Insight into the multi-scale structure and retrogradation of corn starch by partial gelatinization synergizing with epicatechin/epigallocatechin gallate.

Starch retrogradation is of great importance to the quality of starch-based food. This study investigated the effect of partial gelatinization (PG) synergizing with polyphenol (epicatechin, EC; epigallocatechin gallate, EGCG) on the multi-scale structure and short/long-term retrogradation of corn starch (CS). The PG synergizing with EC/EGCG substantially suppressed the short/long-term retrogradation properties of CS. These could be confirmed by the decreased storage modulus and viscosity, the relative crystallinity (1.54%, 3.56%), and the retrogradation degree (9.99%, 20.18%) of CS during storage for 1, 14 days after PG synergizing with EGCG and EC, respectively. This is because PG treatment promoted the hydrogen bond interaction between disordered starch molecules and EC/EGCG. These were proven by the larger aggregation, more and brighter fluorescents, and the reduced long/short-range order structures in CS after PG synergizing with EC/EGCG. This study is helpful for the development of foods with enhanced nutrition and low-retrogradation.

Covalent conjugation of Inca peanut albumin and polyphenols with different phenolic hydroxyl numbers through laccase catalysis to improve functional properties.

BACKGROUND: Enzymatic crosslinking is a method that can be used to modify Inca peanut albumin (IPA) using polyphenols, and provides desirable functionalities; however, the effect of polyphenol structures on conjugate properties is unclear. In this study, we selected four polyphenols with different numbers of phenolic hydroxyl groups [para-hydroxybenzoic acid (HBA), protocatechuic acid (PCA), gallic acid (GA), and epigallocatechin gallate (EGCG)] for covalent modification of IPA by enzymatic crosslinking, and explored the structure-function changes of the IPA-polyphenol conjugates. RESULTS: Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis showed that laccase successfully promoted covalent crosslinking of IPA with polyphenols, with the order of degree of conjugation as EGCG > GA > PCA > HBA, the IPA-EGCG conjugate showed the highest polyphenol binding equivalents (98.35 g kg-1 protein), and a significant reduction in the content of free amino, sulfhydryl, and tyrosine group. The oxidation of polyphenols by laccase forms quinone or semiquinone radicals that are covalently crosslinked to the reactive groups of IPA, leading to significant changes in the secondary and tertiary structures of IPA, with spherical structures transforming into dense lamellar structures. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging ability and emulsification stability of IPA-EGCG conjugates improved by almost 6-fold and 2.7-fold, respectively, compared with those of unmodified IPA. CONCLUSION: These data suggest that the higher the number of polyphenol hydroxyl groups, the higher the degree of IPA-polyphenol conjugation; additionally, enzymatic crosslinking can significantly improve the functional properties of IPA. © 2024 Society of Chemical Industry.

Differences in the structural properties of three OSA starches and their effects on the performance of high internal phase Pickering emulsions.

The emulsifying properties of emulsions are significantly influenced by the structural properties of octenyl succinic anhydride (OSA) starch. The purpose of this work was to elucidate the effect of the structure of OSA starch on its performance as an emulsifier to stabilize Pickering high-internal-phase emulsions (HIPEs). The degrees of substitution (DS) of the three OSA starches were 0.0137, 0.0177 and 0.0236, and their degrees of branching (DB) were 13.96 %, 14.20 % and 14.32 % measured by 1H NMR, which were sequentially labeled as OSA1, OSA2, and OSA3. The OSA3 starch with higher DS and DB had a lower critical micelle concentration (CMC) (0.11 mg/mL). Its emulsification activity (EAI) and emulsion stability (ES) were 61.8 m2/g and 72.5 min, respectively, which were higher than OSA1 and OSA2 starches. The contact angle of the three OSA starches increased from 45.35° to 80.03° with increasing DS and DB. Therefore, it is hypothesized that OSA3 starches have better emulsification properties. The results of physical stability of HIPEs confirmed the above results. These results indicated that DS and DB have a synergistic effect on emulsion properties, and OSA starch with higher DS and DB values were more conducive to the construction of stable HIPEs systems.

Insight into the improvement in pasting and gel properties of waxy corn starch by critical melting treatments.

To improve the pasting and gel properties of waxy corn starch (WCS), the native starch was modified by critical melting (CM) at the onset temperature (TO), peak temperature (TP), and conclusion temperature (TC) (labeled CMO, CMP, and CMC respectively). CM treatments significantly enhanced the thermal stability of the WCS, as indicated by the increase in the peak gelatinization temperature, pasting temperature, and peak time. In addition, after CMP treatment, the storage modulus, hardness, gumminess, springiness, and chewiness of starch gels significantly increased by 43.29 %, 31.14 %, 23.36 %, 8.26 %, and 61.43 %, respectively, and the syneresis rate significantly decreased by 19.69 % (p < 0.05). These results indicated that CMP treatments significantly improved the gelling ability and freeze-thaw stability of the WCS. These results are ascribed to the partial disruption and enhanced rearrangement of the starch crystalline structure. CMP treatment induced the crystalline structure of starch to be partially disrupted and a hard structure was formed on the surface of starch granules. The hard structure in CMP-treated starch supplied more attachment points for crystalline structure rearrangement during gelatinization. Therefore, the above results indicated that CMP treatments can be used to modify starch to improve the pasting and gel properties of starch-based food products.

Structural properties of Phoenix oolong tea polysaccharide conjugates and the interfacial stability in nanoemulsions.

BACKGROUND: Tea polysaccharide conjugate (TPC) is a naturally occurring active substance that is extracted from tea. Owing to its benefits in enhancing human immunity and antioxidant effects, TPC is widely used in culinary products. The binding mode of polysaccharides and proteins in TPC, however, has not been well studied; it may be closely related to their functional properties, especially emulsification. RESULTS: The molecular weights and monosaccharide compositions of TPC were determined by ion chromatography and high-performance gel permeation chromatography. Although the functional groups of polysaccharides and proteins were confirmed by infrared spectroscopy, the presence of proteins could not be detected by sodium dodecyl sulfate polyacrylamide gel electrophoresis and ultraviolet spectroscopy. It was hypothesized that the hydrophobic groups of the proteins in TPC were wrapped by polysaccharide chains, thus making the proteins undetectable. The rheology and interfacial protein adsorption results show that TPC forms a viscoelastic film at the oil-water interface to prevent the aggregation of oil droplets, thereby enhancing the stability of the emulsion. Based on these structural and emulsifying properties of TPC, the binding mode of polysaccharides and proteins along with their phase behavior at the oil-water interface of the emulsion was speculated. CONCLUSION: In TPC, the hydrophilic groups of the proteins are linked to polysaccharides by covalent interactions, where the hydrophobic groups are wrapped with the polysaccharide chains with the help of hydrophobic forces to form a hydrophobic core. The unique binding of polysaccharides and proteins in TPC enhances its amphiphilic properties, which can be effectively distributed at the oil-water interface and form stable emulsions. © 2023 Society of Chemical Industry.

Ultrasound-assisted reverse micelle extraction and characterization of tea protein from tea residue.

BACKGROUND: In this study, ultrasonic-assisted reverse micelles were used to extract tea protein from tea residues. First, the extraction conditions of ultrasonic power, ionic strength and pH were optimized by response surface methodology. Then, structural comparison of ultrasonic-assisted reverse micelle extraction of tea protein (UARME) and ultrasonic-assisted alkali extraction (UAAE) were performed using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and amino acid composition. RESULTS: The optimum process conditions were determined as follows: ultrasonic power 300 W, KCl 0.15 mol L-1 , pH 8. The extraction rate was 46.29%, which was close to the theoretical value (46.44%). SEM showed that the protein particles extracted by UARME were smaller than those by UAAE. The results of FTIR spectroscopy showed that the protein extracted by UARME had higher α-helix, ß-sheet and ß-turn, and the contents were 20%, 62.3% and 17.1%, respectively. The content of random coil was 0%, which was significantly lower than that of alkali extraction, indicating that the secondary structure of protein extracted by UARME was more orderly. By comparing the amino acid composition of the two methods, the amino acid content of tea protein extracted by UARME was significantly higher than that of UAAE. CONCLUSION: The biological activity of tea protein is closely related to its structure. Compared with alkali extraction, reverse micelles can better protect the secondary structure of proteins, which is of great significance for studying their functional properties. © 2022 Society of Chemical Industry.

Physical modification of maize starch by gelatinizations and cold storage.

The effects of gelatinization at three selected temperatures (DSC characteristic peaks temperature: TO, TP, and TC) and subsequent cold storage (CS) treatment on structural characteristics, pasting, and rheological properties of maize starch (MS) were investigated. The pasting, rheological properties of MS was changed with the increase of gelatinization temperature from TO to TC, but were not further significantly changed if the gelatinization temperature was higher than TC. Pasting and thermal properties analysis suggested that gelatinization at TC (TC treatment) significantly increased the gelatinization and pasting temperature of MS. Moreover, TC treatment decreased breakdown viscosity by 8.49 times and setback viscosity by 2.53 times. Dynamic rheological measurements revealed that the TC treatment caused the lower G' and G" of MS, and decreased the thickening coefficient by 55.17 %. These results indicated that TC treatment could enhance the thermal stability properties of MS, inhibiting the shear and short-term retrogradation, the shear-thinning behavior of MS. Interestingly, the CS treatment further inhibited the shear and short-term retrogradation and the shear-thinning behavior of MS. The leaked starch molecules aggregate to form a harder structure after gelatinization and starch molecules were further aggregated after CS treatment, these all were hypothesized to be responsible for these results.

Activation mechanism of whey protein isolate mediated by free radicals generated in the ascorbic acid/hydrogen peroxide system.

Free radical grafting is a promising method that has been used to modify whey protein isolate (WPI) using polyphenol and provides desirable functionalities, but the reaction mechanism is unclear. This work investigated the grafting mechanism of WPI - (-)-Epigallocatechin-3-gallate (EGCG) through experimental techniques and molecular docking. The results showed that only the ascorbic acid radical anion (Asc•-) is generated in the Asc/ H2O2 system. Asc•- removed hydrogen atoms from amino and sulfhydryl groups, resulting in a decrease in their content. Cystine, proline, methionine, and histidine were discerned to be the grafting sites between WPI and EGCG for more sensitiveness. Furthermore, Asc•- and •OH changed the secondary structure of WPI, but Asc•- further induced oxidative deamination of amino acids. Therefore, the grafting mechanism is presumed that the Asc•- catches hydrogen atoms in protein-sensitive amino acids and generates macromolecular radicals that induce the formation of WPI-EGCG graft.

[Intergrating problem-based-learning with flipped classroom teaching in "Principles of chemical engineering" for biological engineering undergraduates].

New engineering program requires training models that conform acceptable time span and principles of engineering education. Considering the program "Principles of chemical engineering" and the limitations of traditional teaching methods, we integrated problem-based learning method and flipped classroom teaching model to reform the course. Through a three-stage systematic teaching design including knowledge learning before class, knowledge internalization in class, and consolidation and expansion after class, we effectively stimulated students' interest and enthusiasm in learning, cultivated students' independent learning ability and engineering thinking, and achieved good teaching effect. It can provide reference for the construction of "Principles of chemical engineering" course and training of engineering talents in agricultural colleges.

Theoretical Insight into the Interaction between Chloramphenicol and Functional Monomer (Methacrylic Acid) in Molecularly Imprinted Polymers.

Molecular imprinting technology is a promising method for detecting chloramphenicol (CAP), a broad-spectrum antibiotic with potential toxicity to humans, in animal-derived foods. This work aimed to investigate the interactions between the CAP as a template and functional monomers required for synthesizing efficient molecularly imprinted polymers for recognition and isolation of CAP based on density functional theory. The most suitable monomer, methacrylic acid (MAA), was determined based on interaction energies and Gibbs free energy changes. Further, the reaction sites of CAP and MAA was predicted through the frontier molecular orbitals and molecular electrostatic potentials. Atoms in molecules topology analysis and non-covalent interactions reduced density gradient were applied to investigate different types of non-covalent and inter-atomic interactions. The simulation results showed that CAP was the main electron donor, while MAA was the main electron acceptor. Moreover, the CAP-MAA complex simultaneously involved N-H···O and C=O···H double hydrogen bonds, where the strength of the latter was greater than that of the former. The existence of hydrogen bonds was also confirmed by theoretical and experimental hydrogen nuclear magnetic resonance and Fourier transform infrared spectroscopic analyses. This research can act as an important reference for intermolecular interactions and provide strong theoretical guidance regarding CAP in the synthesis of molecularly imprinted polymers.

An Investigation of the Intermolecular Interactions and Recognition Properties of Molecular Imprinted Polymers for Deltamethrin through Computational Strategies.

Deltamethrin (DM) is a toxic pesticide that is nonetheless widely used to control insect pests in agricultural production. Although the number of DM molecularly imprinted polymers (MIPs) is increasing in many scientific applications, the theoretical aspects of the participating intramolecular forces are not fully understood. This paper aims to explore the intermolecular interactions between the template molecule DM and the functional monomer acrylamide (AM) through density functional theory (DFT), analysis of hydrogen nuclear magnetic resonance (1H-NMR), Fourier transform infrared spectroscopy (FTIR), and adsorption thermodynamics. The results indicated that there is strong hydrogen bonding between O19 of DM and H9 of AM, suggesting that it is the preferable site for the binding of the target molecule. The existence of interaction sites was found to play an important role in the recognition process. The results from selective adsorption experiments showed that the DM MIPs exhibited the highest adsorption capacity for DM (Q = 75.72 mg g-1) as compared to the five structural analogs. Furthermore, the recovery rates of spiked DM from various teas using the DM MIPs as solid-phase extraction filler also possessed a high value (all greater than 83.68%), which enables them to be used as separate and recognition functional materials.

Effects of liquefaction parameters of cellulose in supercritical solvents of methanol, ethanol and acetone on products yield and compositions.

Cellulose extracted from cornstalk was liquefied in supercritical organic solvents at different liquefaction parameters. Different organic solvents (methanol, ethanol and acetone) were used to disintegrate cellulose at different temperatures (240, 260, 280, 300 and 320 °C), reaction time (0, 30, 60, 90 and 120 min) and solvents dosage (0, 80, 120, 160 and 200 mL). The results showed that similar liquefaction characteristics of cellulose were observed in three different solvents. The larger bio-oil yield and smaller residue yield obtained from cellulose liquefaction in solvents were achieved under the suitable conditions (320 °C, 160 mL, 60-90 min), respectively. And the type of solvents was the main effect to the distribution of the composition of bio-oil. The dominant constituents of bio-oil that were produced in supercritical methanol was hydrocarbon, and ketones and esters were mainly produced in supercritical ethanol, whereas ketones compounds were primarily derived in supercritical acetone.