Amylose content controls the V-type structural formation and in vitro digestibility of maize starch-resveratrol complexes and their effect on human gut microbiota.

The chain structure of starch affects its interaction with polyphenol molecules which in turn determines the nutritional function of starch. In this study, starch with different amylose content including waxy maize starch (WMS), normal maize starch (NMS) and G50 high-amylose maize starch (G50) were selected to complex with resveratrol (RA) in high-pressure homogenization (HPH) environment, and structural changes of the complexes, together with their effects on in vitro digestibility and gut microbiota were discussed. The results showed that with increasing amylose content, RA could form more inclusion complex with starch through non-covalent bonds accompanied by the increased single helix structure, V-type crystalline structure, compact nano-aggregates and total ordered structure content, which thus endowed the complex lower digestibility and intestinal probiotic function. Notably, when RA addition reached 3 %, the resistant starch (RS) content of HP-G50-3 % rose to 29.2 %, correspondingly increased the relative abundance of beneficial gut microbiota such as Megamonas and Bifidobacterium, as well as the total short-chain fatty acids (SCFAs) content. Correlation analysis showed that V-type crystalline structure positively correlated with the growth of Pediococcu and Blautia (p < 0.05) for producing SCFAs. These findings provided feasible ideas for the development of personalized nutritional starch-based foods.

Gallic acid forms V-amylose complex structure with starch through hydrophobic interaction.

This study aimed to investigate the role of amylose and amylopectin in the formation of starch-polyphenol complex and elucidate the interaction mechanisms. Gallic acid (GA) was used to complex with maize starch with various amylose contents. Results showed GA formed V-type crystals with normal maize starch (NMS) and high amylose maize starch (HAMS), while higher relative crystallinity was exhibited in HAMS-GA complexes than NMS counterparts. Molecular structure analysis revealed more amylose in GA-starch complexes than in treated starch counterparts without GA, and this was more apparent in HAMS than NMS, implying amylose is preferred to complex with GA than amylopectin. FTIR detected higher R1047/1022 value in starch-GA complexes than their starch counterparts without GA, suggesting increased short-range ordered structrure of complexes. Typical signatures of hydrophobic interactions were further revealed by isothermal titration calorimetry, indicating the complexation of GA to starch is mainly through hydrophobic bonds. More binding sites were observed for HAMS (72.50) than NMS (11.33), which proves the preferences of amylose to bind with GA. Molecular dynamics simulated the complexation of GA to amylose, and confirmed hydrophobic bond is the main interaction force. These findings would provide guidance for precise design and utilization of starch-polyphenol complexes in functional foods.

Extraction process, physicochemical properties, and digestive performance of red yeast rice starch.

In the present study, taking red yeast rice (RYR) as the raw material, the optimum extraction process of RYR starch was investigated through a single-factor experiment and the Box-Behnken design: The liquid-to-solid ratio was 5 mL/g, the concentration of sodium hydroxide solution was 0.075 mol/L, and the extraction time was 3.1 h. Under these extraction conditions, the extraction rate of starch reached 90.077%. To explore the influence of solid-state fermentation on RYR starch, three different fermentation stages of RYR starch, raw rice starch, semi-gelatinized rice starch, and RYR starch were used as test materials to determine the changes in the physicochemical properties and glycemic index (GI) values of RYR starch during solid-state fermentation. The results showed that with the advancement of the RYR solid-state fermentation process, the starch particle size gradually increased, the light transmittance gradually decreased, and the solubility and swelling power significantly increased. In addition, the amylose content of starch gradually increased, whereas the amylopectin content gradually decreased; the content of fast digestible starch and slow digestible starch decreased, whereas the content of resistant starch increased. In parallel, during solid-state fermentation, the hydrolysis index significantly decreased, and the GI values also decreased. In summary, solid-state fermentation reduced the digestibility of RYR starch. These results provide a theoretical basis for the structural and physicochemical properties of RYR starch and lay a foundation for its subsequent application and expansion of RYR starch.

The interaction and physicochemical properties of the starch-polyphenol complex: Polymeric proanthocyanidins and maize starch with different amylose/amylopectin ratios.

This study investigated the impact of polymeric proanthocyanidins (PPC) on the physicochemical characteristics of maize starch with varying amylose content, and their potential interaction mechanism. PPC with a lower content (1 %) reduced the viscoelasticity of the high amylose maize starch (HAM) system, inhibited amylose rearrangement, and enhanced its fluidity. However, excessive PPC restrained the interaction between PPC and amylose. In contrast to HAM, PPC improved the gelation ability of waxy maize starch (WAM) as PPC concentration was raised. PPC suppressed the recrystallization of starch during storage, and PPC had a superior inhibition influence on the retrogradation of WAM in comparison to HAM. This indicated that amylopectin was more likely to interact with PPC than amylose. Hydrogen bonds were the main driving force between PPC and starch chains, which was clarified by Fourier transform-infrared, nuclear magnetic resonance, X-ray diffraction, iodine bonding reaction, and dynamic light scattering data. Additionally, the mechanism of interaction between PPC and the two starch components may be similar, and variance in physicochemical attributes can be primarily credited to the percentage of amylose to amylopectin in starch.

Different oil-modified cross-linked starches: In vitro digestibility and its relationship with their structural and rheological characteristics.

This study investigated the structure, rheological behaviors and in vitro digestibility of oil-modified cross-linked starches (Oil-CTS). Gelatinized Oil-CTS were hard to be digested due to its intact granule shapes and the presence of surface-oil, which acted as physical barriers that inhibited the diffusion and penetration of enzymes to starch. Besides, the less amylose content in Oil-CTS (23.19-26.96%) than other starches (26.84-29.20%) contributed to its low digestibility because amylose with less α-1,6 linkages was more easily attacked by amyloglucosidase than amylopectin. Moreover, heat treatment during oil could shorten the amylopectin chain length and destroy the ordered structures, thus increasing enzymatic hydrolysis on starch. Pearson correlation analysis indicated rheological parameters were not significantly correlated with digestion parameters (p > 0.05). Overall, despite the damage caused by heat to molecular structures, physical barrier effect caused by surface-oil layers and integrity of swollen granules was the most critical contributor to the low digestibility of Oil-CTS.

Effect of starch-protein interaction on regulating the digestibility of waxy rice starch under radio frequency treatment with added CaCl2.

This study investigated the effect of starch-protein interaction on regulating the digestibility of waxy rice starch under radio frequency (RF) treatment with added salts. The results showed that starch-protein interactions could significantly reduce the digestibility of waxy rice starch (WRS) under synergetic Ca2+-RF treatment. With the increase of Ca2+ content (0-2 %), the resistant starch content of WRS-WPI, WRS-SPI and WRS-PPI increased from 35.53 %, 36.12 % and 38.78 % to 51.05 %, 52.82 % and 55.93 %, respectively. The addition of appropriate Ca2+ content could increase the short-range ordered structure and lamella structure and form a more compact and uniform microstructure. In addition, the interaction between WRS and protein was mainly through hydrogen bonding and hydrophobic interactions during RF treatment. Furthermore, the presence of Ca2+ could improve the distribution and mobility of water molecules and regulate the rheological properties of WRS-protein complexes. This study offers theoretical guidance for the design and production of rice starch-based products with lower digestibility.

Amylose content and pre-freezing regulate the structure and oil absorption of polyelectrolytes-based starch cryogel.

Starch cryogel is a potential material for oil absorption. This study provided a facile and convenient polyelectrolyte-based preparation strategy of starch cryogel, in which the structural properties of the cryogel were regulated by amylose content and pre-freezing without long-time retrogradation. Sodium laurate was used as a guest model to form starch-fatty acid salt complex (polyelectrolyte). The amount of amylose content and sodium laurate added led more polyelectrolytes, significantly increased V-type crystallinity from 3.72 % to 22.40 % and complexing index from 4.32 % to 28.48 %. As the uniform pore structure improved the oil absorption ability of starch cryogel, the starch cryogel prepared by waxy maize starch followed by quick pre-freezing showed the highest specific surface area (9.87 m2/g) and oil absorption capacity (32.94 g/g). Our findings suggest that polyelectrolyte properties have great potential in the preparation of starch-based cryogels, which could be applied in the design of novel starch-based porous materials.

Increase of resistant starch content by hydrolysis of potato amylopectin and its microstructural studies by 2D and 3D imaging.

The effect of amylopullulanase treatment on recrystallization behaviour and the formation of resistant starch crystals have been investigated. Extracted potato starch (Solanum tuberosum) has been subjected to the enzymatic assisted bioprocessing without any physical or chemical treatment, where 120 min of incubation, 7 % (v/v) of enzyme and 8 mL/g of water content were found to be optimum to increase the resistant starch content by 41.88 %. The resistant starch crystals showed the characteristic behaviour of B-type allomorph with an increase in 21.32 % crystallinity. The modified crystals portrayed less reduction in actual weight when assessed by thermo-gravimetric analysis. The compact linear arrangement of the linear amylose chains within the crystallized granule of starch has been evidenced by Bright Field Microscopy. The microstructure of the resistant starch crystals showed 33.18 % reduction in porosity when the 3-dimensional structural form was analysed by X-ray micro-Computed Tomography.

Removal of starch granule-associated surface and channel lipids alters the properties of sodium trimetaphosphate crosslinked maize starch.

Starch granule-associated surface and channel lipids (SGALs) were effectively removed from waxy maize starch (WMS) and normal maize starch (NMS), then the starches were crosslinked by different levels of sodium trimetaphosphate (STMP) (0.25 %, 0.5 %, 1 % and 2 %). The effective removal of SGALs and successful crosslinking, were evidenced by the disappearance of surface-fluorescence and channel-fluorescence of Pro-Q Diamond-stained granules, and the increased phosphorus content respectively. STMP crosslinking increased peak and final viscosity for WMS and NMS. Crosslinking at high STMP levels (0.5 %, 1 % and 2 %) transformed the starch pastes from thixotropic to anti-thixotropic. STMP crosslinking significantly decreased the tan δ values of maize starches, enhancing the elastic structure of the gel. Crosslinked maize starches without SGALs had lower breakdown than crosslinked starches at same STMP level, indicating higher tightened crosslinked starch granules after SGALs removal. Removal of SGALs increased the anti-thixotropy of crosslinked starches, facilitating the reorientation of crosslinked amylopectin/amylose molecules during shearing. Removal of SGALs increased the tan δ values from frequency sweep of WMS and NMS during STMP crosslinking, indicating the presence of surface-lipids and channel-lipids could enhance the elastic gel network structure of crosslinked maize starch.

Chemical modification of waxy maize starch by esterification with saturated fatty acid chlorides: Synthesis, physicochemical and emulsifying properties.

In the current study, the physicochemical and emulsifying properties of modified waxy maize starch obtained through a new environmentally friendly method of esterification were evaluated. The starch modification was carried out in NaOH solution with different levels of octanoyl, myristoyl, and stearoyl chlorides. Increasing the fatty acid chlorides concentration led to the degree of substitution increment, while reaction efficiency and yield decreased. Based on fourier transform infrared spectroscopy results, the presence of two new bands of carbonyl (1740-1750 cm-1) and carboxyl (1570 cm-1) groups in the ester bond confirmed the successful starch esterification process. The level of 0.1 mL fatty acid chlorides/g of starch demonstrated the highest emulsifying properties. Upon esterification, the crystalline structure of amylopectin was destroyed, indicating no gelatinization features. Therefore, using the fatty acid chlorides in an alkaline condition could be suggested as a feasible way to modify waxy maize starch toward hydrophobicity increment with desirable properties.

Interaction with longan seed polyphenols affects the structure and digestion properties of maize starch.

This study investigated effects of longan seed polyphenols (LSPs) on the structure and digestion properties of starch, and discussed the interaction mechanism between starch and LSPs. The results showed cooking with 20 % LSPs did not change amylopectin chain length distribution of normal maize starch, however, the amylose content was reduced from 21.60 to 14.03 %. This suggests LSPs may interact with starch via non-covalent bond. Isothermal titration microcalorimetry and XRD results confirmed the existence of non-covalent interaction, and indicated that LSPs may enter the hydrophobic cavity of amylose, forming V-type inclusion complex. LSPs did not affect gelatinization temperatures of maize starch, whereas 20 % LSPs decreased the enthalpy change by about 26 %. The digestion results indicate significant inhibition effect of LSPs on the digestion of cooked starch, attributing to the interaction of LSPs with starch. These suggest potential applications of LSPs as functional ingredients in modulating postprandial glycemic response of starchy food.

Tailoring the surface properties and flexibility of starch-based films using oil and waxes recovered from potato chips byproducts.

Agrofood byproducts may be exploited as a source of biomolecules suitable for developing bioplastic materials. In this work, the feasibility of using starch, oil, and waxes recovered from potato chips byproducts for films production was studied. The recovered potato starch-rich fraction (RPS) contained an amylopectin/amylose ratio of 2.3, gelatinization temperatures varying from 59 to 71 °C, and a gelatinization enthalpy of 12.5 J/g, similarly to a commercial potato starch (CPS). Despite of its spherical and oval granules identical to CPS, RPS had a more amorphous structure and gave rise to low viscous suspensions, contradicting the typical B-type polymorph crystal structure and sluggish dispersions of CPS, respectively. When used for films production, RPS originated transparent films with lower roughness and wettability than CPS-based films, but with higher stretchability. In turn, when combined with RPS and CPS, oil or waxes recovered from frying residues and potato peels, respectively, allowed to develop transparent yellowish RPS- and CPS-based films with increased surface hydrophobicity, mechanical traction resistance, elasticity, and/or plasticity. Therefore, potato chips industry byproducts revealed to have thermoplastic and hydrophobic biomolecules that can be used to efficiently develop biobased plastics with improved surface properties and flexibility, opening an opportunity for their valorization.

Development and application of an amylopectin-graft-poly(methyl acrylate) solidifier for rapid and efficient containment and recovery of heavy oil spills in aqueous environments.

Effective oil spill preparedness and response are crucial to ensure environmental protection and promote the responsible development of the petroleum industry. Hence, interest in developing new approaches and/or improving existing oil spill response measures has increased greatly in the past decade. Solidifiers are an attractive and underutilized option to mitigate the effects of oil spills, as they interact with oil to contain the spill, prevent it from spreading, and facilitate its removal from the environment. In this work, we have synthesized an inexpensive and easy-to-make natural-based sorbent, a subclass of solidifiers. Our amylopectin-graft-poly(methyl acrylate) (AP-g-PMA) sorbent is highly oleophilic and hydrophobic, and selectively solidifies diluted bitumen and conventional crude oil from biphasic mixtures of oil and water. The complete solidification of conventional crude oil and diluted bitumen by the AP-g-PMA sorbent occurs within 8 and 32 min, respectively, and even a low solidifier-to-oil ratio of 4% w/w is sufficient to enable complete recovery of diluted bitumen. This innovative natural-based polymeric sorbent may be applied as a key component of oil spill response procedures, especially for heavy oils. The AP-g-PMA sorbent combines the biodegradability and non-toxicity of the amylopectin with the hydrophobicity and oleophilicity of the synthetic polymer poly(methyl acrylate).

Impact of mineral ions on the release of starch and gel forming capacity of potato flakes in relation to water dynamics and oil uptake during the production of snacks made thereof.

Potato flakes (PFs) are made by boiling, mashing and subsequent drying of steam peeled potatoes. Their cold-water swelling starch readily develops viscosity upon hydration. That potato starch amylopectin (AP) contains esterified phosphate groups results in rapid swelling and high viscosity of PF suspensions. This study is the first report on the impact of sodium, calcium and aluminum chloride on (i) the physicochemical properties of PFs and (ii) the water dynamics in relation to oil uptake in the production of deep-fried crisps made thereof. Adding 125 µmol cation/g PF dry matter (dm) of these salts to PF suspensions (8.0% dm) in a Rapid Visco Analyzer (RVA) decreased the peak viscosities by 5% (sodium chloride) and 20% (calcium or aluminum chloride). While monovalent cations shield the negative charges of the phosphate monoesters on the starch chains, divalent and trivalent cations bridge phosphate groups of adjacent AP molecules and thereby reduce swelling even further. Moreover, the latter ions result in up to 20% higher RVA cold paste viscosity readings even if they do not affect amylose (AM) aggregation. They thus enhance the gelation of PFs by AP bridging. For producing deep-fried crisps, PFs, emulsifier and maltodextrin were hydrated, mixed, sheeted into dough, and deep-fried. Including the above dosage of calcium ions in its recipe increased the specific strength of the dough sheet by about 15%. Time domain proton nuclear magnetic resonance analysis of dough sheets showed that these ions increase the rigidity of the starchy gel network while AM crystallization remains largely unaffected. This is evidence that ionic cross-linking of AP directly strengthens the dough sheet. Moreover, the calcium ions lowered the lipid content of the deep-fried crisps by about 5% due to stronger interaction of starch polymers with water. Ionic cross-linking of AP thus improves the gel forming capacity of PFs and strengthens the starchy gel network during manufacturing of potato-based snacks resulting in crisps with a significantly lower lipid content.

Synthesis, Characterization and Adsorptive Performances of a Composite Material Based on Carbon and Iron Oxide Particles.

The aim of this paper was to produce a new composite material based on carbon and iron oxides, starting from soluble starch and ferric chloride. The composite material was synthesized by simple thermal decomposition of a reaction mass obtained from starch and iron chloride, in an inert atmosphere. Starch used as a carbon source also efficiently stabilizes the iron oxides particles obtained during the thermal decomposition. The reaction mass used for the thermal decomposition was obtained by simultaneously mixing the carbon and iron oxide precursors, without addition of any precipitation agent. The proper composite material can be obtained by rigorously adhering to the stirring time, temperature, and water quantity used during the preparation of the reaction mass, as well as the thermal regime and the controlled atmosphere used during the thermal decomposition. Synthesized materials were characterized using thermogravimetric analysis, X-Ray Diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infra-red spectroscopy (FT-IR). The performances of the obtained material were highlighted by studying their adsorbent properties and by determining the maximum adsorption capacity for arsenic removal from aqueous solutions.

Antioxidant starch films containing sunflower hull extracts.

This study explores the preparation of antioxidant starch food packaging materials by the incorporation of valuable phenolic compounds extracted from sunflower hulls, which are an abundant by-product from food industry. The phenolic compounds were extracted with aqueous methanol and embedded into starch films. Their effect on starch films was investigated in terms of antioxidant activity, optical, thermal, mechanical, barrier properties and changes in starch molecular structure. The starch molecular structure was affected during thermal processing resulting in a decrease in molar mass, smaller amylopectin molecules and shorter amylose branches. Already 1-2% of extracts were sufficient to produce starch films with high antioxidant capacity. Higher amounts (4-6%) of extract showed the highest antioxidant activity, the lowest oxygen permeability and high stiffness and poor extensibility. The phenolic extracts affected predominantly the mechanical properties, whereas other changes could mainly be correlated to the lower glycerol content which was partially substituted by the extract.

Resistant starch formation through intrahelical V-complexes between polymeric proanthocyanidins and amylose.

Reducing starch digestibility can significantly benefit efforts to combat obesity and associated chronic diseases. Polymeric proanthocyanidins (PA) form complexes with starch via unknown mechanisms, resulting in dramatically decreased starch digestibility. We hypothesized that V-type complexes are involved in these interactions. Sorghum derived PA was complexed with amylose, amylopectin, and granular maize starches in regular and deuterated solvents, and structural properties and in vitro digestibility of the complexes investigated. Based on iodine binding, X-ray diffraction patterns, crystallinity, and thermal properties, we demonstrated, for the first time, that type II semi-crystalline V-complexes are formed between amylose and PA. Furthermore, suppression of H-bonding led to amorphous complexes, suggesting extensive H-bonding facilitate and/or stabilize the V-complexes. We speculate that the complexation involves inclusion of B-rings of the PA units into the amylose helical cavity. The V-complex formation significantly increased resistant starch in gelatinized normal starch and pure amylose (by 35-45%), indicating likely physiological benefits.

Spectroscopic investigation of a hyperbranched cationic amylopectin derivative as a multi-guest molecular host for targeted delivery of a photosensitizer to pancreatic cancer cells.

To increase pancreatic tumor-targeted phototoxicity of photosensitizers, a hyperbranched cationic amylopectin derivative conjugated with 3-(dimethylamino)-1-propylamine (DMAPA-Amp) was invevstigated as a multi-guest molecular host for the targeted delivery of a photosensitizer to human pancreatic cancer (Panc-1) cells. We selected protoporphyrin IX (PpIX) and folic acid as a photosensitizer and a tumor-targeting factor, respectively. The complexation mechanism of DMAPA-Amp with PpIX and folic acid was characterized using NMR spectroscopy including 1H NMR, two-dimensional diffusion ordered spectroscopy (2D DOSY) NMR, fluorescence and UV-vis spectroscopy. The results indicated that the DMAPA-Amp derivative could serve as a host for the encapsulation of two guests, PpIX and folic acid, through intermolecular interactions. The complex showed high phototoxicity against Panc-1 cells, and its folic-acid-mediated cancer-cell-targeting property was confirmed by laser confocal microscopy and flow cytometry analysis. We provide a method to study hyperbranched cationic polymer-based complexes containing multiple guests, which could facilitate the design of multi-functional complexes in the drug delivery field.

Measurement and characterization of external oil in the fried waxy maize starch granules using ATR-FTIR and XRD.

Concerns regarding increased dietary oil uptake have prompted efforts to investigate the oil absorption and distribution in fried starchy foods. In the present study, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, together with a chloroform-methanol method, was used to analyze the external and internal oil contents in fried starchy samples. The micromorphology of fried starchy samples was further investigated using scanning electron microscope (SEM), polarized light microscope (PLM) and confocal laser scanning microscopy (CLSM). The results indicated that large amounts of oil were absorbed in or within waxy maize starch, but the majority of oil was located near the surface layer of the starch granules. After defatting, the internal oil was thoroughly removed, while a small amount of external oil remained. As evidenced by the changes of the crystalline characteristics with the help of X-ray diffraction (XRD), the interaction between starch and lipids on the surface was confirmed to form V-type complex compounds during frying at high moisture.

Effects of dietary starch types on early postmortem muscle energy metabolism in finishing pigs.

This study aimed to investigate the effects of different dietary starch types on early postmortem muscle energy metabolism in finishing pigs. Ninety barrows (68.0±2.0kg) were randomly allotted to three experimental diets with five replicates of six pigs, containing pure waxy maize starch (WMS), nonwaxy maize starch (NMS), and pea starch (PS) (amylose/amylopectin were 0.07, 0.19 and 0.28 respectively). Compared with the WMS diet, pigs fed the PS diet exhibited greater creatine kinase activity, higher adenosine triphosphate and adenosine diphosphate contents, lower phosphocreatine (PCr), adenosine monophosphate and glycogen contents, and lower glycolytic potential (P<0.05). Moreover, the PS diet led to reduced percentage of bound hexokinase activity, decreased level of phosphorylated AKT (P<0.05) and increased level of hypoxia-inducible factor-1α (P<0.05). In conclusion, diet with high amylose content might promote PCr degradation and inhibit the rate of glycolysis, followed by attenuation of early postmortem glycolysis in finishing pigs.