Formation and Characterization of ß-Lactoglobulin and Gum Arabic Complexes: the Role of pH.

Protein-polysaccharide complexes have received increasing attention as delivery systems to improve the stability and bioavailability of multiple bioactive compounds. However, deep and comprehensive understanding of the interactions between proteins and polysaccharides is still required for enhancing their loading efficiency and facilitating targeted delivery. In this study, we fabricated a type of protein-polysaccharide complexes using food-grade materials of ß-lactoglobulin (ß-Lg) and gum arabic (GA). The formation and characteristics of ß-Lg-GA complexes were investigated by determining the influence of pH and other factors on their turbidity, zeta-potential, particle size and rheology. Results demonstrated that the ß-Lg and GA suspension experienced four regimes including co-soluble polymers, soluble complexes, insoluble complexes and co-soluble polymers when the pH ranged from 1.2 to 7 and that ß-Lg-GA complexes formed in large quantities at pH 4.2. An increased ratio of ß-Lg in the mixtures was found to promote the formation of ß-Lg and GA complexes, and the optimal ß-Lg/GA ratio was found to be 2:1. The electrostatic interactions between the NH3+ group in ß-Lg and the COO- group in GA were confirmed to be the main driving forces for the formation of ß-Lg/GA complexes. The formed structure also resulted in enhanced thermal stability and viscosity. These findings provide critical implications for the application of ß-lactoglobulin and gum arabic complexes in food research and industry.

SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts.

The SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph3 P=N-PPh3 ]+ [HF2 ]- as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of side chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry-based post-polymerization modification.

Mechanisms and reactivity differences for cycloaddition of anhydride to alkyne catalyzed by palladium and nickel catalysts: insight from density functional calculations.

Mechanisms and reactivity differences for the cycloaddition of anhydride to alkyne catalyzed by the palladium and nickel catalysts have been investigated by extensive density functional theory (DFT) calculations. The predicted free energy profiles for the Pd- and Ni-catalyzed reactions have been used to evaluate possible mechanisms for the formation of different products. Calculations show that the formation of isocoumarin via the decarbonylative addition of anhydride to alkyne is kinetically more favorable than the channel to indenone in the Ni-catalyzed reaction. On the contrary, the preparation of naphthalene through sequential liberation of CO2 and CO is kinetically more favorable than that the formation of indenone in the Pd-catalyzed process. The bonding differences between Pd-C and Ni-C bonds, arising from the relativistic effect of late transition metals, play an important role in regulating their catalytic activity. The calculation results show good agreement with the experiments.

Seaweed soluble dietary fibre replacement modulates the metabolite release of cakes after in vitro digestion.

Soluble dietary fibre (SDF) has gained growing interest because of its multiple functional and nutritional benefits. In the current study, the effect of SDF extracted from eucheuma seaweed on both the physicochemical properties and the released metabolites of yellow cakes was evaluated systematically. The results revealed that the addition of SDF induced increases in specific gravity, specific volume and water content of yellow cakes, and caused a decrease in weight loss and changes in texture and colour. In addition, sensory evaluation showed that up to 10 % substitution of flour with SDF was acceptable. In vitro digestion of cakes demonstrated that flour substitution with SDF at different levels (8 %-14 %) significantly reduced the release of glucose, ranging from 11.24 % to 29.12 %. In addition to the increased apparent viscosity of the cake digesta, the metabolite analysis based on nuclear magnetic resonance spectroscopy identified a total of 29 metabolites, including amino acids, fatty acids and sugars. Notably, the addition of SDF reduced the release of amino acids and fatty acids after digestion. These findings suggested that seaweed SDF was a potential substitute for some food components, which would provide functional benefits to the digestive characteristics.

Enhancing viability of Lactobacillus plantarum encapsulated by alginate-gelatin hydrogel beads during gastrointestinal digestion, storage and in the mimic beverage systems.

To improve the viability of Lactobacillus plantarum (P) during digestion and storage, the probiotics were encapsulated by alginate (ALG) and alginate-gelatin (ALG-GE) hydrogels beads. ALG-P-GE showed much better physicochemical properties than ALG-P. The scanning electron microscopy (SEM) results validated the incorporation of bacterial cells into the beads. ALG-P-GE exhibited good encapsulation efficiency of 97.7 %, and the storage and thermal stability of probiotic were increased by 15 % and 8 %, respectively, when comparing with ALG-P. ALG-P-GE beads could protect the probiotics from inactivation in simulated gastric fluid and then release it in simulated intestinal fluid. The protective mechanism of ALG-GE for probiotics was further studied by fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and found that ALG and GE can form gel network through hydrogen bonding and electrostatic interactions. In the mimic beverage systems, ALG-P-GE beads could protect the encapsulated probiotics and increase its viability. The storage, thermal, and digestion stability of encapsulated probiotic were significantly increased and showed high viability in the mimic beverage systems. ALG-P-GE beads have great potential for the protection and delivery of probiotics in food systems.

Highly biologically active and pH-sensitive collagen hydrolysate-chitosan film loaded with red cabbage extracts realizing dynamic visualization and preservation of shrimp freshness.

Accurate and efficient detection of food freshness is of great significance to guarantee food safety. Herein, pH sensitive colorimetric films with considerable biological activities have been prepared by combining red cabbage anthocyanin extracts (RCE) with collagen hydrolysate-chitosan (CH-CS) matrix film. The formation mechanism of CH-CS-RCE films was discussed by SEM, FT-IR and XRD, which showed that RCE was successfully fixed in CH-CS film through hydrogen bonding and electrostatic interaction. The CH-CS-RCE films exhibited good mechanical properties, high barrier ability, excellent thermal stability, significant antioxidant and antimicrobial activity, and especially sensitive response to pH and ammonia. Fickian diffusion was the main mechanism for the release of RCE from CH-CS-RCE films and such release mechanism facilitated the maintenance of functional features of films. During the storage of shrimps at 4 °C, CH-CS-RCE2% showed a remarkable preservation effect on shrimps, and their shelf life was prolonged from 2 d to 5 d. Furthermore, CH-CS-RCE2% provided a dynamic visual color switching to detect the freshness of shrimp, realizing real-time monitoring of freshness. Color information (RGB) extracted via smartphone APP was used to enhance the accuracy and universality of freshness indication. Thus, this multifunctional film has great potential in food preservation and freshness monitoring.

Improved antioxidant activity and delivery of peppermint oil Pickering emulsion stabilized by resveratrol-grafted zein covalent conjugate/quaternary ammonium chitosan nanoparticles.

Novel nanoparticles (Z-R/H) were successfully fabricated by a resveratrol-grafted zein covalent conjugate (Z-R) combined with quaternary ammonium chitosan (HTCC), which were used as stabilizers to prepare peppermint oil (PO) Pickering emulsions with antioxidant activity. HTCC effectively adjusted wettability of Z-R conjugate, and three-phase contact angle of Z-R/H3:1 was moderate (95.01°). The influencing factors of Pickering emulsion formation, including volume fraction of PO, concentration of Z-R/H, and mass ratio of Z-R to HTCC, were evaluated by droplet size, ζ-potential, microscopic observation, and stability index analysis. Pickering emulsions stabilized by Z-R/H3:1 showed excellent physical stability under heat treatment. Z-R/H nanoparticles adsorbed on the oil-water interface yielded a dense filling layer as a physical barrier to improve the emulsion stability, which was validated by confocal laser-scanning microscopy. After 4 weeks of storage, retention rate of PO in Pickering emulsion stabilized by Z-R/H3:1 remained high (72.1 %). Electronic nose analysis showed that Z-R/H3:1-stabilized emulsion effectively prevented volatilization of PO aroma components. Additionally, PO and Z-R/H nanoparticles provided an additive antioxidant effect of Pickering emulsions against DPPH and ABTS free radicals. In summary, these novel Z-R/H nanoparticle offer promising applications as a stabilizer with great potential in preparing functional Pickering emulsions to improve essential oil delivery.

Encapsulation of EGCG by Zein-Gum Arabic Complex Nanoparticles and In Vitro Simulated Digestion of Complex Nanoparticles.

Epigallocatechin gallate (EGCG) has many excellent qualities such as its antitumor, antiradiation and anti-oxidation properties, but its application is limited because its oral bioavailability is low and stability is poor. In this paper, zein and gum arabic (GA) were used as wall materials to prepare Zein-GA complex nanoparticles for encapsulating and protecting the EGCG. The particle size of Zein-GA-EGCG complex nanoparticles ranged from 128.03-221.23 nm, and the EGCG encapsulation efficiency reached a maximum of 75.23% when the mass ratio of zein to GA was 1:1. The FTIR and XRD results illustrated that the components of the Zein-GA-EGCG complex nanoparticles interacted by electrostatic, hydrogen bonding, and hydrophobic interactions. The EGCG release rate of Zein-GA-EGCG nanoparticles (16.42%) was lower than that of Zein-EGCG (25.52%) during gastric digestion, and a large amount of EGCG was released during intestinal digestion, suggesting that the Zein-GA-EGCG nanoparticles could achieve the sustained release of EGCG during in vitro digestion. Hence, using Zein-GA complexes to encapsulate EGCG effectively increased the encapsulation efficiency of EGCG and realized the purpose of sustained release during simulated gastrointestinal digestion.

Preparation of zein-lecithin-EGCG complex nanoparticles stabilized peppermint oil emulsions: Physicochemical properties, stability and intelligent sensory analysis.

Peppermint oil emulsions were prepared by using zein-lecithin-EGCG (Z-L/E) complex nanoparticles as emulsifiers. The preparation conditions of emulsions were optimized via measuring the particle size, surface tension and stability of emulsions, and peppermint oil of 3% (particle size = 375 nm, polydispersity index (PDI) = 0.45), the zein:lecithin ratio of 4:1 (w/w) (particle size = 396 nm), and the zein:EGCG ratio of 10:1 (w/w) (surface tension = 47.32 N/m) was the optimal condition. The rapid stability analysis showed that the instability mechanism of emulsions was ascribed to creaming and stratification, and the stability mechanism of emulsions was explored, indicating that the complex nanoparticles adsorbed on the surface of oil droplets to give Pickering emulsions. Electronic tongue experiments showed that the Z-E/L4:1 stabilized emulsion was distinguished from the other three samples due to its good stability. The electronic nose experiment could distinguish the emulsions with different droplet sizes.

Fabrication of Antioxidant Pickering Emulsion Based on Resveratrol-Grafted Zein Conjugates: Enhancing the Physical and Oxidative Stability.

Lipid oxidation is still a major problem complicating the development of food emulsions. In this study, an antioxidant Pickering emulsion stabilized by resveratrol-grafted zein (Z-R) conjugates and pectin (P) complex particles was prepared. The hydrophilic pectin successfully adjusted the wettability of Z-R; when the mass ratio of Z-R to P was 2:1 (Z-R/P2:1), the three-phase contact angle was 90.68°, and the wettability of the particles was close to neutral. Rheological analysis showed that the emulsion formed an elastic gel structure. FTIR spectra indicated that there was a hydrogen bond and electrostatic interaction between Z-R and P. The disappearance of characteristic infrared peaks of corn oil was due to a dense protective film formed on the surface of oil drops by Z-R/P2:1 particles, which was confirmed by confocal laser scanning microscopy. The emulsion stabilized by Z-R/P2:1 had excellent physical stability at a wide range of pH values (4-9), salt ion concentrations (0.04-0.15 mol·L-1) and storage times (0-30 days). The anti-lipid oxidation ability of the emulsion was outstanding; after storage for 14 days at room temperature, the MDA content in the emulsion was only 123.85 µmol/kg oil. In conclusion, the Z-R/P2:1 particles prepared in this study can effectively stabilize a Pickering emulsion and expand the usability of the method for constructing antioxidant Pickering emulsions.

The fabrication of novel zein and resveratrol covalent conjugates: Enhanced thermal stability, emulsifying and antioxidant properties.

Novel zein and resveratrol conjugates were fabricated by alkaline and free radical grafting reactions. The grafting efficiency and total phenolic content of alkaline treated conjugates were slightly higher than those of free radical grafting. Compared to native and alkaline treated zein, the sulfhydryl contents of conjugates were obviously decreased, confirming that nucleophilic addition of resveratrol to sulfhydryl group of zein formed stable CS covalent bonds. The conformation changes of zein modified by resveratrol were revealed by fourier transform infrared spectroscopy and fluorescence spectroscopy. Moreover, covalent modification changed isoelectric point of zein from 6.5 to 5.4 (alkaline) or 5.6 (free radical grafting), and broadening the pH application range of zein. It was worth mentioning that the conjugates showed much higher thermal stability, antioxidant activity, and emulsify activity than those of native zein. This study provides an effective way for the design of novel delivery systems to encapsulate bioactive substances.

Preparation of alginate-whey protein isolate and alginate-pectin-whey protein isolate composites for protection and delivery of Lactobacillus plantarum.

Probiotics are sensitive to external conditions, resulting in low survival rates after being ingested or during food production, transportation and storage. In order to improve the survival rate of Lactobacillus plantarum (LP) during gastrointestinal digestion, storage, and freeze-drying, alginate-whey protein isolate (ALG-WPI) and alginate-pectin-whey protein isolate (ALG-PEC-WPI) composites were employed to encapsulate LP. The encapsulation efficiency of ALG-WPI-LP and ALG-PEC-WPI-LP beads both reached more than 99 %. Scanning electron microscopy (SEM) indicated that dense and rough aggregates were formed on the surface of both composites, and attached LP cells could be observed inside the beads. The ALG-WPI and ALG-PEC-WPI composites can protect the viability of LP in simulated gastric fluid (SGF) and release the probiotics in simulated intestinal fluid (SIF). The storage stability of LP at 4 °C was improved by about 15 % in comparison with bare LP and the survival rates of LP in ALG-WPI-LP and ALG-PEC-WPI-LP powders after freeze-drying were increased by 65.37 % and 72.06 %, respectively. The formation mechanism of ALG-WPI and ALG-PEC-WPI composites was further explored by fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The ALG-WPI and ALG-PEC-WPI composites have great potential to protect and deliver probiotics in food systems.

Characterization and stability of peppermint oil emulsions using polyglycerol esters of fatty acids and milk proteins as emulsifiers.

Three peppermint oil emulsions using polyglycerol esters of fatty acids-casein (PGFE-CN), polyglycerol esters of fatty acids-sodium caseinate (PGFE-NaCN), and polyglycerol esters of fatty acids-whey protein isolate (PGFE-WPI) as emulsifiers were fabricated, and the droplet size, zeta potential, viscosity, and stability of emulsions were determined. The experimental results showed that the emulsion containing PGFE-CN has relatively smaller droplet size of 231.77 ± 0.49 nm. No significant changes were observed on the average particle size, polydispersity index and zeta potential during 4-week of storage, indicating that the emulsions kept stable against pH, salt ion, freeze-thaw, and storage. Fourier transform infrared spectrometer (FTIR) results showed that the electrostatic interaction occurs between CN and PGFE in the emulsion. The confocal laser scanning microscope (CLSM) was used to observe the microstructure of the emulsion, proving that droplets were evenly distributed throughout the aqueous phase by PGFE-CN emulsifier. The protein-stabilized emulsions can be used as potential carriers for the delivery of the lipophilic nutrients such as peppermint oil. PRACTICAL APPLICATION: PGFE-CN emulsifier can be directly added to the beverage systems containing oil or protein, such as coconut milk, peanut milk, and walnut milk. It can enhance the stability of beverage, prevent the precipitation, stratification, and oil floating, improve the homogeneity of the system and therefore extend the shelf life.

Exploration of the Microstructure and Rheological Properties of Sodium Alginate-Pectin-Whey Protein Isolate Stabilized Β-Carotene Emulsions: To Improve Stability and Achieve Gastrointestinal Sustained Release.

Sodium alginate (SA)-pectin (PEC)-whey protein isolate (WPI) complexes were used as an emulsifier to prepare ß-carotene emulsions, and the encapsulation efficiency for ß-carotene was up to 93.08%. The confocal laser scanning microscope (CLSM) and scanning electron microscope (SEM) images showed that the SA-PEC-WPI emulsion had a compact network structure. The SA-PEC-WPI emulsion exhibited shear-thinning behavior and was in a semi-dilute or weak network state. The SA-PEC-WPI stabilized ß-carotene emulsion had better thermal, physical and chemical stability. A small amount of ß-carotene (19.46 ± 1.33%) was released from SA-PEC-WPI stabilized ß-carotene emulsion in simulated gastric digestion, while a large amount of ß-carotene (90.33 ± 1.58%) was released in simulated intestinal digestion. Fourier transform infrared (FTIR) experiments indicated that the formation of SA-PEC-WPI stabilized ß-carotene emulsion was attributed to the electrostatic and hydrogen bonding interactions between WPI and SA or PEC, and the hydrophobic interactions between ß-carotene and WPI. These results can facilitate the design of polysaccharide-protein stabilized emulsions with high encapsulation efficiency and stability for nutraceutical delivery in food and supplement products.

The regulation of sodium alginate on the stability of ovalbumin-pectin complexes for VD3 encapsulation and in vitro simulated gastrointestinal digestion study.

The ovalbumin (OVA)-pectin (PEC)-sodium alginate (SA)-Vitamin D3 (VD3) complex nanoparticles were fabricated by antisolvent precipitation method, and the excellent encapsulation efficiency and loading capacity of VD3 were obtained by 96.6% and 2.8%, respectively. Compared with ternary OVA-PEC-VD3 complexes, the addition of SA with strong negative charge effectively regulated the OVA-PEC complexes and significantly improved the stability of OVA-PEC-SA-VD3 complex nanoparticles with preferable size as small as 126 nm. The storage stability was also investigated after low temperature storage for 31 d, and the particle size of quaternary complexes was increased only 40 nm. In vitro digestion results elucidated that the complex nanoparticles had good stability in the simulated gastric fluid, and almost completely released in the simulated intestinal fluid confirmed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) experiments and scanning electron microscope (SEM) images. The release kinetics study clarified that it was close to Fick release. Fluorescence and Fourier transform infrared spectroscopy (FTIR) experiments showed that quaternary complex nanoparticles were mainly combined by electrostatic, hydrophobic and hydrogen bonding interactions. The novel quaternary protein-polysaccharide complexes have excellent stability and great sustained-release performance for VD3, which may be helpful for the digestion and absorption of vitamin by human body, thus have potential applications in the food and drug industry.

Complexation of ß-lactoglobulin with gum arabic: Effect of heat treatment and enhanced encapsulation efficiency.

Heat treatment is widely used in food industry. Proteins and polysaccharides as important natural polymers in food, under heat treatment, the interactions between them could mediate the conformation and functional properties of proteins. Thermally induced ß-lactoglobulin-gum arabic complexes (ß-Lg-GA) were fabricated, and the effect of heat treatment on physicochemical properties of the complexes was systematically investigated. The average particle size of ß-Lg-GA complexes decreased with temperature increased, at 85°C, a smaller size of 273 nm was obtained. A saturated adsorption of GA was found when mass ratio of ß-Lg/GA was <1:2. At pH = 4.2-7.0, electrostatic attraction between ß-Lg and GA was low and a fairly constant turbidity was observed, the formed composite particles had good stability to the pH value. Through UV, fluorescence, and FTIR spectroscopy, it was found that formation of the nanoparticles relied on thermal denaturation and aggregation of protein, the electrostatic, hydrophobic, and hydrogen bonding interactions between ß-Lg and GA were also important. Scanning electron microscope further indicated ß-Lg and GA had good compatibility, and the complexes had a spherical core-shell structure at molecular level. In addition, these prepared natural nanoparticles by heat treatment show significantly higher encapsulation efficiency for (-)-epigallocatechin-3-gallate (EGCG) than that of unheated, thus could be used as a promising carrier for biologically active substances.

Preparation of ß-lactoglobulin/gum arabic complex nanoparticles for encapsulation and controlled release of EGCG in simulated gastrointestinal digestion model.

In this work, the ß-lactoglobulin/gum arabic (ß-Lg-GA) complexes were prepared to encapsulate epigallocatechin gallate (EGCG), forming ß-Lg-GA-EGCG complex nanoparticles with an average particle size of 133 nm. The ß-Lg-GA complexes exhibited excellent encapsulation efficiency (84.5%), and the antioxidant performance of EGCG in vitro was improved after encapsulation. It was recorded that 86% of EGCG could be released in simulated intestinal fluid after 3 h of digestion, much faster than that in simulated gastric fluid, indicating that the ß-Lg-GA complexes were effective in enhancing EGCG stability, which was confirmed using SDS-PAGE and SEM. Further spectrum results demonstrated that various intramolecular interactions including electrostatic, hydrophobic and hydrogen bonding interactions contribute to the formation of ß-Lg-GA-EGCG complex nanoparticles. Also, XRDexperiments indicated that EGCG was successfully encapsulated by ß-Lg-GA complexes. Therefore, the ß-Lg-GA complexes hold great potentials in the protective delivery of sensitive bioactives.

Fabrication of Zein-Lecithin-EGCG complex nanoparticles: Characterization, controlled release in simulated gastrointestinal digestion.

The Zein-Lecithin-Epigallocatechin gallate (EGCG) complex nanoparticles were fabricated by anti-solvent coprecipitation method. The Zein-Lecithin (Z-L) nanocomplexes exhibited great encapsulation efficiency of 68.5% for EGCG, and the encapsulated EGCG still had good antioxidative capacity. The cumulative release of EGCG in simulated gastric fluid (SGF) and simulated intestinal fluid (SIF) were 19% and 92%, respectively, and the release was closest to Fick release in SGF and First release in SIF. Fluorescence spectroscopy (FL), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) experiments revealed that the EGCG was successfully encapsulated by Z-L nanocomplexes through electrostatic, hydrophobic and hydrogen bonding interactions. The Zein-Lecithin-EGCG complex nanoparticles exhibited excellent stability and great sustained-release performance, which will be the alternative for potential application in the food industry.

Fabrication and characterization of oil-in-water pickering emulsions stabilized by ZEIN-HTCC nanoparticles as a composite layer.

In this work, the ZEIN-HTCC nanoparticles formed by zein and N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC) were used as stabilizers to prepare oil-in-water (O/W) Pickering emulsions. The preparation conditions including shearing time, volume fraction of corn oil, mass ratio of ZEIN:HTCC and total concentration of ZEIN-HTCC of emulsions were optimized by measuring the droplet size, zeta potential, PDI and surface tension of emulsions. The ZEIN-HTCC emulsions are stable at the pH range of 4-9 and in the low salt ion concentrations up to 0.2 mol L-1, and can keep stable up to 21 d during low temperature storage. Fourier transform infrared spectroscopy (FTIR), the confocal laser scanning microscope (CLSM) and scanning electron microscopy (SEM) were used to analyze the interaction between emulsion components, revealing that zein and HTCC form a composite layer by flocculation to adsorb on the surface of oil droplets, thus preventing emulsion droplets from aggregation. This novel, long-term stable, surfactant-free, and edible zein-based Pickering emulsion could be used as potential carriers for lipophilic nutrients delivery.

Ultrasonic irradiation accelerated cyclopalladated ferrocenylimines catalyzed Suzuki reaction in neat water.

Both conventional heating and ultrasound effect on the cyclopalladated ferrocenylimines catalyzed Suzuki reaction of phenylboronic acid with a range of arylhalides in neat water was investigated. Heterogenous reaction of electron-withdrawing arylchlorides with phenylboronic acid could also result in good yields by using Cat. 2. It was found that the ultrasonic irradiation could dramatically accelerate the Suzuki reaction to achieve comparable results.