Evaluation of intramolecular energy transfer process in the lanthanide(III) bis- and tris-(TTA) complexes: Photoluminescent and triboluminescent behavior

This work reports the energy transfer mechanism process of [Eu(TTA)(2)(NO(3))(TPPO)(2)] (bis-TTA complex) and [Eu(TTA)(3)(TPPO)(2)] (tris-TTA complex) based on experimental and theoretical spectroscopic properties, where TTA = 2-thienoyltrifluoroacetone and TPPO = triphenylphosphine oxide. These complexes were synthesized and characterized by elemental analyses, infrared spectroscopy and thermogavimetric analysis. The theoretical complexes geometry data by using Sparkle model for the calculation of lanthanide complexes (SMLC) is in agreement with the crystalline structure determined by single-crystal X-ray diffraction analysis. The emission spectra for [Gd(TTA)(3)(TPPO)(2)] and [Gd(TTA)(2) (NO(3))(TPPO)(2)] complexes are associated to T -> S(0) transitions centered on coordinated TTA ligands. Experimental luminescent properties of the bis-TTA complex have been quantified through emission intensity parameters Omega(lambda)(lambda = 2 and 4), spontaneous emission rates (A(rad)), luminescence lifetime (tau), emission quantum efficiency (eta) and emission quantum yield (q), which were compared with those for tris-TTA complex. The experimental data showed that the intensity parameter value for bis-TTA complex is twice smaller than the one for tris-TTA complex, indicating the less polarizable chemical environment in the system containing nitrate ion. A good agreement between the theoretical and experimental quantum yields for both Eu(Ill) complexes was obtained. The triboluminescence (TL) of the [Eu(TTA)(2)(NO(3))(TPPO)(2)] complexes are discussed in terms of ligand-to-metal energy transfer. (c) 2007 Elsevier B.V. All fights reserved.

Time resolved emission spectroscopy of poly(2,5-dicyano-p-phenylene-vinylene) films

Films of poly (2,5-dicyano-p-phenylene vinylene), DCNPPV, were obtained by electrochemical synthesis over gold thin layer (20 nm) transparent electrode deposited on a glass plate. The DCNPPV films of 4 µm thickness were produced by electropolymerization process of α,α,α',α'-tetrabromo-2-5-dicyano-p-xilene at different applied potentials (-0.15, -0.25, -0.40, -0.60, -0.80, and -1.0 V) using 0.1 mol L-1 of tetraethylammonium bromide in acetonitrile as the supporting electrolyte. The emission decays have three exponential components: a fast component in the picosecond range (200-400 ps), and two other of about one and five nanoseconds at 293 K. The fluorescence quenching process seems to occur by exciton trapping in a low-energy site and quenching by residual bromine monomer attached at the end of the polymer chain. However, the electrochemical synthesis generates entrapped bromide or ion pairs during the growth step of the film which also contributes to the deactivation. The change of the electrolyte from bromide to perchlorate reduces significantly this additional quenching effect by allowing ion exchange of formed bromide with the nonquenching perchloride anion.

Electrochemical and photocatalytic reactions of polycyclic aromatic hydrocarbons investigated by raman spectroscopy

This paper presents the study of photochemical behavior of polycyclic aromatic hydrocarbons (PAHs), potential pollutants in secondary reactions in aerosols, through Raman spectroscopy compared with its electrochemical behavior. The PAHs studied include pyrene, anthracene, phenanthrene and fluorene. These were adsorbed onto TiO2 and irradiated with ultraviolet light (254 nm). Their electrochemical oxidation was studied by in situ Surface-enhanced Raman Scattering (SERS) and led to the formation of carbonyl-containing products. Oxidized intermediates bearing the C=O group were also formed during photodegradation. The joint analysis of the photodegradation data with those produced by electrochemical means - using spectroscopic techniques for the identification and characterization of the products - revealed the formation of identical products for anthracene, but not for pyrene. A reasonable explanation for this difference in results is that photochemical and electrochemical oxidation reactions proceed via different mechanisms. While photocatalytic degradation over TiO2 is initiated by hydroxyl radicals, electrochemical oxidation is initiated by the direct electron transfer from adsorbed PAH to the electrode, generating PAH cation radicals that undergo subsequent reactions.

Evaluation of Femtosecond Laser-Induced Breakdown Spectroscopy for Analysis of Animal Tissues

The aim of this work was to evaluate the performance of femtosecond laser-induced breakdown spectroscopy (fs-LIBS) for the determination of elements in animal tissues. Sample pellets were prepared from certified reference materials, such as liver, kidney, muscle, hepatopancreas, and oyster, after cryogenic grinding assisted homogenization. Individual samples were placed in a two-axis computer-controlled translation stage that moved in the plane orthogonal to a beam originating from a Ti:Sapphire chirped-pulse amplification (CPA) laser system operating at 800 mu and producing a train of 840 mu J and 40 fs pulses at 90 Hz. The plasma emission was coupled into the optical fiber of a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Time-resolved characteristics of the laser-produced plasmas showed that the best results were obtained with delay times between 80 and 120 ns. Data obtained indicate both that it is a matrix-independent sampling process and that fs-LIBS can be used for the determination of Ca, Cu, Fe, K, Mg, Na, and P, but efforts must be made to obtain more appropriate detection limits for Al, Sr, and Zn.

Phase transformation and residual stress probed by Raman spectroscopy in diamond-turned single crystal silicon

Single-point diamond turning of monocrystalline semiconductors is an important field of research within brittle materials machining. Monocrystalline silicon samples with a (100) orientation have been diamond turned under different cutting conditions (feed rate and depth of cut). Micro-Raman spectroscopy and atomic force microscopy have been used to assess structural alterations and surface finish of the samples diamond turned under ductile and brittle modes. It was found that silicon undergoes a phase transformation when machined in the ductile mode. This phase transformation is evidenced by the creation of an amorphous surface layer after machining which has been probed by Raman scattering. Compressive residual stresses are estimated for the machined surface and it is observed that they decrease with an increase in the feed rate and depth of cut. This behaviour has been attributed to the formation of subsurface cracks when the feed rate is higher than or equal to 2.5 mu m/rev. The surface roughness was observed to vary with the feed rate and the depth of cut. An increase in the surface roughness was influenced by microcrack formation when the feed rate reached 5.0 mu m/rev. Furthermore, a high-pressure phase transformation induced by the tool/material interaction and responsible for the ductile response of this typical brittle material is discussed based upon the presented Raman spectra. The application of this machining technology finds use for a wide range of high quality components, for example the creation of a micrometre-range channel for microfluidic devices as well as microlenses used in the infrared spectrum range.

NEAR INFRARED SPECTROSCOPY FOR ESTIMATING SUGARCANE BAGASSE CONTENT IN MEDIUM DENSITY FIBERBOARD

Medium density fiberboard (MDF) is an engineered wood product formed by breaking down selected lignin-cellulosic material residuals into fibers, combining it with wax and a resin binder, and then forming panels by applying high temperature and pressure. Because the raw material in the industrial process is ever-changing, the panel industry requires methods for monitoring the composition of their products. The aim of this study was to estimate the ratio of sugarcane (SC) bagasse to Eucalyptus wood in MDF panels using near infrared (NIR) spectroscopy. Principal component analysis (PCA) and partial least square (PLS) regressions were performed. MDF panels having different bagasse contents were easily distinguished from each other by the PCA of their NIR spectra with clearly different patterns of response. The PLS-R models for SC content of these MDF samples presented a strong coefficient of determination (0.96) between the NIR-predicted and Lab-determined values and a low standard error of prediction (similar to 1.5%) in the cross-validations. A key role of resins (adhesives), cellulose, and lignin for such PLS-R calibrations was shown. PLS-DA model correctly classified ninety-four percent of MDF samples by cross-validations and ninety-eight percent of the panels by independent test set. These NIR-based models can be useful to quickly estimate sugarcane bagasse vs. Eucalyptus wood content ratio in unknown MDF samples and to verify the quality of these engineered wood products in an online process.

Time-resolved fluorescence spectroscopy of white-spot caries in human enamel

The objective is to differentiate noncavitated caries enamel through time-resolved fluorescence and to find excitation and emission parameters that can be applied in future clinical practice for detection of caries lesions that are not clearly visible to the professional. Sixteen human teeth with noncavitiated white-spot caries were selected for this work. Fluorescence intensity decay was measured by using an apparatus based on the time-correlated single-photon counting method. An optical fiber bundle was employed for sample excitation (440 nm), and the fluorescence collected by the same bundle (500 nm) was registered. The average lifetime for sound enamel was 7: 93 +/- 0: 09, 2: 46 +/- 0: 04, and 0: 51 +/- 0: 02 ns, whereas for the carious enamel the lifetimes were 4: 84 +/- 0: 06, 1: 35 +/- 0: 02, and 0: 16 +/- 0: 01 ns. It was concluded that it is possible to differentiate between carious and sound regions by time-resolved fluorescence and that, although the origin of enamel fluorescence is still uncertain, the lifetime values seem to be typical of fluorophores like collagen I. (C) 2010 Optical Society of America

Fluorescence and reflectance spectroscopy for identification of atherosclerosis in human carotid arteries using principal components analysis

Objectives: The aim of this work was to verify the differentiation between normal and pathological human carotid artery tissues by using fluorescence and reflectance spectroscopy in the 400- to 700-nm range and the spectral characterization by means of principal components analysis. Background Data: Atherosclerosis is the most common and serious pathology of the cardiovascular system. Principal components represent the main spectral characteristics that occur within the spectral data and could be used for tissue classification. Materials and Methods: Sixty postmortem carotid artery fragments (26 non-atherosclerotic and 34 atherosclerotic with non-calcified plaques) were studied. The excitation radiation consisted of a 488-nm argon laser. Two 600-mu m core optical fibers were used, one for excitation and one to collect the fluorescence radiation from the samples. The reflectance system was composed of a halogen lamp coupled to an excitation fiber positioned in one of the ports of an integrating sphere that delivered 5 mW to the sample. The photo-reflectance signal was coupled to a 1/4-m spectrograph via an optical fiber. Euclidean distance was then used to classify each principal component score into one of two classes, normal and atherosclerotic tissue, for both fluorescence and reflectance. Results: The principal components analysis allowed classification of the samples with 81% sensitivity and 88% specificity for fluorescence, and 81% sensitivity and 91% specificity for reflectance. Conclusions: Our results showed that principal components analysis could be applied to differentiate between normal and atherosclerotic tissue with high sensitivity and specificity.

High spatial resolution spectroscopy of W51IRS 2E and IRS 2W: Two very massive young stars in early formation stages

We present K-band spectra of the near infrared counterparts to IRS 2E and IRS 2W which is associated with the ultracompact H II region W51d, both of them embedded sources in the Galactic compact H II region W51 IRS 2. The high spatial resolution observations were obtained with the laser guide star facility and Near-infrared Integral Field Spectrograph (NIFS) mounted at the Gemini-North observatory. The spectrum of the ionizing source of W51d shows the photospheric features N III ( 21155 angstrom) in emission and He II ( 21897 angstrom) in absorption which lead us to classify it as a young O3 type star. We detected CO overtone in emission at 23000 angstrom in the spectrum of IRS 2E, suggesting that it is a massive young object still surrounded by an accretion disk, probably transitioning from the hot core phase to an ultracompact H II region.

[O/Fe] ESTIMATES FOR CARBON-ENHANCED METAL-POOR STARS FROM NEAR-INFRARED SPECTROSCOPY

We report on oxygen abundances determined from medium-resolution near-infrared spectroscopy for a sample of 57 carbon-enhanced metal-poor (CEMP) stars selected from the Hamburg/ESO Survey. The majority of our program stars exhibit oxygen-to-iron ratios in the range +0.5 < [O/Fe]< + 2.0. The [O/Fe] values for this sample are statistically compared to available high-resolution estimates for known CEMP stars as well as to high-resolution estimates for a set of carbon-normal metal-poor stars. Carbon, nitrogen, and oxygen abundance patterns for a sub-sample of these stars are compared to yield predictions for very metal-poor asymptotic giant branch (AGB) abundances in the recent literature. We find that the majority of our sample exhibit patterns that are consistent with previously studied CEMP stars having s-process-element enhancements and thus have very likely been polluted by carbon- and oxygen-enhanced material transferred from a metal-poor AGB companion.

Age and metallicity of star clusters in the Small Magellanic Cloud from integrated spectroscopy

Context. Analysis of ages and metallicities of star clusters in the Magellanic Clouds provide information for studies on the chemical evolution of the Clouds and other dwarf irregular galaxies. Aims. The aim is to derive ages and metallicities from integrated spectra of 14 star clusters in the Small Magellanic Cloud, including a few intermediate/old age star clusters. Methods. Making use of a full-spectrum fitting technique, we compared the integrated spectra of the sample clusters to three different sets of single stellar population models, using two fitting codes available in the literature. Results. We derive the ages and metallicities of 9 intermediate/old age clusters, some of them previously unstudied, and 5 young clusters. Conclusions. We point out the interest of the newly identified as intermediate/old age clusters HW1, NGC 152, Lindsay 3, Lindsay 11, and Lindsay 113. We also confirm the old ages of NGC 361, NGC 419, Kron 3, and of the very well-known oldest SMC cluster, NGC 121.

The pulsations of the B5IVe star HD 181231 observed with CoRoT and ground-based spectroscopy

Context. HD 181231 is a B5IVe star, which has been observed with the CoRoT satellite during similar to 5 consecutive months and simultaneously from the ground in spectroscopy and spectropolarimetry. Aims. By analysing these data, we aim to detect and characterize as many pulsation frequencies as possible, to search for the presence of beating effects possibly at the origin of the Be phenomenon. Our results will also provide a basis for seismic modelling. Methods. The fundamental parameters of the star are determined from spectral fitting and from the study of the circumstellar emission. The CoRoT photometric data and ground-based spectroscopy are analysed using several Fourier techniques: CLEAN-NG, PASPER, and TISAFT, as well as a time-frequency technique. A search for a magnetic field is performed by applying the LSD technique to the spectropolarimetric data. Results. We find that HD 181231 is a B5IVe star seen with an inclination of similar to 45 degrees. No magnetic field is detected in its photosphere. We detect at least 10 independent significant frequencies of variations among the 54 detected frequencies, interpreted in terms of non-radial pulsation modes and rotation. Two longer-term variations are also detected: one at similar to 14 days resulting from a beating effect between the two main frequencies of short-term variations, the other at similar to 116 days due either to a beating of frequencies or to a zonal pulsation mode. Conclusions. Our analysis of the CoRoT light curve and ground-based spectroscopic data of HD 181231 has led to the determination of the fundamental and pulsational parameters of the star, including beating effects. This will allow a precise seismic modelling of this star.

AUTOMATED DETERMINATION OF [Fe/H] AND [C/Fe] FROM LOW-RESOLUTION SPECTROSCOPY

We develop an automated spectral synthesis technique for the estimation of metallicities ([Fe/H]) and carbon abundances ([C/Fe]) for metal-poor stars, including carbon-enhanced metal-poor stars, for which other methods may prove insufficient. This technique, autoMOOG, is designed to operate on relatively strong features visible in even low- to medium-resolution spectra, yielding results comparable to much more telescope-intensive high-resolution studies. We validate this method by comparison with 913 stars which have existing high-resolution and low- to medium-resolution to medium-resolution spectra, and that cover a wide range of stellar parameters. We find that at low metallicities ([Fe/H] less than or similar to -2.0), we successfully recover both the metallicity and carbon abundance, where possible, with an accuracy of similar to 0.20 dex. At higher metallicities, due to issues of continuum placement in spectral normalization done prior to the running of autoMOOG, a general underestimate of the overall metallicity of a star is seen, although the carbon abundance is still successfully recovered. As a result, this method is only recommended for use on samples of stars of known sufficiently low metallicity. For these low- metallicity stars, however, autoMOOG performs much more consistently and quickly than similar, existing techniques, which should allow for analyses of large samples of metal-poor stars in the near future. Steps to improve and correct the continuum placement difficulties are being pursued.

Synchrotron X-ray powder diffraction and extended X-ray absorption fine structure spectroscopy studies on nanocrystalline ZrO(2)-CaO solid solutions

The crystal structure and the local atomic order of a series of nanocrystalline ZrO(2)-CaO solid solutions with varying CaO content were studied by synchrotron radiation X-ray powder diffraction and extended X-ray absorption fine structure (EXAFS) spectroscopy. These samples were synthesized by a pH-controlled nitrate-glycine gel-combustion process. For CaO contents up to 8 mol%, the t' form of the tetragonal phase (c/a > 1) was identified, whereas for 10 and 12 mol% CaO, the t '' form (c/a=1; oxygen anions displaced from their ideal positions in the cubic phase) was detected. Finally, the cubic phase was observed for solid solutions with CaO content of 14 mol% CaO or higher. The t'/t '' and t ''/cubic compositional boundaries were determined to be at 9 (1) and 13 (1) mol% CaO, respectively. The EXAFS study demonstrated that this transition is related to a tetragonal-to-cubic symmetry change of the first oxygen coordination shell around the Zr atoms.

The influence of adsorption phenomena on the impedance spectroscopy of an electrolytic cell

In this work we investigate the influence of the adsorption of ions on the impedance spectroscopy of an electrolytic cell. We consider that the positive and negative ions present in a dielectric liquid are adsorbed in the electrode surfaces with different adsorption energies. This difference in adsorption energies causes an additional plateaux in the limit of the low-frequency range of the real part of the impedance Z. In the same frequency range, a second minimum in the imaginary part of Z is predicted. The theory is illustrated with measurements of the impedance of an electrolytic solution in the frequency range from 10(-2) Hz to 1 KHz. A comparison between the present model and others from the literature to describe the experimental results is also made.