Cellulose nanocrystal-stabilized Pickering emulsion gels as vehicles for follicular delivery of minoxidil.

Minoxidil (MXD) is the only topical over-the-counter medicine approved by the United States Food and Drug Administration for the treatment of androgenetic alopecia. For the purpose of targeting the delivery of MXD to dermal papilla in the hair follicle, MXD Pickering emulsion gels were fabricated based on the designability of deep eutectic solvent (DES) and the versatility of cellulose nanocrystal (CNC) and sodium carboxymethyl cellulose (CMC-Na). Structural studies and theoretical calculations results suggest that CNC can stabilize the interface between the MXD-DES and water, leading to the formation of Pickering emulsions. The rheological properties and stabilities of MXD Pickering emulsions were enhanced through gelation using CMC-Na, which highlights the good compatibility and effectiveness of natural polysaccharides in emulsion gels. Due to the particle size of emulsion droplets (679 nm) and the rheological properties of emulsion gel, the fabricated MXD formulations show in vivo hair regrowth promotion and hair follicle targeting capabilities. Interestingly, the MXD Pickering emulsion-based formulations exert therapeutic effects by upregulating the expression of hair growth factors. The proposed nanodrug strategy based on supramolecular strategies of CNC and CMC-Na provides an interesting avenue for androgenetic alopecia treatment.

Physicochemical properties and in vitro digestive behavior of astaxanthin loaded Pickering emulsion gel regulated by konjac glucomannan and κ-carrageenan.

This study aimed to elaborate the combination effect of polysaccharides on physicochemical properties and in vitro digestive behavior of astaxanthin (AST)-loaded Pickering emulsion gel. AST-loaded Pickering emulsion gel was prepared by heating Pickering emulsion with konjac glucomannan (KGM) and κ-carrageenan (CRG). The microstructure revealed that adding the two polysaccharides resulted in Pickering emulsion forming a network structure. It exhibited a denser and more uniform network structure, enhancing its mechanical properties four times and increasing its water-holding capacity by 20 %. In vitro digestion experiments demonstrated that the release of free fatty acids from the Pickering emulsion gel (4.25 %) was notably lower than that from conventional Pickering emulsion (17.19 %), whereas AST bioaccessibility was remarkably low at 0.003 %. It provided a feasible strategy to regulate the bioaccessibility in Pickering emulsion, which has theoretical significance to guide the current eutrophic diet people.

Cholic Acid/Glutathione-Assembled Nanofibrils for Stabilizing Pickering Emulsion Biogels.

Achieving the delicate balance required for both emulsion and gel characteristics, while also imparting biological functionality in gelled emulsions, poses a significant challenge. Herein, Pickering emulsion biogels stabilized is reported by novel biological nanofibrils assembled from natural glutathione (GSH) and a tripod cholic acid derivative (TCA) via electrostatic interactions. GSH, composed of tripeptides with carboxyl groups, facilitates the protonation and dissolution of TCA compounds in water and the electrostatic interactions between GSH and TCA trigger nanofibrillar assembly. Fibrous nuclei initially emerge, and the formed mature nanofibrils can generate a stable hydrogel at a low solid concentration. These nanofibrils exhibit efficient emulsifying capability, enabling the preparation of stable Pickering oil-in-water (O/W) emulsion gels with adjustable phase volume ratios. The entangled nanofibrils adsorbed at the oil-water interface restrict droplet movement, imparting viscoelasticity and injectability to the emulsions. Remarkably, the biocompatible nanofibrils and stabilized emulsion gels demonstrate promising scavenging properties against reactive oxygen species (ROS). This strategy may open new scenarios for the design of advanced emulsion gel materials using natural precursors and affordable building blocks for biomedical applications.

Pickering emulsion gel of polyunsaturated fatty acid-rich oils stabilized by zein-tannic acid green nanoparticles for storage and oxidation stability enhancement.

HYPOTHESIS: Poor storage stability and oxidative deterioration are the common drawbacks of edible oils rich in polyunsaturated fatty acids (PUFAs). We hypothesized that the natural zein/tannic acid self-assembly nanoparticles (ZT NPs) could be employed as stabilizers to anchor at the oil-water interface, thus constructing Pickering emulsion gel (PKEG) system for three types of PUFA-rich oils, soybean oil (SO), fish oil (FO) and cod liver oil (CLO), to improve the storage and oxidation stability. EXPERIMENTS: ZT NPs were prepared by the anti-solvent coprecipitation method, and the three-phase contact angle, FT-IR, and XRD were mainly characterized. To observe the shell-core structure and oil-water interface details of SO/FO/CLO PKEGs by confocal laser scanning microscope and cryo-scanning electron microscope. Accelerated oxidation of FO was performed to assess the protective effect of PKEG on lipids. FINDINGS: The SO, FO, and CLO PKEGs stabilized by 2 % ZT NPs, with oil fraction (φ = 0.5-0.6), were obtained. PKEGs show high viscoelasticity, clear shell-core structure spatial network structure, and ideal storage stability. Under accelerated oxidation, the degree of oxidative rancidity of FO PKEG was obviously lower than that of free FO. Overall, this work opens up new possibilities for using natural PKEG to prevent oxidative deterioration and prolong the shelf-life of PUFA-rich oils.

Exploring the role of γ-Oryzanol on stabilization mechanism of Pickering emulsion gels loaded by α-Lactalbumin or ß-Lactoglobulin via multiscale approaches.

The research explored the role of γ-oryzanol (γs) on stabilization behavior of Pickering emulsion gels (PEGs) loaded by α-lactalbumin (α-LA) or ß-lactoglobulin (ß-LG), being analyzed by experimental and computer methods (molecular dynamic simulation, MD). Primarily, the average particle size of ß-LG-γS was expressed 100.07% decrease over that of α-LA-γS. In addition, γs decreased the dynamic interfacial tension of two proteins with the order of ß-LG < α-LA. Meanwhile, quartz crystal microbalance with dissipation proved that ß-LG-γS exhibited higher adsorption mass and denser rigid interface layer than α-LA-γS. Moreover, the hydrophobic group of γS had electrostatic repulsion with polar water molecules in the aqueous phase, which spread to the oil phase. ß-LG-γS had lower RMSD/Rg value and narrower fluctuation compared with α-LA-γS. This work strength the exploration of interfacial stabilization mechanism of whey protein-based PEGs, which enriched its theoretical research for industrial-scale production as the replacement of trans fat and cholesterol.

Fabrication, characterization and application of Pickering emulsion gels stabilized by defatted grape seed powder.

The feasibility of defatted grape seed powder (DGSP) stabilizing Pickering emulsion gels as butter substitute was investigated. The Pickering emulsion gel was constructed using DGSP through high-speed homogenization, and the effects of particle concentration (c) and oil-phase (Medium chain triglyceride) volume fraction (φ) on its structure and properties were investigated. Its application as a butter substitute was also evaluated. The results showed that DGSP had various particle shapes, a wide particle size distribution (3-130 µm), and a three-phase contact angle of 128.9 ± 2.3°. The O/W Pickering emulsion gels with φ ≥ 60% could be obtained at c ≥ 2%. The droplet diameter was negatively correlated with c and positively correlated with φ, while the gel strength was positively related to c and φ. The resulting emulsion gel demonstrated solid-like viscoelastic behavior and pseudoplasticity, and had the potential to serve as a butter substitute. The results can promote the application of grape seeds in food.

O1/W/O2 double emulsion gels based on nanoemulsions and Pickering particles for co-encapsulating quercetin and cyanidin: A functional fat substitute.

An O1/W/O2 double emulsion gel, as a functional fat substitute and based on nanoemulsions and hydrophobic Pickering particles, is prepared by two-step emulsification to co-encapsulate hydrophilic cyanidin and hydrophobic quercetin. Nanoemulsions loading quercetin are fabricated by Tween-80 and combining high-speed and high-pressure emulsification. Phytosterol nanoparticles stabilize the W-O2 interface of the secondary emulsion to load cyanidin in the W phase. The concentration of Tween-80 is optimized as 0.3% by the droplet size and viscosity of nanoemulsions. The structural stability of double emulsion gels will be weakened along with the increase of nanoemulsions, showing lower modulus and encapsulation efficiency (EE) and bigger droplets. In double emulsion gels, the EE of quercetin and cyanidin reaches 93% and 85.6%, respectively. Analysis of molecular interaction indicates that Tween-80 would decrease the in-situ hydrophobicity of phytosterol nanoparticles by hydrogen bonding adsorption, thereby weakening the emulsification. The pH-chromic 3D printing of double emulsion gels is designed according to the pH sensitivity of cyanidin. Texture profile analysis is performed to test the textural properties of 3D-printed objects. The simulated digestion is conducted on double emulsion gels. The double emulsion gel with fewer nanoemulsions is beneficial for protecting quercetin and improving the delivery due to the higher structural stability, while that with more nanoemulsions is conducive to the digestion of cyanidin and camellia oil due to weakened semi-solid properties. This double emulsion gel further simulates fat tissues by co-encapsulating hydrophilic and hydrophobic substances, promoting the application of fat substitutes in the food industry.

Fabrication and 3D printing of Pickering emulsion gel based on Hypsizygus marmoreus by-products protein.

Pickering emulsion gel (PEG) stabilized by the protein extracted from the by-product of Hypsizygus marmoreus, combining with xanthan gum (XG), was formulated as 3D printing ink. Hydrogen bonds are formed in XG/protein hybrid particles. Afterwards, PEG was developed. Results indicated that it has shear-thinning properties. The apparent viscosity, yield stress, Elastic modulus (G') and gel strength increased with the increased XG addition, while the size of emulsion decreased. XG incorporation improved the 3D printing performance with desired self-supporting capability and printing precision if its concentration reached 2.0% (w/v). This study provides ideas for the application of Hypsizygus marmoreus by-products protein in stabilizing PEG used for 3D printing, which has a potential to replace traditional hydrogenated cream for cake decoration.

Novel Pickering emulsion gels stabilized solely by phenylalanine amidated pectin: Characterization, stability and curcumin bioaccessibility.

Pickering emulsion gels represent a novel class of non-toxic and biocompatible emulsions, offering extensive applications in the pharmaceutical and food additive sectors. This study delineates the synthesis of Pickering emulsion gels utilizing native and amidated pectin samples. Phenylalanine amidated pectin (AP) was procured via an ultra-low temperature enzyme method, while the control group (LP) adhered to an identical procedure without papain catalysis. Experimental outcomes revealed that the AP Pickering emulsion gel manifested superior stability compared to pectin emulsion samples (PE and LP). The Pickering emulsion gel from 5 % amidated pectin (5AP) retained stability throughout a 14-day emulsion stability assessment. Furthermore, all emulsion samples were evaluated for their capacity to deliver and sustain curcumin within an in vitro digestion simulation. Rheological properties and oil droplet size results indicated that the 5AP Pickering emulsion gel exhibited optimal cream index and emulsion stability, effectively inhibiting premature water-oil stratification within the emulsion and augmenting curcumin bioaccessibility. Within the in vitro digestion simulation, the 5AP Pickering emulsion gel demonstrated the highest curcumin bioaccessibility, measured at 17.96 %.

Incorporation of probiotics into 3D printed Pickering emulsion gel stabilized by tea protein/xanthan gum.

Different xanthan gum (XG) concentrations on the rheological/texture properties of Pickering emulsion (PE) gel stabilized by tea protein/xanthan gum (TP/XG) were studied to achieve an ink feasible for 3D printing. Afterwards, the effects of 3D printing and digestion process on the viability of probiotics were studied when encapsulated in the PE gel. Results indicated that gel strength, stability, storage modulus (G') and loss modulus (G″) increased as XG concentration increased. Nozzle diameter and printing temperature of 45 and 55℃ had no significant effect on probiotic's viability, but printing temperature of 65℃ reduced viable probiotics from 8.07 to 6.59 log CFU/g. No significant change of probiotics viability in 3D printed samples was observed during 11-day storage at 4℃. PE gel encapsulated probiotic's viability was significantly improved under heat treatment and simulated gastrointestinal environment. This study gives insights on the production of 3D printed foods using PE gel incorporating probiotics.

Starch-lauric acid complex-stabilised Pickering emulsion gels enhance the thermo-oxidative resistance of flaxseed oil.

Hydrophobic-modified starch complexes have the potential to form Pickering emulsions and improve the oxidative stability of flaxseed oil. Here, V-type starch-lauric acid complexes (SLACs) were fabricated via solid encapsulation within 0.5-12 h and applied in flaxseed oil Pickering emulsions. Complexing index, X-ray diffraction and differential scanning calorimetry analyses confirmed that the degree of complexation increased with the reaction time. Pickering emulsion gels stabilised by SLACs generated with reaction times of 6 h and 12 h exhibited good storage stability and high yield stress, G' values and apparent viscosity. Confocal laser scanning microscopy and cryo-scanning electron microscopy revealed a gelation mechanism involving increased interface roughness and enhanced droplet-droplet interaction. In comparison to pure flaxseed oil, higher thermo-oxidative resistance was observed at 130 °C, with a markedly longer oxidation induction for emulsions and emulsion gels stabilised by SLACs. Our findings could assist in the design of hydrophobic-modified starch and provide a new paradigm for delaying oil oxidation.

Soft κ-carrageenan microgels stabilized pickering emulsion gels: Compact interfacial layer construction and particle-dominated emulsion gelation.

HYPOTHESIS: The well-known gelling ability of κ-carrageenan can make aqueous solutions into soft materials, which are crisp and can be mechanically treated into the nano-sized microgel particle (MP) as the building block for constructing the Pickering emulsion gel (PEG). MPs are expected to adhere and further create the network structure in PEGs due to their viscoelastic texture. Herein, properties of PEGs should be possibly altered by using MPs with different pH and ionic strength. EXPERIMENTS: MPs were prepared by shearing and gelling κ-carrageenan solutions simultaneously. Effects of pH and ionic strength on MPs were formulated, and physical properties of PEGs prepared from corresponding MPs were investigated. The interaction between κ-carrageenan molecules was analyzed by FTIR, and the formation process of the interfacial layer was traced by the interfacial rheological technique. FINDINGS: The moderate K+ could increase the flocculation and hardness of MPs to improve the viscoelasticity of PEGs. Prepared MPs were more favorable for forming PEGs when pH was 8 and 9. The oil fraction impacted physical properties of PEGs slightly. MPs constantly moved to the interface from the continuous phase, forming the compact adsorption layer due to the extrusion of MPs.

Pickering emulsion gels stabilized by high hydrostatic pressure-induced whey protein isolate gel particles: Characterization and encapsulation of curcumin.

In this study, whey protein isolate (WPI) gel particles were fabricated via high hydrostatic pressure (HHP) treatment and homogenization and the potential of using the particles as food-grade stabilizers to form Pickering emulsions and emulsion gels were studied. The result showed that pH had a significant effect on the properties of WPI gel particles. In the pH range near the isoelectric point (pI) (around pH 5.0), the particles exhibited spherical structure with larger size. The droplet size, creaming stability, microstructure and rheological properties of the Pickering emulsions stabilized by the WPI gel particles were influenced by pH and ionic strength, particle concentration and oil fraction. Pickering emulsion gels were formed from the Pickering emulsions stabilized by the particles at pH 5.0 after storage for 3 days at room temperature (25 °C). Confocal laser scanning microscopy (CLSM) demonstrated that the WPI gel particles formed a densely packed particle layer on the surface of oil droplet, suggesting the potential of these particles as Pickering emulsion stabilizers. Besides, the Pickering emulsion gels had the highest loading efficiency of curcumin and best stability against light degradation.

Pickering emulsion gel stabilized by octenylsuccinate quinoa starch granule as lutein carrier: Role of the gel network.

Octenylsuccinate quinoa starch (OSQS) granule that stabilized Pickering emulsion gel with different gel networks by modulating the oil volume fraction (Φ) was developed as a carrier for lutein. Pickering emulsion gels stabilized by OSQS were achieved at Φ values ranging from 30% to 60%. Increasing Φ progressively increased the droplet size, storage modulus, and apparent viscosity, resulting in the formation of gel-like structure. Confocal laser scanning microscopy showed that OSQS formed a densely packed layer at the oil/water interface, the degree of aggregation between droplets increased, and the gel network enhanced through droplet flocculation with increasing Φ. After 31 days of storage, the retention index of lutein in the emulsion gel could reach 55.38%, and the corresponding half-life times increased from 12 to 41 days. This study will be useful for designing starch-based Pickering emulsion gel with tunable gel network and desirable characteristics as delivery carrier of sensitive bioactive compounds.

Pickering Emulsion Gels Prepared by Hydrogen-Bonded Zein/Tannic Acid Complex Colloidal Particles.

Food-grade colloidal particles and complexes, which are formed via modulation of the noncovalent interactions between macromolecules and natural small molecules, can be developed as novel functional ingredients in a safe and sustainable way. For this study was prepared a novel zein/tannic acid (TA) complex colloidal particle (ZTP) based on the hydrogen-bonding interaction between zein and TA in aqueous ethanol solution by using a simple antisolvent approach. Pickering emulsion gels with high oil volume fraction (φ(oil) > 50%) were successfully fabricated via one-step homogenization. Circular dichroism (CD) and small-angle X-ray scattering (SAXS) measurements, which were used to characterize the structure of zein/TA complexes in ethanol solution, clearly showed that TA binding generated a conformational change of zein without altering their supramolecular structure at pH 5.0 and intermediate TA concentrations. Consequently, the resultant ZTP had tuned near neutral wettability (θ(ow) ∼ 86°) and enhanced interfacial reactivity, but without significantly decreased surface charge. These allowed the ZTP to stabilize the oil droplets and further triggered cross-linking to form a continuous network among and around the oil droplets and protein particles, leading to the formation of stable Pickering emulsion gels. Layer-by-layer (LbL) interfacial architecture on the oil-water surface of the droplets was observed, which implied a possibility to fabricate hierarchical interface microstructure via modulation of the noncovalent interaction between hydrophobic protein and natural polyphenol.