Dual Modification of Cassava Starch Using Physical Treatments for Production of Pickering Stabilizers.

Cassava starch nanoparticles (SNP) were produced using the nanoprecipitation method after modification of starch granules using ultrasound (US) or heat-moisture treatment (HMT). To produce SNP, cassava starches were gelatinized (95 °C/30 min) and precipitated after cooling, using absolute ethanol. SNPs were isolated using centrifugation and lyophilized. The nanoparticles produced from native starch and starches modified using US or HMT, named NSNP, USNP and HSNP, respectively, were characterized in terms of their main physical or functional properties. The SNP showed cluster plate formats, which were smooth for particles produced from native starch (NSNP) and rough for particles from starch modified with US (USNP) or HMT (HSNP), with smaller size ranges presented by HSNP (~63-674 nm) than by USNP (~123-1300 nm) or NSNP (~25-1450 nm). SNP had low surface charge values and a V-type crystalline structure. FTIR and thermal analyses confirmed the reduction of crystallinity. The SNP produced after physical pretreatments (US, HMT) showed an improvement in lipophilicity, with their oil absorption capacity in decreasing order being HSNP > USNP > NSNP, which was confirmed by the significant increase in contact angles from ~68.4° (NSNP) to ~76° (USNP; HSNP). A concentration of SNP higher than 4% may be required to produce stability with 20% oil content. The emulsions produced with HSNP showed stability during the storage (7 days at 20 °C), whereas the emulsions prepared with NSNP exhibited phase separation after preparation. The results suggested that dual physical modifications could be used for the production of starch nanoparticles as stabilizers for Pickering emulsions with stable characteristics.

Eco-friendly and effective antimicrobial Melaleuca alternifolia essential oil Pickering emulsions stabilized with cellulose nanofibrils against bacteria and SARS-CoV-2.

Melaleuca alternifolia essential oil (MaEO) is a green antimicrobial agent suitable for confection eco-friendly disinfectants to substitute conventional chemical disinfectants commonly formulated with toxic substances that cause dangerous environmental impacts. In this contribution, MaEO-in-water Pickering emulsions were successfully stabilized with cellulose nanofibrils (CNFs) by a simple mixing procedure. MaEO and the emulsions presented antimicrobial activities against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Moreover, MaEO deactivated the SARS-CoV-2 virions immediately. FT-Raman and FTIR spectroscopies indicate that the CNF stabilizes the MaEO droplets in water by the dipole-induced-dipole interactions and hydrogen bonds. The factorial design of experiments (DoE) indicates that CNF content and mixing time have significant effects on preventing the MaEO droplets' coalescence during 30-day shelf life. The bacteria inhibition zone assays show that the most stable emulsions showed antimicrobial activity comparable to commercial disinfectant agents such as hypochlorite. The MaEO/water stabilized-CNF emulsion is a promissory natural disinfectant with antibacterial activity against these bacteria strains, including the capability to damage the spike proteins at the SARS-CoV-2 particle surface after 15 min of direct contact when the MaEO concentration is 30 % v/v.

A Review of Pickering Emulsions: Perspectives and Applications.

Pickering emulsions are systems composed of two immiscible fluids stabilized by organic or inorganic solid particles. These solid particles of certain dimensions (micro- or nano-particles), and desired wettability, have been shown to be an alternative to conventional emulsifiers. The use of biodegradable and biocompatible stabilizers of natural origin, such as clay minerals, presents a promising future for the development of Pickering emulsions and, with this, they deliver some advantages, especially in the area of biomedicine. In this review, the effects and characteristics of microparticles in the preparation and properties of Pickering emulsions are presented. The objective of this review is to provide a theoretical basis for a broader type of emulsion, in addition to reviewing the main aspects related to the mechanisms and applications to promote its stability. Through this review, we highlight the use of this type of emulsion and its excellent properties as permeability promoters of solid particles, providing ideal results for local drug delivery and use in Pickering emulsions.

Squalene-Rich Amaranth Oil Pickering Emulsions Stabilized by Native α-Lactalbumin Nanoparticles.

The stabilization of Pickering emulsions by nanoparticles has drawn great interest in the field of food science and technology. In this study, α-Lactalbumin nanoparticles prepared by the desolvation and cross-linking method from protein solutions with initial pH values of 9 and 11 were used to stabilize squalene-rich amaranth oil Pickering o/w emulsions. The effect of different concentrations of nanoparticles on the size, size distribution, ζ potential, and emulsion stability was evaluated using dynamic light scattering, electron microscopy, and light backscattering. Dependence of the emulsions' droplet size on the nanoparticle concentration was observed, and the critical coverage ratio was reached when 5-10% nanoparticles concentration was used. Our findings suggest that α-LA nanoparticles at a 10% concentration can be used as novel stabilizers for Pickering emulsions to provide protection for beneficial lipophilic bioactive compounds. This is the first time that native α-LA nanoparticles have been used as stabilizers of Pickering emulsions.

Advantages and challenges of Pickering emulsions applied to bio-based films: a mini-review.

The strategy of adding hydrophobic compounds to bio-based films (usually based on hydrophilic matrices), forming films containing emulsions, is a technique that has been used to improve some physical properties (such as reducing water solubility and water vapor permeability) and / or to impart properties, such as antioxidant and antimicrobial effects by carrying hydrophobic active components that would otherwise be insoluble in hydrophilic matrices. Although Pickering emulsions have been reported as presenting greater stability when compared with surfactant-stabilized emulsions, little is known about the drying stability of Pickering emulsions (which is important for film applications). Anyway, several studies have indicated that Pickering emulsions are interesting systems to improve the water vapor barrier properties of bio-based films and coatings, and to act as carriers of active hydrophobic components. On the other hand, the tensile properties of those films are usually impaired by the presence of Pickering emulsions. The objective of this review is to present recent developments and future perspectives in bio-based films loaded with Pickering emulsions. © 2020 Society of Chemical Industry.

Synthetic semicrystalline cellulose oligomers as efficient Pickering emulsion stabilizers.

Nanocellulose are promising Pickering emulsion stabilizers for being sustainable and non-toxic. In this work, semicrystalline cellulose oligomers (SCCO), which were synthesized from maltodextrin using cellobiose as primer by in vitro enzymatic biosystem, were exploited as stabilizers for oil-in-water Pickering emulsions. At first, the morphology, structure, thermal and rheological properties of SCCO suspensions were characterized, showing that SCCO had a sheet morphology and typical cellulose-Ⅱ structure with 56 % crystallinity. Then the kinetic stabilities of emulsions containing various amounts of SCCO were evaluated against external stress such as pH, ionic strength, and temperature. Noting that SCCO-Pickering emulsions exhibited excellent stabilities against changes in centrifugation, pH, ionic strengths, and temperatures, and it was also kinetically stable for up to 6 months. Both SCCO suspensions and their emulsions exhibited gel-like structures and shear-thinning behaviors. These results demonstrated great potential of SCCO to be applied as nanocellulosic emulsifiers in food, cosmetic and pharmaceutical industries.

Lignin assisted Pickering emulsion polymerization to microencapsulate 1-tetradecanol for thermal management.

This work explored the use of Pickering emulsion stabilized by lignin nanoparticles (LNPs) to microencapsulate 1-tetradecanol (TDA) via polymerization of acrylates for thermal management. The morphology and thermal performance of the resulting microcapsules were explored using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). A highest encapsulation ratio of 81.4% and melting enthalpy of 190 J/g could be achieved when the core/shell mass ratio was 2:1, and 10 wt% of the crosslinking monomer pentaerythritol tetraacrylate (PETRA) was used. Results of the leakage and accelerated thermal cycling tests showed that the microcapsules had good thermal and chemical stability. When the microcapsules were combined with gypsum, an effective thermal storage composite was obtained, showing good potential for thermal management in the construction field.

Antibacterial phase change microcapsules obtained with lignin as the Pickering stabilizer and the reducing agent for silver.

This paper provides a novel and facile method to synthesize antibacterial phase change microcapsules (microPCMs) decorated with silver particles, where lignin was acting as both the Pickering stabilizer and the reducing agent for silver. First lignin Pickering emulsions at various oil-to-water ratios and lignin loading were prepared. Then, n-eicosane encapsulated in polyurea (PU) shells was prepared via interfacial polymerization of isophorone diisocyanate (IPDI) and ethylene diamine/diethylene triamine (EDA/DETA) in a Pickering emulsion stabilized by lignin particles. The results showed that the lignin particles were embedded in the microPCMs shell. These lignin particles were utilized to reduce silver ions, resulting in silver particles decorated microPCMs (Ag/lignin microPCMs). The resulting Ag/lignin microPCMs exhibited a well-defined core-shell spherical morphology with high phase-transition enthalpy (177.6 J/g), high encapsulation efficiency (69.0%) and good thermal durability. As well, the Ag/lignin microPCMs presented good antibacterial activity, showing great potential in industrial applications such as biomedical, textile and construction areas.

Pickering emulsion stabilized by cashew gum- poly-l-lactide copolymer nanoparticles: Synthesis, characterization and amphotericin B encapsulation.

In this work, we provide proof-of-concept of formation, physical characteristics and potential use as a drug delivery formulation of Pickering emulsions (PE) obtained by a novel method that combines nanoprecipitation with subsequent spontaneous emulsification process. To this end, pre-formed ultra-small (d.∼10 nm) nanoprecipitated nanoparticles of hydrophobic derivatives of cashew tree gum grafted with polylactide (CGPLAP), were conceived to stabilize Pickering emulsions obtained by spontaneous emulsification. These were also loaded with Amphotericin B (AmB), a drug of low oral bioavailability used in the therapy of neglected diseases such as leishmaniasis. The graft reaction was performed in two CG/PLA molar ratio conditions (1:1 and 1:10). Emulsions were prepared by adding the organic phase (Miglyol 812®) in the aqueous phase (nanoprecipitated CGPLAP), resulting the immediate emulsion formation. The isolation by centrifugation does not destabilize or separate the nanoparticles from oil droplets of the PE emulsion. Emulsions with CGPLAP 1:1 presented unimodal distributions at different CGPLA concentration, lower values in size and PDI and the best stability over time. The AmB was incorporated in the emulsions with a process efficiency of 21-47%, as determined by UV-vis. AmB in CGPLAP emulsions is in less aggregated state than observed in commercial AmB formulation.