that in the case of starch within cooked noodles with a high degree of swelling, the quantitative analysis of each ring was sufficient to represent the structural differences. Changes occurring in starch inside noodles during cooking were not homogeneous. The structural modifications of starch in the outer ring were greater than in the inner ring along with the extension of cooking time. The main reason responsible for the high hardness was attributed to low swelling degree and high short-range order of starch in the center. Water migration from the periphery to the center of the noodles, which was closely related to the fine structure of amylopectin, determined the state of central starch. Wheat starch with more large amylopectin molecules and more long amylopectin chains could enhance the inhibition of water migration and decrease the swelling degree of starch in the center, in order to endow a high hardness to noodles. These results will be useful for the ingredients selection for the production of noodles with desirable quality. In addition, the analysis method established in this work promoted the realization of quantitative comparison of the cooked noodles microstructure, that is an effective tool to clarify the structural basis of macroscopic quality of noodles.

Potential use of other starch sources in the treatment of glycogen storage disease type Ia - an in vitro study.

BACKGROUND: Glycogen storage disease type Ia (GSD-Ia) is one of the most common hepatic GSD. Its treatment mainly consists of a diet including a high intake of slow-digestion carbohydrates such as raw cornstarch and the restriction of simple sugars. This enables the maintenance of euglycemia and prevents secondary metabolic disorders. Starch is a glucose polymer formed by amylose and amylopectin, which can be obtained from distinct sources. Although uncooked cornstarch has been successfully used in the treatment of GSD-Ia, it can lead to hyperglycemia and weight gain. in vitro andin vivo tests indicated that sweet manioc starch can be potentially used in the treatment of GSD-Ia. RESULTS: The moisture analysis revealed a variation from 10.3 to 12.8% in the sweet manioc starch samples, whereas the moisture content of uncooked cornstarch ranged from 7.3 to 11.1%. Quantifiable sugar was detected in 3/5 samples of sweet manioc starch and 1/3 samples of uncooked cornstarch. Notably, this uncooked cornstarch brand is widely employed in GSD-Ia treatment in Brazil. Products B and E had higher values of amylopectin and undetectable levels of sugars. A clinical trial is warranted to compare samples F and G and determine the impact of sugar trace in the same dietary source of starch. CONCLUSIONS: Collectively, the results demonstrated possible therapeutic alternatives for GSD-Ia in addition to traditional uncooked cornstarch.

Structures, gelatinization properties and enzyme hydrolyses of starches from transparent and floury grains of rices subjected to field natural extreme high temperature.

Three rice varieties underwent the field natural extreme high temperature (EHT) with daily average temperature over 30 °C from 21 to 89 days after sowing, and had transparent, chalky and floury grains. The structures, gelatinization properties and enzyme hydrolyses of starches from transparent and floury grains were investigated. Compared with control transparent grains, floury grains subjected to EHT markedly decreased the contents of amylose molecules, amylopectin A chains and amylopectin B1 chains and increased the contents of amylopectin B2 and B3+ chains and the average branch-chain length of amylopectin. Both transparent and floury grains had A-type starches, but floury grain starches exhibited higher relative crystallinity, gelatinization temperature, retrogradation and pasting viscosities than transparent grain starches. Floury grain starches had lower hydrolysis rates than transparent grain starches. Native starches were more resistant to digestion but gelatinized and retrograded starches were more prone to digestion in floury grains than in transparent grains.

Constructing an interaction in plant polyphenol-modified carbon fiber with amylopectin-based waterborne polyurethane sizing agent via hydrogen bonding to improve the interfacial performance of carbon fiber/nylon 6 composites.

The adhesive strength between the sizing agent and carbon fiber (CF) plays a crucial role in improving the interfacial properties of composites, while such a vital aspect has been consistently disregarded. In this study, a hyperbranched waterborne polyurethane (HWPU) sizing agent was synthesized from biogenetically raw materials including gallic acid, l-Lysine diisocyanate and amylopectin. Concurrently, hydrogen-bonded cross-linked network structures were established utilizing a botanical polyphenol tannin as coupling agent to effectively connect CF with HWPU. This meticulous process yielded CF/nylon 6 composites with improved properties and their mechanical characteristics were systematically investigated. The findings showcased a noteworthy boost in flexural strength and interlaminar shear strength (ILSS), showing enhancements of 54.6 % and 61.4 %, respectively, surpassing those of untreated CF. Furthermore, the interfacial shear strength (IFSS) test indicated a remarkable 70.3 % improvement. This approach presents a highly promising concept aimed at developing sustainable green waterborne polyurethane sizing agent and improving the interfacial performance of CF composite materials.

Highly stretchable, self-healing, antibacterial, conductive, and amylopectin-enhanced hydrogels with gallium droplets loading as strain sensors.

In this study, we address the challenge of developing highly conductive hydrogels with enhanced stretchability for use in wearable sensors, which are critical for the precise detection of human motion and subtle physiological strains. Our novel approach utilizes amylopectin, a biopolymer, for the uniform integration of liquid metal gallium into the hydrogel matrix. This integration results in a conductive hydrogel characterized by remarkable elasticity (up to 7100 % extensibility) and superior electrical conductance (Gauge Factor = 31.4), coupled with a minimal detection limit of less than 0.1 % and exceptional durability over 5000 cycles. The hydrogel demonstrates significant antibacterial activity, inhibiting microbial growth in moist environments, thus enhancing its applicability in medical settings. Employing a synthesis process that involves ambient condition polymerization of acrylic acid, facilitated by a hydrophobic associative framework, this hydrogel stands out for its rapid gelation and robust mechanical properties. The potential applications of this hydrogel extend beyond wearable sensors, promising advancements in human-computer interaction through technologies like wireless actuation of robotic systems. This study not only introduces a viable material for current wearable technologies but also sets a foundation for future innovations in bio-compatible sensors and interactive devices.

Molecular changes and interactions of wheat flour biopolymers during bread-making: Implications to upcycle bread waste into bioplastics.

This study aims to understand the molecular and supramolecular transformations of wheat endosperm biopolymers during bread-making, and their implications to fabricate self-standing films from stale white bread. A reduction in the Mw of amylopectin (51.8 × 106 vs 425.1 × 106 g/mol) and water extractable arabinoxylans WEAX (1.79 × 105 vs 7.63 × 105 g/mol), and a decrease in amylose length (245 vs 748 glucose units) was observed after bread-baking. The chain length distribution of amylopectin and the arabinose-to-xylose (A/X) ratio of WEAX remained unaffected during bread-making, suggesting that heat- or/and shear-induced chain scission is the mechanism responsible for molecular fragmentation. Bread-making also resulted in more insoluble cell wall residue, featured by water unextractable arabinoxylan of lower A/X and Mw, along with the formation of a gluten network. Flexible and transparent films with good light-blocking performance (<30 % transmittance) and DPPH-radical scavenging capacity (~8.5 %) were successfully developed from bread and flour. Bread films exhibited lower hygroscopicity, tensile strength (2.7 vs 8.5 MPa) and elastic modulus (67 vs 501 MPa) than flour films, while having a 6-fold higher elongation at break (10.0 vs 61.2 %). This study provides insights into the changes in wheat biopolymers during bread-making and sets a precedent for using stale bread as composite polymeric materials.

Dynamic development of changes in multi-scale structure during grain filling affect gelatinization properties of rice starch.

Rice was collected over the entire grain filling period (about 40 days) to explore the multi-structure evolution and gelatinization behavior changes of starch. During the early stage (DAA 6-14), the significant reduction in lamellar repeat distance (10.04 to 9.68 nm) and relative crystallinity (26.6 % to 22.7 %) was due to initial rapid accumulation of amylose (from 9.38 % to 14.05 %) and short amylopectin chains. Meanwhile, the decreased proportion of aggregation structure resulted in a decrease in the gelatinization temperature and a narrowed range of gelatinization temperature also indicated an increase in homogeneity as starch matured. Gelatinization enthalpy was mainly controlled by aggregation structure, which was negatively and positively related to the amylose content and the degree of order respectively. Peak viscosity of starch pasting increased and reached a maximum (924 cP) at DAA-21 due to larger granule size. Amylose and short amylopectin chains with degree of polymerization 6-12 showed positive and negative correlation with short-term retrogradation ability (setback value) respectively. The dynamics of different scale structure during grain filling had varying degrees of impact on gelatinization properties.

Insights into starch synthesis and amino acid composition of common buckwheat in response to phosphate fertilizer management strategies.

To investigate the response and the regulatory mechanism of common buckwheat starch, amylose, and amylopectin biosynthesis to P management strategies, field experiments were conducted in 2021 and 2022 using three phosphorus (P) levels. Results revealed that the application of 75 kg hm-2 phosphate fertilizer significantly enhanced amylopectin and total starch content in common buckwheat, leading to improved grain weight and starch yield, and decreased starch granule size. The number of upregulated differentially expressed proteins induced by phosphate fertilizer increased with the application rate, with 56 proteins identified as shared differential proteins between different P levels, primarily associated with carbohydrate and amino acid metabolism. Phosphate fertilizer inhibited amylose synthesis by downregulating granule-bound starch synthase protein expression and promoted amylopectin accumulation by upregulating 1,4-alpha-glucan branching enzyme and starch synthase proteins expression. Additionally, Phosphate fertilizer primarily promoted the accumulation of hydrophobic and essential amino acids. These findings elucidate the mechanism of P-induced starch accumulation and offer insights into phosphate fertilizer management and high-quality cultivation of common buckwheat.

The effects of chain-length distributions on starch-related properties in waxy rices.

Normal rice starch consists of amylopectin and amylose, whose relative amounts and chain-length distributions (CLDs) are major determinants of the digestibility and rheology of cooked rice, and are related to metabolic health and consumer preference. Here, the mechanism of how molecular structural features of pure amylopectin (waxy) starches affect starch properties was explored. Following debranching, chain-length distributions of seven waxy varieties were measured using size-exclusion chromatography, and parameterized using biosynthesis-based models, which involve breaking up the chain-length distribution into contributions from five enzyme sets covering overlapping ranges of chain length; structure-property correlations involving the fifth set were found to be statistically significant. Digestibility was measured in vitro, and parameters for the slower and longer digestion phase quantified using non-linear least-squares fitting. The coefficient for the significant correlation involving amylopectin fine structure for the fifth set was -0.903, while the amounts of amylopectin short and long chains were found to dominate breakdown viscosity (correlation coefficients 0.801 and - 0.911, respectively). This provides a methodology for finding or developing healthier starch in terms of lower digestion rate, while also having acceptable palatability. As rice breeders can to some extent control CLDs, this can help the development of waxy rices with improved properties.

Multi-scale structural insights on starch digestibility of instant rice.

Multi-scale structures were investigated to understand starch digestibility of instant rice. A wide range of maximum starch digested ratio, up to about 20%, was observed among instant rice prepared from different rice varieties. Instant rice with a smooth and densely packed cross-section showed slower starch digestibility than those with a porous and loosely packed structure. All samples displayed B + V type crystallinity, with V-type crystallinity negatively correlating with maximum starch digested percentage. After digestion, starch chain-length distributions were significantly altered: rapidly digested starch comprised long amylose and short amylopectin chains, while slowly digested starch comprised chains with a peak degree of polymerization (DP) around 130. These results indicate that instant rice with a compact microstructure, high V-type crystallinity, and DP 130 fractions during digestion can reduce starch digestibility. This study provides insights for food industry to develop instant rice products with slow starch digestibility, potentially improving human health.

Mild alkali treatment alters structure and properties of maize starch: The potential role of alkali in starch chemical modification.

Normal and waxy maize starches were treated with mild alkali treatment (pH 8.5, 9.9, 11.3) in two temperature-time combinations (25 °C for 1 h and 50 °C for 18 h) to investigate the effect on starch structure and properties. Mild alkali treatment partly removed the starch granule-associated proteins and lipids of normal (from 0.31 % to 0.24 % and from 0.77 % to 0.55 %, respectively) and waxy maize starches (from 0.22 % to 0.18 % and from 0.24 % to 0.15 %, respectively). Gelatinization enthalpy of waxy maize starch increased with alkali treatment from 16.20 J·g-1 to 21.95 J·g-1, indicating that amylopectin (AP) rearrangement and AP-AP double helices formation might occur. But amylose could inhibit these effects by restricting mobility of amylopectin, and no such changes occurred for normal maize starch. Alkali treatment decreased gelatinization temperature and increased peak and final viscosity. Alkali treatment decreased trough viscosity and increased setback of normal maize starch. The hydrothermal treatment promoted the effect of alkali, attributed to the more rapid molecular motion at higher temperature. Normal and waxy starches showed different changes after alkali treatment, indicating that amylose played an important role in controlling the effect of alkali and hydrothermal treatment, primarily as an obstructer of amylopectin rearrangement in mild alkali treatment.

Insight to starch retrogradation through fine structure models: A review.

The retrogradation of starch is crucial for the texture and nutritional value of starchy foods products. There is mounting evidence highlighting the significant impact of starch's fine structures on starch retrogradation. Because of the complexity of starch fine structure, it is a formidable challenge to study the structure-property relationship of starch retrogradation. Several models have been proposed over the years to facilitate understanding of starch structure. In this review, from the perspective of starch models, the intricate structure-property relationship is sorted into the correlation between different types of structural parameters and starch retrogradation performance. Amylopectin B chains with DP 24-36 and DP ≥36 exhibit a higher tendency to form ordered crystalline structures, which promotes starch retrogradation. The chains with DP 6-12 mainly inhibit starch retrogradation. Based on the building block backbone model, a longer inter-block chain length (IB-CL) enhances the realignment and reordering of starch. The mathematical parameterization model reveals a positive correlation between amylopectin medium chains, amylose short chains, and amylose long chains with starch retrogradation. The review is structured according to starch models; this contributes to a clear and comprehensive elucidation of the structure-property relationship, thereby providing valuable references for the selection and utilization of starch.

The importance of starch chain-length distribution for in vitro digestion of ungelatinized and retrograded foxtail millet starch.

The digestibility of ungelatinized, short-term retrograded and long-term retrograded starch from foxtail millet was investigated and correlated with starch chain length distributions (CLDs). Some variations in starch CLDs of different varieties were obtained. Huangjingu and Zhonggu 9 had higher average chain lengths of debranched starch and lower average chain length ratios of amylopectin and amylose than Dajinmiao and Jigu 168. Compared to ungelatinized starch, retrogradation significantly increased the estimated glycemic index (eGI), whereas significantly decreased the resistant starch (RS). In contrast, long-term retrograded starches have lower eGI (93.33-97.37) and higher RS (8.04-14.55%) than short-term retrograded starch. PCA and correlation analysis showed that amylopectin with higher amounts of long chains and longer long chains contributed to reduced digestibility in ungelatinized starch. Both amylose and amylopectin CLDs were important for the digestibility of retrograded starch. This study helps a better understanding of the interaction of starch CLDs and digestibility during retrogradation.

Starch exploration in Nelumbo nucifera and Trapa natans: Understanding physicochemical and functional variations for future perspectives.

The current research emphasis on identifying unconventional starch sources with varied properties to broaden industrial applications. The focus of this research is on the search for alternative sources of starch with different properties in order to expand their potential use in the industrial sector. Starch was extracted from Trapa natans and Nelumbo nucifera and analyzed for their physicochemical and functional properties. They had similar protein (0.35 %) and ash contents, but the nitrogen-free extract was slightly higher in Nelumbo starch (87.58 %) than in Trapa starch (85.09 %). The amylose and amylopectin contents were 23.89 % and 76.11 % in Trapa starch and 15.70 % and 84.30 % in Nelumbo starch, respectively. Fourier-transform infrared spectroscopy identified both as polysaccharides. The characteristic absorption bands assigned to the stretching of OH groups (3324 cm-1; 3280 cm-1), the asymmetric and symmetric stretching of aliphatic chain groups (2925 cm-1; 2854 cm-1), the bending vibration of CHO groups (1149 cm-1; 1144 cm-1) were present in both the starch samples, with the exception of CH3 which could not be detected in Trapa natans starch. X-ray diffraction confirmed hexagonal and orthorhombic crystal structures in Nelumbo nucifera and Trapa natans starch. Scanning electron microscopy revealed a smooth oval and a rough cuboidal shape for lotus and chestnut starch, respectively. Rheological analysis showed that both starch solutions exhibited gel behavior, with Trapa showing stronger gel behavior after the crossover point. These results suggest potential applications in various industries, including the food industry and beyond.

Starch chain-length distributions affect the processing and digestion characteristics of proso millet starch.

Starch chain-length distributions play a key role in regulating the processing and digestion characteristics of proso millet starch. Waxy proso millet starch has higher endothermic enthalpy (13.06-16.73 J/g) owing to its higher relative crystallinity (27.83%-32.04%), while nonwaxy proso millet starch has lower peak viscosity (1.0630-1.1930 Pa∙s) and stronger viscoelasticity owing to its higher amylose content (21.72%-24.34%). Non-waxy proso millet starch exhibited two different digestion phases and its resistant starch content (18.37%-20.80%) was higher than waxy proso millet starch. Correlation analysis showed proso millet starch with longer amylopectin B1 chains and more amylopectin B2 chains exhibited excellent thermal ability and retrograde resistance, whereas proso millet starch with shorter and more amylose medium/long-chains not only reduced the digestion rate and increased the resistant starch content but also exhibited stronger viscoelasticity and excellent retrogradation properties. These results could provide more insights into efficient utilization of proso millet starch.

Insights into wheat-starch biosynthesis from two-dimensional macromolecular structure.

Starch structure is often characterized by the chain-length distribution (CLD) of the linear molecules formed by breaking each branch-point. More information can be obtained by expanding into a second dimension: in the present case, the total undebranched-molecule size. This enables answers to questions unobtainable by considering only one variable. The questions considered here are: (i) are the events independent which control total size and CLD, and (ii) do ultra-long amylopectin (AP) chains exist (these chains cannot be distinguished from amylose chains using simple size separation). This was applied here to characterize the structures of one normal (RS01) wheat and two high-amylose (AM) mutant wheats (an SBEIIa knockout and an SBEIIa and SBEIIb knockout). Absolute ethanol was used to precipitate collected fractions, then size-exclusion chromatography for total molecular size and for the size of branches. The SBEIIa and SBEIIb mutations significantly increased AM and IC contents and chain length. The 2D plots indicated the presence of small but significant amounts of long-chain amylopectin, and the asymmetry of these plots shows that the corresponding mechanisms share some causal effects. These results could be used to develop plants producing improved starches, because different ranges of the chain-length distribution contribute independently to functional properties.

Insights into multiscale structure and digestive characteristic of starch from two cultivars of chestnut during kernel development.

Multiscale structure and digestive characteristic of starch during kernel development of Castanea henryi ('Jinzhui' (YS) and 'Baiyan No.1' (WS)) were investigated in this study. Structural analysis revealed that the surface of starch granules became smooth, the amylopectin content decreased (from 71.32 % to 70.47 %, from 71.44 % to 68.37 %, respectively), the chain length distribution of amylopectin reduced (the proportion of B1 chain decreased from 52.35 % to 50.60 %, from 52.22 % to 50.59 %, respectively) while the amorphous and semi-crystalline lamellae of starch increased during development, which was consistent with the decreasing relative crystallinity (from 28.79 % to 24.11 %, from 29.57 % to 23.66 %, respectively) and short-range ordering degree. The degradation of ordered structure further resulted in the increase of digestibility, especially in the late developmental stage, supported by a significant decrease of resistant starch content (from 70.21 % to 61.70 % and from 73.58 % to 58.86 %, respectively). Transcriptome analysis and RT-qPCR were performed to explore the possible molecular mechanisms affecting starch structure. The high expression of several key genes including AGPase, GBSS, SBE, SSS, ISA and PUL in late development stage might be the reason of structural changes during development. The results provided valuable information for starch accumulation during kernel development of Castanea henryi.

Molecular Basis of the Granular Characteristics of Small-Granule Starch: A Comparative Study.

Small-granule starches (SGSs) have technological advantages over starches of conventional sizes for many applications. The study compared the granular characteristics of three SGSs (from amaranth, quinoa, and taro) with those of maize and potato starches and revealed their molecular basis. The results indicated that the supramolecular architecture of starch granules was not necessarily correlated with granule size. Acid hydrolysis of amaranth and quinoa starches was fast due to not only their small granule sizes but also the defects in the supramolecular structure, to which short external and internal chain lengths of amaranth and quinoa amylopectins contributed. By comparison, the granular architecture of taro starch granules was more stable partly due to the longer external chain length of taro amylopectin. Comparison of the molecular composition of branched subunits (released by using α-amylase of Bacillus amyloliquefaciens) in amylopectins and that in lintnerized starches suggested a significant heterogeneous degradation of amaranth and quinoa starches at supramolecular levels.

Effects of different extrusion temperatures on the physicochemical properties, edible quality and digestive attributes of multigrain reconstituted rice.

Multigrain reconstituted rice, as a nutritious and convenient staple, holds considerable promise for the food industry. Furthermore, highland barley, corn, and other coarse cereals are distinguished by their low glycemic index (GI), rendering them effective in mitigating postprandial blood glucose levels, thereby underscoring their beneficial physiological impact. This study investigated the impact of extrusion temperature on the physicochemical properties, edible quality, and digestibility of multigrain reconstituted rice. The morphology revealed that starch particles that are not fully gelatinized in multigrain reconstituted rice are observed at an extrusion temperature range of 60 °C-90 °C. As the extrusion temperature increased, the degree of gelatinization (DG) increased, while the contents of water, protein, total starch, and amylopectin decreased substantially. Concurrently, the relative crystallinity, orderliness of starch, and heat absorption enthalpy (ΔH) decreased significantly, and water absorption (WAI) and water solubility (WSI) increased markedly. Regarding edible quality, sensory evaluation displayed an initial increase followed by a decrease. In terms of digestibility, the estimated glycemic index (eGI) increased from 61.10 to 70.81, and the GI increased from 60.41 to 75.33. In addition, the DG was significantly correlated with both eGI (r = 0.886**) and GI (r = 0.947**). The results indicated that the ideal extrusion temperature for multigrain reconstituted rice was 90 °C. The findings underscored the pivotal role of optimal extrusion temperatures in the production of multigrain reconstituted rice, which features low GI and high nutritional quality.