Síntese e caracterização de complexos de Co(II) e Ni(II) com l-dopa, carbidopa e benzimidazol

Were synthesized in this work in the following aqueous solution coordination compounds: [Ni(LDP)(H2O)2Cl2].2H2O, [Co(LDP)Cl2].3H2O, [Ni(CDP)Cl2].4H2O, [Co(CDP)Cl2].4H2O, [Ni(BDZ)2Cl2].4H2O and [Co(BDZ)2Cl2(H2O)2]. These complexes were synthesized by stoichiometric addition of the binder in the respective metal chloride solutions. Precipitation occurred after drying the solvent at room temperature. The characterization and proposed structures were made using conventional analysis methods such as elemental analysis (CHN), absorption spectroscopy in the infrared Fourier transform spectroscopy (FTIR), X-ray diffraction by the powder method and Technical thermoanalytical TG / DTG (thermogravimetry / derivative thermogravimetry) and DSC (differential scanning calorimetry). These techniques provided information on dehydration, coordination modes, thermal performance, composition and structure of the synthesized compounds. The results of the TG curve, it was possible to establish the general formula of each compound synthesized. The analysis of X-ray diffraction was observed that four of the synthesized complex crystal structure which does not exhibit the complex was obtained from Ldopa and carbidopa and the complex obtained from benzimidazole was obtained crystal structures. The observations of the spectra in the infrared region suggested a monodentate ligand coordination to metal centers through its amine group for all complexes. The TG-DTG and DSC curves provide important information and on the behavior and thermal decomposition of the synthesized compounds. The molar conductivity data indicated that the solutions of the complexes formed behave as a nonelectrolyte, which implies that chlorine is coordinated to the central atom in the complex.

The AGN, star-forming, and morphological properties of luminous ir-bright/optically-faint galaxies

We present the active galactic nucleus (AGN), star-forming, and morphological properties of a sample of 13 MIR-luminous (∫_24 700 μJy) IR-bright/optically-faint galaxies (IRBGs, ∫_24/f_R≲ 1000). While these z ∼ 2 sources were drawn from deep Chandra fields with >200 ks X-ray coverage, only seven are formally detected in the X-ray and four lack X-ray emission at even the 2σ level. Spitzer InfraRed Spectrograph (IRS) spectra, however, confirm that all of the sources are AGN-dominated in the mid-IR, although half have detectable polycyclic aromatic hydrocarbon (PAH) emission responsible for ∼25% of their mid-infrared flux density. When combined with other samples, this indicates that at least 30%–40% of luminous IRBGs have star formation rates in the ultraluminous infrared galaxy (ULIRG) range (∼100–2000 M_⨀ yr^−1). X-ray hardness ratios and MIR to X-ray luminosity ratios indicate that all members of the sample contain heavily X-ray obscured AGNs, 80% of which are candidates to be Compton thick. Furthermore, the mean X-ray luminosity of the sample, log L_2–10 keV(erg s^−1) ∼44.6, indicates that these IRBGs are Type 2 QSOs, at least from the X-ray perspective. While those sources most heavily obscured in the X-ray are also those most likely to display strong silicate absorption in the mid-IR, silicate absorption does not always accompany X-ray obscuration. Finally, ∼70% of the IRBGs are merger candidates, a rate consistent with that of sub-mm galaxies (SMGs), although SMGs appear to be physically larger than IRBGs. These characteristics are consistent with the proposal that these objects represent a later, AGN-dominated, and more relaxed evolutionary stage following soon after the star-formation-dominated one represented by the SMGs.

Infrared Excess sources: Compton thick QSOs, low-luminosity Seyferts or starbursts?

We explore the nature of Infrared Excess sources (IRX), which are proposed as candidates for luminous [L_X(2–10 keV) > 10^43 erg s^−1] Compton thick (NH > 2 × 1024 cm−2) QSOs at z≈ 2. Lower redshift, z≈ 1, analogues of the distant IRX population are identified by first redshifting to z= 2 the spectral energy distributions (SEDs) of all sources with secure spectroscopic redshifts in the AEGIS (6488) and the GOODS-North (1784) surveys and then selecting those that qualify as IRX sources at that redshift. A total of 19 galaxies are selected. The mean redshift of the sample is z≈ 1. We do not find strong evidence for Compton thick QSOs in the sample. For nine sources with X-ray counterparts, the X-ray spectra are consistent with Compton thin active galactic nucleus (AGN). Only three of them show tentative evidence for Compton thick obscuration. The SEDs of the X-ray undetected population are consistent with starburst activity. There is no evidence for a hot dust component at the mid-infrared associated with AGN heated dust. If the X-ray undetected sources host AGN, an upper limit of L_X(2–10 keV) = 10^43 erg s^−1 is estimated for their intrinsic luminosity. We propose that a large fraction of the z≈ 2 IRX population is not Compton thick quasi-stellar objects (QSOs) but low-luminosity [L_X(2–10 keV) < 10^43 erg s^−1], possibly Compton thin, AGN or dusty starbursts. It is shown that the decomposition of the AGN and starburst contribution to the mid-IR is essential for interpreting the nature of this population, as star formation may dominate this wavelength regime.

Local luminous infrared galaxies. I. Spatially resolved observations with the Spitzer infrared spectrograph

We present results from the Spitzer Infrared Spectrograph spectral mapping observations of 15 local luminous infrared galaxies (LIRGs). In this paper, we investigate the spatial variations of the mid-IR emission which includes fine structure lines, molecular hydrogen lines, polycyclic aromatic features (PAHs), continuum emission, and the 9.7 μm silicate feature. We also compare the nuclear and integrated spectra. We find that the star formation takes place in extended regions (several kpc) as probed by the PAH emission, as well as the [Ne II]12.81 μm and [Ne III]15.56 μm emissions. The behavior of the integrated PAH emission and 9.7 μm silicate feature is similar to that of local starburst galaxies. We also find that the minima of the [Ne III]15.56 μm/[Ne II]12.81 μm ratio tends to be located at the nuclei and its value is lower than that of H II regions in our LIRGs and nearby galaxies. It is likely that increased densities in the nuclei of LIRGs are responsible for the smaller nuclear [Ne III]15.56 μm/[Ne II]12.81 μm ratios. This includes the possibility that some of the most massive stars in the nuclei are still embedded in ultracompact H II regions. In a large fraction of our sample, the 11.3 μm PAH emission appears more extended than the dust 5.5 μm continuum emission. We find a dependency of the 11.3 μm PAH/7.7 μm PAH and [Ne II]12.81 μm/11.3 μm PAH ratios with the age of the stellar populations. Smaller and larger ratios, respectively, indicate recent star formation. The estimated warm (300 K

Local luminous infrared galaxies: Spatially resolved mid-infrared observations with Spitzer/IRS

Luminous Infrared (IR) Galaxies (LIRGs, L_IR=10^11-10 L_⨀) are an important cosmological class of galaxies as they are the main contributors to the co-moving star formation rate density of the universe at z=1. In this paper we present a guaranteed time observation (GTO) Spitzer InfraRed Spectrograph (IRS) program aimed to obtain spectral mapping of a sample of 14 local d<76Mpc LIRGs. The data cubes map, at least, the central 20arcsec X 20arcsec to 30 arcsec X 30 arcsec regions of the galaxies, and use all four IRS modules covering the full 5-38 μ m spectral range. The final goal of this project is to characterize fully the mid-IR properties of local LIRGs as a first step to understanding their more distant counterparts. In this paper we present the first results of this GTO program. The IRS spectral mapping data allow us to build spectral maps of the bright mid-IR emission lines (e.g., [Ne II] 12.81 μ m, [Ne III]15.56 μ m, [S III] 18.71 μ m, H_2 at 17 μ m), continuum, the 6.2 and 11.3 μ m polycyclic aromatic hydrocarbon (PAH) features, and the 9.7 μ m silicate feature, as well as to extract 1D spectra for regions of interest in each galaxy. The IRS data are used to obtain spatially resolved measurements of the extinction using the 9.7 μ m silicate feature, and to trace star forming regions using the neon lines and the PAH features. We also investigate a number of active galactic nuclei (AGN) indicators, including the presence of high excitation emission lines and a strong dust continuum emission at around 6 9.7 μ m . We finally use the integrated Spitzer/IRS spectra as templates of local LIRGs. We discuss several possible uses for these templates, including the calibration of the star formation rate of IR-bright galaxies at high redshift. We also predict the intensities of the brightest mid-IR emission lines for LIRGs as a function of redshift, and compare them with the expected sensitivities of future space IR missions.

Mid-infrared spectroscopy of lensed galaxies at 1 < z < 3: The nature of sources near the MIPS confusion limit

We present Spitzer IRS mid-infrared spectra for 15 gravitationally lensed, 24 μm-selected galaxies, and combine the results with four additional very faint galaxies with IRS spectra in the literature. The median intrinsic 24 μm flux density of the sample is 130 μJy, enabling a systematic survey of the spectral properties of the very faint 24 μm sources that dominate the number counts of Spitzer cosmological surveys. Six of the 19 galaxy spectra (32%) show the strong mid-IR continuua expected of AGNs; X-ray detections confirm the presence of AGNs in three of these cases, and reveal AGNs in two other galaxies. These results suggest that nuclear accretion may contribute more flux to faint 24 μm-selected samples than previously assumed. Almost all the spectra show some aromatic (PAH) emission features; the measured aromatic flux ratios do not show evolution from z = 0. In particular, the high signal-to-noise mid-IR spectrum of SMM J163554.2+661225 agrees remarkably well with low-redshift, lower luminosity templates. We compare the rest-frame 8 μm and total infrared luminosities of star-forming galaxies, and find that the behavior of this ratio with total IR luminosity has evolved modestly from z = 2 to z = 0. Since the high aromatic-to-continuum flux ratios in these galaxies rule out a dominant contribution by AGNs, this finding implies systematic evolution in the structure and/or metallicity of infrared sources with redshift. It also has implications for the estimates of star-forming rates inferred from 24 μm measurements, in the sense that at z ~ 2, a given observed frame 24 μm luminosity corresponds to a lower bolometric luminosity than would be inferred from low-redshift templates of similar luminosity at the corresponding rest wavelength.

Multiscale photoacoustic tomography using reversibly switchable bacterial phytochrome as a near-infrared photochromic probe.

Photoacoustic tomography (PAT) of genetically encoded probes allows for imaging of targeted biological processes deep in tissues with high spatial resolution; however, high background signals from blood can limit the achievable detection sensitivity. Here we describe a reversibly switchable nonfluorescent bacterial phytochrome for use in multiscale photoacoustic imaging, BphP1, with the most red-shifted absorption among genetically encoded probes. BphP1 binds a heme-derived biliverdin chromophore and is reversibly photoconvertible between red and near-infrared light-absorption states. We combined single-wavelength PAT with efficient BphP1 photoswitching, which enabled differential imaging with substantially decreased background signals, enhanced detection sensitivity, increased penetration depth and improved spatial resolution. We monitored tumor growth and metastasis with ∼ 100-μm resolution at depths approaching 10 mm using photoacoustic computed tomography, and we imaged individual cancer cells with a suboptical-diffraction resolution of ∼ 140 nm using photoacoustic microscopy. This technology is promising for biomedical studies at several scales.

(Table 1) Salinity, dissolved organic carbon and absorption characteristics of surface river waters around Hudson Bay

Composition and concentration of colored dissolved organic matter (CDOM) have been determined in Hudson Bay and Hudson Strait by excitation emission matrix spectroscopy (EEM) and parallel factor analysis (PARAFAC). Based on 63 surface samples, PARAFAC identified three fluorescent components, which were attributed to two humic- and one protein-like components. One humic-like component was identified as representing terrestrial organic matter and showed a conservative behaviour in Hudson Bay estuaries. The second humic-like component, traditionally identified as peak M, originated both from land and produced in the marine environment. Component 3 had spectra resembling protein-like material and thought to be plankton-derived. The distribution and composition of CDOM were largely controlled by water mass mixing with protein-like component being the least affected. Distinctive fluorescence patterns were also found between Hudson Bay and Hudson Strait, suggesting different sources of CDOM. The optically active fraction of DOC (both absorbing and fluorescing) was very high in the Hudson Bay (up to 89%) suggesting that fluorescence and absorbance can be used as proxies of the DOC concentration.

Effect of dental tissue conditioners and matrix metalloproteinase inhibitors on type I collagen microstructure analyzed by Fourier transform infrared spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Exploring Habitability Markers, Biosignatures, and Their False Positives Using Spectral Models of Terrestrial Exoplanets

Thesis (Ph.D.)--University of Washington, 2016-08

Pulling Back the Veil: The Characterization and Habitability of Enshrouded Worlds

Thesis (Ph.D.)--University of Washington, 2016-08

Photochemical dynamics of laser-irradiated semiconductor nanostructures

Thesis (Ph.D.)--University of Washington, 2016-08

Dynamics of coupled modes in two-section semiconductor lasers with saturable absorption

Semiconductor lasers have the potential to address a number of critical applications in advanced telecommunications and signal processing. These include applications that require pulsed output that can be obtained from self-pulsing and mode-locked states of two-section devices with saturable absorption. Many modern applications place stringent performance requirements on the laser source, and a thorough understanding of the physical mechanisms underlying these pulsed modes of operation is therefore highly desirable. In this thesis, we present experimental measurements and numerical simulations of a variety of self-pulsation phenomena in two-section semiconductor lasers with saturable absorption. Our theoretical and numerical results will be based on rate equations for the field intensities and the carrier densities in the two sections of the device, and we establish typical parameter ranges and assess the level of agreement with experiment that can be expected from our models. For each of the physical examples that we consider, our model parameters are consistent with the physical net gain and absorption of the studied devices. Following our introductory chapter, the first system that we consider is a two-section Fabry-Pérot laser. This example serves to introduce our method for obtaining model parameters from the measured material dispersion, and it also allows us to present a detailed discussion of the bifurcation structure that governs the appearance of selfpulsations in two-section devices. In the following two chapters, we present two distinct examples of experimental measurements from dual-mode two-section devices. In each case we have found that single mode self-pulsations evolve into complex coupled dualmode states following a characteristic series of bifurcations. We present optical and mode resolved power spectra as well as a series of characteristic intensity time traces illustrating this progression for each example. Using the results from our study of a twosection Fabry-Pérot device as a guide, we find physically appropriate model parameters that provide qualitative agreement with our experimental results. We highlight the role played by material dispersion and the underlying single mode self-pulsing orbits in determining the observed dynamics, and we use numerical continuation methods to provide a global picture of the governing bifurcation structure. In our concluding chapter we summarise our work, and we discuss how the presented results can inform the development of optimised mode-locked lasers for performance applications in integrated optics.

The Evolution of Massive Young Stellar Objects in the Large Magellanic Cloud

This thesis presents an analysis of the largest catalog to date of infrared spectra of massive young stellar objects in the Large Magellanic Cloud. Evidenced by their very different spectral features, the luminous objects span a range of evolutionary states from those most embedded in their natal molecular material to those that have dissipated and ionized their surroundings to form compact HII regions and photodissociation regions. We quantify the contributions of the various spectral features using the statistical method of principal component analysis. Using this analysis, we classify the YSO spectra into several distinct groups based upon their dominant spectral features: silicate absorption (S Group), silicate absorption and fine-structure line emission (SE), polycyclic aromatic hydrocarbon (PAH) emission (P Group), PAH and fine-structure line emission (PE), and only fine-structure line emission (E). Based upon the relative numbers of sources in each category, we are able to estimate the amount of time massive YSOs spend in each evolutionary stage. We find that approximately 50% of the sources have ionic fine-structure lines, indicating that a compact HII region forms about half-way through the YSO lifetime probed in our study. Of the 277 YSOs we collected spectra for, 41 have ice absorption features, indicating they are surrounded by cold ice-bearing dust particles. We have decomposed the shape of the ice features to probe the composition and thermal history of the ice. We find that most the CO2 ice is embedded a polar ice matrix that has been thermally processed by the embedded YSO. The amount of thermal processing may be correlated with the luminosity of the YSO. Using the Australia Telescope Compact Array, we imaged the dense gas around a subsample of our sources in the HII complexes N44, N105, N113, and N159 using HCO+ and HCN as dense gas tracers. We find that the molecular material in star forming environments is highly clumpy, with clumps that range from subparsec to ~2 parsecs in size and with masses between 10^2 to 10^4 solar masses. We find that there are varying levels of star formation in the clumps, with the lower-mass clumps tending to be without massive YSOs. These YSO-less clumps could either represent an earlier stage of clump to the more massive YSO-bearing ones or clumps that will never form a massive star. Clumps with massive YSOs at their centers have masses larger than those with massive YSOs at their edges, and we suggest that the difference is evolutionary: edge YSO clumps are more advanced than those with YSOs at their centers. Clumps with YSOs at their edges may have had a significant fraction of their mass disrupted or destroyed by the forming massive star. We find that the strength of the silicate absorption seen in YSO IR spectra feature is well-correlated with the on-source HCO+ and HCN flux densities, such that the strength of the feature is indicative of the embeddedness of the YSO. We estimate that ~40% of the entire spectral sample has strong silicate absorption features, implying that the YSOs are embedded in circumstellar material for about 40% of the time probed in our study.