A novel nanostructured composite formed by interaction of copper octa(3-aminopropyl)octasilsesquioxane with azide ligands: Preparation, characterization and a voltammetric application

This study presents the preparation, characterization and application of copper octa(3-aminopropyl)octasilsesquioxane following its subsequent reaction with azide ions (ASCA). The precursor (AC) and the novel compound (ASCA) were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), scanning electronic microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric analyses and voltammetric technique. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E(1/2)(ox)) = 0.30 V and an irreversible process at 1.1 V (vs. Ag/AgCl; NaCl 1.0 M; v = 20 mV s(-1)). The material is very sensitive to nitrite concentrations. The modified graphite paste electrode (GPE-ASCA) gives a linear range from 1.0 x 10(-4) to 4.0 x 10(-3) mol L(-1) for the determination of nitrite, with a detection limit of 2.1 x 10(-4) mol L(-1) and the amperometric sensitivity of 8.04 mA/mol L(-1). (C) 2010 Elsevier Ltd. All rights reserved.

DERIVING METALLICITIES FROM THE INTEGRATED SPECTRA OF EXTRAGALACTIC GLOBULAR CLUSTERS USING THE NEAR-INFRARED CALCIUM TRIPLET

The Ca II triplet (CaT) feature in the near-infrared has been employed as a metallicity indicator for individual stars as well as integrated light of Galactic globular clusters (GCs) and galaxies with varying degrees of success, and sometimes puzzling results. Using the DEIMOS multi-object spectrograph on Keck we obtain a sample of 144 integrated light spectra of GCs around the brightest group galaxy NGC 1407 to test whether the CaT index can be used as ametallicity indicator for extragalactic GCs. Different sets of single stellar population models make different predictions for the behavior of the CaT as a function of metallicity. In this work, the metallicities of the GCs around NGC 1407 are obtained from CaT index values using an empirical conversion. The measured CaT/metallicity distributions show unexpected features, the most remarkable being that the brightest red and blue GCs have similar CaT values despite their large difference in mean color. Suggested explanations for this behavior in the NGC 1407 GC system are (1) the CaT may be affected by a population of hot blue stars, (2) the CaT may saturate earlier than predicted by the models, and/or (3) color may not trace metallicity linearly. Until these possibilities are understood, the use of the CaT as a metallicity indicator for the integrated spectra of extragalactic GCs will remain problematic.

Nuclear and extended spectra of NGC 1068-I. Hints from near-infrared spectroscopy

We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).

Nuclear and extended spectra of NGC 1068-II. Near-infrared stellar population synthesis

We performed stellar population synthesis on the nuclear and extended regions of NGC 1068 by means of near-infrared spectroscopy to disentangle their spectral energy distribution components. This is the first time that such a technique is applied to the whole 0.8-2.4 mu m wavelength interval in this galaxy. NGC 1068 is one of the nearest and probably the most studied Seyfert 2 galaxy, becoming an excellent laboratory to study the interaction between black holes, the jets that they can produce and the medium in which they propagate. Our main result is that traces of young stellar population are found at similar to 100 pc south of the nucleus. The contribution of a power-law continuum in the centre is about 25 per cent, which is expected if the light is scattered from a Seyfert 1 nucleus. We find peaks in the contribution of the featureless continuum about 100-150 pc from the nucleus on both sides. They might be associated with regions where the jet encounters dense clouds. Further support to this scenario is given by the peaks of hot dust distribution found around these same regions and the H(2) emission-line profile, leading us to propose that the peaks might be associated to regions where stars are being formed. Hot dust also has an important contribution to the nuclear region, reinforcing the idea of the presence of a dense, circumnuclear torus in this galaxy. Cold dust appears mostly in the south direction, which supports the view that the south-west emission is behind the plane of the galaxy and is extinguished very likely by dust in the plane. Intermediate-age stellar population contributes significantly to the continuum, especially in the inner 200 pc.

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.

The metal content of bulge field stars from FLAMES-GIRAFFE spectra - I. Stellar parameters and iron abundances

Aims. We determine the iron distribution function (IDF) for bulge field stars, in three different fields along the Galactic minor axis and at latitudes b = -4 degrees, b = -6 degrees, and b = -12 degrees. A fourth field including NGC 6553 is also included in the discussion. Methods. About 800 bulge field K giants were observed with the GIRAFFE spectrograph of FLAMES@VLT at spectral resolution R similar to 20 000. Several of them were observed again with UVES at R similar to 45 000 to insure the accuracy of the measurements. The LTE abundance analysis yielded stellar parameters and iron abundances that allowed us to construct an IDF for the bulge that, for the first time, is based on high-resolution spectroscopy for each individual star. Results. The IDF derived here is centered on solar metallicity, and extends from [Fe/H] similar to -1.5 to [Fe/H] similar to + 0.5. The distribution is asymmetric, with a sharper cutoff on the high-metallicity side, and it is narrower than previously measured. A variation in the mean metallicity along the bulge minor axis is clearly between b = -4 degrees and b = -6 degrees ([Fe/H] decreasing similar to by 0.6 dex per kpc). The field at b = -12 degrees. is consistent with the presence of a gradient, but its quantification is complicated by the higher disk/bulge fraction in this field. Conclusions. Our findings support a scenario in which both infall and outflow were important during the bulge formation, and then suggest the presence of a radial gradient, which poses some challenges to the scenario in which the bulge would result solely from the vertical heating of the bar.

Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors

The combination of metallic phthalocyanines (MPcs) and biomolecules has been explored in the literature either as mimetic systems to investigate molecular interactions or as supporting layers to immobilize biomolecules. Here, Langmuir-Blodgett (LB) films containing the phospholipid dimyristoyl phosphatidic acid (DMPA) mixed either with iron phthalocyanine (FePc) or with lutetium bisphthalocyanine (LuPc(2)) were applied as ITO modified-electrodes in the detection of catechol using cyclic voltammetry. The mixed Langmuir films of FePc + DMPA and LuPc(2) + DMPA displayed surface-pressure isotherms with no evidence of molecular-level interactions. The Fourier Transform Infrared (FTIR) spectra of the multilayer LB films confirmed the lack of interaction between the components. The DMPA and the FePc molecules were found to be oriented perpendicularly to the substrate, while LuPc(2) molecules were randomly organized. The phospholipid matrix induced a remarkable electrocatalytic effect on the phthalocyanines; as a result the mixed LB films deposited on ITO could be used to detect catechol with detection limits of 4.30 x 10(-7) and 3.34 x 10(-7) M for FePc + DMPA and LuPc(2) + DMPA, respectively. Results from kinetics experiments revealed that ion diffusion dominated the response of the modified electrodes. The sensitivity was comparable to that of other non-enzymatic sensors, which is sufficient to detect catechol in the food industry. The higher stability of the electrochemical response of the LB films and the ability to control the molecular architecture are promising for further studies with incorporation of biomolecules.

Constraints on the infrared behavior of the ghost propagator in Yang-Mills theories

We present rigorous upper and lower bounds for the momentum-space ghost propagator G(p) of Yang-Mills theories in terms of the smallest nonzero eigenvalue (and of the corresponding eigenvector) of the Faddeev-Popov matrix. We apply our analysis to data from simulations of SU(2) lattice gauge theory in Landau gauge, using the largest lattice sizes to date. Our results suggest that, in three and in four space-time dimensions, the Landau gauge ghost propagator is not enhanced as compared to its tree-level behavior. This is also seen in plots and fits of the ghost dressing function. In the two-dimensional case, on the other hand, we find that G(p) diverges as p(-2-2 kappa) with kappa approximate to 0.15, in agreement with A. Maas, Phys. Rev. D 75, 116004 (2007). We note that our discussion is general, although we make an application only to pure gauge theory in Landau gauge. Our simulations have been performed on the IBM supercomputer at the University of Sao Paulo.

Polymer matrix sensitizing effect on photoluminescence properties of Eu(3+)-beta-diketonate complex doped into poly-beta-hydroxybutyrate (PHB) in film form

In this work is reported the sensitization effect by polymer matrices on the photoluminescence properties of diaquatris(thenoyltrifluoroacetonate)europium(III), [Eu(tta)(3)(H(2)O)(2)], doped into poly-beta-hydroxybutyrate (PHB) with doping percentage at 1, 3, 5, 7 and 10% (mass) in film form. TGA results indicated that the Eu(3+) complex precursor was immobilized in the polymer matrix by the interaction between the Eu(3+) complex and the oxygen atoms of the PHB polymer when the rare earth complex was incorporated in the polymeric host. The thermal behaviour of these luminescent systems is similar to that of the undoped polymer, however, the T(onset) temperature of decomposition decreases with increase of the complex doping concentration. The emission spectra of the Eu(3+) complex doped PHB films recorded at 298 K exhibited the five characteristic bands arising from the (5)D(0) -> (7)F(J) intraconfigurational transitions (J = 0-4). The fact that the quantum efficiencies eta of the doped film increased significantly revealed that the polymer matrix acts as an efficient co-sensitizer for Eu(3+) luminescent centres and therefore enhances the quantum efficiency of the emitter (5)D(0) level. The luminescence intensity decreases, however, with increasing precursor concentration in the doped polymer to greater than 5% where a saturation effect is observed at this specific doping percentage, indicating that changes in the polymeric matrix improve the absorption property of the film, consequently quenching the luminescent effect.

In situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction

Early reports stated that Au was a catalyst of choice for the BOR because it would yield a near complete faradaic efficiency. However, it has recently been suggested that gold could yield to some extent the heterogeneous hydrolysis of BH(4)(-),therefore lowering the electron count per BH(4)(-), especially at low potential. Actually, the blur will exist regarding the BOR mechanism on Au as long as no physical proof regarding the reaction intermediates is not put forward. In that frame, in situ physical techniques like FTIR exhibit some interest to study the BOR. Consequently, in situ infrared reflectance spectroscopy measurements (SPAIRS technique) have been performed in 1 M NaOH/1 M NaBH(4) on a gold electrode with the aim to detect the intermediate species. We monitored several bands in B-H ((nu) over bar similar to 1180,1080 and 972 cm(-1)) and B-O bond regions ((nu) over bar =1325 and similar to 1425cm(-1)), which appear sequentially as a function of the electrode polarization. These absorption bands are assigned to BH(3), BH(2) and BO(2)(-) species. At the light of the experimental results, possible initial elementary steps of the BOR on gold electrode have been proposed and discussed according to the relevant literature data.

Near infrared spectroscopy for soil bulk density assessment

P>Soil bulk density values are needed to convert organic carbon content to mass of organic carbon per unit area. However, field sampling and measurement of soil bulk density are labour-intensive, costly and tedious. Near-infrared reflectance spectroscopy (NIRS) is a physically non-destructive, rapid, reproducible and low-cost method that characterizes materials according to their reflectance in the near-infrared spectral region. The aim of this paper was to investigate the ability of NIRS to predict soil bulk density and to compare its performance with published pedotransfer functions. The study was carried out on a dataset of 1184 soil samples originating from a reforestation area in the Brazilian Amazon basin, and conventional soil bulk density values were obtained with metallic ""core cylinders"". The results indicate that the modified partial least squares regression used on spectral data is an alternative method for soil bulk density predictions to the published pedotransfer functions tested in this study. The NIRS method presented the closest-to-zero accuracy error (-0.002 g cm-3) and the lowest prediction error (0.13 g cm-3) and the coefficient of variation of the validation sets ranged from 8.1 to 8.9% of the mean reference values. Nevertheless, further research is required to assess the limits and specificities of the NIRS method, but it may have advantages for soil bulk density predictions, especially in environments such as the Amazon forest.

Comparison of univariate and multivariate calibration for the determination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry

The application of laser induced breakdown spectrometry (LIBS) aiming the direct analysis of plant materials is a great challenge that still needs efforts for its development and validation. In this way, a series of experimental approaches has been carried out in order to show that LIBS can be used as an alternative method to wet acid digestions based methods for analysis of agricultural and environmental samples. The large amount of information provided by LIBS spectra for these complex samples increases the difficulties for selecting the most appropriated wavelengths for each analyte. Some applications have suggested that improvements in both accuracy and precision can be achieved by the application of multivariate calibration in LIBS data when compared to the univariate regression developed with line emission intensities. In the present work, the performance of univariate and multivariate calibration, based on partial least squares regression (PLSR), was compared for analysis of pellets of plant materials made from an appropriate mixture of cryogenically ground samples with cellulose as the binding agent. The development of a specific PLSR model for each analyte and the selection of spectral regions containing only lines of the analyte of interest were the best conditions for the analysis. In this particular application, these models showed a similar performance. but PLSR seemed to be more robust due to a lower occurrence of outliers in comparison to the univariate method. Data suggests that efforts dealing with sample presentation and fitness of standards for LIBS analysis must be done in order to fulfill the boundary conditions for matrix independent development and validation. (C) 2009 Elsevier B.V. All rights reserved.

Visible and near-infrared luminescent Eu(3+) or Er(3+) doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

Laponite-derived materials represent promising materials for optical applications. In this work, Eu(3+)- or Er(3+)-doped laponite xerogels and films were prepared from colloidal dispersion. Homogeneous, crack-free and transparent single layers were deposited on soda-lime substrates with a thickness of 10 mu m. Structural and spectroscopic properties were analyzed by thermal analyses, X-ray diffractometry, transmission electron microscopy, infrared spectroscopy, and luminescence spectroscopy. The addition of a rare earth ion to the laponite does not promote any changes in thermal stability or phase transition. Laponite clay was identified after annealing up to 500 degrees C, with a decrease in basal spacing when the annealing temperature is changed from 100 degrees C to 500 degrees C. Enstatite polymorphs and amorphous silicate phases were observed after heat treatment at 700 degrees C and 900 degrees C. Stationary and time-dependent luminescence spectra in the visible region for Eu(3+), and (5)D(0) lifetime are discussed in terms of thermal treatment and structural evolution. In the layered host, the Eu(3+) ions are distributed in many different local environments. However, Eu(3+) ions were found to occupy at least two symmetry sites, and the ions are preferentially incorporated into the crystalline enstatite for the materials annealed at 700 degrees C and 900 degrees C. A (5)D(0) lifetime of 1.3 ms and 3.1 ms was obtained for Eu(3+) ions in an amorphous silicate and crystalline MgSiO(3) local environment, respectively. Strong Er(3+) emission at the 1550 nm region was observed for the materials annealed at 900 degrees C, with a bandwidth of 44 nm. (C) 2008 Elsevier B.V. All rights reserved.

Independent component analysis applied to raman spectra for classification of in vitro human coronary arteries

Optical diagnostic methods, such as near-infrared Raman spectroscopy allow quantification and evaluation of human affecting diseases, which could be useful in identifying and diagnosing atherosclerosis in coronary arteries. The goal of the present work is to apply Independent Component Analysis (ICA) for data reduction and feature extraction of Raman spectra and to perform the Mahalanobis distance for group classification according to histopathology, obtaining feasible diagnostic information to detect atheromatous plaque. An 830nm Ti:sapphire laser pumped by an argon laser provides near-infrared excitation. A spectrograph disperses light scattered from arterial tissues over a liquid-nitrogen cooled CCD to detect the Raman spectra. A total of 111 spectra from arterial fragments were utilized.

Near-infrared integral field spectroscopy of the Homunculus nebula around eta Carinae using Gemini/CIRPASS

This work presents the first integral field spectroscopy of the Homunculus nebula around eta Carinae in the near-infrared spectral region (J band). We confirmed the presence of a hole on the polar region of each lobe, as indicated by previous near-IR long-slit spectra and mid-IR images. The holes can be described as a cylinder of height (i.e. the thickness of the lobe) and diameter of 6.5 and 6.0 x 10(16) cm, respectively. We also mapped the blue-shifted component of He I lambda 10830 seen towards the NW lobe. Contrary to previous works, we suggested that this blue-shifted component is not related to the Paddle but it is indeed in the equatorial disc. We confirmed the claim of N. Smith and showed that the spatial extent of the Little Homunculus matches remarkably well the radio continuum emission at 3 cm, indicating that the Little Homunculus can be regarded as a small H II region. Therefore, we used the optically thin 1.3 mm radio flux to derive a lower limit for the number of Lyman-continuum photons of the central source in eta Car. In the context of a binary system, and assuming that the ionizing flux comes entirely from the hot companion star, the lower limit for its spectral type and luminosity class ranges from O5.5 III to O7 I. Moreover, we showed that the radio peak at 1.7 arcsec NW from the central star is in the same line-of-sight of the `Sr-filament` but they are obviously spatially separated, while the blue-shifted component of He I lambda 10830 may be related to the radio peak and can be explained by the ultraviolet radiation from the companion star.