Low-Frequency Ultrasound Effects on Cellulose Nanocrystals for Potential Application in Stabilizing Pickering Emulsions.

Cellulose, in the form of cellulose nanocrystals (CNCs), is a promising biomaterial for stabilizing Pickering emulsions (PEs). PEs are commonly formed using low-frequency ultrasound (LFU) treatment and impact CNC properties. The present study investigated the specific effects of LFU treatment on CNCs' chemical and physical properties. CNCs were characterized using dynamic light scattering, ζ;-potential determination, Fourier transform infrared spectroscopy, X-ray diffraction, and contact angle measurement. CNC suspensions were studied using rheological analysis and static multiple light scattering. LFU treatment broke CNC aggregates and modified the rheological behavior of CNC suspensions but did not affect the CNCs' chemical or crystallographic structures, surface charge, or hydrophilic properties. During the storage of CNC suspensions and PEs, liquid crystal formation was observed with cross-polarized light. Hypotheses related to the impact of liquid crystal CNCs on PE stability were proposed.

Influence of Alginate Properties and Calcium Chloride Concentration on Alginate Bead Reticulation and Size: A Phenomenological Approach.

Two types of alginates, AlgLF and AlgP, were used in this study to produce alginate beads by electro-vibratory extrusion. AlgLF and AlgP exhibited different Mannuronate/Guluronate (M/G) ratios and molecular weights as measured by NMR and SEC-MALS. The calcium chloride concentration was found to have the greatest effect on bead size. Higher concentrations resulted in smaller beads. AlgLF with a higher molecular weight and a lower proportion of G blocks showed smaller beads. For both alginates, the bead size was also influenced by the flow rate and vibration frequency. Alginate solution aging showed a minimal effect. Alginate reticulation was modeled using a mathematical equation. The study provides insights for the optimization of alginate-based materials in different applications by shedding light on the main factors influencing bead size. The importance of the molecular weight, M/G ratio and calcium ion concentration in the gelling process is highlighted, providing opportunities for the tailoring of alginate materials through a phenomenological model.

Phase Diagram of Pickering Emulsions Stabilized by Cellulose Nanocrystals.

Cellulose is a promising renewable and biocompatible biopolymer for stabilizing Pickering emulsions (PEs). In the present study, PEs were produced by low-frequency ultrasounds with cellulose nanocrystals (CNCs) and caprylic/capric triglycerides. Phase diagrams allowed to understand mechanisms of formation and long-term stabilization of PEs. Emulsion type, continuous phase viscosity, and yield of oil incorporation were studied after PEs formation. Droplet size, oil release, and stability were measured weekly up to 56 days of storage. Results showed that oil mass fraction above 70% w/w led to unstable W/O PEs. Lower oil mass fraction formed O/W PEs of stability depending on CNC content and oil mass fraction. Droplet size stability increased with CNCs/oil ratio. A very low CNCs/oil ratio led to phase separation and oil release. High CNC content stabilized oil droplets surface, increased aqueous phase viscosity, and prevented creaming. Highly stable PEs were produced for CNC content above 3% (w/w) and oil mass fraction below 50% (w/w). Mechanisms for PEs formation and stabilization were proposed for various CNC contents and oil mass fractions.

Alginate Based Core-Shell Capsules Production through Coextrusion Methods: Recent Applications.

Encapsulation is used in various industries to protect active molecules and control the release of the encapsulated materials. One of the structures that can be obtained using coextrusion encapsulation methods is the core-shell capsule. This review focuses on coextrusion encapsulation applications for the preservation of oils and essential oils, probiotics, and other bioactives. This technology isolates actives from the external environment, enhances their stability, and allows their controlled release. Coextrusion offers a valuable means of preserving active molecules by reducing oxidation processes, limiting the evaporation of volatile compounds, isolating some nutrients or drugs with undesired taste, or stabilizing probiotics to increase their shelf life. Being environmentally friendly, coextrusion offers significant application opportunities for the pharmaceutical, food, and agriculture sectors.

Alginate Core-Shell Capsules Production through Coextrusion Methods: Principles and Technologies.

This paper provides an overview of coextrusion methods for encapsulation. Encapsulation involves the coating or entrapment of a core material such as food ingredients, enzymes, cells, or bioactives. Encapsulation can help compounds add to other matrices, stabilize compounds during storage, or enable controlled delivery. This review explores the principal l coextrusion methods available that can be used to produce core-shell capsules through the use of coaxial nozzles. Four methods for encapsulation by coextrusion are examined in detail, including dripping, jet cutting, centrifugal, and electrohydrodynamic systems. The targeted capsule size determines the appropriate parameters for each method. Coextrusion technology is a promising encapsulation technique able to generate core-shell capsules in a controlled manner, which can be applied to cosmetic, food, pharmaceutical, agriculture, and textile industries. Coextrusion is an excellent way to preserve active molecules and present a significant economic interest.

Study and optimization of oil-in-water emulsions formulated by low- and high-frequency ultrasounds.

OBJECTIVE: A combined treatment using both low-frequency (20 kHz) and high-frequency ultrasounds (1.63 MHz) is a promising new process to stabilize emulsions with minimalist formulation. In order to optimize process parameters, a Doehlert experimental design was performed with oil-in-water emulsions, presently used for cosmetic products, composed of water, caprylic/capric triglycerides and oleic acid. METHODS: Effects of treatment time, oil content and oleic acid content were studied on emulsion properties (droplet size, polydispersity index, ζ-potential and yield of oil incorporation) and on emulsion stability after a 28-day storage (creaming index, Turbiscan stability index (TSI) and oil release). RESULTS: From experimental data, a model was established that allowed to study effects of each parameter and their interactions on emulsion formation and stability. Oleic acid content had a great impact on emulsion formation: It reduced droplet size, PDI and ζ-potential and increased yield of oil incorporation. However, a critical value could be highlighted, beyond which oleic acid effects reversed. Treatment time had an important beneficial effect on emulsion stability as it decreased creaming index, TSI and oil release after 28 days of storage. Oil content had a negative effect on emulsion formation and on emulsion stability. However, treatment time and oil content often had a beneficial synergistic effect. CONCLUSION: The optimized conditions for emulsion processing were obtained through a desirability approach. They were experimentally validated.

OBJECTIF: Un traitement combiné utilisant à la fois des ultrasons à basse fréquence(20 kHz) et à haute fréquence (1,63 MHz) est un nouveau procédé prometteur pour stabiliser les émulsions avec une formulation minimaliste. Afin d'optimiser les paramètres du procédé, un plan d'expériences de Doehlert a été réalisé avec des émulsions huile-dans- eau, actuellement utilisées pour des produits cosmétiques, composées d'eau, de triglycérides capryliques/capriques et d'acide oléique. METHODES: Les effets du temps de traitement, de la teneur en huile et de la teneur en acide oléique ont été étudiés sur les propriétés des émulsions (taille des gouttelettes, indice de polydispersité, potentiel-ζ et rendement d'incorporation de l'huile) et sur la stabilité des émulsions après un stockage de 28 jours (indice de crémage, indice de stabilité au Turbiscan (TSI) et relargage de l'huile). RESULTATS: A partir des données expérimentales, un modèle a été établi et a permis d'étudier les effets de chaque paramètre et leurs interactions sur la formation et la stabilité des émulsions. La teneur en acide oléique a eu un impact important sur la formation des émulsions : elle a réduit la taille des gouttelettes, le PDI et le potentiel-ζ, et a augmenté le rendement d'incorporation de l'huile. Cependant, une valeur critique a pu être mise en évidence, au-delà de laquelle les effets de l'acide oléique s'inversent. Le temps de traitement a eu un effet bénéfique important sur la stabilité des émulsions car il a diminué l'indice de crémage, le TSI et le relargage d'huile après 28 jours de stockage. La teneur en huile a eu un effet négatif sur la formation des émulsions et sur leur stabilité. Cependant, le temps de traitement et la teneur en huile ont souvent eu un effet synergique bénéfique. CONCLUSION: Les conditions optimisées pour le traitement des émulsions ont été obtenues par une approche de désirabilité. Elles ont été validées expérimentalement.

Review of High-Frequency Ultrasounds Emulsification Methods and Oil/Water Interfacial Organization in Absence of any Kind of Stabilizer.

Emulsions are multiphasic systems composed of at least two immiscible phases. Emulsion formulation can be made by numerous processes such as low-frequency ultrasounds, high-pressure homogenization, microfluidization, as well as membrane emulsification. These processes often need emulsifiers' presence to help formulate emulsions and to stabilize them over time. However, certain emulsifiers, especially chemical stabilizers, are less and less desired in products because of their negative environment and health impacts. Thus, to avoid them, promising processes using high-frequency ultrasounds were developed to formulate and stabilize emulsifier-free emulsions. High-frequency ultrasounds are ultrasounds having frequency greater than 100 kHz. Until now, emulsifier-free emulsions' stability is not fully understood. Some authors suppose that stability is obtained through hydroxide ions' organization at the hydrophobic/water interfaces, which have been mainly demonstrated by macroscopic studies. Whereas other authors, using microscopic studies, or simulation studies, suppose that the hydrophobic/water interfaces would be rather stabilized thanks to hydronium ions. These theories are discussed in this review.

Structure, gelation, and antioxidant properties of curcumin-doped casein micelle powder produced by spray-drying.

The encapsulation of curcumin in micellar caseins (MCs) and the production of powder were performed by spray-drying. Nearly 97% of the curcumin was retained and the yellow powder showed a typical high casein powder morphology. The hygroscopic properties were determined, slight differences reflected less available hydrophobic sites when curcumin was bound to casein, favoring interactions with water in curcumin-enriched MC powders. No difference was detected on the internal MC structure via SAXS. The antioxidant activity of doped-curcumin powder presented 88% of active curcumin. For 60 days at 40 °C storage, the antioxidant activity of curcumin measured by ABTS and FRAP assays was preserved with a percentage of 82 ± 2.0% and 84 ± 1.1%, respectively. Curcumin doped powders presented similar features to classical casein powders (rehydration and gelling abilities). It was demonstrated that curcumin encapsulation in MCs in its powder form helped in protecting its antioxidant activity without influencing the techno-functional properties of MCs. This study allowed the incorporation of curcumin via the MC matrix as an active food ingredient available in a powder state usable as classical milk powder in several food formulations.

Structure and gelation properties of casein micelles doped with curcumin under acidic conditions.

In this study, the ability of micellar casein (MC) to interact with curcumin during acidification and to produce acid gel was investigated. Steady-state fluorescence spectroscopy of curcumin variation and fluorescence quenching of caseins upon binding with curcumin molecules were evidenced. Increasing the temperature from 20 to 35 °C enhanced MC-curcumin interactions as reflected by the increase in the binding constant from 0.6 ± 0.3 × 10(4) to 6.6 ± 0.6 × 10(4) M(-1). From changes in entropy, enthalpy and Gibbs free energy, hydrophobic interactions were proposed as major binding forces. Static fluorescence MC quenching was demonstrated for the MC-curcumin complex during acidification. From pH 7.4 to pH 5.0, the binding site numbers varied in the range from 1.25 ± 0.05 to 1.49 ± 0.05 and the binding constant kb varied from 3.9 ± 0.4 × 10(4) to 7.5 ± 0.7 × 10(4) M(-1). Small angle X-ray scattering profiles demonstrated that the MC internal structure was unchanged upon curcumin binding. The ζ-potential value of curcumin-doped MC indicated that curcumin did not modify the global charge of MC particles. Acid gelation studied by oscillation rheology and static multiple light scattering at 20 and 35 °C led to a similar behavior for native and curcumin-doped MC suspensions. For the first time, it was demonstrated that the colloidal and functional properties of MC were unchanged when doped with curcumin during acidification.

Antioxidant activity and bioaccessibility of phenols-enriched edible casein/caseinate coatings during in vitro digestion.

Active films were developed for food coating applications. Entrapped phenol susceptibility to digestion was studied. Sodium caseinate (Na-CN) coatings were formulated with 0, 10, 20% Casein (CN) incorporating selected phenols as model antioxidants. This study investigated phenol/CN/Na-CN interactions, in vitro bioaccessibility of phenols and CN role in phenols retention during in vitro gastric and pancreatic digestion. The antioxidant activity of catechin (CAT), rutin (RUT), chlorogenic acid (CHL), gallic acid (GAL), and tannic acid (TA) in coatings varied with the phenolic compound type and CN concentration and was related to phenol hydrophobic binding to CN. ABTS method gave activities ranged from 412 down to 213, and DPPH method gave values from 291·7 to 190·9. An inverse relationship was found with CN content due to CN/phenol interaction. During digestion, a part of phenols was degraded by alkaline pH of pancreatic fluid. Simultaneously, CN proteolysis led to release of phenols and the bioaccessibility index remained above 80% for all phenols. The results suggested the possibility of protecting phenols against oxidation and digestive alteration by entrapment in CN and Na-CN coating films. These positive results showed the ability to produce antioxidant-enriched edible coatings to increase food protection and phenol nutritional intake.

Interactions of three soil bacteria species with phyllosilicate surfaces in hybrid silica gels.

To simulate iron consumption in soils, iron leaching from silicate minerals due to three heterotrophic bacterial strains and a chemical treatment was studied using hybrid silica gel (HSG) doped with two phyllosilicates, nontronite (NAu-2) or low-iron-content montmorillonite (SWy-2). HSG methodology, a novel way of separating bacteria cells from a colloidal mineral source, consisted in embedding colloidal mineral particles into an amorphous porous silica matrix using a classical sol-gel procedure. Pantoae agglomerans PA1 and Rahnella aquatilis RA1 were isolated from silicate-rich soils, that is, beech and wheat rhizospheres (Vosges, France); Burkholderia sp. G5 was selected from acidic and nutrient-poor podzol soils (Vosges, France). Fe release from clay minerals and production of bacterial metabolites, that is, low molecular weight organic acids (LMWOA) and siderophores, were monitored. Two LMWOA profiles were observed with major gluconate production (> 9000 µM) for Burkholderia sp. G5 and moderate production of lactate, acetate, propionate, formate, oxalate, citrate, and succinate (< 300 µM) for R. aquatilis RA1 and P. agglomerans PA1. HSG demonstrated its usefulness in revealing clay mineral-microorganisms interactions. The effect of bacterial exsudates was clearly separated from physical contact effect.

Bio-dissolution of colloidal-size clay minerals entrapped in microporous silica gels.

Four colloidal-size fractions of strongly anisotropic particles of nontronite (NAu-2) having different ratios of basal to edge surfaces were incubated in the presence of heterotrophic soil bacteria to evaluate how changes in mineral surface reactivity influence microbial dissolution rate of minerals. To avoid any particle aggregation, which could change the reactive surface area available for dissolution, NAu-2 particles were immobilized in a biocompatible TEOS-derived silica matrix. The resulting hybrid silica gels support bacterial growth with NAu-2 as the sole source of Fe and Mg. Upon incubation of the hybrid material with bacteria, between 0.3% and 7.5% of the total Fe included in the mineral lattice was released with a concomitant pH decrease. For a given pH value, the amount of released Fe varied between strains and was two to twelve-fold higher than under abiotic conditions. This indicates that complexing agents produced by bacteria play an important role in the dissolution process. However, in contrast with proton-promoted NAu-2 dissolution (abiotic incubations) that was negatively correlated with particle size, bacterial-enhanced dissolution was constant for all size fractions used. We conclude that bio-dissolution of nontronite particles under acidic conditions seems to be controlled by bacterial metabolism rather than by the surface reactivity of mineral.

Calcium carbonate-hydrolyzed soy protein complexation in the presence of citric acid.

The influence of hydrolyzed soy proteins on calcium carbonate stabilization was studied in citric acid solution. Calcium-soy proteins interactions were characterized using a calcium ion selective electrode, turbidity, and Isothermal Titration Calorimetry. Once the meta-stable phase was reached or just after soy protein addition, spray-drying was performed and SEM, XRD, and XPS analysis were carried out on spray-dried powders. In citric acid solution calcite crystals were eroded giving rise to smaller amorphous particles. In the presence of soy proteins, complexation exothermic in nature occurred with the mineral phase, which prevented CaCO(3) from recrystallisation and kept the system in an amorphous state. SEM performed on spray-dried powder showed that soy proteins were swollen in presence of mineral phase and resulted in a decrease of calcium concentration at the extreme surface of the studied powders as demonstrated by XPS.

Study of calcium-soy protein interactions by isothermal titration calorimetry and pH cycle.

The aim of this work was to understand Ca-induced soy protein (nonhydrolyzed, NH; or hydrolyzed, H) aggregation and to characterize the involved interactions using ITC and pH cycle. The endothermic signals obtained upon titration of soy proteins with Ca were fitted with a one set of sites model. NH soy proteins bound more Ca than H soy proteins ( approximately 52 and approximately 2 mg of Ca/g of proteins, respectively). The binding constant K indicated the easier Ca binding onto H soy proteins than for NH soy proteins. The exothermic part involved by electrostatic interactions was completely hidden by the strong endothermic signal from the water molecule release. Ca binding onto soy proteins should be described as a H(+)/Ca(2+) exchange. Whatever the soy proteins, the positive value of heat capacity changes indicated a reduction in the number of surface-exposed polar residues. Ca-induced soy protein aggregation was irreversible for pH cycle to 3.5.

Relationships between dairy powder surface composition and wetting properties during storage: importance of residual lipids.

The relationships between powder surface composition and powder rehydration properties under variable conditions of storage are investigated in this paper. A rheological approach was used to evaluate the modifications induced by storage on the rehydration properties of native phosphocaseinate powder. Concurrently, the powder surface composition (i.e., lactose, proteins, and lipids) was evaluated by X-ray photoelectron spectroscopy (XPS). A strong correlation was found between the powder wetting time lengthening and the migration of lipids on the powder surface during storage. XPS studies indicated also an over-representation of lipids on the powder surface (6%) in comparison with total lipids (0.4%) even on fresh powder before storage. Detailed investigation of powder lipids revealed the presence of high levels of polar lipids (66% compared with <1% in milk lipids). Their amphiphilic nature and their melting points could explain the extensive enrichment of lipids observed at the powder surface during processing and storage.

Milk powders ageing: effect on physical and functional properties.

Milk powders are now considered as food ingredients, mainly because of the functional properties of milk proteins. During the storage of milk powders, many physicochemical damages, mainly dependent on lactose glass transition occur. They have important consequences on physical (flowability) and functional properties (solubility, emulsifying, and foaming properties) of milk powders. First, lactose crystallization modifies the microstructure and chemical composition of the surface of powder particles. Thus, milk powders flowability is decreased. Since the structure of milk proteins is destabilized, its solubility is damaged. Moreover, particle collapse and caking occur and mainly decrease the physical properties of milk powders (density and flowability). The mechanical stresses involved may also enhance proteins unfolding, which is detrimental to solubility. Finally, molecular mobility is favored upon ageing, and both chemical (Maillard reaction) and enzymatic reactions occur. Maillard reaction and oxidation enhance protein interactions and aggregations, which mainly lessen milk powders solubility. Maillard reaction also decreases emulsifying and foaming properties. Storage temperature and relative humidity have been considered as the predominant factors involved, but time, milk components, and their physical state also have been implied.

Milk proteins for edible films and coatings.

Due to the recent increase in ecological consciousness, research has turned toward finding edible materials. Viable edible films and coatings have been produced using milk proteins. These films and coatings may retard moisture loss, are good oxygen barriers, show good tensile strength and moderate elongation, are flexible, and generally have no flavor or taste. Incorporation of lipids in protein films, either in an emulsion or as a coating, improve their properties as barriers to moisture vapor. Interactions between chemical, structural properties, as well as film-forming conditions and functional properties of edible milk films are elucidated. Some potential uses of milk protein packaging, which are hinged on film properties, are described with examples.