CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

Ceria (CeO2) plays a vital role in emerging technologies for environmental and energy-related applications. The catalytic efficiency of ceria nanoparticles depends on its morphology. In this study, CeO2 nanoparticles were synthesized by a microwave-assisted hydrothermal method under different synthesis temperatures. The samples were characterized by X-ray diffraction, transmission electron microscopy, Raman scattering spectroscopy, electron paramagnetic resonance spectroscopy and by the Brunauer-Emmett-Teller method. The X-ray diffraction and Raman scattering results indicated that all the synthesized samples had a pure cubic CeO2 structure. Rietveld analysis and Raman scattering also revealed the presence of structural defects due to an associated reduction in the valence of the Ce4+ ions to Ce3+ ions caused by an increasing molar fraction of oxygen vacancies. The morphology of the samples was controlled by varying the synthesis temperature. The TEM images show that samples synthesized at 80 degrees C consisted of spherical particles of about 5 nm, while those synthesized at 120 degrees C presented a mix of spherical and rod-like nanoparticles and the sample synthesized at 160 degrees C consisted of nanorods with 10 nm average diameter and 70 nm length. The microwave-assisted method proved to be highly efficient for the synthesis of CeO2 nanoparticles with different morphologies.

SnO2 nanocrystals synthesized by microwave-assisted hydrothermal method: towards a relationship between structural and optical properties

The exploration of novel synthetic methodologies that control both size and shape of functional nanostructure opens new avenues for the functional application of nanomaterials. Here, we report a new and versatile approach to synthesize SnO2 nanocrystals (rutile-type structure) using microwave-assisted hydrothermal method. Broad peaks in the X-ray diffraction spectra indicate the nanosized nature of the samples which were indexed as a pure cassiterite tetragonal phase. Chemically and physically adsorbed water was estimated by TGA data and FT-Raman spectra to account for a new broad peak around 560 cm(-1) which is related to defective surface modes. In addition, the spherical-like morphology and low dispersed distribution size around 3-5 nm were investigated by HR-TEM and FE-SEM microscopies. Room temperature PL emission presents two broad bands at 438 and 764 nm, indicating the existence of different recombination centers. When the size of the nanospheres decreases, the relative intensity of 513 nm emission increases and the 393 nm one decreases. UV-Visible spectra show substantial changes in the optical absorbance of crystalline SnO2 nanoparticles while the existence of a small tail points out the presence of localized levels inside the forbidden band gap and supplies the necessary condition for the PL emission.

Photoprotection and the Photophysics of Acylated Anthocyanins

The proposed role of anthocyanins in protecting plants against excess solar radiation is consistent with the occurrence of ultrafast (525 ps) excited-state proton transfer as the major de-excitation pathway of these molecules. However, because natural anthocyanins absorb mainly in the visible region of the spectra, with only a narrow absorption band in the UV-B region, this highly efficient deactivation mechanism would essentially only protect the plant from visible light. On the other hand, ground-state charge-transfer complexes of anthocyanins with naturally occurring electron-donor co-pigments, such as hydroxylated flavones, flavonoids, and hydroxycinnamic or benzoic acids, do exhibit high UV-B absorptivities that complement that of the anthocyanins. In this work, we report a comparative study of the photophysics of the naturally occurring anthocyanin cyanin, intermolecular cyanincoumaric acid complexes, and an acylated anthocyanin, that is, cyanin with a pendant coumaric ester co-pigment. Both inter- and intramolecular anthocyaninco-pigment complexes are shown to have ultrafast energy dissipation pathways comparable to those of model flavylium cationco-pigment complexes. However, from the standpoint of photoprotection, the results indicate that the covalent attachment of co-pigment molecules to the anthocyanin represents a much more efficient strategy by providing the plant with significant UV-B absorption capacity and at the same time coupling this absorption to efficient energy dissipation pathways (ultrafast internal conversion of the complexed form and fast energy transfer from the excited co-pigment to the anthocyanin followed by adiabatic proton transfer) that avoid net photochemical damage.

Development of Novel Guava Puree Films Containing Chitosan Nanoparticles

One of the overall goals of industries is to use packages that do not cause environmental problems at disposal time, but that have the same properties as the conventional ones. The goal of this study is to synthesize edible films based on hydroxypropyl methylcellulose (HPMC) with guava puree and chitosan (CS) nanoparticles. This was divided into two stages, the first is the synthesis of chitosan nanoparticles and the second is the production of the films. For the nanoparticles, average size and zeta potential measurements were performed. The characterizations of mechanical and thermal properties, solubility and water vapor permeability tests were conducted in the films. It was observed that when the nanoparticles were added to HPMC and guava puree films, they improved their mechanical and thermal properties, as well as decreased the films solubility and permeability. The potential application of the films prepared would be in edible films with flavor and odor to extend the shelf life of products.

Adsorption of Sodium Dodecyl Sulfate on Ge Substrate: The Effect of a Low-Polarity Solvent

This paper describes the adsorption of sodium dodecyl sulfate (SDS) molecules in a low polar solvent on Ge substrate by using Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy and atomic force microscopy (AFM). The maximum SDS amount adsorbed is (5.0 +/- 0.3) x 10(14) molecules cm(-2) in CHCl3, while with the use of CCl4 as subphase the ability of SDS adsorbed is 48% lower. AFM images show that depositions are highly disordered over the interface, and it was possible to establish that the size of the SDS deposition is around 30-40 nm over the Ge surface. A complete description of the infrared spectroscopic bands for the head and tail groups in the SDS molecule is also provided.

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 mu M; dynamic range: 2-200 mu M, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: +/- 7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE. We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 degrees C. Activation energies (E-a) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the E-a was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.

Selectivity and Mechanisms Driven by Reaction Dynamics: The Case of the Gas-Phase OH-+CH3ONO2 Reaction

Well-established statistical approaches such as transition-state theory based on high-level calculated potential energy profiles are unable to account for the selectivity observed in the gas-phase OH- + CH3ONO2 reaction. This reaction can undergo bimolecular nucleophilic displacement at either the carbon center (S(N)2@C) or the nitrogen center (S(N)2@N) as well as a proton abstraction followed by dissociation (E(CO)2) pathway. Direct dynamics simulations yield an S(N)2:E(CO)2 product ratio in close agreement with experiment and show that the lack of reactivity at the nitrogen atom is due to the highly negative electrostatic potential generated by the oxygen atoms in the ONO2 group that scatters the incoming OH-. In addition to these dynamical effects, the nonstatistical behavior of these reactions is attributed to the absence of equilibrated reactant complexes and to the large number of recrossings, which might be present in several ion-molecule gas-phase reactions.

Density Functional Theory (DFT) Study of Edaravone Derivatives as Antioxidants

Quantum chemical calculations at the B3LYP/6-31G* level of theory were employed for the structure-activity relationship and prediction of the antioxidant activity of edaravone and structurally related derivatives using energy (E), ionization potential (IP), bond dissociation energy (BDE), and stabilization energies(Delta E-iso). Spin density calculations were also performed for the proposed antioxidant activity mechanism. The electron abstraction is related to electron-donating groups (EDG) at position 3, decreasing the IP when compared to substitution at position 4. The hydrogen abstraction is related to electron-withdrawing groups (EDG) at position 4, decreasing the BDECH when compared to other substitutions, resulting in a better antioxidant activity. The unpaired electron formed by the hydrogen abstraction from the C-H group of the pyrazole ring is localized at 2, 4, and 6 positions. The highest scavenging activity prediction is related to the lowest contribution at the carbon atom. The likely mechanism is related to hydrogen transfer. It was found that antioxidant activity depends on the presence of EDG at the C-2 and C-4 positions and there is a correlation between IP and BDE. Our results identified three different classes of new derivatives more potent than edaravone.

Gamma Radiation Induced Oxidation and Tocopherols Decrease in In-Shell, Peeled and Blanched Peanuts

In-shell, peeled and blanched peanut samples were characterized in relation to proximate composition and fatty acid profile. No difference was found in relation to its proximate composition. The three major fatty acids were palmitic acid, oleic acid, and linoleic acid. In order to investigate irradiation and storage effects, peanut samples were submitted to doses of 0.0, 5.0, 7.5 or 10.0 kGy, stored for six months at room temperature and monitored every three months. Peanuts responded differently to irradiation, particularly with regards to tocopherol contents, primary and secondary oxidation products and oil stability index. Induction periods and tocopherol contents were negatively correlated with irradiation doses and decreased moderately during storage. alpha-Tocopherol was the most gamma radiation sensitive and peeled samples were the most affected. A positive correlation was found among tocopherol contents and the induction period of the oils extracted from irradiated samples. Gamma radiation and storage time increased oxidation compounds production. If gamma radiation is considered an alternative for industrial scale peanut conservation, in-shell samples are the best feedstock. For the best of our knowledge this is the first article with such results; this way it may be helpful as basis for future studies on gamma radiation of in-shell crops.

COMPLETE H-1 AND C-13 NMR STRUCTURAL ASSIGNMENTS FOR A GROUP OF FOUR GOYAZENSOLIDE-TYPE FURANOHELIANGOLIDES

Four goyazensolide-type sesquiterpene lactones - lychnofolide, centratherin, goyazensolide and goyazensolide acetate - were thoroughly studied by NMR experimental techniques. H-1 NMR, C-13 NMR {H-1}, COSY, HMQC, HMBC, J-res. and NOE experiments were performed to provide the needed structural information. Complete and unequivocal assignment, including the determination of all multiplicities, was obtained for each structure and the data collections are presented in tables.

Mapping the Energy Distribution of SERRS Hot Spots from Anti-Stokes to Stokes Intensity Ratios

The anomalies in the anti-Stokes to Stokes intensity ratios in single-molecule surface-enhanced resonance Raman scattering were investigated. Brilliant green and crystal violet dyes were the molecular probes, and the experiments were carried out on an electrochemically activated Ag surface. The results allowed new insights into the origin of these anomalies and led to a new method to confirm the single-molecule regime in surface-enhanced Raman scattering. Moreover, a methodology to estimate the distribution of resonance energies that contributed to the imbalance in the anti-Stokes to Stokes intensity ratios at the electromagnetic hot spots was proposed. This method allowed the local plasmonic resonance energies on the metallic surface to be spatially mapped.

Multi-Walled Carbon Nanotubes and Poly(lactic acid) Nanocomposite Fibrous Membranes Prepared by Solution Blow Spinning

Nanocomposite fibers based on multi-walled carbon nanotubes (MWCNT) and poly(lactic acid) (PLA) were prepared by solution blow spinning (SBS). Fiber morphology was characterized by scanning electron microscopy (SEM) and optical microscopy (OM). Electrical, thermal, surface and crystalline properties of the spun fibers were evaluated, respectively, by conductivity measurements (4-point probe), thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), contact angle and X-ray diffraction (XRD). OM analysis of the spun mats showed a poor dispersion of MWCNT in the matrix, however dispersion in solution was increased during spinning where droplets of PLA in solution loaded with MWCNT were pulled by the pressure drop at the nozzle, producing PLA fibers filled with MWCNT. Good electrical conductivity and hydrophobicity can be achieved at low carbon nanotube contents. When only 1 wt% MWCNT was added to low-crystalline PLA, surface conductivity of the composites increased from 5 x 10(-8) to 0.46 S/cm. Addition of MWCNT can slightly influence the degree of crystallinity of PLA fibers as studied by XRD and DSC. Thermogravimetric analyses showed that MWCNT loading can decrease the onset degradation temperature of the composites which was attributed to the catalytic effect of metallic residues in MWCNT. Moreover, it was demonstrated that hydrophilicity slightly increased with an increase in MWCNT content. These results show that solution blow spinning can also be used to produce nanocomposite fibers with many potential applications such as in sensors and biosensors.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Preparação de vidros e vitrocerâmicas de óxidos de metais pesados contendo prata: propriedades ópticas, estruturais e eletroquímicas

Silver containing heavy metal oxide glasses and glass ceramics of the system WO3-SbPO4-PbO-AgCl with different AgCl contents have been prepared and their thermal, structural and optical properties characterized. Glass ceramics containing metallic silver nanoparticles have been prepared by annealing glass samples at temperatures above the glass transition and analyzed by transmission electron microscopy and energy dispersive X-ray microanalysis. The presence of the metallic clusters has been also confirmed by the observation of a surface plasmon resonimce band in the visible range. Cyclic voltammetric measurements indicated the presence of metallic silver into the glasses, even before to perform the thermal treatment.