André Galembeck

BiVO4 thin film preparation by metalorganic decomposition

This paper describes the first obtention of BiVO4 thin films. These films were prepared with the Metalorganic Decomposition technique, starting from bismuth 2-ethyl-hexanoate and vanadium (IV) (oxy)acetylacetonate precursors. These compounds were dissolved in freshly distilled acetylacetone, dip-coated on common borosilicate glass substrates and pyrolysed at 400°C. Film thickness ranged from 50 to 100 nm, depending on the number of deposition steps. Films are transparent, allowing the first obtention of UV–vis absorption spectra acquisition in transmission mode. Raman microprobe spectra confirmed the obtention of BiVO4 deposited as an homogeneous film. Scanning electron micrographs showed a continuous and porous surface.

Modeling, Structural, and Spectroscopic Studies of Lanthanide-Organic Frameworks

In this paper, we report the hydrothermal synthesis of three lanthanide-organic framework materials using as primary building blocks the metallic centers Eu(3+), Tb(3+), and Gd(3+) and residues of mellitic acid: [Ln(2)(MELL)(H(2)O)(6)] (where Ln(3+) = Eu(3+), Tb(3+), and Gd(3); hereafter designated as (1), (2) and (3)). Structural characterization encompasses single-crystal X-ray diffraction studies, thermal analysis, and vibrational spectroscopy, plus detailed investigations on the experimental and predicted (using the Sparkle/AM1 model) photophysical luminescent properties. Crystallographic investigations showed that the compounds are all isostructural, crystallizing in the orthorhombic space group Pnnm and structurally identical to the lanthanum 3D material reported by the group of Williams. (2) is highly photoluminescent, as confirmed by the measured quantum yield and lifetime (37% and 0.74 ms, respectively). The intensity parameters (Omega(2), Omega(4), and Omega(6)) of (1) were first calculated using the Sparkle/AM1 structures and then employed in the calculation of the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield derived from the Sparkle/AM1 structures was approximately 16%, and the experimental value was 8%. We attribute the registered differences to the fact that the theoretical model does not consider the vibronic coupling with O-H oscillators from coordinated water molecules. These results clearly attest for the efficacy of the theoretical models employed in all calculations and open a new window of interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

A New “Silver-Bullet” to treat caries in children – Nano Silver Fluoride: A randomised clinical trial

BACKGROUND Untreated dental caries in children remains a public health challenge in poor communities. OBJECTIVES This prospective controlled clinical trial investigated the effectiveness of a new anti-caries agent, Nano Silver Fluoride (NSF), applied once a year to arrest caries in children. METHODS One hundred thirty decayed primary teeth were randomly divided into two groups: NSF as the experimental agent and water as the control group. Teeth were clinically diagnosed and treated by one masked examiner and followed up at seven days and five and 12 months by another calibrated examiner who was blinded to the type of treatment. The criteria of the ICDAS II were followed to determine the activity of lesion and the diagnosis of caries. The Pearsons chi-square test was used to compare the groups during different follow-up exams. RESULTS At seven days, 81% of teeth in the NSF group exhibited arrested caries, whereas in controls, no teeth had arrested decay (p<0.001) [PF, prevented fraction=81%]. After five months, the NSF group had 72.7% with arrested decay, and the control group had 27.4% (p<0.001) [PF=62.5%]. At 12 months, 66.7% of the lesions treated with NSF were still arrested, while the control group had 34.7% remaining arrested (p=0.003) [PF=50%]. The number need to treat (NNT) at five months was two, and at 12 months, the number was three. CLINICAL SIGNIFICANCE The NSF formulation is effective to arrest active dentine caries and not stain teeth. CONCLUSIONS NSF was demonstrated to be effective in arresting caries in children in poor communities.

Random laser action in dye solutions containing Stöber silica nanoparticles

Random laser action is obtained in a diffusive weakly scattering regime using an alcohol solution of rhodamine 640 with silica nanoparticles prepared by the Stober method, with different average diameters of 49, 90, 219, and 490 nm. Particle size and concentration has proven to affect the random laser performance. It is also shown that silica nanoparticles contributes for a much slower photodegradation of the dye molecules than titania nanoparticles that has been used in the majority of the dye random lasers. This fact makes it advantageous to use silica nanoparticles for the fundamental studies of random laser, due to its increase in lifetime under pumping conditions.Random laser action is obtained in a diffusive weakly scattering regime using an alcohol solution of rhodamine 640 with silica nanoparticles prepared by the Stober method, with different average diameters of 49, 90, 219, and 490 nm. Particle size and concentration has proven to affect the random laser performance. It is also shown that silica nanoparticles contributes for a much slower photodegradation of the dye molecules than titania nanoparticles that has been used in the majority of the dye random lasers. This fact makes it advantageous to use silica nanoparticles for the fundamental studies of random laser, due to its increase in lifetime under pumping conditions.

Improved Synthesis of Gold and Silver Nanoshells

Metallic nanoshells have been in evidence as multifunctional particles for optical and biomedical applications. Their surface plasmon resonance can be tuned over the electromagnetic spectrum by simply adjusting the shell thickness. Obtaining these particles, however, is a complex and time-consuming process, which involves the preparation and functionalization of silica nanoparticles, synthesis of very small metallic nanoparticles seeds, attachment of these seeds to the silica core, and, finally, growing of the shells in a solution commonly referred as K-gold. Here we present synthetic modifications that allow metallic nanoshells to be obtained in a faster and highly reproducible manner. The main improved steps include a procedure for quick preparation of 2.3 ± 0.5 nm gold particles and a faster approach to synthesize the silica cores. An investigation on the effect of the stirring speed on the shell growth showed that the optimal stirring speeds for gold and silver shells were 190 and 1500 rpm, respectively. In order to demonstrate the performance of the nanoshells fabricated by our method in a typical plasmonic application, a method to immobilize these particles on a glass slide was implemented. The immobilized nanoshells were used as substrates for the surface-enhanced Raman scattering from Nile Blue A.

Bismuth vanadate synthesis by metallo-organic decomposition: thermal decomposition study and particle size control

Polycrystalline bismuth vanadate, BiVO4, was synthesized by metallo-organic decomposition (MOD), starting from bismuth 2-ethyl-hexanoate and vanadium (IV) oxy-acetylacetonate solutions in an organic solvent. The pyrolysis of the precursors at 500°C lead to single-phase samples, with particle sizes ranging from 0.65 to 1.40 μm, depending upon the heating time. The activation energies for the thermal decomposition of the precursors were estimated as 100.0 kJ/mol and 90.5 kJ/mol for bismuth and vanadium precursors, respectively. The method allows for the synthesis of powdered polycrystalline and/or thin film samples and may provide a route to doped/substituted compounds with minimal changes in the experimental procedures.

Friction, tribochemistry and triboelectricity: recent progress and perspectives

Production of electricity by friction is well known but poorly understood, and is the source of electrostatic discharge causing serious accidents. Recent results are in agreement with one of the conflicting views on this problem, according to which triboelectricity in polymers is triggered by mechanochemical and wear or mass transfer phenomena. These results also challenge the widely accepted paradigm of one-way charge transfer that is the basis of the triboelectric series. Experimental results from powerful analytical techniques coupled to surface charge mapping support the following hypothesis: charge-bearing species are ionic polymer fragments formed through mechanical action. Beyond this, the atmosphere participates through tribocharge build-up and dissipation due to reactive plasma formation and charge exchange at the gas–solid interface, mediated by adsorption of non-neutral water, or ion partition during water adsorption, as in hygroelectricity phenomena.

Scanning electric potential microscopy imaging of polymers: electrical charge distribution in dielectrics

Scanning electric potential images of polymer surfaces are presented and compared to standard non-contact AFM images. Samples used were a latex film with a well-known distribution of chemical constituents and thus of ionic electrical charges, as well as finished industrial products. Topography and electric potential images show a variable degree of correlation, thus evidencing the independence of topographic and electrical features of the samples, in the micro- and nanoscopic scales. Domains with non-zero negative or positive electric potentials are observed, extending for a few tenths of a micron and creating an electric mosaic in the otherwise neutral polymers. Large electric potential gradients are observed, e.g. in a HDPE film.

Photoreactive surfactants: a facile and clean route to oxide and metal nanoparticles in reverse micelles.

A new class of photoreactive surfactants (PRSs) is presented here, consisting of amphiphiles that can also act as reagents in photochemical reactions. An example PRS is cobalt 2-ethylhexanoate (Co(EH)(2)), which forms reverse micelles (RMs) in a hydrocarbon solvent, as well as mixed reversed micelles with the standard surfactant Aerosol-OT (AOT). Small-angle neutron scattering (SANS) data show that mixed AOT/PRS RMs have a spherical structure and size similar to that of pure AOT micelles. Excitation of the ligand-to-metal charge transfer (LMCT) band in the PRSs promotes electron transfer from PRS to associated metal counterions, leading to the generation of metal and metal-oxide nanoparticles inside the RMs. This work presents proof of concept for employing PRSs as precursors to obtain nearly monodisperse inorganic nanoparticles: here both Co(3)O(4) and Bi nanoparticles have been synthesized at high metal concentration (10(-2) M) by simply irradiating the RMs. These results point toward a new approach of photoreactive self-assembly, which represents a clean and straightforward route to the generation of nanomaterials.

High-order nonlinearity of silica-gold nanoshells in chloroform at 1560 nm.

The nonlinear response of silica--gold nanoshells (SGNs) in chloroform was studied using laser pulses of 65 fs at 1560 nm. The experiments were performed using the thermally managed Z--scan technique that allows measurements of the electronic contribution for the nonlinear response, free from thermal influence. The results were analyzed using an analytical approach based on the quasi--static approximation that allowed extraction of the nonlinear susceptibility of a SGN from the data. High third--order susceptibility, χsh((3)) = - 1.5 x 10(-11) m(2)/V(2), approximately four orders of magnitude larger than for gold nanospheres in the visible, and large fifth--order susceptibility, χsh((5)) = - 1.4 x 10(-24) m(4)/V(4), were obtained. The present results offers new perspectives for nonlinear plasmonics in the near--infrared.