Structural, physicochemical, and digestive properties of enzymatic debranched rice starch modified by phenolic compounds with varying structures.

The physicochemical properties of starch and phenolic acid (PA) complexes largely depend on the effect of non-covalent interactions on the microstructure of starch. However, whether there are differences and commonalities in the interactions between various types of PAs and starch remains unclear. The physicochemical properties and digestive characteristics of the complexes were investigated by pre-gelatinization of 16 structurally different PAs and pullulanase-modified rice starches screened. FT-IR and XRD results revealed that PA complexed with debranched rice starch (DRS) through hydrogen bonding and hydrophobic interaction. Benzoic/phenylacetic acid with polyhydroxy groups could enter the helical cavities of the starch chains to promote the formation of V-shaped crystals, and cinnamic acid with p-hydroxyl structure acted between starch chains in a bridging manner, both of which increased the relative crystallinity of DRS, with DRS-ellagic acid increasing to 20.03 %. The digestion and hydrolysis results indicated that the acidification and methoxylation of PA synergistically decreased the enzyme activity leading to a decrease in the digestibility of the complexes, and the resistant starch content of the DRS-vanillic acid complexes increased from 28.27 % to 71.67 %. Therefore, the selection of structurally appropriate PAs can be used for the targeted preparation of starch-based foods and materials.

Structural Factors That Determine the Amylolytic Properties of Starch-Lipid Complexes.

Structural factors that determine the amylolysis of starch-lipid complexes have remained unclear. Understanding the relationship between the structure and amylolysis of starch-lipid complexes is important for the design and preparation of complexes with predictable digestibility. In this study, the multiscale structures and amylolytic properties of complexes formed under different conditions between debranched high-amylose starch (DHAMS) and lauric, myristic, palmitic, and stearic acids were investigated. Higher complexing temperatures facilitated the formation of DHAMS-fatty acid (FA) complexes, especially the more stable type II crystallites. Longer complexing times also promoted the formation of complexes and the type II crystallites, except for DHAMS-lauric acid (LA). Molecular dynamics simulations showed that the binding free energy for the formation of DHAMS-LA complexes (10 kJ/mol) was lower than those for the other three DHAMS-FA complexes (20-50 kJ/mol), accounting for the lower stability of DHAMS-LA complexes at longer complexing times. The rate and extent of enzymatic digestion of the DHAMS-FA complexes were much lower in comparison to those of gelatinized HAMS. Correlation analyses showed that the rate and extent of enzymic digestion of DHAMS-FA complexes were mainly determined by the degree of crystallite perfection of the complexes.

Rheological, thermal, and structural properties of heat-induced gluten gel: Effects of starch with varying degrees of debranching.

This study evaluated the effects of starch with varying degree of debranching on the rheological, thermal, and structural properties of heat-induced gluten gel. As the duration of starch debranching treatment increased from 0 to 8 h, the viscoelasticity of the gel containing debranched starch (DBS) improved. Compared with the gluten gel (G), the gel strength of the G + DBS (8 h) sample increased by 65.2 %. The degradation temperature of gluten was minimally affected by DBS, while the weight loss rate increased by 4.4 %. Furthermore, the α-helical structure of gluten decreased, concomitant with an increase in ß-sheet content. Notably, DBS treated for 8 h exhibited more hydrogen bonds with the tyrosine of gluten and triggered disulfide bridge conformation to transition from g-g-g to t-g-g, thereby reducing the stability of the molecular conformation of gluten proteins, as evidenced by the decreased height and width of the molecular chains observed in atomic force microscopy images. Overall, the composite gel structure induced by DBS exhibited a more continuous and homogeneous owing to the improved compatibility between DBS and gluten proteins, favoring the formation of a robust gel. These findings provide valuable insights for utilizing DBS to enhance gluten gel properties.

Characteristics of Citrate-Esterified Starch and Enzymatically Debranched Starch and Their Effects on Diabetic Mice.

Chickpea has significant benefits as an adjuvant treatment for type 2 diabetes mellitus (T2DM). The properties of chickpea resistant starches (RSs) and their abilities to reduce T2DM symptoms and control intestinal flora were investigated. The RS content in citrate-esterified starch (CCS; 74.18%) was greater than that in pullulanase-modified starch (enzymatically debranched starch (EDS); 38.87%). Compared with those of native chickpea starch, there were noticeable changes in the granular structure and morphology of the two modified starches. The CCS showed surface cracking and aggregation. The EDS particles exhibited irregular layered structures. The expansion force of the modified starches decreased. The CCS and EDS could successfully lower blood glucose, regulate lipid metabolism, lower the levels of total cholesterol (TC) and low-density lipoprotein cholesterol (LDL-C), reduce the expressions of interleukin-6 (IL-6) and interleuki n-10 (IL-10), and decrease diabetes-related liver damage. Moreover, the CCS and EDS altered the intestinal flora makeup in mice with T2DM. The abundance of Bacteroidota increased. Both types of chickpea RSs exhibited significant hypoglycaemic and hypolipidaemic effects, contributing to the reduction in inflammatory levels and the improvement in gut microbiota balance.

Hypoglycemic effect of recrystallized resistant starch on high-fat diet- and streptozotocin-induced type 2 diabetic mice via gut microbiota modulation.

The hypoglycemic effects of two recrystallized resistant starches, A-type (ARS) and B-type (BRS), were investigated in type 2 diabetic mice. Mice were treated with low-, medium-, or high-dose ARS, high-dose BRS, or high-dose ARS combined with BRS (ABRS). After 10 weeks of continuous intervention, the medium-dose ARS group showed a significant reduction in fasting blood glucose, area under the curve of glucose, triglyceride (P < 0.01), and low-density lipoprotein (P < 0.05) levels compared to the model group and an increase in high-density lipoprotein levels (P < 0.01). The peptide YY and glucagon-like peptide-1 levels in the high-dose ARS, BRS, and ABRS groups and the butyric acid yield in the medium-dose ARS and BRS groups were significantly increased (P < 0.01) compared to those in the model group. Medium- and high-dose ARS intervention efficiently increased the relative abundance of beneficial Bacteroidetes, Lactobacillus, Lachnospiraceae_NK4A136_group, and Faecalibaculum, and lowered the ratio of Firmicutes to Bacteroidetes. Overall, ARS exhibited greater advantages than BRS in lowering blood sugar levels.

Novel and safe debranched starch-zinc complexes with endoconcave structure as zinc supplements.

Zinc deficiency is a serious risk to human health and growth, especially in children. The development of zinc supplements can effectively reduce this harm. Here, a series of debranched starch­zinc complexes (DS-Zn) were prepared, whose zinc complexation was inversely proportional to the amylopectin content in the debranched starch (DS). The physicochemical properties of DS-Zn were characterized using the conductivity, XRD, iodine staining and thermogravimetry. Combined with XPS, solid-state 13C NMR and IR, it was elucidated that the structure of DS-Zn is endoconcave structure with 2-O and 3-O of DS on the inner side and 6-O of DS on the outer side, where zinc is located. The DS-Zn exhibits good biosafety including blood, cellular and mutagenicity. In vitro simulations of digestion and zinc-deficient cellular models showed that DS-Zn was more tolerant to the gastrointestinal environment and more effective in zinc supplementation (increased by 33 %) than inorganic zinc supplements. Utilizing the compressibility of starch, DS-Zn was prepared as a more palatable oral cartoon tablet for children. This study will provide important support to advance the development and application of novel starch-based zinc nutritional supplements.

Recrystallized resistant starch by encapsulation with konjac glucomannan: Structural changes, digestibility, and its effect on glucose response and short-term satiety in mice.

The effects of the structure and digestibility of konjac glucomannan (KGM)-recrystallized resistant starch complex (KRS3) on the glycemic response and short-term satiety in mice were investigated. KRS3 samples were prepared by recrystallized debranched starch (RS3) at 50 °C, and then combined with KGM. The RS3 and KRS3 samples displayed an A-type pattern and maintained peak temperature values above 110 °C. With an increase in KGM, the swelling power and apparent viscosity of KRS3 increased. The results of in vitro and in vivo digestion revealed that KRS3 with a resistant starch content ranging from 69.4 % to 78.8 % could effectively maintain postprandial blood glucose levels. KRS3, particularly with 0.5 % KGM, slowed gastric emptying of mice from 82.7 % to 36.6 % and intestinal propulsion rate from 60.9 % to 35.3 %, resulting in strong satiety. RS3 combined with KGM could serve as a new approach to develop RS3 based foods with low glycemic responses and high-satiety.

A novel method for obtaining high amylose starch fractions from debranched starch.

High amylose starch shows wide applications in food and non-food-based industries. Traditional complex-precipitation approach for the amylose fractionation required a large volume of organic reagents and was possibly risky for food safety. The object of this work was to establish a novel method to obtain starch fractions rich in amylose from debranch starch through repeated short-term retrogradation and centrifugation. Four starch fractions were obtained with the amylose content of 52.08% (C1), 62.28% (C2), 63.58% (C3), and 64.74% (C4). The thermograms of samples displayed that multiple endothermic peaks were detected in C1 and C2 and only one endothermic peak with melting temperature over 120 °C were observed in C3 and C4, indicating their differences in retrogradation behavior. The chain length distribution results of sample exhibited that C1 and C2 contained more short chains (DP ≤ 24), while C3 and C4 consisted of mainly long chains (DP ≥ 25). Accordingly, the differences in fine structures could provide more choices for these fractionated high amylose starch to utilize in practical applications.

A dual physical crosslinking starch-based hydrogel exhibiting high strength, fatigue resistance, excellent biocompatibility, and biodegradability.

Simultaneous realization of high strength, toughness, and fatigue resistance in natural starch-based hydrogel materials is challenging. A facile method of in situ self-assembly and a freeze-thaw cycle was proposed to construct double-network nanocomposite hydrogels of debranched corn starch/polyvinyl alcohol (Gels). Rheology, chemical structure, microstructure, and mechanical property of Gels were investigated. Notably, short linear starch chains were self-assembled into nanoparticles and subsequently into 3D microaggregates, which were tightly wrapped by starch and PVA network. Compared with corn starch single-network and starch/PVA double-network hydrogels, the Gels reached up to a higher compressive strength (ca. 1095.7 kPa), and then achieved to ∼20-30-fold improvement in compressive strength. Recovery efficiency exceeded 85% after 20 successive compression loading-unloading cycle tests. Furthermore, the Gels had good biocompatibility to L929 cells. Hence, the high-performance starch hydrogels are thought to serve as a biodegradable and biocompatible material to replace synthetic hydrogels, which can broaden their application fields.

Recrystallized Resistant Starch: Structural Changes in the Stomach, Duodenum, and Ileum and the Impact on Blood Glucose and Intestinal Microbiome in Mice.

The structure and properties of resistant starch (RS) and its digestive products were assessed in mice. Digestion of recrystallized (group RS3, including RS3a and RS3b) and control RS (RS2, RS4, and RS5) in the stomach, duodenum, and ileum of mice was systematically analyzed along with in vivo digestive degradation of RS3. RS3a and RS3b significantly reduced the release of blood glucose. During in vivo digestion, the proportion of ultrashort and A chains in the RS3a and RS3b digestive residues gradually increased, whereas the proportion of B1 and B2 chains gradually reduced. B3+ chain proportions did not change. The final digestive residues in the ileum (RS3a-I90 and RS3b-I90) maintained a high proportion of suitable chain length, accounting for more than 60%. The crystalline structure of RS3a-I90 was weakened, indicating the hydrolysis of partial crystal structure. In comparison, RS3b-I90 maintained an orderly crystalline structure, indicating its higher resistance to enzymatic hydrolysis. In vivo experiments showed that RS could maintain the normal growth of mice and effectively control weight gain. RS3a significantly increased the concentrations of acetic, propionic, and butyric acids, while reducing the abundance of Firmicutes to Bacteroidetes ratio, further confirming the benefits of RS3 in gastrointestinal health.

Impact of de-branched starch molecules and fatty acid complexes on the attenuation of ageing-induced cognitive impairment.

BACKGROUND: Ageing and associated cognitive impairments are becoming serious issues around the world. In this study, the physiological properties of three kinds of complexes of fatty acid (capric, stearic and oleic acid, respectively) and de-branched starch molecules were investigated via a d-galactose-induced ageing model. This study revealed differences in the regulation of cognitive impairment and brain damage following intervention of different complexes, which might highlight a potent approach for the prevention of this chronic disease. RESULTS: Data indicated that three complexes improved response time and cognitive function and the bio-parameter markers associated with oxidative stress in ageing rats. Among them, the complexes prepared from de-branched starch-oleic acid showed a greater improvement compared to others. In addition, de-branched starch-capric acid complex showed a higher improvement in the morphology of colon cells and hippocampal neuronal cells. The consumption of de-branched starch-capric acid and -oleic acid complexes generated more short-chain fatty acids in the gut. More importantly, the complexation of de-branched starch with either caprate or stearate enhanced gut Akkermansia. Therefore, it was proposed that the richness in Akkermansia and gut metabolites might be associated with reduced damage of the hippocampal neuronal cells induced by the ageing progress. Moreover, the AMPK (AMP-activated protein kinase) pathway was activated in liver in de-branched starch-capric acid complex diet. In summary, de-branched starch-capric acid complex exhibited a greater effect on the attenuation of ageing-induced cognitive impairment. CONCLUSION: This study might highlight a new approach for intervening in the cognitive impairment during the ageing progress via a food supply. © 2023 Society of Chemical Industry.

Multiscale structure and precipitation mechanism of debranched starch precipitated by different alcohols.

Alcohol solution is a cheap, simple, and effective precipitating solvent frequently used for separating debranched starch (DBS), yet little is known about the precipitation mechanism of DBS by different alcohols. This study precipitated DBS from pullulanase-hydrolyzed starch using ethanol, n-butanol, and isopentanol. The multiscale structures of DBS were characterized, including chain length, single/double helix, and crystalline. The chain conformation and precipitation mechanism of DBS in different alcohols was investigated using molecular dynamics (MD) simulation. DBS precipitated by n-butanol contained the largest proportion of short chain (DP6-24, 83.2 %), the highest V-type crystallinity (21.1 %), and the largest single-helix content (24.7 %). A single helix conformation of DBS chain was determined in alcohols, where alcohol molecules entered the helix cavity. Intra/inter-molecular hydrogen bonds stabilized the helix, with a large number of hydrogen bonds leading to strong molecular interaction and stable helical structure. The solvent accessible surface area of DBS chain decreased by 7.88-19.32 % in alcohols, and the radial distribution function revealed that the first solvent layer of DBS chain at 0.29 nm was closely related to hydrogen bonding. This study provides a basis for the choice of precipitation solvent for preparing DBS with different chain lengths and physicochemical properties.

An investigation into structural properties and stability of debranched starch-lycopene inclusion complexes with different branching degrees.

Debranched starch (DBS) has great probability as carrier for bioactive ingredients, but effects of branching degree (DB) on the complex formation of starch remain unclear. This study investigated the potential of DBS with different DB to load lycopene and characterized the structural properties of inclusion complexes. Glutinous rice starch was debranched to get DBS with different molecular weights, where DBS with a branching degree of 11.42 % had the greatest encapsulation efficiency (64.81 %). SEM, particle size, and zeta-potential results showed that the complexes form stable spherical crystals through electrostatic interactions. The structures of complexes were resolved by FTIR, XRD, TGA, and 13C CP/MAS NMR analytical techniques, indicating that lycopene can be loaded on DBS by the self-assembly through hydrophobic and hydrogen bonding interactions. Degradation experiments revealed that retention of complexes was significantly higher than the unencapsulated one. Our study reveals the structural features of the complex between DBS and lycopene, providing theoretical guidance for developing and producing novel nutraceuticals.

Preparation and characterization of debranched starches: Influence of botanical source and debranching time.

The influence of botanical source (waxy corn, glutinous rice, tapioca and potato), either based on crystallization or morphology, and the debranching time (6-48 h) on the physicochemical properties of debranched starches (DBSs) were systematically investigated. The divergence of depolymerization among different botanical sources within same hydrolysis time suggested that the debranching treatment was not only depending on the molecular profile and crystalline structure, but also related with the granular size and morphology of native starches. Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) suggested that long-term debranching reaction produced DBSs with improved degree of crystallization and reduced iodine binding capacity. Simulated in-vitro digestion assay showed that the proportion of digestive fractions from different botanical originated DBSs differed greatly. Additionally, prolonging the debranching time yielded increased level of resistant starch. The study may provide guidance for exploring DBSs with various molecular weight to fulfill their tailored applications.

Debranched waxy maize resistant dextrin: Synthesis, ethanol fractionation, crystallization, and characterization.

Waxy maize (Zea mays L.) dextrins (WMD), prepared by enzymatic debranching, were fractionated through precipitation in different concentrations of aqueous ethanol (50 %, 60 %, and 80 %). The fractionated WMDs were then crystallized at 4 °C or 50 °C for 2 days to prepare resistant dextrins (RD). Recovery yield, chain distribution, crystalline structure, thermal transition, and in vitro digestibility of the fractionated/crystallized WMDs were evaluated. Crystallization at 4 °C resulted in higher yields (>90 %) than that at 50 °C, regardless of the fractionation condition. The chain profile of the dextrins recovered at different temperatures appeared similar, but the longer chains had a greater tendency to associate. Crystal arrangement (A- or B-type) depended on the fractionation and crystallization conditions. Most crystals showed a typical B-type arrangement, except for the crystals prepared at 50 °C with 80 % ethanol (A-type). The enzyme resistance ranged from 49.9 % to 92.4 % depending on the fractionation and crystallization conditions.

Dual-modified starch nanoparticles containing aromatic systems with highly efficient encapsulation of curcumin and their antibacterial applications.

A series of cinnamic acid (CA)-esterified debranched starch (CDS) containing aromatic systems were prepared and successfully fabricated as nanoparticles to encapsulate curcumin by taking advantage of the additional π-π interactions provided from CA. The CDS nanoparticles (CDS NPs) have good dispersion (polydispersity index of 0.124-0.314) and sizes range of 130-330 nm. The excellent biosafety of CDS NPs was demonstrated by hemolysis, cytotoxicity and mutagenicity assays. Efficient encapsulation (LC = 26.86 %) and sustained release of curcumin were achieved, and the curcumin-encapsulated CDS NPs (CDS-Cur NPs) increased 266-fold water solubility and 2.3-6.5-fold photothermal stability for curcumin, compared to free curcumin. Functional studies showed that CDS-Cur NPs exhibited superior biofilm scavenging ability, with a 2-4.3-fold improvement compared to free curcumin. In addition, CDS-Cur NPs also exhibited far superior antibacterial effects than free curcumin in a bacteriostatic food model of chicken breast. This study not only provides a new scheme for the efficient loading of curcumin, but also provides new ideas for the usage of starch-based materials in antibacterial applications.

Mesona chinensis polysaccharide accelerates the short-term retrogradation of debranched waxy corn starch.

The effect of non-starch polysaccharides on the structural and functional properties of native starch have been extensively studied. However, the effect of non-starch polysaccharides on the structural characteristics of debranched starch, a kind of enzymatic modified starch, remains unclear. The aim of this study is to investigate the effects of Mesona chinensis polysaccharide (MP) on starch retrogradation and structural properties of debranched waxy corn starch (DWS). The results showed that only appropriate addition of MP (0.5 or 1%) can effectively promote the short-term retrogradation of DWS, while excessive MP (3 or 5%) had a negative effect. Gel hardness results revealed that the short-term retrogradation (24 h) of DWS could be divided into two phases. The retrogradation of DWS-MP gels mainly occurred at first stage (0-4 h), which was demonstrated by the rapid increase of gel hardness and relative crystallinity in this stage. In the second stage (4-24 h), DWS-MP gels were more likely to undergo the aggregation of starch granules as proved by SEM and particle size results. The degree of short-range ordered decreased during the total retrogradation stage. Overall, this work aims to provide an insight into the effect of non-starch polysaccharides on the short-term retrogradation of DWS.

Preparation of rutin-loaded microparticles by debranched lentil starch-based wall materials: Structure, morphology and in vitro release behavior.

Different treatments of autoclaving, pullulanase debranching and/or ultrasound were applied to prepare debranched lentil starch (DBLS). Their fine structures can affect the retrogradation patterns of DBLSs, which consequently could affect their potential use as delivery carrier of sensitive bioactive compounds. An attempt was made to use these DBLSs as wall materials to encapsulate rutin, aiming to improve the bioaccessibility, meanwhile to enhance the aqueous solubility and stability of rutin molecules. Their encapsulation efficiency, structural characteristics, thermal stability, morphological features, antioxidant activity and in vitro release behavior under simulated upper gastrointestinal tract environment were evaluated. The results suggested that rutin was dispersed in the DBLS polymer matrix, showing the amorphous nature that further authenticates the encapsulation and entrapment of rutin. The structural analyses of microparticles revealed that rutin could interacted with DBLS biopolymer chains by hydrogen bonds, making the starch molecular chains less susceptible to interact with themselves for reordering. The encapsulation efficiency was found to be in an opposite trend with those values obtained for relative crystallinity, melting enthalpy, degree of order/double helices of DBLS wall materials before encapsulation. The release rate results indicated that DBLS carrier with lower Mw, DPn and higher molecular order was beneficial for the slower release of rutin encapsulated in the microparticles.

Morphology, crystalline structure and digestibility of debranched starch nanoparticles varying in average degree of polymerization and fabrication methods.

The objective of this study is to investigate physicochemical characteristics and digestibility of starch nanoparticles (SNPs) fabricated from debranched cassava starch varying degree of polymerization (DP¯n) using nanoprecipitation and microemulsion methods. The high DP¯n starch (HDPS) with DP¯n > 35 monomers, medium DP¯n starch (MDPS) with 15 < DP¯n < 30) and low DP¯n starch (LDPS) with DP¯n < 10 were used. The SNPs fabricated from the HDPS were well-dispersed and smaller size, whereas those prepared from the MDPS and LDPS had bigger size and more aggregation. The SNPs produced by the microemulsion method were larger and more aggregated than those by the nanoprecipitation method. All SNPs exhibited the V + B-type X-ray diffraction pattern with higher relative crystallinity and more ordered structure than native starch. The SNPs fabricated from the LDPS also had higher amount of RS with lower blood glucose response in mice than those from the MDPS and HDPS.

Characterization of complexes formed between debranched starch and fatty acids having different carbon chain lengths.

Recently, amylose-lipid complexes have attracted widespread attention because of their various applications. However, DBS complexed with fatty acids of different carbon chain length are rarely studied. This study aimed to probe the complexation of DBS with saturated fatty acids having different carbon chain lengths (C6-C18). The results revealed that DBS was able to form V-type complexes with all the fatty acids considered. Compared to DBS, the relative crystallinity of the complexes increased 2-3 times. DBS with lauric acid and myristic acid formed three types V-type complexes (type I, type IIa, and type IIb). The complexing index followed the order of hexanoic acid > octanoic acid > capric acid > lauric acid > myristic acid > palmitic acid > stearic acid. Furthermore, lauric acid and myristic acid formed complexes with DBS more easily compared with other fatty acids.