Titania-Cored Janus Multipods as UV-Protective Pickering Emulsifiers for Sunscreens.

Pickering emulsifiers have gained significant interest as alternatives for conventional surfactants in various applications that includes pharmaceutics, food, homecare products, and cosmetics. However, their function is primarily focused on enhancing emulsion stability of which still remains to be resolved. Herein, Janus multipods are presented that simultaneously shield UV while offering high emulsion stability. These particles are prepared by growing multiple silicon dioxide (SiO2) nanopods using sol-gel method on a spherical titanium dioxide (TiO2) core with a thin SiO2 shell. The incorporation of high refractive index TiO2 in the core is shown to effectively shield UV while the SiO2 shell suppresses the photocatalytic activity. Moreover, by utilizing wax colloidosomes as templates, these multipod nanoparticles are further modified to exhibit Janus characteristics. This leads to strong adsorption of the Janus multipods at the oil/water emulsion interface where the multipod feature additionally reinforces the interfacial stabilization by interdigitation and interlocking of the Janus multipods to suppress detachment of the highly dense particles from the interface. As these Janus multipods offer effective UV protection as well as excellent emulsion stability, it is envisioned that they have great potential in advanced cosmetic formulations which require both enhanced sunscreen performance and better feeling in skincare products.

Starch-based particles as stabilizers for Pickering emulsions: modification, characteristics, stabilization, and applications.

The potential utilization of starch as a particle-based emulsifier in the preparation of Pickering emulsions is gaining interest within the food industry. Starch is an affordable and abundant functional ingredient, which makes it an excellent candidate for the stabilization of Pickering emulsions. This review article focuses on the formation, stabilization, and properties of Pickering emulsions formulated using starch-based particles and their derivatives. First, methods of isolating and modifying starch-based particles are highlighted. The key parameters governing the properties of starch-stabilized Pickering emulsions are then discussed, including the concentration, size, morphology, charge, and wettability of the starch-based particles, as well as the type and size of the oil droplets. The physicochemical mechanisms underlying the ability of starch-based particles to form and stabilize Pickering emulsions are also discussed. Starch-based Pickering emulsions tend to be more resistant to coalescence than conventional emulsions, which is useful for some food applications. Potential applications of starch-stabilized Pickering emulsions are reviewed, as well as recent studies on their gastrointestinal fate. The information provided may stimulate the utilization of starch-based Pickering emulsions in food and other industries.

Wide pH, Adaptable High Internal Phase Pickering Emulsion Stabilized by a Crude Polysaccharide from Thesium chinense Turcz.

The ultrasound-assisted extraction conditions of Thesium chinense Turcz. crude polysaccharide (TTP) were optimized, and a TTP sample with a yield of 11.9% was obtained. TTP demonstrated the ability to stabilize high-internal-phase oil-in-water emulsions with an oil phase volume reaching up to 80%. Additionally, the emulsions stabilized by TTP were examined across different pH levels, ionic strengths, and temperatures. The results indicated that the emulsions stabilized by TTP exhibited stability over a wide pH range of 1-11. The emulsion remained stable under ionic strengths of 0-500 mM and temperatures of 4-55 °C. The microstructure of the emulsions was observed using confocal laser scanning microscopy, and the stabilization mechanism of the emulsion was hypothesized. Soluble polysaccharides formed a network structure in the continuous phase, and the insoluble polysaccharides dispersed in the continuous phase, acting as a bridge structure, which worked together to prevent oil droplet aggregation. This research was significant for developing a new food-grade emulsifier with a wide pH range of applicability.

Characteristics of hairtail surimi gels treated with myofibrillar protein-stabilized Pickering emulsions.

BACKGROUND: Hairtail (Trichiurus haumela) surimi exhibits poor gelation properties and a dark gray appearance, which hinder its utilization in high-quality surimi gel products. The effect of Pickering emulsions stabilized by myofibrillar proteins (MPE) on the gel properties of hairtail surimi has been unclear. In particular, the impact of MPE under NaCl and KCl treatments on the quality of hairtail surimi gels requires further elucidation. RESULTS: Pickering emulsions stabilized by myofibrillar proteins and treated with NaCl or KCl (Na-MPE, K-MPE) were added to hairtail surimi in amounts of 10-70 g kg-1. The addition of 50 g kg-1 Na-MPE and K-MPE improved the gel strength, textural properties, whiteness, and water-holding capacity (WHC) of hairtail surimi. The relative content of ß-turn and ß-sheet in the surimi gels increased and the relative content of random coils and α-helix decreased with the addition of oil. The addition of Na-MPE and K-MPE did not affect the secondary structure of surimi gels but stimulated the gelation of hairtail surimi gels. Hairtail surimi containing K-MPE demonstrated similar performance in terms of hardness, microstructure, and WHC compared with the addition of Na-MPE. CONCLUSION: The quality of hairtail surimi gels can be improved by the addition of Na-MPE or K-MPE. The K-MPE proved to be an effective option for enhancing the properties of hairtail surimi gels at 50 g kg-1 to replace Na-MPE. © 2024 Society of Chemical Industry.

Nanofibers from soybean hull insoluble polysaccharides as Pickering stabilizers in oil-in-water emulsions formulated under acidic conditions.

BACKGROUND: Pickering emulsions are a kind of emulsion stabilized by solid particles. These particles generate a physical or mechanical barrier that provides long-term stability to emulsion. Cellulose nanofibers are effective Pickering emulsifiers given their long length, high flexibility and entanglement capability. In this work, soybean hull insoluble polysaccharides (HIPS) were used as source of cellulose nanofibers by using a combination of chemical and mechanical treatment. The chemical composition, morphology, flow behavior, water holding capacity (WHC) and emulsifying properties of the nanofibers were studied. RESULTS: Nanofibers with diameters between 35 and 110 nm were obtained. The WHC increased significantly after the mechanical treatment, and the rheological behavior of the nanofibers was typical of cellulosic materials. Nanofibers were effective emulsifiers in oil-in-water (O/W) emulsions formulated under acidic conditions, without the need of using any additional surfactant. Emulsions were not affected by changes in the pH of the medium (3.00-5.00), and were stable to coalescence. CONCLUSION: It is possible that cellulose nanofibers form an entangled network which acts as a mechanical steric barrier, providing stability to coalescence. These results are important for the development of effective O/W Pickering emulsifiers/stabilizers, with large applications in the food industry. © 2023 Society of Chemical Industry.

Cage-like microstructures via sequential Ugi reactions in aqueous emulsions.

Cage-like microstructures were obtained in two steps by sequential Ugi reactions. At the first stage, submicron colloidal particles based on carboxymethylcellulose and chitosan with a domain structure were obtained in an aqueous suspension. In the second stage, the Ugi reaction was carried out on the surface of the Pickering emulsions with toluene. Removal of toluene and redissolution in water resulted in colloidosomes with large holes on the surface. Varying the cross-link density during the Ugi reaction made it possible to obtain structures with different hole sizes.

Adding nanoparticles to improve emulsion efficiency and enhance microbial degradation in Pickering emulsions.

Interfacial microbial degradation of alkane in Pickering emulsions stabilized by hydrophobic bacterial cells is a new mechanism for microbial degradation of water-insoluble chemicals, where both water-insoluble chemicals in the oil phase and water-soluble nutrients (such as nitrogen and phosphorus) in the water phase are bio-accessible to living microorganisms anchoring onto the oil-water interfaces. In the present work, super-hydrophobic Mycobacterium sp. (contact angle 168.6°) degradation of tetradecane was set up as a model. Addition of fumed SiO2 particles (Aerosil® R974) as a new strategy was developed to enhance tetradecane degradation where the biodegradation rate (based on the accumulated biomass) increased by approximately 80%. The enhanced effect of SiO2 particles on the tetradecane degradation attributed to the synergistic effect of SiO2 particles on the emulsion efficiency of Pickering emulsions stabilized by bacterial cells and then on the enhancement of interfacial microbial degradation in Pickering emulsions. KEY POINTS: • Interfacial microbial degradation in bacterial cells stabilized Pickering emulsions. • Adding fumed SiO2 particles to enhance microbial degradation of tetradecane. • Correlation relationship between emulsion efficiency and interfacial microbial degradation.

Soy Protein Isolate-Chitosan Nanoparticle-Stabilized Pickering Emulsions: Stability and In Vitro Digestion for DHA.

The purpose of the study was to investigate the stability and oral delivery of DHA-encapsulated Pickering emulsions stabilized by soy protein isolate-chitosan (SPI-CS) nanoparticles (SPI-CS Pickering emulsions) under various conditions and in the simulated gastrointestinal (GIT) model. The stability of DHA was characterized by the retention rate under storage, ionic strength, and thermal conditions. The oral delivery efficiency was characterized by the retention and release rate of DHA in the GIT model and cell viability and uptake in the Caco-2 model. The results showed that the content of DHA was above 90% in various conditions. The retention rate of DHA in Pickering emulsions containing various nanoparticle concentrations (1.5 and 3.5%) decreased to 80%, while passing through the mouth to the stomach, and DHA was released 26% in 1.5% Pickering emulsions, which was faster than that of 3.5% in the small intestine. After digestion, DHA Pickering emulsions proved to be nontoxic and effectively absorbed by cells. These findings helped to develop a novel delivery system for DHA.

Lignin nanoparticles as co-stabilizers and modifiers of nanocellulose-based Pickering emulsions and foams.

Nanocellulose is very hydrophilic, preventing interactions with the oil phase in Pickering emulsions. This limitation is herein addressed by incorporating lignin nanoparticles (LNPs) as co-stabilizers of nanocellulose-based Pickering emulsions. LNP addition decreases the oil droplet size and slows creaming at pH 5 and 8 and with increasing LNP content. Emulsification at pH 3 and LNP cationization lead to droplet flocculation and rapid creaming. LNP application for emulsification, prior or simultaneously with nanocellulose, favors stability given the improved interactions with the oil phase. The Pickering emulsions can be freeze-dried, enabling the recovery of a solid macroporous foam that can act as adsorbent for pharmaceutical pollutants. Overall, the properties of nanocellulose-based Pickering emulsions and foams can be tailored by LNP addition. This strategy offers a unique, green approach to stabilize biphasic systems using bio-based nanomaterials without tedious and costly modification procedures. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05399-y.

Preparation and Characterization of Eugenol Incorporated Pullulan-Gelatin Based Edible Film of Pickering Emulsion and Its Application in Chilled Beef Preservation.

The purpose of this study was to develop a composite film composed of eugenol Pickering emulsion and pullulan-gelatin, and to evaluate its preservation effect on chilled beef. The prepared composite film was comprehensively evaluated in terms of the stability of emulsion, the physical properties of the film, and an analysis of freshness preservation for chilled beef. The emulsion size (296.0 ± 10.2 nm), polydispersity index (0.457 ± 0.039), and potential (20.1 ± 0.9 mV) proved the success of emulsion. At the same time, the films displayed good mechanical and barrier properties. The index of beef preservation also indicated that eugenol was a better active ingredient than clove essence oil, which led to the rise of potential of hydrogen, chroma and water content, and effectively inhibited microbial propagation, protein degradation and lipid oxidation. These results suggest that the prepared composites can be used as promising materials for chilled beef preservation.

Pickering Emulsions Based in Inorganic Solid Particles: From Product Development to Food Applications.

Pickering emulsions (PEs) have attracted attention in different fields, such as food, pharmaceuticals and cosmetics, mainly due to their good physical stability. PEs are a promising strategy to develop functional products since the particles' oil and water phases can act as carriers of active compounds, providing multiple combinations potentiating synergistic effects. Moreover, they can answer the sustainable and green chemistry issues arising from using conventional emulsifier-based systems. In this context, this review focuses on the applicability of safe inorganic solid particles as emulsion stabilisers, discussing the main stabilisation mechanisms of oil-water interfaces. In particular, it provides evidence for hydroxyapatite (HAp) particles as Pickering stabilisers, discussing the latest advances. The main technologies used to produce PEs are also presented. From an industrial perspective, an effort was made to list new productive technologies at the laboratory scale and discuss their feasibility for scale-up. Finally, the advantages and potential applications of PEs in the food industry are also described. Overall, this review gathers recent developments in the formulation, production and properties of food-grade PEs based on safe inorganic solid particles.

Enzyme-Polymer-Conjugate-Based Pickering Emulsions for Cell-Free Expression and Cascade Biotransformation.

In this study, we addressed the limitations of conventional enzyme-polymer-conjugate-based Pickering emulsions for interfacial biocatalysis, which traditionally suffer from nonspecific and uncontrollable conjugation positions that can impede catalytic performance. By introducing a non-canonical amino acid (ncAA) at a specific site on target enzymes, we enabled precise polymer-enzyme conjugation. These engineered conjugates then acted as biocatalytically active emulsifiers to stabilize Pickering emulsions, while encapsulating a cell-free protein synthesis (CFPS) system in the aqueous phase for targeted enzyme expression. The resulting cascade reaction system leveraged enzymes expressed in the aqueous phase and on the emulsion interface for optimized chemical biosynthesis. The use of the cell-free system eliminated the need for intact whole cells or purified enzymes, representing a significant advancement in biocatalysis. Remarkably, the integration of Pickering emulsion, precise enzyme-polymer conjugation, and CFPS resulted in a fivefold enhancement in catalytic performance as compared to traditional single-phase reactions. Therefore, our approach harnesses the combined strengths of advanced biochemical engineering techniques, offering an efficient and practical solution for the synthesis of value-added chemicals in various biocatalysis and biotransformation applications.

pH- and Redox-Responsive Pickering Emulsions Based on Cellulose Nanocrystal Surfactants.

Nanoparticle surfactants (NPSs), formed by using dynamic interactions between nanoparticles and complementary ligands at the liquid-liquid interface, have emerged as "smart emulsifiers" with attributes of high emulsification efficiency, long-term stability, and on-demand emulsification/demulsification capabilities. However, only pH-responsiveness can be adopted for the assembly of reported NPSs formed by electrostatic interactions. Here, we propose an alternative design strategy, by taking advantage of the ferrocenium (Fc+ ) sulfate ion pair, to develop a new type of cellulose nanocrystal (CNC) surfactant. The Fc+ groups are sensitive to pH, redox reagents and voltage, imparting the CNC surfactants and derived Pickering emulsions with multi-stimuli-responsiveness, and showing promising applications in controllable delivery, release, and biphasic biocatalysis.

Spatial Localization of Two Enzymes at Pickering Emulsion Droplet Interfaces for Cascade Reactions.

Developing biocatalytic cascades in abiological conditions is of utmost significance, but such processes often suffer from low reaction efficiency because of incompatible reaction environments and suppressed intermediate transportation. Herein we report a new type of biocatalytic cascade by localizing two different enzymes separately in the outer and inner interfacial layers of Pickering emulsion droplets. This versatile approach enables the localization of two enzymes in their preferred reaction microenvironments and simultaneously in nanoscale proximity of each other. The thus-designed interfacial biocatalytic cascades show outstanding catalytic efficiency in alkene epoxidation and thioether oxidation with in situ generation of hydrogen peroxide under mild conditions, 6.9-13.6 times higher than the catalytic efficiency of the free enzymes in solution and their multi-enzymatic counterparts. The remarkable interfacial effect of Pickering droplets was found to be responsible for the significantly enhanced cascading efficiency.

Recent advances in self-assembly behaviors of prolamins and their applications as functional delivery vehicles.

Prolamins are a group of storage proteins (zeins, kafirins, hordeins, secalins, gliadins, glutenins, and avenins) found in the endosperm of cereal grains and characterized by high glutamine and proline content. With the high proportion of nonpolar amino acids (40-80%) and peculiar solubility (alcohol (60-90%), acetic acid, and alkaline solutions), prolamins exhibit tunable self-assembly behaviors. In recent years, research practices of utilizing prolamins as green building materials of functional delivery vehicles to improve the health benefits of bioactive compounds have surged due to their attractive advantages (e.g. sustainability, biocompatibility, fabrication potential, and cost-competitiveness). This article covers the recent advances in self-assembly behaviors leading to the fabrication of nanoparticles, fibers, and films in the bulk water phase, at the air-liquid interface, and under the electrostatic field. Different fabrication methods, including antisolvent precipitation, evaporation induced self-assembly, thermal treatment, pH-modulation, electrospinning, and solvent casting for assembling nanoarchitectures as functional delivery vehicles are highlighted. Emerging industrial applications by mapping patents, including encapsulation and delivery of bioactive compounds and probiotics, active packaging, Pickering emulsions, and as functional additives to develop safer, healthier, and sustainable food products are discussed. A future perspective concerning the fabrication of prolamins as advanced materials to promote their commercial food applications is proposed.

Stimuli-Responsive Pickering Emulsions Regulated via Polymerization-Induced Self-Assembly Nanoparticles.

With the development of reversible deactivated radical polymerization techniques, polymerization-induced self-assembly (PISA) is emerging as a facile method to prepare block copolymer nanoparticles in situ with high concentrations, providing wide potential applications in different fields, including nanomedicine, coatings, nanomanufacture, and Pickering emulsions. Polymeric emulsifiers synthesized by PISA have many advantages comparing with conventional nanoparticle emulsifiers. The morphologies, size, and amphiphilicity can be readily regulated via the synthetic process, post-modification, and external stimuli. By introducing stimulus responsiveness into PISA nanoparticles, Pickering emulsions stabilized with these nanoparticles can be endowed with "smart" behaviors. The emulsions can be regulated in reversible emulsification and demulsification. In this review, the authors focus on recent progress on Pickering emulsions stabilized by PISA nanoparticles with stimuli-responsiveness. The factors affecting the stability of emulsions during emulsification and demulsification are discussed in details. Furthermore, some viewpoints for preparing stimuli-responsive emulsions and their applications in antibacterial agents, diphase reaction platforms, and multi-emulsions are discussed as well. Finally, the future developments and applications of stimuli-responsive Pickering emulsions stabilized by PISA nanoparticles are highlighted.

Pickering Emulsions Stabilized with Curcumin-Based Solid Dispersion Particles as Mayonnaise-like Food Sauce Alternatives.

Pickering emulsions, which are emulsions stabilized by colloidal particles, are being increasingly positioned as novel strategies to develop innovative food product solutions. In this context, the present work aims to develop Pickering emulsions stabilized by natural-based curcumin-loaded particles produced by the solid dispersion technique as promising mayonnaise-like food sauce alternatives. Two particle formulations (KC1 and KC2) were produced using k-carrageenan as the matrix material and different curcumin contents, then employed in the preparation of three Pickering emulsion formulations comprising different oil fractions (φ) and particle concentrations (KC1 φ 0.4 (4.7%), KC2 φ 0.4 (4.7%) and KC2 φ 0.6 (4.0%)). The creaming index tests accompanied by the optical microscopy analysis evidenced the good stability of the developed products for the tested period of 28 days. The final products were tested concerning color attributes, pH, oxidative stability, textural, and nutritional composition, and compared with two commercial mayonnaises (traditional and light products). Overall, the produced emulsions were characterized by a bright yellow color (an appealing attribute for consumers), an acidic pH (similar to mayonnaise), and a considerably improved oxidative stability, implying a foreseeable longer shelf life. The sauce KC1 φ 0.4 (4.7%) showed a similar texture to the light commercial mayonnaise, being a promising alternative to conventional sauces, holding a low-fat content and potentially added benefits due to the curcumin and virgin olive oil intrinsic properties.

Preparation, characterization, and bioactivity of Zingiber officinale Roscoe powder-based Pickering emulsions.

BACKGROUND: Biocompatible Pickering emulsions (PE) stabilized by tailor-made antioxidant-loaded particles have been known for some time now, but antioxidant-rich natural plant particle-based emulsions are much less well known. This study aimed to investigate the physico-chemical properties of commercial Zingiber officinale powders obtained from biological and conventional agricultural practice and ginger powder-based PE. RESULTS: The physico-chemical and biological properties of Zingiber officinale powders (GDPs) obtained from conventional (GDPC1 and GDPC2) and biological agricultural (GDPBIO) practices, and the properties of derived PE (PE_GDPs) were examined. All GDPs showed weak aggregation in aqueous media and a sufficiently hydrophobic surface to stabilize oil-in-water (O/W) PE against coalescence for at least 1 month. Zingiber officinale powders (2% w/w) derived from biological agricultural practices (GDPBIO) demonstrated the best emulsifying properties. The Zingiber officinale powders and PE_GDPs were also characterized by their phytochemical profiles. All the investigated samples exhibited ferric reducing ability power greater than the positive control, butylated hydroxytoluene (BHT), with values ranging from 91.21 to 102.63 µmol L-1 Fe (II) g-1 for GDPC2 and 05PE_GDPC1 (O/W=1:1), respectively. In ß-carotene bleaching test the following trend GDPC1 > GDPBIO > GDPC2 was observed. A 05PE_GDPBIO sample with the oil volume fraction equal to 50% was stable to oxidation and exhibited a promising α-amylase inhibitory activity. CONCLUSION: The results suggest that ginger powder should be used as a starting point to design biocompatible PEs for different applications in the functional food, nutraceutical, and pharmaceutical industries. In fact, powder and based PE are characterized by a promising antioxidant activity, carbohydrate hydrolyzing enzyme and lipase inhibitory properties. Further in vivo studies are necessary to confirm these findings. © 2022 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Fabrication and characterization of Pickering emulsions stabilized by desalted duck egg white nanogels and sodium alginate.

BACKGROUND: The waste of salted egg white resources has always been a serious problem in the food industry. In this current study, we report on a kind of Pickering emulsion system, which was stabilized by duck egg white nanogels (DEWNs) and sodium alginate (SA), followed by which this system was crosslinked by calcium carbonate (CaCO3 ) via controlling the gluconolactone (GDL) concentrations, aiming to open up a promising route for making full use of these protein resources. RESULTS: The droplet size of the emulsion exhibited a reduction with an increase in SA concentrations, indicating that higher negative charges and steric hindrance was useful for a stable emulsion system. Meanwhile, the result of rheology measurement showed that storage modulus (G') values were higher than loss modulus (G″) values of the samples at higher GDL concentration, revealing the formation of elastic gel-like networks in the system, which was fabricated by SA and Ca2+ released by the CaCO3 particles. The gel-like network structure in the continuous phase improved both the freeze-thaw and thermal stability of the obtained Pickering emulsion system. Encouragingly, the Pickering high internal phase emulsions (HIPEs, φ = 0.75) stabilized by DEWN/SA3 -GDL3 were prepared, which could be stored at 4 °C for at least 30 days without oiling-off and creaming. CONCLUSION: These findings not only develop a green ultra-stable Pickering emulsion system but also extend the potential commercial applications of duck egg white proteins in the food, cosmetics, and pharmaceutical industries. © 2021 Society of Chemical Industry.

Zein/pullulan complex colloidal particle-stabilized Pickering emulsions for oral delivery of polymethoxylated flavones: protection effect and in vitro digestion.

BACKGROUND: Polymethoxylated flavones (PMFs) show multiple biological functions, while their high hydrophobicity leads to a low bioaccessibility and limits their wide applications. The design of a reasonable food-grade drug delivery system is an effective strategy to improve the low bioaccessibility of PMFs. In this study, sinensetin, tangeretin and nobiletin were encapsulated in Pickering emulsions stabilized by zein/pullulan complex colloidal particles (ZPPs), and the protection effect and in vitro digestion were characterized. RESULTS: Rheological analysis revealed that ZPP-Pickering emulsion loading with PMFs maintained a strong gel-like network structure. Moreover, the ability to scavenge free radicals of PMFs was improved by the emulsion delivery system. The antioxidant activity of PMFs encapsulated in Pickering emulsion was positively correlated with the oil volume fraction (φ). ZPP-Pickering emulsion loading with PMFs can effectively delay lipid oxidation, and the φ (70%) of Pickering emulsion showed the most pronounced effects, in which the lipid hydroperoxide content and malondialdehyde content decreased by 64.3% and 38.3% after 15 days of storage, compared with the bulk oil group, respectively. The bioaccessibility of the three PMFs has been increased by ZPP-Pickering emulsion simultaneously and it presented the highest values as its φ was 50%, in which the bioaccessibility of sinensetin, tangeretin and nobiletin increased by 2.5, 3.2 and 3.9 times, compared with the bulk oil group, respectively. CONCLUSION: Pickering emulsion stabilized by ZPPs is an excellent nutrient delivery system for delivering three PMFs simultaneously and imparting functional properties to bioactive delivery systems. © 2022 Society of Chemical Industry.