Characteristics of laser-induced plasma from highTc superconductor

The spectroscopic analysis of the emission from the plasma produced by irradiating a highT c superconducting GdBa2Cu3O7 target with a high power Nd:YAG laser beam shows the existence of the bands from different oxides in addition to the lines from neutrals and ions of the constituent elements. The spectral emissions by oxide species in laser-induced plasma show considerable time delays as compared to those from neutral and ionic species. Recombination processes taking place during the cooling of the hot plasma, rather than the plasma expansion velocities, have been found to be responsible for the observed time delays in this case. The decays of emission intensities from various species are found to be non-exponential.

The water vapour continuum in near-infrared windows – current understanding and prospects for its inclusion in spectroscopic databases

Spectroscopic catalogues, such as GEISA and HITRAN, do not yet include information on the water vapour continuum that pervades visible, infrared and microwave spectral regions. This is partly because, in some spectral regions, there are rather few laboratory measurements in conditions close to those in the Earth’s atmosphere; hence understanding of the characteristics of the continuum absorption is still emerging. This is particularly so in the near-infrared and visible, where there has been renewed interest and activity in recent years. In this paper we present a critical review focusing on recent laboratory measurements in two near-infrared window regions (centred on 4700 and 6300 cm−1) and include reference to the window centred on 2600 cm−1 where more measurements have been reported. The rather few available measurements, have used Fourier transform spectroscopy (FTS), cavity ring down spectroscopy, optical-feedback – cavity enhanced laser spectroscopy and, in very narrow regions, calorimetric interferometry. These systems have different advantages and disadvantages. Fourier Transform Spectroscopy can measure the continuum across both these and neighbouring windows; by contrast, the cavity laser techniques are limited to fewer wavenumbers, but have a much higher inherent sensitivity. The available results present a diverse view of the characteristics of continuum absorption, with differences in continuum strength exceeding a factor of 10 in the cores of these windows. In individual windows, the temperature dependence of the water vapour self-continuum differs significantly in the few sets of measurements that allow an analysis. The available data also indicate that the temperature dependence differs significantly between different near-infrared windows. These pioneering measurements provide an impetus for further measurements. Improvements and/or extensions in existing techniques would aid progress to a full characterisation of the continuum – as an example, we report pilot measurements of the water vapour self-continuum using a supercontinuum laser source coupled to an FTS. Such improvements, as well as additional measurements and analyses in other laboratories, would enable the inclusion of the water vapour continuum in future spectroscopic databases, and therefore allow for a more reliable forward modelling of the radiative properties of the atmosphere. It would also allow a more confident assessment of different theoretical descriptions of the underlying cause or causes of continuum absorption.

Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.

Human regulatory protein Ki-1/57 has characteristics of an intrinsically unstructured protein

The human protein Ki-1/57 was first identified through the cross reactivity of the anti-CD30 monoclonal antibody Ki-1; in Hodgkin lymphoma cells. The expression of Ki-1/57 in diverse cancer cells and its phosphorylation in peripheral blood leukocytes after mitogenic activation suggested its possible role in cell signaling. Ki-1/57 interacts with several other regulatory proteins involved in cellular signaling, transcriptional regulation and RNA metabolism, suggesting it may have pleiotropic functions. In a previous spectroscopic analysis, we observed a low content of secondary structure for Ki-1/57 constructs. Here, Circular dichroism experiments, in vitro RNA binding analysis, and limited proteolysis assays of recombinant Ki-1/57(122-413) and proteolysis assays of endogenous full length protein from human HEK293 cells suggested that Ki-1/57 has characteristics of an intrinsically unstructured protein. Small-angle X-ray scattering (SAXS) experiments were performed with the C-terminal fragment Ki-1/57(122-413). These results indicated an elongated shape and a partially unstructured conformation of the molecule in solution, confirming the characteristics of an intrinsically unstructured protein. Experimental curves together with ab initio modeling approaches revealed an extended and flexible molecule in solution. An elongated shape was also observed by analytical gel filtration. Furthermore, sedimentation velocity analysis suggested that Ki-1/57 is a highly asymmetric protein. These findings may explain the functional plasticity of Ki-1/57, as suggested by the wide array of proteins with which it is capable of interacting in yeast two-hybrid interaction assays.

Characterization of organic matter from composting of different residues by physicochemical and spectroscopic methods

Chemical and spectroscopic methods were used to characterize organic matter transformations during the composting process. Four different residue mixtures were studied: P1 - garden trimmings (GT) only, P2 - GT plus fresh cattle manure, P3 - GT plus orange pomace and P4 - GT plus filter cake. The thermophilic phase was not reached in PI compost, but the P2, P3 and P4 composts showed all three typical process phases. The thermophilic phase and CEC/C ratio stabilized after 90 days, while C/N ratio and the ash content stabilized after 60 days. The increasing E(4)/E(6) ratio indicated oxidation reactions occurring during the process in the material from P2, P3 and P4. The (13)C NMR and FTIR results suggested extraction of both pectin and lignin in the HA-like fraction. The CEC/C ratio, temperature and E(4)/E(6) ratio showed that within 90 days P2, P3 and P4 composts were humified. However, material from P1 did not show characteristics of humified compost. From these data, it is apparent that C/N ratio and ash content are not reliable methods for monitoring the composting process. (C) 2009 Elsevier Ltd. All rights reserved.

IMPEDANCE CHARACTERISTICS of La3/2Bi3/2Fe5O12 CERAMICS

Polycrystalline La3/2Bi3/2Fe5O12 (LBIO) compound was prepared by a high-temperature solid-state reaction technique. The complex impedance of LBIO was measured over a wide temperature (i.e., room temperature to 500 C) and frequencies (i.e., 10(2)-10(6) Hz) ranges. This study takes advantage of plotting ac data simultaneously in the form of impedance and modulus spectroscopic plots and obey non-Debye type of relaxation process. The Nyquist's plot showed the presence of grain effects in the material at high temperature. The ac conductivity spectrum was found to obey Jonscher's universal power law. The dc conductivity was found to increase with rise in temperature. The activation energy of the compound was found to be 0.24 and 0.51 eV in the low and high-temperature region, respectively, for conduction process.

Electron microprobe and Raman spectroscopic investigation of monazite from chromitites of Cedrolina (Goias State, Brazil)

Monazite from chromitites of Cedrolina (Goias State, Brazil) was investigated by electron microprobe and Raman spectroscopy. Monazite has been rarely encountered in chromitites. In Brazil, it was previously reported from chromitites of the Campo Formoso layered intrusion. Comparison between the two occurrences indicates similar morphology and textural characteristics, but remarkable differences in chemical composition. In both cases, monazite occurs as irregular grains (up to 200 mu m) preferentially located in the chlorite-serpentine matrix of the chromitite, more rarely included in chromite. However, the monazite from Cedrolina is characterized by higher Ce/La ratio, and Pr, Nd, Th contents, compared with the monazite from Campo Formoso. The obtained Raman spectra are very similar in the two cases, suggesting that the compositional variation of monazites and the spectral resolution of the Raman do not allow a conclusive chemical analysis with Raman spectra. Textural evidence indicates that, in both occurrences, monazite precipitation did not take place at high temperature, concomitantly with the host chromitite. In the Campo Formoso chromitites, precipitation of monazite has been related with percolation of hydrothermal, aqueous and acid fluids emanating from a granite batholith. on the contrary, the Cedrolina monazite probably formed during one of the metamorphic events that affected the area in which the host chromitite occurs.

Rare earth doped HfO2 nanoparticles embedded in SiO2-HfO2 planar waveguides. Preparation, optical, structural and spectroscopic characterization

In this work we present results on the preparation of planar waveguides based on HfO2 and HfO2-SiO2. Stable sols containing europium and erbium doped HfO2 nanoparticles have been prepared and characterized. The nanosized sol was either deposited (spin-coating) on quartz substrates or embedded in (3-glycidoxipropil)trimethoxisilane (GPTS) used as a hybrid host for posterior deposition. The refractive index dispersion and luminescence characteristics were determined for the resulting HfO2 films. The optical parameters of the waveguides such as refractive index, thickness and propagation losses were measured for the hybrid composite. The planar waveguides present thickness of a few micra and support well confined propagating modes.

Influence of the preparation route on the structural, morphological and spectroscopic properties of SrTiO3 and SrTiO3:eu3+ powders

This research shows the influence of the synthesis route in the structural and morphological characteristics as well as in the luminescent properties of doped with europium and pure SrTiO3 (STO) powders prepared by microwave assisted hydrothermal synthesis, MWH, and by the polymeric precursor method, PPM. The XRD at room temperature of the STO powders nominally pure obtained by PPM at 700°C for 3 hours, as well as by the MWH at 190°C by 30 minutes present all the reflection peaks for the cubic perovskite structure (JCPDS-ICDD 35-734). The morphology varies according to the synthesis route. The particles of pure STO obtained by PPM presents morphology in the form of plates and the morphology of the particles synthesized by MWH is spherical with approximately 150 nm. The photoluminescent analysis shows for pure STO wide bands associated with the transition of charge transfer from the titanates group (TiO3)2- that are centered on 450 nm. In both preparation methods the emission bands obtained in the composites spectra were found to be asymmetric and low intense. However, in the case of the STO prepared by the PPM a bigger FWHM of the band can be observed. The excitation of the samples was done using a laser (Coherent Innova) with wavelength of 350 nm.

Effect of the vanadium(V) concentration on the spectroscopic properties of nanosized europium-doped yttrium phosphates

Nanosized rare earth phosphovanadate phosphors (Y(P,V)O-4:Eu3+) have been prepared by applying the organic-inorganic polymeric precursors methodology. Luminescent powders with tetragonal structure and different vanadate concentrations (0%, 1%, 5%, 10%, 20%, 50%, and 100%, with regard to the phosphate content) were then obtained for evaluation of their structural and spectroscopic properties. The solids were characterized by scanning electron microscopy, X-ray diffractometry, vibrational spectroscopy (Raman and infrared), and electronic spectroscopy (emission, excitation, luminescence lifetimes, chromaticity, quantum efficiencies, and Judd-Ofelt intensity parameters). The solids exhibited very intense D-5(0) -> F-7(J) Eu3+ transitions, and it was possible to control the luminescent characteristics, such as excitation maximum, lifetime and emission colour, through the vanadium(V) concentration. The observed luminescent properties correlated to the characteristics of the chemical environments around the Eu3+ ions with respect to the composition of the phosphovanadates. The Eu3+ luminescence spectroscopy results indicated that the presence of larger vanadium(V) amounts in the phosphate host lattice led to more covalent and polarizable chemical environments. So, besides allowing for control of the luminescent properties of the solids, the variation in the vanadate concentration in the obtained YPO4:Eu3+ phosphors enabled the establishment of a strict correlation between the observable spectroscopic features and the chemical characteristics of the powders.

Fluorescence Characteristics of Size-Fractionated Dissolved Organic Matter: Implications for a Molecular Assembly Based Structure?

Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.

Phenotypic and Genotypic Characteristics of Members of the Genus Streptobacillus

The genus Streptobacillus (S.) remained monotypic for almost 90 years until two new species were recently described. The type species, S. moniliformis, is one of the two etiological agents of rat bite fever, an under-diagnosed, worldwide occurring zoonosis. In a polyphasic approach field isolates and reference strains of S. moniliformis, S. hongkongensis, S. felis as well as divergent isolates were characterized by comparison of molecular data (n = 29) and from the majority also by their physiological as well as proteomic properties (n = 22). Based on growth-independent physiological profiling using VITEK2-compact, API ZYM and the Micronaut system fastidious growth-related difficulties could be overcome and streptobacilli could definitively be typed despite generally few differences. While differing in their isolation sites and dates, S. moniliformis isolates were found to possess almost identical spectra in matrix-assisted laser desorption ionization-time of flight mass spectrometry and Fourier transform infrared spectroscopy. Spectroscopic methods facilitated differentiation of S. moniliformis, S. hongkongensis and S. felis as well as one divergent isolate. Sequencing of 16S rRNA gene as well as functional genes groEL, recA and gyrB revealed only little intraspecific variability, but generally proved suitable for interspecies discrimination between all three taxa and two groups of divergent isolates.

Calcium sulfate fillers and binders in Portuguese 15th and 16th centuries: Ground layers from a family painting workshop — Study by multianalytical spectroscopic techniques

This study presents results on a developed methodology to characterize ground layers in Portuguese workshops. In this work a set of altarpieces of the 15th and 16th centuries, assigned to Coimbra painting workshop was studied, overall the masters Vicente Gil (doc. Coimbra 1498–1525), Manuel Vicente (doc. Coimbra 1521–1530) and Bernardo Manuel (act. c. 1559–94), father, son and grandson, encompassing from late gothic to mannerist periods. The aim of the study is to compare ground layers, fillers and binders of Coimbra workshop, and to correlate their characteristics to understand the technical evolution of this family of painters, using complementary microscopic techniques. The cross-sections from the groups of paintings were examined by optical microscopy and the results were integrated through the analysis obtained by μ-X–ray diffraction, scanning electron microscopy with energy dispersive X–ray Spectrometry, μ-confocal Raman and occasionally with μ-Fourier transform infrared spectroscopy imaging. Ground layers are of calcium sulfate, present as gesso grosso (mainly anhydrite with small amounts of gypsum) in the first and last phases of the workshop and gesso mate (mainly gypsum with small amounts of anhydrite) in an intermediate period. Binders have protein and oleic characteristics.

The'cave' mineral oxammite: a high resolution thermogravimetry and Raman spectroscopic study

The thermal decomposition of natural ammonium oxalate known as oxammite has been studied using a combination of high resolution thermogravimetry coupled to an evolved gas mass spectrometer and Raman spectroscopy coupled to a thermal stage. Three mass loss steps were found at 57, 175 and 188°C attributed to dehydration, ammonia evolution and carbon dioxide evolution respectively. Raman spectroscopy shows two bands at 3235 and 3030 cm-1 attributed to the OH stretching vibrations and three bands at 2995, 2900 and 2879 cm-1, attributed to the NH vibrational modes. The thermal degradation of oxammite may be followed by the loss of intensity of these bands. No intensity remains in the OH stretching bands at 100°C and the NH stretching bands show no intensity at 200°C. Multiple CO symmetric stretching bands are observed at 1473, 1454, 1447 and 1431cm-1, suggesting that the mineral oxammite is composed of a mixture of chemicals including ammonium oxalate dihydrate, ammonium oxalate monohydrate and anhydrous ammonium oxalate.

Near-infrared spectroscopic study of basic aluminum sulfate and nitrate

The tridecameric Al-polymer [AlO4Al12(OH)24(H2O)12]7+ was prepared by forced hydrolysis of Al3+ up to an OH/Al molar ratio of 2.2. Under slow evaporation crystals were formed of Al13-nitrate. Upon addition of sulfate the tridecamer crystallised as the monoclinic Al13-sulfate. These crystals have been studied using near-infrared spectroscopy and compared to Al2(SO4)3.16H2O. Although the near-infrared spectra of the Al13-sulfate and nitrate are very similar indicating similar crystal structures, there are minor differences related to the strength with which the crystal water molecules are bonded to the salt groups. The interaction between crystal water and nitrate is stronger than with the sulfate as reflected by the shift of the crystal water band positions from 6213, 4874 and 4553 cm–1 for the Al13 sulfate towards 5925, 4848 and 4532 cm–1 for the nitrate. A reversed shift from 5079 and 5037 cm–1 for the sulfate towards 5238 and 5040 cm–1 for the nitrate for the water molecules in the Al13 indicate that the nitrate-Al13 bond is weakened due to the influence of the crystal water on the nitrate. The Al-OH bond in the Al13 complex is not influenced by changing the salt group due to the shielding by the water molecules of the Al13 complex.