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.

Adsorção do corante azul de metileno em partículas de argilominerais: análise dos tamanhos das partículas

Interactions of cationic dye methylene blue (MB) with clay particles in aqueous suspension have been extensively studied. As already known, the number of natural negative charges on the clay modifies significantly the particle sizes dispersed in water and therefore the nature of the interaction with the dye. This work evaluated with UV-Vis spectroscopy method how the clay particle sizes weighted on the adsorption and rearrangement of the dye molecules in aqueous system. The results obtained from light-scattering measurements confirmed that larger particles are found in suspensions containing the high-charged clays as the visible absorption band related to the MB aggregates (570 nm) on these suspensions prevailed.

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.

Frequency upconversion luminescence from Yb(+3)-Tm(+3) codoped PbO-GeO(2) glasses containing silver nanoparticles

Infrared-to-visible and infrared-to-infrared frequency upconversion processes in Yb(3+)-Tm(3+) doped PbO-GeO(2) glasses containing silver nanoparticles (NPs) were investigated. The experiments were performed by exciting the samples with a diode laser operating at 980 nm (in resonance with the Yb(3+) transition (2)F(7/2)->(2)F(5/2)) and observing the photoluminescence (PL) in the visible and infrared regions due to energy transfer from Yb(3+) to Tm(3+) ions followed by excited state absorption in the Tm3+ ions. The intensified local field in the vicinity of the metallic NPs contributes for enhancement in the PL intensity at 480 nm (Tm(3+) :(1)G(4)->(3)H(6)) and at 800 nm (Tm(3+) : (3)H(4) -> (3)H(6)). (C) 2009 American Institute of Physics. [doi:10.1063/1.3211300]

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.

Alpha element abundances and gradients in the Milky Way bulge from FLAMES-GIRAFFE spectra of 650 K giants

Aims. We present the analysis of the [alpha/Fe] abundance ratios for a large number of stars at several locations in the Milky Way bulge with the aim of constraining its formation scenario. Methods. We obtained FLAMES-GIRAFFE spectra (R = 22 500) at the ESO Very Large Telescope for 650 bulge red giant branch (RGB) stars and performed spectral synthesis to measure Mg, Ca, Ti, and Si abundances. This sample is composed of 474 giant stars observed in 3 fields along the minor axis of the Galactic bulge and at latitudes b = -4 degrees, b = -6 degrees, b = -12 degrees. Another 176 stars belong to a field containing the globular cluster NGC 6553, located at b = -3 degrees and 5 degrees away from the other three fields along the major axis. Stellar parameters and metallicities for these stars were presented in Zoccali et al. (2008, A&A, 486, 177). We have also re-derived stellar parameters and abundances for the sample of thick and thin disk red giants analyzed in Alves-Brito et al. (2010, A&A, 513, A35). Therefore using a homogeneous abundance database for the bulge, thick and thin disk, we have performed a differential analysis minimizing systematic errors, to compare the formation scenarios of these Galactic components. Results. Our results confirm, with large number statistics, the chemical similarity between the Galactic bulge and thick disk, which are both enhanced in alpha elements when compared to the thin disk. In the same context, we analyze [alpha/Fe] vs. [Fe/H] trends across different bulge regions. The most metal rich stars, showing low [alpha/Fe] ratios at b = -4 degrees disappear at higher Galactic latitudes in agreement with the observed metallicity gradient in the bulge. Metal-poor stars ([Fe/H] < -0.2) show a remarkable homogeneity at different bulge locations. Conclusions. We have obtained further constrains for the formation scenario of the Galactic bulge. A metal-poor component chemically indistinguishable from the thick disk hints for a fast and early formation for both the bulge and the thick disk. Such a component shows no variation, neither in abundances nor kinematics, among different bulge regions. A metal-rich component showing low [alpha/Fe] similar to those of the thin disk disappears at larger latitudes. This allows us to trace a component formed through fast early mergers (classical bulge) and a disk/bar component formed on a more extended timescale.

[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.

Optical identification of the transient supersoft X-ray source RX J0527.8-6954, in the LMC

Context. Close binary supersoft X-ray sources (CBSS) are binary systems that contain a white dwarf with stable nuclear burning on its surface. These sources, first discovered in the Magellanic Clouds, have high accretion rates and near-Eddington luminosities (10(37)-10(38) erg s(-1)) with high temperatures (T = 2-7 x 10(5) K). Aims. The total number of known objects in the MC is still small and, in our galaxy, even smaller. We observed the field of the unidentified transient supersoft X-ray source RX J0527.8-6954 in order to identify its optical counterpart. Methods. The observation was made with the IFU-GMOS on the Gemini South telescope with the purpose of identifying stars with possible He II or Balmer emission or else of observing nebular extended jets or ionization cones, features that may be expected in CBSS. Results. The X-ray source is identified with a B5e V star that is associated with subarcsecond extended H alpha emission, possibly bipolar. Conclusions. If the primary star is a white dwarf, as suggested by the supersoft X-ray spectrum, the expected orbital period exceeds 21 h; therefore, we believe that the 9.4 h period found so far is not associated to this system.

The peculiar nova V1309 Scorpii/nova Scorpii 2008 A candidate twin of V838 Monocerotis

Aims. Nova Scorpii 2008 was the target of our Director Discretionary Time proposal at VLT+UVES in order to study the evolution, origin and abundances of the heavy-element absorption system recently discovered in 80% of classical novae in outburst. Methods. The early decline of nova Scorpii 2008 was monitored with high resolution echelle spectroscopy at 5 different epochs. The analysis of the absorption and the emission lines show many unusual characteristics. Results. Nova Scorpii 2008 is confirmed to differ from a common classical nova as well as a symbiotic recurrent nova, and it shows characteristics which are common to the so called, yet debated, red-novae. The origin of this new nova remains uncertain.

A SEARCH FOR UNRECOGNIZED CARBON-ENHANCED METAL-POOR STARS IN THE GALAXY

We have developed a new procedure to search for carbon-enhanced metal-poor (CEMP) stars from the Hamburg/ESO (HES) prism-survey plates. This method employs an extended line index for the CH G band, which we demonstrate to have superior performance when compared to the narrower G-band index formerly employed to estimate G-band strengths for these spectra. Although CEMP stars have been found previously among candidate metal-poor stars selected from the HES, the selection on metallicity undersamples the population of intermediate-metallicity CEMP stars (-2.5 <= [Fe/H] <= -1.0); such stars are of importance for constraining the onset of the s-process in metal-deficient asymptotic giant branch stars (thought to be associated with the origin of carbon for roughly 80% of CEMP stars). The new candidates also include substantial numbers of warmer carbon-enhanced stars, which were missed in previous HES searches for carbon stars due to selection criteria that emphasized cooler stars. A first subsample, biased toward brighter stars (B < 15.5), has been extracted from the scanned HES plates. After visual inspection (to eliminate spectra compromised by plate defects, overlapping spectra, etc., and to carry out rough spectral classifications), a list of 669 previously unidentified candidate CEMP stars was compiled. Follow-up spectroscopy for a pilot sample of 132 candidates was obtained with the Goodman spectrograph on the SOAR 4.1 m telescope. Our results show that most of the observed stars lie in the targeted metallicity range, and possess prominent carbon absorption features at 4300 angstrom. The success rate for the identification of new CEMP stars is 43% (13 out of 30) for [Fe/H] < -2.0. For stars with [Fe/H] < -2.5, the ratio increases to 80% (four out of five objects), including one star with [Fe/H] < -3.0.