Thibault Roques-Carmes

Surface-engineered quantum dots for the labeling of hydrophobic microdomains in bacterial biofilms.

Quantum dots (QDs) nanoprobes are emerging as alternatives to small-molecule fluorescent probes in biomedical technology. This paper reports an efficient and rapid method of producing highly dispersed and stable CdSe-core QDs with a hydrophobic gradient. Amphiphilic core/shell CdSe/ZnS QDs were prepared by ligand exchange at the surface of lipophilic CdSe/ZnS QDs using the dihydrolipoic acid (DHLA) dithiol ligand linked to leucine or phenylalanine amino acids. Contact angle relaxations on a hydrophobic surface and surface tension measurements indicated that aqueous dispersions of CdSe/ZnS@DHLA-Leu or CdSe/ZnS@DHLA-Phe QDs exhibit increased hydrophobicity compared to CdSe-core QDs capped by the hydrophilic 3-mercaptopropionic acid (MPA) ligand. We found that the surface functional groups and the ligand density at the periphery of these QDs significantly dictated their interactions with a complex biological matrix called biofilm. Using fluorescence confocal microscopy and an autocorrelation function (semi-variogram), we demonstrated that MPA-capped QDs were homogeneously associated to the biopolymers, while amphiphilic CdSe/ZnS@DHLA-Leu or CdSe/ZnS@DHLA-Phe QDs were specifically confined allowing identification of hydrophobic microdomains of the biofilms. Results obtained clearly point out that the final destination of QDs in biofilms can properly be controlled by an appropriate design of surface ligands.

Metallo-solid lipid nanoparticles as colloidal tools for meso-macroporous supported catalysts.

Meso-macroporous silica containing iron oxide nanoparticles (15-20 nm) was synthesized by formulating solid lipid nanoparticles and metallosurfactant as both template and metal source. Because of the high active surface area of the catalyst, the material exhibits an excellent performance in a Fenton-like reaction for methylene blue (MB) degradation, even at low amount of iron oxide (5% TOC after 14 h).

Impact of the design and the materials of rectangular microchannel reactors on the photocatalytic decomposition of organic pollutant

Abstract The objective of this article is to find the optimal design of rectangular microchannel reactors, in terms of reactor dimensions and materials, in order to increase the photocatalytic activity. Microchannel reactors with immobilized titanium dioxide (TiO2) as photocatalyst have been designed, fabricated, and tested. The photocatalytic degradation of salicylic acid is investigated as a function of microchannel size, materials that constitute the reactor, contaminant concentration and flow rate. All the reactors exhibit the same behavior. Higher degradation is observed for low pollutant concentrations and flow rates. The nature of the constituent element of the reactor has practically no influence on the photocatalytic process. The degradation performance is affected by the microchannel dimensions. The reactor with the largest channel width and length, and the lowest channel height displays the highest photocatalytic activity. For an optimal design of the rectangular microchannel reactors a relation between the degradation ratio X and the dimensions of the microchannel is reported. A linear relationship between X and wL/h2 (L: length, w: width, h: height of the channel) is found experimentally. The product wL emphasizes the uniform irradiance over the entire catalyst surface and confirms that the bottom of the channel covered with TiO2 is photoactivated. The term in 1/h2 is necessary to take into account the mass transfer limitation.

Materials for Stereolithography

Stereolithography (SL) is a rapid prototyping method for three-dimensional polymer part fabrication [3, 34, 49, 53, 63]. The technique is based on the process of photopolymerization, in which a liquid resin is converted into a solid polymer under laser irradiation [4, 34]. The models are produced by curing successive layers of the resin material until a three-dimensional object is formed. The advantages of stereolithography are its flexibility in manufacturing parts with different geometries and dimensions, its accuracy and its quickness. The challenge is to extend the stereolithography method to directly fabricate parts with complex shapes and good mechanical properties [30, 47, 58]. Recently, polymer/ceramic composite were successively fabricated by stereolithography [29, 46, 52, 62]. The manufacturing process requires the formulation of a photoreactive medium containing a photocurable resin and powders prior to laser exposure. Once polymerized, the photopolymer constitutes a though matrix around ceramic particles.

Influence of Zn ion addition on the properties of ordered mesoporous TiO2

Herein, we report the preparation and characterization of mesoporous zinc titanate materials. The Zn contents have been estimated by elemental analysis. Samples have been characterized by SAXS, XRD, EDX, nitrogen adsorption–desorption, XPS, Raman and UV spectroscopy. SAXS analysis has shown that the hexagonal array is lost when the zinc content in the materials increases beyond 7 mol%. As proven by XRD and Raman experiments anatase is the predominant phase, however upon zinc addition the crystallinity decreases and the formation of ZnTiO3 is promoted. Finally the photocatalytic activity of the zinc titanate materials has been tested in the photodegradation of methyl orange.

The application of titanium dioxide, zinc oxide, fullerene, and graphene nanoparticles in photodynamic therapy

Nanoparticles (NPs) have been shown to have good ability to improve the targeting and delivery of therapeutics. In the field of photodynamic therapy (PDT), this targeting advantage of NPs could help ensure drug delivery at specific sites. Among the commonly reported NPs for PDT applications, NPs from zinc oxide, titanium dioxide, and fullerene are commonly reported. In addition, graphene has also been reported to be used as NPs albeit being relatively new to this field. In this context, the present review is organized by these different NPs and contains numerous research works related to PDT applications. The effectiveness of these NPs for PDT is discussed in detail by collecting all essential information described in the literature. The information thus assembled could be useful in designing new NPs specific for PDT and/or PTT applications in the future.

Surface modification of TiO2 nanoparticles with AHAPS aminosilane: distinction between physisorption and chemisorption

This paper addresses the surface modification of TiO2 nanoparticles with n-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS) using various initial aminosilane concentrations. The main objective of this article is to show experimentally the importance of the physisorption during the grafting process. The distinction between chemisorbed and physisorbed aminosilane molecules on TiO2 is thoroughly analyzed. The surface of bare and modified TiO2 particles has been characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to gain a better understanding of the adsorption mechanism of AHAPS on TiO2. Quantitative information on surface energy of TiO2, in terms of adsorption energy sites and heterogeneity, has been investigated by quasi-equilibrium low-pressure adsorption technique using nitrogen and argon as probe molecules. The FTIR and XPS data are combined to estimate and discuss the chemisorbed and physisorbed contribution. The results demonstrate that both physisorption and chemisorption occurs but they display a different behavior. The physisorbed amounts are much higher than the chemisorbed amounts. This shows that the main part of the adsorbed layer is composed of physisorbed molecules. The physisorbed uptake depends highly on the AHAPS concentration while the chemisorbed amount remains constant. Quasi-equilibrium Ar derivative adsorption isotherms reveal that the AHAPS molecules are mostly located on the {101} and {001} faces of titania and that the two faces display the same reactivity toward AHAPS sorption. Nitrogen adsorption experiments show that the sorption takes place on the three polar surface sites of high energy. The molecules are chemisorbed onto the site displaying the highest energy while they are physisorbed on the two lower energy sites.

Use of surfactants to reduce the driving voltage of switchable optical elements based on electrowetting.

The advantage of using electrowetting as a novel principle for a reflective display has been previously demonstrated. The principle is based on the controlled two-dimensional movement of an oil/water interface across a hydrophobic fluoropolymer insulator. The main objective of this paper is to show experimentally the influence of surfactants on the electro-optic behavior of a single electrowetting pixel. The concentration and type of nonionic surfactant (Tween 80 and Span 20) have been varied. The experimental data are compared with calculations from the electro-optic model developed previously. The electro-optic performance is significantly affected by the nature and the concentration of surfactant. In the presence of Tween, at concentrations lower than the critical micelle concentration (CMC), and mixtures of Tween and Span the electro-optic behavior can be related to the interfacial tension. When decreasing the oil/water interfacial tension, the amplitude of the driving voltage required for obtaining a given oil displacement decreases and the switching curve becomes steeper. These effects can be accurately reproduced by means of the previously developed electro-optic model. Mixtures of Tween and Span produce a significant synergetic reduction of the driving voltage. For Tween concentrations higher than the CMC and Span, a strong disagreement is observed between the previously developed model and experimental data. Here a new physical model is reported that describes the electro-optic behavior of electrowetting-based optical elements in the presence of surfactants. The model takes into account the actual voltage used to control the liquid movement in electrowetting (lower than the applied voltage), the amount of surfactant adsorbed at the decane/water interface, and the dipole moment of the surfactant molecules. The calculated results are in very good agreement with experimental data without employing fitting parameters. The dipoles interact with the applied field and lower the actual applied field. This reduction of the effective electric field across the solid-liquid interface induces a decrease in the charge density at the solid-liquid interface and reduces the electrowetting force. For surfactant concentrations higher than the CMC, the electro-optic performance does not depend on the surfactant concentration. This demonstrates that the reduction of the electrowetting field due to the large dipole moment of the surfactant molecules occurs at the oil/water interface. A new method for the test cell fabrication is also presented.

Modelling and design of microchannel reactor for photocatalysis

Chemical reactions in a microreactor can offer new possibilities for many chemical engineering application fields and have been employed in photocatalysis studies. The purpose of this work is to investigate the photocatalytic degradation of salicylic acid (SA) as a pollutant model, in a continuous flow microchannel reactor in order to evaluate the influence of radial concentration profile on the photocatalytic efficiency. The study has been developed on both experimental and theoretical aspects. Microreactors have been manufactured by stereolithography in epoxy resin (Accura® SI 30) and are composed of a channel with a rectangular cross-section of about 1 mm2 with different aspect ratios defined as width/depth. Photocatalytic experiments have been performed at different flow rates. Results can be predicted by the Langmuir-Hinshelwood (LH) kinetic model coupled with surface diffusion. Computational fluid dynamics (CFD-Comsol Multiphysics) can model phenomena and confirmed the reliability of our experimental results with diffusion limitation at low flow rate.

Efficient synthetic access to thermo-responsive core/shell nanoparticles

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe3O4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe3O4/polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.