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.

Efficiency of emulsifier-free emulsions in delivering caffeine and α-tocopherol to human skin.

OBJECTIVE: Increasing consumer demand for natural and environmentally friendly products is driving the cosmetic industry to seek greener and safer processes. High-frequency ultrasound technology (HFUT) stabilizes emulsions without adding emulsifying surfactants (ES). In this work, the formulation characteristics of an HFUT-treated emulsion and a Reference emulsion were compared for both caffeine and α-tocopherol. METHODS: A comparison was made between ES-free emulsions and the Reference emulsions based on droplet size, viscosity, pH and rheology behaviour for both active cosmetic ingredients. The permeation of caffeine and the skin retention of α -tocopherol were studied in vitro using Franz diffusion cells on human skin biopsies, considered the gold standard for permeation assays. RESULTS: The formulations developed were stable and showed suitable droplet size distribution. In the case of ES-free emulsions, the average droplet size was inferior to 1.5 µm regardless of the polarity of the active. All formulations presented a shear-thinning pseudoplastic behaviour, an attribute usually desired for cosmetic products. The skin permeation studies showed that in the case of caffeine (model hydrophilic molecule), the ES-free emulsion presented a delivery capacity similar to that of the Reference emulsion. However, for α-tocopherol (highly lipophilic model molecule), differences were observed in the distribution of the active in the stratum corneum with an advantage for the Reference emulsion, probably due to the impact of surfactants on the SC lipids. CONCLUSION: This work demonstrates that HFUT is a reliable tool that is able to prepare stable ES-free emulsions loaded with hydrophilic or lipophilic active ingredients. Skin permeation studies confirm that the emulsions produced by HFUT promote the delivery of the actives to the human skin. In the case of α-tocopherol, the delivery efficiency was lower than with the Reference emulsion, especially in the SC layers, due to the absence of surfactants. Nevertheless, the ES-free emulsion still represents a good compromise between efficacy and the need for green cosmetics in the market.

OBJECTIF: La demande croissante des consommateurs pour des produits naturels et respectueux de l'environnement encourage l'industrie cosmétique à développer des procédés plus écologiques et plus sûrs. La technologie des ultrasons à haute fréquence (HFUT) permet de stabilizer les émulsions sans ajouter de tensioactifs émulsionnants (ES). Dans ce travail, les caractéristiques d'une émulsion traitée par HFUT et d'une émulsion de référence ont été comparées. La caféine et l'α-tocophérol ont été utilisés comme actifs modèles. MÉTHODES: Les émulsions sans ES et les émulsions de référence on été comparées en termes de taille des gouttelettes, de viscosité, de pH et de comportement rhéologique pour les deux actifs. La perméation de la caféine et la rétention cutanée de l'α-tocophérol ont été étudiées in vitro sur des biopsies de peau humaine, en utilisant des cellules de diffusion de Franz, le 'gold standard' des tests de perméation. RÉSULTATS: Les formulations développées sont stables et présentent une distribution appropriée de la taille des gouttelettes. La taille moyenne des gouttelettes des émulsions sans ES est inférieure à 1.5 µm, quelle que soit la polarité de l'actif. Toutes les formulations présentent un comportement rhéofluidifiant adapté à un usage cosmétique. Les études de perméation cutanée montrent que l'émulsion sans ES contenant de la caféine (molécule modèle hydrophile) présente une capacité de délivrance similaire à celle de l'émulsion de référence. Dans le cas de l'α-tocophérol (molécule modèle lipophile), des différences ont été observées dans la distribution de l'actif dans le stratum corneum (SC) avec un avantage pour l'émulsion de référence, probablement lié à l'interaction entre les tensioactifs et les lipides du SC. CONCLUSION: Ce travail démontre que le traitement par HFUT permet de préparer des émulsions stables sans ES, quelle que soit la polarité des actifs cosmétiques à véhiculer. Les études de perméation cutanée confirment que les émulsions produites par HFUT permettent la diffusion cutanée des actifs dans la peau humaine. Même si dans le cas de l'α-tocophérol la quantité accumulée était plus faible, l'émulsion traitée par HFUT propose un bon compromis entre efficacité et éco-responsabilité.

Highlighting the efficiency of ultrasound-based emulsifier-free emulsions to penetrate reconstructed human skin.

OBJECTIVE: The cosmetic industry endeavours to strengthen the greener and safer claims of processes to respond to the high demand from customers for natural and environmentally friendly products. High-frequency ultrasonication technology (HFUT) is a physical process enabling the stabilization of emulsions without requiring additional ingredients, such as emulsifying surfactants (ES) to be introduced into the formulations. In this study, key formulation characteristics of an emulsion synthesized by HFUT and a reference emulsion (RE) were compared, as well as the permeation kinetics of caffeine, used as a model active cosmetic ingredient, from both types of emulsions. METHODS: The pH, droplet size and viscosity of emulsions prepared by the HFUT and the RE were determined and compared. The permeation of caffeine from the HFUT emulsion and the RE applied to the surface of reconstructed human epidermis (RHE) models was compared. RESULTS: The ES-free formulations prepared by HFUT displayed a nearly 2-fold lower average droplet size and over 3-fold greater viscosity, compared to the RE. Despite these differences, the absence of ES in the HFUT emulsion did not significantly alter the permeation kinetics of caffeine through RHE. The caffeine steady-state flux, lag time and permeability coefficients differed by 20%-30% only. CONCLUSION: This study demonstrates the potential of the HFUT to yield topical cosmetic products with lower requirements ingredients-wise, without losing efficacy, supporting the possible implementation of the technology in the cosmetic industry.

OBJECTIF: l'industrie cosmétique œuvre à renforcer les revendications plus écologiques et plus sûres des processus pour répondre à la forte demande des clients de produits naturels et plus respectueux de l'environnement. La technologie d'ultrasons à haute fréquence (High-Frequency Ultrasonication Technology, HFUT) est un processus physique permettant de stabiliser les émulsions sans qu'il soit nécessaire d'ajouter des ingrédients supplémentaires, tels que des surfactants émulsifiants, aux formulations. Dans cette étude, les principales caractéristiques de formulation d'une émulsion synthétisée par HFUT et d'une émulsion de référence ont été comparées, ainsi que la cinétique de perméation de la caféine, utilisée comme ingrédient cosmétique actif modèle, dans les deux types d'émulsion. MÉTHODES: le pH, la taille des gouttelettes, et la viscosité de l'émulsion préparée par HFUT et de l'émulsion de référence ont été déterminés et comparés. La perméation de la caféine de l'émulsion HFUT et de l'émulsion de référence appliquées à la surface de modèles d'épiderme humain reconstruit a été comparée. RÉSULTATS: la formulation sans surfactants émulsifiants préparée par HFUT présentait une taille moyenne de gouttelettes presque 2 fois plus faible et une viscosité plus de 3 fois supérieure comparée à l'émulsion de référence. Malgré ces différences, l'absence de surfactants émulsifiants dans l'émulsion HFUT n'a pas significativement modifié la cinétique de perméation de la caféine dans l'épiderme humain reconstruit. Le flux à l'état d'équilibre de la caféine, le temps de latence et les coefficients de perméabilité différaient de 20 à 30 % uniquement. CONCLUSION: cette étude démontre le potentiel de la technologie HFUT à générer des produits cosmétiques topiques possédant des exigences plus faibles en termes d'ingrédients, sans perte d'efficacité, soutenant la mise en œuvre éventuelle de la technologie dans l'industrie cosmétique.

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.

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.

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.

Psychotherapy mediated by videogames.

Our purpose in this article is to propose an overview of the specificities of therapeutic mediation through video games. We analyse the clinical implications of using a video game interface and its different functionalities. The use of the video game set-up involves requirements, like adjustment between the subject, the machine and the virtual environment. With the computer game interface, we are interested in the creation and use of an avatar. From a clinical case, we show how the avatar can be invested as an interface of communication with the other and with oneself. Another specificity of digital mediation by video games concerns what is called gameplay, that is to say, the set of internal rules of the software. The description of its different functions gives points of reference to how the processes of "symbolization", according to Roussillon, can be mobilized in the video game worlds. Then we describe the specific forms of transfer in the use of the video game medium, based on the technical aspects of the medium and its immersive properties. The description of the different components of the video game set-up highlights the therapeutic potential of this type of medium.

Interest of Pickering Emulsions for Sustainable Micro/Nanocellulose in Food and Cosmetic Applications.

In the present review, natural and non-toxic particles made of micro/nanocellulose were specifically targeted as stabilizers of emulsions located at dispersed and continuous phases interfaces (called Pickering Emulsions, PEs). PEs are biphasic systems stabilized by solid particles with a recent interest in food and cosmetic domains. PEs have been more and more studied in the last ten years due to their advantages compared to conventional emulsions with surfactants. PEs have already been stabilized with various types of particles and particularly cellulose. Even if some studies showed that PEs were more stable when cellulose was chemically modified, numerous other recent studies showed that unmodified micro/nanocellulose is also promising biomaterial to stabilize PEs. Micro/nanocelluloses can be extracted by various green processes from numerous agricultural wastes and co-products, as banana peels, corncob, ginkgo seed shells, lime residues, mangosteen rind, oil palm empty fruit bunches, pistachio shells, as well as wheat straw. Main green processes used to treat cellulose are grinding, high pressure homogenization, microfluidization, enzymatic hydrolysis, subcritical water, extrusion, electron beam irradiation, cryocrushing, microwaves or sonication. PEs formulated with cellulose clearly participate to a global sustainable development but, additional studies will be necessary to better understand PEs stability and improve properties.

Non-Leachable Hydrophilic Additives for Amphiphilic Coatings.

Amphiphilic surfaces are particularly effective at inhibiting the adhesion of microorganisms (bacteria, cells, microalgae, etc.) in liquid media. The aim of this study is to determine the best hydrophilic linker to promote bonding between poly(ethylene glycol) (PEG) as a hydrophilic additive and poly(dimethyl siloxane) (PDMS) as the hydrophobic matrix. Various parameters have been studied (molecular weight, linker type, and polymer end-group), as well as the efficiency of the linking, the capacity of PEG to access to the surface of the film, and overall film homogeneity. According to the results, a PDMS linker paired with a PEG moiety allows for compatibilization of the compounds during cross-linking. This compatibilization seems to provide a good bonding with the matrix and a good surface access to the hydrophilic moiety. Therefore, this structure comprising a linking function attached to the PDMS⁻PEG copolymer has high potential as a non-releasable additive for amphiphilic coating applications.

Emulsification by high frequency ultrasound using piezoelectric transducer: formation and stability of emulsifier free emulsion.

Emulsifier free emulsion was developed with a new patented technique for food and cosmetic applications. This emulsification process dispersed oil droplets in water without any emulsifier. Emulsions were prepared with different vegetable oil ratios 5%, 10% and 15% (v/v) using high frequency ultrasounds generated by piezoelectric ceramic transducer vibrating at 1.7 MHz. The emulsion was prepared with various emulsification times between 0 and 10h. Oil droplets size was measured by laser granulometry. The pH variation was monitored; electrophoretic mobility and conductivity variation were measured using Zêtasizer equipment during emulsification process. The results revealed that oil droplets average size decreased significantly (p<0.05) during the first 6h of emulsification process and that from 160 to 1 µm for emulsions with 5%, 10% and from 400 to 29 µm for emulsion with 15% of initial oil ratio. For all tested oil ratios, pH measurement showed significant decrease and negative electrophoretic mobility showed the accumulation of OH(-) at oil/water interface leading to droplets stability in the emulsion. The conductivity of emulsions showed a decrease of the ions quantity in solution, which indicated formation of positive charge layer around OH(-) structure. They constitute a double ionic layer around oil particles providing emulsion stability. This study showed a strong correlation between turbidity measurement and proportion of emulsified oil.