Odyssée au fil des interfaces: de la physico-chimie des macromolécules à l'enveloppe bactérienne, plate-forme interactive du micro-organisme avec son micro-environnement

This find is registered at Portable Antiquities of the Netherlands with number PAN-0001909

PHYSICAL AGING OF EMULSIONS CONTAINING COATED TIO2-NANOPARTICLES: INTERACTION BETWEEN NANOPARTICLES AND OTHER INGREDIENTS

International audienceTiO2-nanoparticles (NPs) are usually added to cosmetic emulsions because they procure a good UV-protection1. In this study, two natures of NPs surfaces were explored: a hydrophilic silica-coated particle and a hydrophobic one covered with a large organic coating. During emulsion aging and depending on their surfacenature and properties, NPs might interact with the formula by inducing adsorption of formula’s compounds2 or by undergoingcoatings damages. These phenomenamay change the nanoparticle surface properties, their behavior in emulsion, and finally, led to the emulsionsdestabilization. The impact of TiO2-NP surfaces on the physical aging of emulsions was here studied.For this purpose, threeemulsions were formulated differing only by the presence and type of NPs: one NP-free as blank, and two containing hydrophilic and hydrophobic commercial TiO2-NPs, respectively.The emulsification process was optimized to obtain a blank emulsion physically stable and to improve the NPs dispersions. Effects of coatings on fresh emulsions were depicted on the micro and macro scales by several physico-chemical methods.Then, emulsions physical evolutions onnormal or accelerate aging conditionswere monitored.Droplets sizes were similar between the three fresh emulsions, whereas slight differences in term of networksorganization highlighted the impact of the coating nature on the emulsion microstructure. However, initial emulsions properties looked similar by applying rheological and textural analyses. Although the blank emulsion and the one with hydrophilic NPs remained similar after the aging step, the microstructure of the emulsion with hydrophobic NPsquickly evolved: aggregates of both droplets and NPs made the formula less homogeneous. As will be illustrated, this evolution in term of colloids sizes strongly affects the functional properties, as viscosity, consistency or spreading quality of this aged emulsion. These results revealed the impact of coating nature in this kind of complex media. Afterinnovative NPs extractions3 from fresh and aged formulae, their surfaces were characterized. By an original physico-chemical approach, quick surface modifications appeared and changed the surface charges and wettability of particles. These variations might cause the differences in term of stability between emulsions.(1) Serpone, N.; Dondi, D.; Albini, A. Inorganica Chim. Acta2007, 360 (3), 794–802.(2) Rossano, M.; Hucher, N.; Picard, C.; Colleta, D.; Le Foll, F.; Grisel, M. Int. J. Pharm.2014, 461 (1-2), 89–96.(3) Rossano, M. Ph.D thesis: Utilisation des nanoparticules de dioxyde de titane dans les émulsions cosmétiques : impact sur la santé humaine et l’environnement, Université du Havre: Le Havre, 2014

The Hidden Face of Nitrogen Oxides Species: From Toxic Effects to Potential Cure?

Nitrogen oxide (NOx) species represent ones of the most threatening air pollutants due to their prevalence and harmful impact on the environment and human health. The term NOx gathers mainly nitric oxide (NO) and nitrogen dioxide (NO2), mostly produced by anthropogenic activities such as transport and industries. Several cellular constituents were already described as NOx targets. These include membranes, proteins, respiratory chain enzymes, lipids, and DNA. Such damages lead to pathologies of lungs, cardiovascular system, and skin because these organs represent the first barrier toward the environment. On the other hand, NOx is also naturally synthetized by several organisms, playing a mediator role in essential cellular functions. However, few data are yet available on NOx activity toward microorganisms. Here, we review data concerning the double face of NOx, including their use in the medical field against pathogens’ infections that highlight the versatility of these compounds

One-step synthesis of highly reduced graphene hydrogels for high power supercapacitor applications

Graphene hydrogels with high electrical conductivity were prepared by a one-step process using hydrazine hydrate as gel assembly agent (GH-HD). Conventional two-step process of gel formation and further reduction to prepare highly conducting gels was replaced by a single step involving equivalent amount of hydrazine. Optimized graphene oxide concentration was established to facilitate such monolith formation. Extensive characterization and control studies enabled understanding of the material properties and gel formation mechanism. The synthesized gel shows a high electrical conductivity of 1141 S/m. The supercapacitor based on GH-HD delivers a high specific capacitance of 190 F/g at a current density of 0.5 A/g and 123 F/g at very high current density of 100 A/g. Furthermore, excellent power capability and cyclic stability were also observed. 3D macroporous morphology of GH-HD makes it ideal for high rate supercapacitor applications

IMPACT OF A TIO2 [NANO] COSMETICS GRADE ON THE CUTANEOUS MICROBIOTA: NANOPARTICLES BEHAVIOR IN EMULSION AND BACTERIOTOXICITY

International audienceTiO2-nanoparticles (NP) commonly used in cosmetics as physical UV-filters, are surface-modified by applying a first coating in order to quench photo-produced radicals. In addition, a second coating is sometimes added to raise their dispersibility in emulsion. Whereas European regulation mentions the obligation to demonstrate the safety of NP, very few studies took interest on their behavior in use. During formulation and storage, NP are exposed to a variety of environmental conditions which can accelerate aging and induce particles aggregation, adsorption of formula’s compounds or coatings deterioration. Consequently, a crucial question remains their safety while layered on skin and particularly their effect on the skin microflora. We will present the impact of TiO2-nanoparticles on the skin microflora in relation to their physicochemical properties in cosmetic emulsions during aging.A series of cosmetic emulsions were formulated with using conventional cosmetic ingredients, with or without Nanoparticles (NPs): one without NPs considered as blank, and two with hydrophilic and hydrophobic commercial TiO2-NPs, respectively. An emulsification process was developed and optimized to obtain a blank emulsion, physically stable, with improved NPs dispersions in emulsion. Then, emulsions were submitted to accelerate aging.Particles were extracted from the fresh/aged emulsions by original protocols allowing recovering particles with possible adsorbed compounds or cleaned surfaces.Skin bacteria growths were evaluated in emulsions or dispersions to check the toxicity of nanoparticles in use. Then, because of NP opacity, protocols were adapted to measure their effect on bacteria virulence toward skin cells.Microscopic and macroscopic characterizations revealed comparable structures and functional properties between the three fresh emulsions. Then, during aging, different behavior were registered and could be related to nanoparticle coating nature.Extracted NP from the fresh/aged formulas showed quick surface modifications in terms of chemical structures and physical properties that might be caused by adsorption or deterioration at their surfaces.For fresh emulsions, both nanoparticles did not have any impact on skin bacteria strains, S. aureus and P. fluorescens. In the case of aged emulsions, part of NPs seemed to allow the S. aureus growth, whereas others still remained with no effect on microflora. Finally, bacteria generation times and virulence toward skin cells differed depending on NPs surface treatments and exposition time.This work dealt with the impact of nanoparticles on skin microflora along cosmetic emulsion shelf-life. This new approach allows taking into account their safety when used in emulsion.First, through innovative extraction and characterization protocols, it was highlighted that chemical nature and physical properties of nanoparticle surfaces might be altered once in emulsion. These physicochemical observations were related to microbiological tests on skin representative bacteria. Effect of some of the NPs on bacteria growth and virulence evolved after aging. Finally, modification of NPs surface treatment seemed to have an effect on skin microflora

Development of preservative-free nanoparticles-based emulsions: Effects of NP surface properties and sterilization process

International audienceModel emulsions were developed with or without commercial titanium dioxide nanoparticles (NP) carrying various surface treatments in order to get close physicochemical properties whatever the NP surface polarity (hydrophilic and hydrophobic). Rheology and texturometry highlighted that the macroscopic properties of the three formulated emulsions were similar. However, characterizations by optical microscopy, static light scattering and zetametry showed that their microstructures reflected the diversity of the incorporated NP surface properties. In order to use these model emulsions as tools for biological evaluations of the NP in use, they had to show the lowest initial microbiological charge and, specifically for the NP-free emulsion, the lowest bactericidal effect. Hence, formulae were developed preservative-free and a thermal sterilization step was conducted. Efficiency of the sterilization and its impact on the emulsion integrity were monitored. Results highlighted the effect of the NP surface properties: only the control emulsion and the emulsion containing hydrophilic NP fulfilled both requirements. To ensure the usability of these model emulsions as tools to evaluate the 'NP effect' on representative bacteria of the skin microflora (S. aureus and P. fluorescens), impact on the bacterial growth was measured on voluntary inoculated formulae

Impact of gaseous no 2 on P. fluorescens strain in the membrane adaptation and virulence

International audienceNowadays air pollution is increasing due to anthropogenic activity. Among all air pollutants, nitrogen oxides (NOx) such as NO are predominant. It is well known that those compounds exhibit direct toxic effects on human health. However, microorganisms are also exposed to them, but the effect of NOx on the virulence of air microbiota is still poorly understood. In this study, we evaluated the impact of NO on the adaptability and virulence of an airborne strain of P. fluorescens, MFA76a, by exposition of this strain to 45 ppm of NO2. The growth kinetics and cultivability were analysed. A decrease of cultivability coupled with an increase of the lag phase was observed suggesting a potential toxicity of NO2. Since NOx particularly target lipids, the membrane permeability was assessed thanks to Live Dead tests and confocal microscopy. A significant alteration of membrane permeability was observed. Furthermore, more abundant bacterial aggregates were detected compared to the control. Thus, a lipidomic study was performed using MALDI-TOF MS Imaging coupled to HPTLC. Interestingly, bacteria exposed to NO were lacking one putative glycerophospholipid molecule. In agreement with a previous study from Kondakova et al., these data demonstrate the adaptation potential of P. fluorescens MFAF76a to an air pollutant such as NO

Ion Sieving Effects in Chemically Tuned Pillared Graphene Materials for Electrochemical Capacitors

Supercapacitors offer high power densities but require further improvements in energy densities for widespread commercial applications. In addition to the conventional strategy of using large surface area materials to enhance energy storage, recently, matching electrolyte ion sizes to material pore sizes has been shown to be particularly effective. However, synthesis and characterization of materials with precise pore sizes remain challenging. Herein, we propose to evaluate the layered structures in graphene derivatives as being analogous to pores and study the possibility of ion sieving. A class of pillared graphene based materials with suitable interlayer separation were synthesized, readily characterized by X-ray diffraction, and tested in various electrolytes. Electrochemical results show that the interlayer galleries could indeed sieve electrolyte ions based on size constrictions: ions with naked sizes that are smaller than the interlayer separation access the galleries, whereas the larger ions are restricted. These first observations of ion sieving in pillared graphene-based materials enable efficient charge storage through optimization of the d-spacing/ion size couple

Airborne fluorescent pseudomonads : What potential for virulence?

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Investigation of ion transport in chemically tuned pillared graphene materials through electrochemical impedance analysis

Chemically tuned pillared graphene structures show ability to limit restacking of graphene sheets for electrochemical energy storage in SCs. A comprehensive electrochemical characterization using various ion sizes allowed identification of ion-sieving in the cross-linked galleries of reduced pillared graphene materials (RPs). The access to the cross-linked galleries, which provide additional ion sorption sites, offered slightly increased capacitances in RPs compared to completely restacked sheets in reduced graphene oxide (RGO). We performed electrochemical impedance analyses on RPs and RGO to understand the ion transport inside the cross-linked graphene galleries. RGO adsorbs ions in the inter-particle micro/meso pores and the ion access to such sites from the bulk electrolyte occurs with relative ease. RPs sieve ions into their inter-layer gallery pores based on effective ion sizes and the ion transport process is resistive compared to RGO. A control study using 3D pillared graphene hydrogel with improved macro porosity assigns this resistive behavior and the moderate capacitances to limited ion access to the active sites due to excess number of pillars. The obtained results on the ion transport dynamics between graphene layers provide perspectives towards further optimization of these graphene materials for SCs