Electrochemical Properties of Silver Nanoparticles in Mesoporous Silica and Titania Films: Specific Behavior of Titania Composite.

Electrochemical behavior of silver nanoparticles in mesoporous oxides electrodes is investigated. Mesoporous SiO2 and TiO2 films deposited on FTO (fluorine-doped tin oxide) and containing Ag nanoparticles (NPs) are used as electrodes. The study of voltammetric curves (CVs) and the diffusion of Ag+ ions out of the films highlight the importance of the retention of Ag+ ions by the TiO2 films. By varying several factors such as the speed rate or the initial potential, we observe the existence of the two potentials' anodic peaks. These are explained by the nature of two silver NP populations created in two distinct areas in the film and with different size distributions, as shown by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. The size distributions of the two NP populations allow the position and shape of each of the oxidation peaks in the CVs to be adequately simulated.

A novel agonist for the HGF receptor MET promotes differentiation of human pluripotent stem cells into hepatocyte-like cells.

Hepatocyte growth factor (HGF) is the natural ligand of the MET receptor tyrosine kinase. This ligand-receptor couple is essential for the maturation process of hepatocytes. Previously, the rational design of a synthetic protein based on the assembly of two K1 domains from HGF led to the production of a potent and stable MET receptor agonist. In this study, we compared the effects of K1K1 with HGF during the differentiation of hepatocyte progenitors derived from human induced pluripotent stem cells (hiPSCs). In vitro, K1K1, in the range of 20 to 200 nM, successfully substituted for HGF and efficiently activated ERK downstream signaling. Analysis of the levels of hepatocyte markers showed typical liver mRNA and protein expression (HNF4α, albumin, alpha-fetoprotein, CYP3A4) and phenotypes. Although full maturation was not achieved, the results suggest that K1K1 is an attractive candidate MET agonist suitable for replacing complex and expensive HGF treatments to induce hepatic differentiation of hiPSCs.

Photoelectrochemical Behavior of Silver Nanoparticles inside Mesoporous Titania: Plasmon-Induced Charge Separation Effect.

The self-assembly block copolymer method was used to synthesize mesoporous titania films and silver nanoparticles (NPs) were grown inside the films. Such silver NPs-titania films are known for their multicolor photochromic properties due to a photo-oxidation reaction of silver in the presence of titania under light excitation which is attributed to a plasmon induced charge separation. Here, the photoelectrochemical properties of these composite films have been investigated at different light wavelengths and chemical environment in order to characterize the light-induced redox reactivity modifications. Cyclic voltammetry study shows that the Ag+ electro-reduction peak potential varies depending on the light irradiation, which determines the state of the silver nanoparticles complexed or not by titania.

Recent Advances in Palladium Nanoparticles-Based Hydrogen Sensors for Leak Detection.

Along with the development of hydrogen as a sustainable energy carrier, it is imperative to develop very rapid and sensitive hydrogen leaks sensors due to the highly explosive and flammable character of this gas. For this purpose, palladium-based materials are being widely investigated by research teams because of the high affinity between this metal and hydrogen. Furthermore, nanostructured palladium may provide improved sensing performances compared to the use of bulk palladium. This arises from a higher effective surface available for interaction of palladium with the hydrogen gas molecules. Several works taking advantage of palladium nanostructures properties for hydrogen sensing applications have been published. This paper reviews the recent advances reported in the literature in this scope. The electrical and optical detection techniques, most common ones, are investigated and less common techniques such as gasochromic and surface wave acoustic sensors are also addressed. Here, the sensor performances are mostly evaluated by considering their response time and limit of detection.

AlN hollow-nanofilaments by electrospinning.

We present for the first time an original method to elaborate AlN nanofilaments (NFs) by using a preceramic-based electrospinning process. Initially, an Al-containing precursor (poly(ethylimino)alane) is mixed with an organic spinnable polymer to be electrospun and generate polymeric filaments with a homogeneous diameter. A ceramization step at 1000 °C under ammonia and a crystallization step at 1400 °C under nitrogen are performed to get the final product made of AlN NFs with a diameter ranging from 150 to 200 nm. Studies carried out by high resolution electron microscopy and 3D tomography show their regular morphology, with high chemical purity and polycrystalline nature.

Polynuclear complex family of cobalt(II)/sulfonylcalixarene: one-pot synthesis of cluster salt [Co14(II)]+[Co4(II)]- and field-induced slow magnetic relaxation in a six-coordinate dinuclear cobalt(II)/sulfonylcalixarene complex.

In this paper, we report the synthesis and description of a new family of polynuclear cobalt(II) complexes. Starting from the same initial compounds but varying the reaction time results in the formation of several new clusters, an original structure based on [Co14][Co4] clusters was obtained, representing the first one-pot synthesis of a cobalt aggregate salt reported in the literature. The synthesis and magnetic properties of these cobalt compounds are discussed. Three of them display a binuclear molecular structure (1-3) with two encapsulated Co(II) ions and show slow relaxation of magnetization at small applied magnetic field (Ueff = 10.7 K for 2 and Ueff = 20.3 K for 3), a characteristic of single-molecule-magnet materials.

Anionic calixarene-capped silver nanoparticles show species-dependent binding to serum albumins.

The anionic calixarenes para-sulphonatocalix[4]arene and 1,3-di-O-phosphonatocalix[ 4]arene, have been used to cap silver nanoparticles. The binding of these functional particles with regard to various serum albumins (bovine serum albumin, human serum albumin, porcine serum albumin and sheep serum albumin) has been studied by variable temperature fluorescence spectroscopy. The quenching of the fluorescence of the proteins was shown to vary as a function of the anionic calixarene capping molecule and also as a function of the origin of the serum albumin. It is thus possible to discriminate between the different species.

Direct-Writing Electrospun Functionalized Scaffolds for Periodontal Regeneration: In Vitro Studies.

Multiphasic scaffolds that combine different architectural, physical, and biological properties are the best option for the regeneration of complex tissues such as the periodontium. Current developed scaffolds generally lack architectural accuracy and rely on multistep manufacturing, which is difficult to implement for clinical applications. In this context, direct-writing electrospinning (DWE) represents a promising and rapid technique for developing thin 3D scaffolds with controlled architecture. The current study aimed to elaborate a biphasic scaffold using DWE based on two polycaprolactone solutions with interesting properties for bone and cement regeneration. One of the two scaffold parts contained hydroxyapatite nanoparticles (HAP) and the other contained the cementum protein 1 (CEMP1). After morphological characterizations, the elaborated scaffolds were assessed regarding periodontal ligament (PDL) cells in terms of cell proliferation, colonization, and mineralization ability. The results demonstrated that both HAP- and CEMP1-functionalized scaffolds were colonized by PDL cells and enhanced mineralization ability compared to unfunctionalized scaffolds, as revealed by alizarin red staining and OPN protein fluorescent expression. Taken together, the current data highlighted the potential of functional and organized scaffolds to stimulate bone and cementum regeneration. Moreover, DWE could be used to develop smart scaffolds with the ability to spatially control cellular orientation with suitable cellular activity at the micrometer scale, thereby enhancing periodontal and other complex tissue regeneration.

Simple synthetic route for SERS-active gold nanoparticles substrate with controlled shape and organization.

We report a simple synthetic route based on electroless deposition (galvanic displacement) and natural lithography to simultaneously control the shape and organization of Au nanoparticles (NPs). We show for the first time the formation of organized extended domains of Au nanoflowers and nanocrowns with single crystalline tips. The dimension and morphology of the desired nanostructures (NSs) can be tuned easily by controlling the deposition conditions at room temperature using saccharin as an organic additive. The exact role of saccharin on the crystal growth process of Au NPs is also discussed. A systematic surface enhancement Raman spectroscopy (SERS) study of large, ordered areas of organized gold nanoflowers using p-mercaptoaniline (pMA) as the probe molecule shows massive and reproducible enhancements of the Raman signal. By comparing the relative enhancement of the different vibrational modes as a function of the morphology, the specific charge-transfer (chemical effect) SERS mechanism can be distinguished from the general electromagnetic field enhancement (physical effect). A wide range of applications can be envisaged for these SERS substrates.

Iron-based 1D nanostructures by electrospinning process.

Iron-based 1D nanostructures have been successfully prepared using an electrospinning technique and varying the pyrolysis atmospheres. Hematite (Fe(2)O(3)) nanotubes and polycrystalline Fe(3)C nanofibers were obtained by simple air or mixed gas (H(2), Ar) annealing treatments. Using the air annealing treatment, a high control of the morphology as well as of the wall thickness of the nanotubes was demonstrated with a direct influence of the starting polymer concentration. When mixed gases (H(2) and Ar) were used for the annealing treatments, for the first time polycrystalline Fe(3)C nanofibers composed of carbon graphitic planes were obtained, ensuring Fe(3)C nanoparticle stability and nanofiber cohesion. The morphology and structural properties of all these iron-based 1D nanostructures were fully characterized by SEM, TEM, XRD and Raman spectroscopy.

Synthesis of polystyrene coated SiC nanowires as fillers in a polyurethane matrix for electromechanical conversion.

Grafting of polystyrene (PS) from silica coating of silicon carbide nanowires (SiCNWs) has been performed by a two-step nitroxide mediated free radical polymerization (NMP) of styrene. First, an alkoxyamine based on N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide (DEPN) was covalently attached onto NWs through free surface silanol groups. To immobilize the alkoxyamine initiator on the silica surface, alkoxylamine was formed in situ by the simultaneous reaction of polymerizable acryloxy propyl trimethoxysilane (APTMS), azobis isobutyronitrile (AIBN), and DEPN, which was used as a radical trap. Polystyrene chains with controlled molecular weights and narrow polydispersity were then grown from the alkoxyamine-functionalized NWs surface in the presence of a 'free' sacrificial styrylDEPN alkoxyamine. Both the initiator and polystyrene chains were characterized by FTIR and (13)C solid-state NMR and quantified by TGA. Ensuing nanocomposites were characterized by FEG-SEM, TEM and Raman spectroscopy. EDX analysis performed on functionalized nanowires during FEG-SEM analysis also gave evidence of grafting by a strong increase in the average C/Si atomic ratio. Incorporation of 2 wt% NWs into the polyurethane (PU) matrix has been carried out to prepare homogeneous nanocomposite films. The electric field induced thickness strain response has been investigated for the polystyrene-grafted silica coated SiC NWs (PU-SiC@SiO(2)@PS) nanocomposites and compared to pure polyurethane film and PU-SiC@SiO(2) nanocomposite without polystyrene grafting. At a moderate electric field of 10 V microm(-1), SiC@SiO(2)@PS loading increased the strain level of pure PU by a factor of 2.2. This improvement came partially due to polystyrene grafting since PU-SiC@SiO(2) films showed only a 1.7 times increase. The observed higher strain response of these nanocomposites makes them very attractive for micro-electromechanical applications.

Natural superhydrophilicity and photocatalytic properties of sol-gel derived ZnTiO(3)-ilmenite/r-TiO(2) films.

The additive free heteronucleation and nanocrystallization of ternary Zn(x)Ti(y)O(z) sols and coatings is presented. A proper adjustment of the Zn/Ti ratio in the sol allows the formation of elaborate superhydrophilic cubic spinel-like Zn(2)TiO(4), c-ZnTiO(3) or h-ZnTiO(3)-ilmentite/r-TiO(2)-rutile films. Their morphology and natural superhydrophilicity can be fine-tuned by the inclusion of 5% silica. This doping step delivers high dye intake capacities and water contact angle values below 3°. XPS analysis indicates that Zn and Si enrichment enables greater surface hydroxylation and thus improved water wetting behaviour. The transparent h-ZnTiO(3)-ilmenite/r-TiO(2) nanocomposite coatings deposited on glass and Si-wafers show a remarkable activity in the photomineralization of fatty-acids.

Electroactive Area from Porous Oxide Films Loaded with Silver Nanoparticles: Electrochemical and Electron Tomography Observations.

Electrochemical studies of nanomaterial-based electrodes have been widely developed for catalyst and energy-harvesting applications. The evolution of these electrodes over time and their efficiency have been extensively studied and analyzed in order to optimize their performance. However, the electrochemical responses of electrodes are rarely studied in terms of the position of the active species within these electrodes. In this paper, we highlight that the spatial location of silver nanoparticles (NPs) embedded inside semiconductive porous films, TiO2 or Fe2O3, is crucial for the electrochemical response. In fact, by using cycling voltammetry and electron tomography experiments, we show the existence of an "electroactive area", corresponding to a reduced thickness of the sample in close vicinity to a fluorine-doped tin oxide substrate where most of the electrochemical responses originate. Our results demonstrate that, for a film thickness of several hundred nanometers, only less than 30 nm close to the substrate responds electrochemically. However, cyclic voltammetry empties the electroactive area of silver NPs. Therefore, application of chronoamperometry coupled to irradiation allowed regeneration of this area thanks to an increased diffusion of silver species. In this paper, we also show the significant diffusion of silver species within the film during electrochemical experiments, a phenomenon even increased by irradiation. These results are therefore an important step that shows the importance of the localization of active species within a porous film and help in understanding and increasing the durability of nanomaterial-based electrodes.

Improvements in Resolution of Additive Manufacturing: Advances in Two-Photon Polymerization and Direct-Writing Electrospinning Techniques.

In recent years, additive manufacturing (AM) technologies have attracted significant interest in many industrial and research fields, particularly in tissue engineering. Printed structures used as physical and bioactive supports for tissue regeneration are becoming increasingly complex so as to mimic natural tissues in order to answer future medical needs. Reproducing the biological environment of a native tissue from the microscopic to the macroscopic scale appears to be the best strategy for effective regeneration. Recent advances in AM have led to the production of scaffolds designed with a high precision. This Review presents results concerning two AM technologies which enable the highest accuracy of scaffold design to be obtained, with a precision down to the nanoscale. The first technique is based on a two-photon polymerization (TPP) process, while the other is based on a direct-writing electrospinning (DWES) system. Here, we present an overview of the fabrication mechanisms, the final scaffold properties, and their applications in tissue engineering. The production of highly resolved structures offers new possibilities for studying cell behavior in a controlled environment and also for adjusting the desired scaffold properties to address current and future needs in tissue engineering. The current technical limitations and future challenges are thus also discussed in this Review.

Mesoporous silica fillers and resin composition effect on dental composites cytocompatibility.

OBJECTIVE: Many new dental composites containing mesoporous silica fillers have been developed to improve rheological properties and enhance the resin-filler interface. To investigate the correlation between the cytocompatibility of several dental composites and their composition; two aspects have been considered: presence of bisphenol A (BPA)-glycidyl methacrylate (Bis-GMA) or triethyleneglycol-dimethacrylate (TEGDMA) among the resin monomers and presence of porous particles among the filler blends. METHODS: Five commercial composites with different resin matrices and mineral fillers were compared to four experimental composites designed without any BPA-based monomers or TEGDMA. Porous fillers, with or without silanation, were added in some of the experimental composites. Two reference resin matrices were also selected. Cytocompatibility with cultured primary human gingival fibroblasts was assessed by confocal laser scanning microscopy with time-lapse imaging. Fourier transform infrared spectroscopy was used to control monomer conversion rate. RESULTS: Conversion rates of the experimental composites ranged from 57% to 71%, a comparable ratio for dental composites. Experimental samples were better tolerated than tested commercial samples not containing TEGDMA and significantly better than those containing TEGDMA. Experimental composites with porous fillers exhibited good cytocompatibility, especially when surfaces were silanated. SIGNIFICANCE: Cytotoxicity was associated with resin amount and especially resin nature. Composites containing porous fillers might behave as if the resin trapped into pores has no effect on toxicity. The cytotoxicity of composites with and without BPA derivatives was mainly attributed to the release of residual TEGDMA rather than the BPA derivatives.

Synthesis of Continuous Conductive PEDOT:PSS Nanofibers by Electrospinning: A Conformal Coating for Optoelectronics.

A process to synthesize continuous conducting nanofibers were developed using PEDOT:PSS as a conducting polymer and an electrospinning method. Experimental parameters were carefully explored to achieve reproducible conductive nanofibers synthesis in large quantities. In particular, relative humidity during the electrospinning process was proven to be of critical importance, as well as doping post-treatment involving glycols and alcohols. The synthesized fibers were assembled as a mat on glass substrates, forming a conductive and transparent electrode and their optoelectronic have been fully characterized. This method produces a conformable conductive and transparent coating that is well-adapted to nonplanar surfaces, having very large aspect ratio features. A demonstration of this property was made using surfaces having deep trenches and high steps, where conventional transparent conductive materials fail because of a lack of conformability.

Pure &crystallized 2D Boron Nitride sheets synthesized via a novel process coupling both PDCs and SPS methods.

Within the context of emergent researches linked to graphene, it is well known that h-BN nanosheets (BNNSs), also referred as 2D BN, are considered as the best candidate for replacing SiO2 as dielectric support or capping layers for graphene. As a consequence, the development of a novel alternative source for highly crystallized h-BN crystals, suitable for a further exfoliation, is a prime scientific issue. This paper proposes a promising approach to synthesize pure and well-crystallized h-BN flakes, which can be easily exfoliated into BNNSs. This new accessible production process represents a relevant alternative source of supply in response to the increasing need of high quality BNNSs. The synthesis strategy to prepare pure h-BN is based on a unique combination of the Polymer Derived Ceramics (PDCs) route with the Spark Plasma Sintering (SPS) process. Through a multi-scale chemical and structural investigation, it is clearly shown that obtained flakes are large (up to 30 µm), defect-free and well crystallized, which are key-characteristics for a subsequent exfoliation into relevant BNNSs.

Discrete polynuclear manganese(ii) complexes with thiacalixarene ligands: synthesis, structures and photophysical properties.

The synthesis, crystal structure and photophysical properties of the new compound [Mn4(ThiaSO2)2F][K(18-crown-6)], ThiaSO2 = p-tert-butylsulphonylcalix[4]arene, are presented and compared to the ones of [Mn4(ThiaSO2)2F]K. The strong orange luminescence is attributed to the Mn(2+) centred (4)T1→(6)A1 transition. Its temperature and pressure dependence and quenching by molecular dioxygen are reported. The latter is attributed to energy transfer from the (4)T1 state exciting dioxygen to its (1)∑(+)g state. In the solid state, the quenching is much more efficient in [Mn4(ThiaSO2)2F][K(18-crown-6)] than in [Mn4(ThiaSO2)2F]K. This is attributed to the open pore structure of the former allowing fast diffusion of dioxygen into the crystal lattice.

Molecular recognition by gold, silver and copper nanoparticles.

The intrinsic physical properties of the noble metal nanoparticles, which are highly sensitive to the nature of their local molecular environment, make such systems ideal for the detection of molecular recognition events. The current review describes the state of the art concerning molecular recognition of Noble metal nanoparticles. In the first part the preparation of such nanoparticles is discussed along with methods of capping and stabilization. A brief discussion of the three common methods of functionalization: Electrostatic adsorption; Chemisorption; Affinity-based coordination is given. In the second section a discussion of the optical and electrical properties of nanoparticles is given to aid the reader in understanding the use of such properties in molecular recognition. In the main section the various types of capping agents for molecular recognition; nucleic acid coatings, protein coatings and molecules from the family of supramolecular chemistry are described along with their numerous applications. Emphasis for the nucleic acids is on complementary oligonucleotide and aptamer recognition. For the proteins the recognition properties of antibodies form the core of the section. With respect to the supramolecular systems the cyclodextrins, calix[n]arenes, dendrimers, crown ethers and the cucurbitales are treated in depth. Finally a short section deals with the possible toxicity of the nanoparticles, a concern in public health.

Iron oxide nanoparticles with sizes, shapes and compositions resulting in different magnetization signatures as potential labels for multiparametric detection.

Magnetic iron oxide nanoparticles differing in their size, shape (spherical, hexagonal, rods, cubes) and composition have been synthesized and modified using caffeic acid for transfer to aqueous media and stabilization of the particle suspensions at physiological pH. A super quantum interference device and the recently patented magnetic sensor MIAplex®, which registered a signal proportional to the second derivative of the magnetization curve, were used to study the magnetization behavior of the nanoparticles. The differences in the magnetic signatures of the nanoparticles (spheres and rods) make them promising candidates for the simultaneous detection of different types of biological molecules.