Chitin nanocrystals/alginate complex for tuning stability, rheology and bioavailability of cholecalciferol in Pickering emulsions.

In this paper we investigate polyelectrolyte complexes of sodium alginate (Alg) and chitin nanocrystals (ChNC). Formation, stability and transport properties of sunflower oil-in-water emulsions stabilized by ChNC-Alg complex were studied using dynamic light scattering (DLS), laser Doppler electrophoresis, optical microscopy, potentiometric titration, rheology and simulated digestion. It has been established that during emulsions formation, the ChNC-Alg complex is rearranged at the interface and the formation of a two-layer coating of the droplet occurs. Stabilized O/W emulsions are stable during storage, in the pH range 2-9 and centrifugal acceleration up to 2000 RCF. Presence of Ca2+ and Na+ ions in the range up to 150 mM has virtually no effect on the droplet size. Inclusion of 5 wt% Alg in the ChNC-based emulsion stabilizer system leads to a drop in Gibbs adsorption >16 times compared to the ChNC-stabilized emulsion, increase in viscosity and rheopexy index of the systems. We found that chemical properties of colloidal phase surface and rheological properties of emulsions stabilized by ChNC-Alg are mostly dependent on the droplet size, not the type of oil as a result of a comparative study of sunflower oil/liquid paraffin oil. Emulsion drops of an optimized composition are stable in the upper parts of the model gastrointestinal tract system and transport vitamin D3 to the small intestine without significant losses. The bioavailability of vitamin D3 in emulsions stabilized with the ChNC-Alg complex is higher than for emulsions stabilized with ChNC alone.

Anti-Alzheimer Drug Delivery via Pickering Emulsions Stabilized by Plate-like Cellulose Nanocrystals.

In this work, we studied for the first time the formation of olive oil emulsions in water stabilized by plate-like nanocrystals with the supramolecular structure of cellulose II (pCNC). Effects of storage, pCNC concentration, and NaCl on the stability and properties of Pickering emulsions, including the creaming index, droplet size, zeta potential, acid-base surface properties, and rheology, were studied. A significant influence of the shape of nanoparticles (compared to the classical rod-like shape) on the stability parameters and rheological characteristics of emulsions is shown. Plate-like cellulose nanocrystals at a concentration of 16 g/L are able to form delamination-resistant emulsions without added electrolytes. The viscosity of pCNC-stabilized emulsions tends to decrease with increasing electrolyte concentration in the system, which is not characteristic of rod-like CNC-stabilized emulsions. This effect in pCNC-stabilized emulsions assumedly can be associated both with weak mechanical engagement between drops due to the shape of stabilizer particles and with an insignificant participation of background electrolyte cations in the formation of interdroplet interactions. Therefore, the resulting aggregates are unstable and easily destroyed, even under weak mechanical stress. As a consequence, the acid-base properties of the pCNC surface are practically independent of the emulsion preparation method (with or without electrolyte) as well as the concentration of the background electrolyte. The reduced viscosity of pCNC-stabilized emulsions in the presence of an electrolyte, coupled with the absence of acute toxicity, allows us to recommend them as a convenient oral delivery system for fat-soluble, biologically active substances. Our emulsions carrying donepezil (an anti-Alzheimer drug) showed better performance than a solution of donepezil hydrochloride in preventing memory impairment tested on laboratory mice.

Biocompatible Nanoparticle Heteroaggregates as Stabilizers of Pickering Emulsions for Vitamin D3 Efficient Delivery.

Vitamin D3 deficiency is a major public health problem worldwide, and standard cholecalciferol formulations provide poor absorbability of the vitamin. Several biphasic formulas have been proposed to overcome the disadvantages in which Pickering emulsions stand out in particular. This paper describes olive oil-in-water Pickering emulsions stabilized by pseudoboehmite (AlOOH), cellulose nanocrystals (CNC), and their heterocoagulates. Colloidal properties were assessed by laser Doppler microelectrophoresis, potentiometric titration, and rheology. It was shown that the heterocoagulation of CNC and AlOOH led to a drastic change in surface properties (ζ-potential, pKa, and number of active centers), which promoted the formation of more stable emulsions with the smallest size of droplets and the highest viscosity among the studied samples. Simulated digestion studies showed the targeted release in the small intestine medium where cholecalciferol should be delivered. High-performance liquid chromatography showed the efficient encapsulation of cholecalciferol in emulsions (86% of initial concentration). Oral administration to laboratory mice of initial nanoparticles and emulsions stabilized by them showed nontoxicity for all of the components, and they were estimated to be class V materials. The proposed emulsions have great potential as targeted delivery systems of lipophilic drugs.

Surface, rheopexy, digestive stability and toxicity of olive oil emulsions stabilized by chitin nanocrystals for vitamin D3 delivery.

Pickering emulsions are of interest in medicament transport systems. The properties of emulsions are influenced by the type of oil and the surface structure of nanoparticles-stabilizers. The process of formation of o/w emulsions of olive oil stabilized by chitin nanocrystals was investigated, their stability under the influence of physical factors, rheological characteristics, acute toxicity after oral administration, stability under the conditions of a model of the gastrointestinal tract, and their potential for oral transport of vitamin D3 were analyzed. Physically stable emulsions were obtained at a stabilizer concentration of 3.6 g/l. The addition of electrolyte leads to a substantial reduction in the average size of microdroplets. The resulting emulsions have rheopexy properties and the rheopexy index increases at 37 °C. Emulsions are classified as non-toxic when taken orally, physically stable in the upper digestive system, and capable of efficiently transporting vitamin D3 with a full release in the small intestine.

Melamine-Barbiturate Supramolecular Assembly as a pH-Dependent Organic Radical Trap Material.

In the last two decades, a large number of self-assembled materials were synthesized and they have already found their way into large-scale industry and science. Hydrogen-bond-based supramolecular adducts are found to have unique properties and to be perfect host structures for trapping target molecules or ions. Such chemical systems are believed to resemble living matter and can substitute a living cell in a number of cases. Herein, a report on an organic material based on supramolecular assembly of barbituric acid and melamine is presented. Surprisingly, the structure is found to host and stabilize radicals under mild conditions allowing its use for biological applications. The number of free radicals is found to be easily tuned by changing the pH of the environment and it increases when exposed to light up to a saturation level. We describe a preparation method as well as stability properties of melamine-barbiturate self-assembly, potentiometric titration, and hydrogen ions adsorption data and EPR spectra concerning the composite.

Magnetite Hydrosols with Positive and Negative Surface Charge of Nanoparticles: Stability and Effect on the Lifespan of Drosophila melanogaster.

This paper presents sols of uncoated and citric acid-coated Fe3O4 nanoparticles obtained by a combination of coprecipitation and sonochemistry methods. A stable concentrated CA-Fe3O4 sol synthesized by a combination of coprecipitation with an inconvenient Fe2+/Fe3+ ratio, modification with citric acid and US treatment was obtained for the first time. A comparative analysis of the composition and morphology of nanoparticles was performed. The sols are oppositely charged and behave as a typical ferrofluid. The citric acid-modified sol is aggregatively stable over wider ranges of pH and electrolyte concentration, but it becomes less stable with the temperature increase. DLVO calculations showed that steric repulsion forces are a vital factor contributing to increased aggregative stability in a modified Fe3O4 sol. The experiments have revealed the magneto-optical effect in a modified Fe3O4 sol with an electrolyte concentration of 0.025-0.075 M caused by a high potential barrier and a deep secondary minimum in pairwise interaction curves. The "pK spectroscopy" mathematical model to describe the potentiometric curves of synthesized magnetite sols was used for the first time. According to potentiometric titration, the ions of the electrolyte practically do not contribute to formation of a surface charge in modified Fe3O4 with a change in pH due to blocking the magnetite surface by citric acid molecules. Drosophila melanogaster was used as a model to show that Fe3O4 in chronic exposure has a low toxic effect.

Study of heteroaggregation and properties of sol-gel AlOOH-Fe3O4 composites.

In this work, AlOOH-Fe3O4 powder nanocomposites for Cr(VI) adsorption were obtained for the first time using oppositely charged boehmite and citric acid modified magnetite sols. The process of heteroaggregation of oppositely charged AlOOH and Fe3O4 nanoparticles was also studied as one of the stages in the preparation of adsorption active material. Сomposition, surface area, porous structure, thermal and surface properties, adsorption efficiency, and regenerability of nanocomposites were investigated using a wide range of analytical methods. It is noted that a low content of magnetite (2 wt.%) in the AlOOH-Fe3O4 composite promotes an increase in the surface area, weakly affects the Cr(VI) adsorption capacity, and imparts magnetic properties to the composite. Low cost, simplicity of preparation, high Cr(VI) adsorption capacity (up to 21 mg/g), and stability in cyclic use are the advantages of the obtained nanocomposites in comparison with similar systems. They can easily be separated from the purified liquid using a permanent magnet due to their magnetic properties.