Photogeneration of Hydrogen from Water by Hybrid Molybdenum Sulfide Clusters Immobilized on Titania

Two new hybrid molybdenum(IV) Mo3S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3S7Br6]2− by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3S7Br4(diimino) complexes. Adsorption of the Mo3S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.3 V (for 1 mA cm−2) with a turnover frequency as high as 1.4 s−1. The nature of the actual active molybdenum sulfide species has been investigated by X-ray photoelectron spectroscopy. In agreement with the electrochemical results, the modified TiO2 nanoparticles show a high photocatalytic activity for H2 production in the presence of Na2S/Na2SO3 as a sacrificial electron donor system.

Diffuse optical light in galaxy clusters. I. Abell 3888

We are undertaking a program to measure the characteristics of the intracluster light ( ICL; total flux, profile, color, and substructure) in a sample of 10 galaxy clusters with a range of cluster mass, morphology, and redshift. We present here the methods and results for the first cluster in that sample, A3888. We have identified an ICL component in A3888 in V and r that contains 13% +/- 5% of the total cluster light and extends to 700 h(70)(-1) kpc (similar to 0.3r(200)) from the center of the cluster. The ICL color in our smallest radial bin is V - r 0.3 +/- 0.1, similar to the central cluster elliptical galaxies. The ICL is redder than the galaxies at 400 h(70)(-1) kpc < r < 700 h(70)(-1) kpc, although the uncertainty in any one radial bin is high. Based on a comparison of V - r color with simple stellar models, the ICL contains a component that formed more than 7 Gyr ago ( at z less than 1) with a high-metallicity ( 1.0 Z(circle dot) < Z(ICL) less than or similar to 2.5 Z(circle dot)) and a more centralized component that contains stars formed within the past 5 Gyr ( at z similar to 1). The profile of the ICL can be roughly fitted by a shallow exponential in the outer regions and a steeper exponential in the central region. We also find a concentration of diffuse light around a small group of galaxies 1.4 h(70)(-1) Mpc from the center of the cluster. In addition, we find three low surface brightness features near the cluster center that are blue ( V - r 0.0) and contain a total flux of 0.1M*. Based on these observations and X-ray and galaxy morphology, we suggest that this cluster is entering a phase of significant merging of galaxy groups in the core, whereupon we expect the ICL fraction to grow significantly with the formation of a cD galaxy, as well as the infall of groups.

Discovery of "Warm Dust" galaxies in clusters at z ~ 0.3: evidence for stripping of cool dust in the dense environment?

Using far-infrared imaging from the "Herschel Lensing Survey," we derive dust properties of spectroscopically confirmed cluster member galaxies within two massive systems at z ~ 0.3: the merging Bullet Cluster and the more relaxed MS2137.3-2353. Most star-forming cluster sources (~90%) have characteristic dust temperatures similar to local field galaxies of comparable infrared (IR) luminosity (T_dust ~ 30 K). Several sub-luminous infrared galaxy (LIRG; L_IR < 10^11 L_☉) Bullet Cluster members are much warmer (T_dust > 37 K) with far-infrared spectral energy distribution (SED) shapes resembling LIRG-type local templates. X-ray and mid-infrared data suggest that obscured active galactic nuclei do not contribute significantly to the infrared flux of these "warm dust" galaxies. Sources of comparable IR luminosity and dust temperature are not observed in the relaxed cluster MS2137, although the significance is too low to speculate on an origin involving recent cluster merging. "Warm dust" galaxies are, however, statistically rarer in field samples (>3σ), indicating that the responsible mechanism may relate to the dense environment. The spatial distribution of these sources is similar to the whole far-infrared bright population, i.e., preferentially located in the cluster periphery, although the galaxy hosts tend toward lower stellar masses (M_* < 10^10 M_☉). We propose dust stripping and heating processes which could be responsible for the unusually warm characteristic dust temperatures. A normal star-forming galaxy would need 30%-50% of its dust removed (preferentially stripped from the outer reaches, where dust is typically cooler) to recover an SED similar to a "warm dust" galaxy. These progenitors would not require a higher IR luminosity or dust mass than the currently observed normal star-forming population.

Examining the growth and evolution of magnetic fields in clusters of galaxies: a numerical perspective

Magnetic fields are ubiquitous in galaxy cluster atmospheres and have a variety of astrophysical and cosmological consequences. Magnetic fields can contribute to the pressure support of clusters, affect thermal conduction, and modify the evolution of bubbles driven by active galactic nuclei. However, we currently do not fully understand the origin and evolution of these fields throughout cosmic time. Furthermore, we do not have a general understanding of the relationship between magnetic field strength and topology and other cluster properties, such as mass and X-ray luminosity. We can now begin to answer some of these questions using large-scale cosmological magnetohydrodynamic (MHD) simulations of the formation of galaxy clusters including the seeding and growth of magnetic fields. Using large-scale cosmological simulations with the FLASH code combined with a simplified model of the acceleration of cosmic rays responsible for the generation of radio halos, we find that the galaxy cluster frequency distribution and expected number counts of radio halos from upcoming low-frequency sur- veys are strongly dependent on the strength of magnetic fields. Thus, a more complete understanding of the origin and evolution of magnetic fields is necessary to understand and constrain models of diffuse synchrotron emission from clusters. One favored model for generating magnetic fields is through the amplification of weak seed fields in active galactic nuclei (AGN) accretion disks and their subsequent injection into cluster atmospheres via AGN-driven jets and bubbles. However, current large-scale cosmological simulations cannot directly include the physical processes associated with the accretion and feedback processes of AGN or the seeding and merging of the associated SMBHs. Thus, we must include these effects as subgrid models. In order to carefully study the growth of magnetic fields in clusters via AGN-driven outflows, we present a systematic study of SMBH and AGN subgrid models. Using dark-matter only cosmological simulations, we find that many important quantities, such as the relationship between SMBH mass and galactic bulge velocity dispersion and the merger rate of black holes, are highly sensitive to the subgrid model assumptions of SMBHs. In addition, using MHD calculations of an isolated cluster, we find that magnetic field strengths, extent, topology, and relationship to other gas quantities such as temperature and density are also highly dependent on the chosen model of accretion and feedback. We use these systematic studies of SMBHs and AGN inform and constrain our choice of subgrid models, and we use those results to outline a fully cosmological MHD simulation to study the injection and growth of magnetic fields in clusters of galaxies. This simulation will be the first to study the birth and evolution of magnetic fields using a fully closed accretion-feedback cycle, with as few assumptions as possible and a clearer understanding of the effects of the various parameter choices.

Non-thermal phenomena in galaxy clusters: the LOFAR revolution

Turbulence introduced into the intra-cluster medium (ICM) through cluster merger events transfers energy to non-thermal components (relativistic particles and magnetic fields) and can trigger the formation of diffuse synchrotron radio sources. Owing to their steep synchrotron spectral index, such diffuse sources can be better studied at low radio frequencies. In this respect, the LOw Frequency ARray (LOFAR) is revolutionizing our knowledge thanks to its unprecedented resolution and sensitivity below 200 MHz. In this Thesis we focus on the study of radio halos (RHs) by using LOFAR data. In the first part of this work we analyzed the largest-ever sample of galaxy clusters observed at radio frequencies. This includes 309 Planck clusters from the Second Data Release of the LOFAR Two Metre Sky Survey (LoTSS-DR2), which span previously unexplored ranges of mass and redshift. We detected 83 RHs, half of which being new discoveries. In 140 clusters we lack a detected RH; for this sub-sample we developed new techniques to derive upper limits to their radio powers. By comparing detections and upper limits, we carried out the first statistical analysis of populations of clusters observed at low frequencies and tested theoretical formation models. In the second part of this Thesis we focused on ultra-steep spectrum radio halos. These sources are almost undetected at GHz frequencies, but are thought to be common at low frequencies. We presented LOFAR observations of two interesting clusters hosting ultra-steep spectrum radio halos. With complementary radio and X-ray observations we constrained the properties and origin of these targets.

Real-time anomaly detection of gamma-ray bursts for the Cherenkov Telescope Array using deep learning

The Cherenkov Telescope Array (CTA) will be the next-generation ground-based observatory to study the universe in the very-high-energy domain. The observatory will rely on a Science Alert Generation (SAG) system to analyze the real-time data from the telescopes and generate science alerts. The SAG system will play a crucial role in the search and follow-up of transients from external alerts, enabling multi-wavelength and multi-messenger collaborations. It will maximize the potential for the detection of the rarest phenomena, such as gamma-ray bursts (GRBs), which are the science case for this study. This study presents an anomaly detection method based on deep learning for detecting gamma-ray burst events in real-time. The performance of the proposed method is evaluated and compared against the Li&Ma standard technique in two use cases of serendipitous discoveries and follow-up observations, using short exposure times. The method shows promising results in detecting GRBs and is flexible enough to allow real-time search for transient events on multiple time scales. The method does not assume background nor source models and doe not require a minimum number of photon counts to perform analysis, making it well-suited for real-time analysis. Future improvements involve further tests, relaxing some of the assumptions made in this study as well as post-trials correction of the detection significance. Moreover, the ability to detect other transient classes in different scenarios must be investigated for completeness. The system can be integrated within the SAG system of CTA and deployed on the onsite computing clusters. This would provide valuable insights into the method's performance in a real-world setting and be another valuable tool for discovering new transient events in real-time. Overall, this study makes a significant contribution to the field of astrophysics by demonstrating the effectiveness of deep learning-based anomaly detection techniques for real-time source detection in gamma-ray astronomy.

Synthesis and Characterization of Iron carbide carbonyl clusters

This study is focused on the synthesis, characterization and reactivity of new low nuclearity iron carbide carbonyl clusters. In particular, the oxidation of the highly reduced monocarbide tetraanionic cluster [Fe6C(CO)15]4- was studied in details using different oxidants ([Cp2Fe][PF6], HBF4·Et2O, MeI and EtI), different stoichiometries and experimental conditions. Different products were obtained depending on the reaction conditions, among which previously reported [Fe6C(CO)16]2- and [Fe5C(CO)14]2-, and new [Fe6C(CO)14(CO)13]4- and [Fe5C(CO)13(COMe)]3- were isolated and fully characterized. In the second part of this study, the reactions of [Fe6C(CO)15]4- with organic or inorganic molecules containing sulphur (S8, S2Cl2 and PhSH) were investigated aiming at introducing S-atoms within the structure of iron carbide carbonyl clusters. In particular, the reaction of [Fe6C(CO)15]4- with PhSH afforded the new [Fe6C(CO)14(SPh)]3- cluster. Conversely, using S8 and S2Cl2, oxidation of [Fe6C(CO)15]4- occurred following a path similar to that observed with other oxidizing agents. All these species have been analyzed by Single Crystal X-ray diffraction (SC-XRD) and IR spectroscopy.

Monte Carlo Simulation Of The Response Functions Of Cdte Detectors To Be Applied In X-ray Spectroscopy.

In this work, the energy response functions of a CdTe detector were obtained by Monte Carlo (MC) simulation in the energy range from 5 to 160keV, using the PENELOPE code. In the response calculations the carrier transport features and the detector resolution were included. The computed energy response function was validated through comparison with experimental results obtained with (241)Am and (152)Eu sources. In order to investigate the influence of the correction by the detector response at diagnostic energy range, x-ray spectra were measured using a CdTe detector (model XR-100T, Amptek), and then corrected by the energy response of the detector using the stripping procedure. Results showed that the CdTe exhibits good energy response at low energies (below 40keV), showing only small distortions on the measured spectra. For energies below about 80keV, the contribution of the escape of Cd- and Te-K x-rays produce significant distortions on the measured x-ray spectra. For higher energies, the most important correction is the detector efficiency and the carrier trapping effects. The results showed that, after correction by the energy response, the measured spectra are in good agreement with those provided by a theoretical model of the literature. Finally, our results showed that the detailed knowledge of the response function and a proper correction procedure are fundamental for achieving more accurate spectra from which quality parameters (i.e., half-value layer and homogeneity coefficient) can be determined.

Fast And Direct Na And K Determination In Table, Marine, And Low-sodium Salts By X-ray Fluorescence And Chemometrics.

X-ray fluorescence (XRF) is a fast, low-cost, nondestructive, and truly multielement analytical technique. The objectives of this study are to quantify the amount of Na(+) and K(+) in samples of table salt (refined, marine, and light) and to compare three different methodologies of quantification using XRF. A fundamental parameter method revealed difficulties in quantifying accurately lighter elements (Z < 22). A univariate methodology based on peak area calibration is an attractive alternative, even though additional steps of data manipulation might consume some time. Quantifications were performed with good correlations for both Na (r = 0.974) and K (r = 0.992). A partial least-squares (PLS) regression method with five latent variables was very fast. Na(+) quantifications provided calibration errors lower than 16% and a correlation of 0.995. Of great concern was the observation of high Na(+) levels in low-sodium salts. The presented application may be performed in a fast and multielement fashion, in accordance with Green Chemistry specifications.

Are Human Peripheral Nerves Sensitive To X-ray Imaging?

Diagnostic imaging techniques play an important role in assessing the exact location, cause, and extent of a nerve lesion, thus allowing clinicians to diagnose and manage more effectively a variety of pathological conditions, such as entrapment syndromes, traumatic injuries, and space-occupying lesions. Ultrasound and nuclear magnetic resonance imaging are becoming useful methods for this purpose, but they still lack spatial resolution. In this regard, recent phase contrast x-ray imaging experiments of peripheral nerve allowed the visualization of each nerve fiber surrounded by its myelin sheath as clearly as optical microscopy. In the present study, we attempted to produce high-resolution x-ray phase contrast images of a human sciatic nerve by using synchrotron radiation propagation-based imaging. The images showed high contrast and high spatial resolution, allowing clear identification of each fascicle structure and surrounding connective tissue. The outstanding result is the detection of such structures by phase contrast x-ray tomography of a thick human sciatic nerve section. This may further enable the identification of diverse pathological patterns, such as Wallerian degeneration, hypertrophic neuropathy, inflammatory infiltration, leprosy neuropathy and amyloid deposits. To the best of our knowledge, this is the first successful phase contrast x-ray imaging experiment of a human peripheral nerve sample. Our long-term goal is to develop peripheral nerve imaging methods that could supersede biopsy procedures.

Different coordination modes for disulfoxides towards diorganotin(IV) dichlorides. X-ray crystal structures of 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) and adducts [{Ph2SnCl2(meso-bpse)}n] and [{n-Bu2SnCl2(pdtd)}2]

The reactions of meso-1,2-bis(phenylsulfinyl)ethane (meso-bpse) with Ph2SnCl2, 2-phenyl-1,3-dithiane trans-1-trans-3-dioxide (pdtd) with n-Bu2SnCl2 and 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) with Ph2SnCl2, in 1:1 molar ratio, yielded [{Ph2SnCl2(meso-bpse)}n], [{n-Bu2SnCl2(pdtd)}2] and [{Ph2SnCl2(rac,cis-cbpse)}x] (x = 2 or n), respectively. All adducts were studied by IR, Mössbauer and 119Sn NMR spectroscopic methods, elemental analysis and single crystal X-ray diffractometry. The X-ray crystal structure of [{Ph2SnCl2(meso-bpse)}n] revealed the occurrence of infinite chains in which the tin(IV) atoms appear in a distorted octahedral geometry with Cl atoms in cis and Ph groups in trans positions. The X-ray crystal structure of [{n-Bu2SnCl2(pdtd)}2] revealed discrete centrosymmetric dimeric species in which the tin(IV) atoms possess a distorted octahedral geometry with bridging disulfoxides in cis and n-butyl moieties in trans positions. The spectroscopic data indicated that the adduct containing the rac,cis-cbpse ligand can be dimeric or polymeric. The X-ray structural analysis of the free rac-,cis-cbpse sulfoxide revealed that the crystals belong to the C2/c space group.

Synthesis of novel O-acylated-D-ribono-1,5-lactones and structural assignment supported by conventional NOESY-NMR and x-ray analysis

A practical method for the structural assignment of 3,4-O-benzylidene-D-ribono-1,5-lactones and analogues using conventional NMR techniques and NOESY measurements in solution is described. 2-O-Acyl-3,4-O-benzylidene-D-ribono-1,5-lactones were prepared in good yields by acylation of Zinner’s lactone with acyl chlorides under mildly basic conditions. Structural determination of 2-O-(4-nitrobenzoyl)-3,4-O-benzylidene-D-ribono-1,5-lactone was achieved by single crystal x-ray diffraction, which supports the results based on spectroscopic data.

Study of calcium oxalate monohydrate of kidney stones by X-ray diffraction

X-ray powder diffraction was used to study the phase composition of human renal calculi. The stones were collected from 56 donors in Vitoria, Espirito Santo state, southeastern Brazil. An XRD phase quantification revealed that 61% of the studied renal stones were composed exclusively of calcium oxalate [34% formed only by calcium oxalate rnonohydrate (COM) and 27% presents both monohydrate and dihydratate calcium oxalate]. The 39% multi-composed calculi have various other phases such as uric acid and calcium phosphate. Rietveld refinement of XRD data of one apparent monophasic (COM) renal calculus revealed the presence of a small amount of hydroxyapatite. The presence of this second phase and the morphology of the stone (ellipsoidal) indicated that this calculus can be classified as non-papillary type and its nucleation process developed in closed kidney cavities. In order to show some advantages of the X-ray powder diffraction technique, a study of the phase transformation of monohydrate calcium oxalate into calcium carbonate (CaCO(3)) was carried out by annealing of a monophasic COM calculi at 200, 300, and 400 degrees C for 48 h in a N(2) gas atmosphere. The results of the XRD for the heat treated samples is ill good agreement with the thermogravimetric analysis found in the literature and shows that X-ray powder diffraction can be used as a suitable technique to study the composition and phase diagram of renal calculi. (C) 2008 International Centre for Diffraction Data.

WOOD DENSITY VARIATION AND TREE RING DEMARCATION IN Gmelina arborea TREES USING X-RAY DENSITOMETRY

Due to its relationship with other properties, wood density is the main wood quality parameter. Modern, accurate methods - such as X-ray densitometry - are applied to determine the spatial distribution of density in wood sections and to evaluate wood quality. The objectives of this study were to determinate the influence of growing conditions on wood density variation and tree ring demarcation of gmelina trees from fast growing plantations in Costa Rica. The wood density was determined by X-ray densitometry method. Wood samples were cut from gmelina trees and were exposed to low X-rays. The radiographic films were developed and scanned using a 256 gray scale with 1000 dpi resolution and the wood density was determined by CRAD and CERD software. The results showed tree-ring boundaries were distinctly delimited in trees growing in site with rainfall lower than 25 10 mm/year. It was demonstrated that tree age, climatic conditions and management of plantation affects wood density and its variability. The specific effect of variables on wood density was quantified by for multiple regression method. It was determined that tree year explained 25.8% of the total variation of density and 19.9% were caused by climatic condition where the tree growing. Wood density was less affected by the intensity of forest management with 5.9% of total variation.

A spatial approach for the epidemiology of antibiotic use and resistance in community-based studies: the emergence of urban clusters of Escherichia coli quinolone resistance in Sao Paulo, Brasil

Background: Population antimicrobial use may influence resistance emergence. Resistance is an ecological phenomenon due to potential transmissibility. We investigated spatial and temporal patterns of ciprofloxacin (CIP) population consumption related to E. coli resistance emergence and dissemination in a major Brazilian city. A total of 4,372 urinary tract infection E. coli cases, with 723 CIP resistant, were identified in 2002 from two outpatient centres. Cases were address geocoded in a digital map. Raw CIP consumption data was transformed into usage density in DDDs by CIP selling points influence zones determination. A stochastic model coupled with a Geographical Information System was applied for relating resistance and usage density and for detecting city areas of high/low resistance risk. Results: E. coli CIP resistant cluster emergence was detected and significantly related to usage density at a level of 5 to 9 CIP DDDs. There were clustered hot-spots and a significant global spatial variation in the residual resistance risk after allowing for usage density. Conclusions: There were clustered hot-spots and a significant global spatial variation in the residual resistance risk after allowing for usage density. The usage density of 5-9 CIP DDDs per 1,000 inhabitants within the same influence zone was the resistance triggering level. This level led to E. coli resistance clustering, proving that individual resistance emergence and dissemination was affected by antimicrobial population consumption.