Synthesis, spectral studies and X-ray crystal structure of N,N `-(+/-)-trans-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) H-2(t-3-EtOsalchxn)

The synthesis, spectra and X-ray crystal structure of N,N`-(+/-)-trans-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) H-2(t-3-EtOsalchxn), a salen-type ligand, are reported. The Schiff base was characterized by elemental analysis, m.p., IR, electronic spectra, H-1 and C-13 NMR spectra. The spectra are discussed and compared with those of N,N`-(+/-)-trans-1,2-cyclohexylenebis(salicylideneamine), H-2(t-salchxn). The electronic and IR spectra were also resolved by deconvolution. The influence of the ethoxy group on the IR, electronic spectrum, H-1 and C-13 NMR spectra is discussed. Strong intramolecular forces are present as supported by the IR and H-1 NMR spectra and the X-ray crystal structure. An intermolecular hydrogen bond is observed and appears twice in a pair of molecules in the unit cell. (c) 2007 Elsevier B.V. All rights reserved.

Spectral properties of temporally aggregated long memory processes

This paper derives the spectral density function of aggregated long memory processes in light of the aliasing effect. The results are different from previous analyses in the literature and a small simulation exercise provides evidence in our favour. The main result point to that flow aggregates from long memory processes shall be less biased than stock ones, although both retain the degree of long memory. This result is illustrated with the daily US Dollar/ French Franc exchange rate series.

Caracterização ambiental de bancos areno-lamosos nos campos petrolíferos de Macau e Serra (RN), como subsídio às medidas mitigadoras ao processo erosivo

On Rio Grande do Norte northern coast the process of sediment transport are intensely controlled by wind and sea (waves and currents) action, causing erosion and shoreline morphological instability. Due to the importance of such coastal zone it was realized the multi-spectral mapping and physical-chemical characterization of mudflats and mangroves aiming to support the mitigating actions related to the containment of the erosive process on the oil fields of Macau and Serra installed at the study area. The multi-spectral bands of 2000 and 2008 LANDSAT 5 TM images were submitted on the several digital processing steps and RGB color compositions integrating spectral bands and Principal Components. Such processing methodology was important to the mapping of different units on surface, together with field works. It was possible to make an analogy of the spectral characteristics of wetlands with vegetations areas (mangrove), showing the possibility to make a restoration of this area, contributing with the environmental monitoring of that ecosystem. The maps of several units were integrated in GIS environment at 1:60,000 scale, including the classification of features according to the presence or absence of vegetation cover. Thus, the strategy of methodology established that there are 10.13 km2 at least of sandy-muddy and of these approximately 0.89 km2 with the possibility to be used in a reforestation of typical flora of mangrove. The physical-chemical characterization showed areas with potential to introduce local species of mangrove and they had a pH above neutral with a mean of 8.4. The characteristic particle size is sand in the fine fractions, the high levels of carbonate, organic matter and major and trace element in general are concentrated where the sediment had the less particles size, showing the high correlation that those elements have with smaller particles of sediment. The application of that methodological strategy is relevant to the better understanding of features behavior and physical-chemical data of sediment samples collected on field allow the analysis of efficiency/capability of sandy-muddy to reforestation with local mangrove species for mitigation of the erosive action and coastal processes on the areas occupied by the oil industry

Retrievals of a size parameter for phytoplankton and spectral light absorption by colored detrital matter from water-leaving radiances at SeaWiFS channels in a continental shelf region off Brazil

Many efforts are currently oriented toward extracting more information from ocean color than the chlorophyll a concentration. Among biological parameters potentially accessible from space, estimates of phytoplankton cell size and light absorption by colored detrital matter (CDM) would lead to an indirect assessment of major components of the organic carbon pool in the ocean, which would benefit oceanic carbon budget models. We present here 2 procedures to retrieve simultaneously from ocean color measurements in a limited number of bands, magnitudes, and spectral shapes for both light absorption by CDM and phytoplankton, along with a size parameter for phytoplankton. The performance of the 2 procedures was evaluated using different data sets that correspond to increasing uncertainties: ( 1) measured absorption coefficients of phytoplankton, particulate detritus, and colored dissolved organic matter ( CDOM) and measured chlorophyll a concentrations and ( 2) SeaWiFS upwelling radiance measurements and chlorophyll a concentrations estimated from global algorithms. In situ data were acquired during 3 cruises, differing by their relative proportions in CDM and phytoplankton, over a continental shelf off Brazil. No local information was introduced in either procedure, to make them more generally applicable. Over the study area, the absorption coefficient of CDM at 443 nm was retrieved from SeaWiFS radiances with a relative root mean square error (RMSE) of 33%, and phytoplankton light absorption coefficients in SeaWiFS bands ( from 412 to 510 nm) were retrieved with RMSEs between 28% and 33%. These results are comparable to or better than those obtained by 3 published models. In addition, a size parameter of phytoplankton and the spectral slope of CDM absorption were retrieved with RMSEs of 17% and 22%, respectively. If these methods are applied at a regional scale, the performances could be substantially improved by locally tuning some empirical relationships.

Effects of irradiance and spectral composition on the establishment of macroalgae in streams in southern Brazil

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

Análise de séries temporais de coordenadas estimadas com GPS: uma proposta metodológica para detecção, remoção e recuperação de efeitos sazonais

GPS active networks are more and more used in geodetic surveying and scientific experiments, as water vapor monitoring in the atmosphere and lithosphere plate movement. Among the methods of GPS positioning, Precise Point Positioning (PPP) has provided very good results. A characteristic of PPP is related to the modeling and/or estimation of the errors involved in this method. The accuracy obtained for the coordinates can reach few millimeters. Seasonal effects can affect such accuracy if they are not consistent treated during the data processing. Coordinates time series analyses have been realized using Fourier or Harmonics spectral analyses, wavelets, least squares estimation among others. An approach is presented in this paper aiming to investigate the seasonal effects included in the stations coordinates time series. Experiments were carried out using data from stations Manaus (NAUS) and Fortaleza (BRFT) which belong to the Brazilian Continuous GPS Network (RBMC). The coordinates of these stations were estimated daily using PPP and were analyzed through wavelets for identification of the periods of the seasonal effects (annual and semi-annual) in each time series. These effects were removed by means of a filtering process applied in the series via the least squares adjustment (LSQ) of a periodic function. The results showed that the combination of these two mathematical tools, wavelets and LSQ, is an interesting and efficient technique for removal of seasonal effects in time series.

On determining spectral parameters, tracking jitter, and GPS positioning improvement by scintillation mitigation

A method of determining spectral parameters p (slope of the phase PSD) and T (phase PSD at 1 Hz) and hence tracking error variance in a GPS receiver PLL from just amplitude and phase scintillation indices and an estimated value of the Fresnel frequency has been previously presented. Here this method is validated using 50 Hz GPS phase and amplitude data from high latitude receivers in northern Norway and Svalbard. This has been done both using (1) a Fresnel frequency estimated using the amplitude PSD (in order to check the accuracy of the method) and (2) a constant assumed value of Fresnel frequency for the data set, convenient for the situation when contemporaneous phase PSDs are not available. Both of the spectral parameters (p, T) calculated using this method are in quite good agreement with those obtained by direct measurements of the phase spectrum as are tracking jitter variances determined for GPS receiver PLLs using these values. For the Svalbard data set, a significant difference in the scintillation level observed on the paths from different satellites received simultaneously was noted. Then, it is shown that the accuracy of relative GPS positioning can be improved by use of the tracking jitter variance in weighting the measurements from each satellite used in the positioning estimation. This has significant advantages for scintillation mitigation, particularly since the method can be accomplished utilizing only time domain measurements thus obviating the need for the phase PSDs in order to extract the spectral parameters required for tracking jitter determination.

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

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

Sparse one-dimensional discrete Dirac operators II: Spectral properties

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

New palladium(II) complexes with pyrazole ligands Part II. Synthesis, spectral and thermal studies, and antitumor evaluation

This study describes the synthesis, IR, (1)H, and (13)C{(1)H} NMR spectroscopic as well the thermal characterization of the new palladium(II) pyrazolyl complexes [PdCl(2)(HmPz)(2)] 1, [PdBr(2)(HmPz)(2)] 2, [PdI(2)(HmPz)(2)] 3, [Pd(SCN)(2)(HmPz)(2)] 4 {HmPz = 4-methylpyrazole}. The residues of the thermal decomposition were identified as Pd(0) by X-ray powder diffraction. From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 1 > 2 > 4 a parts per thousand 3. The cytotoxic activities of the complexes and the ligand were investigated against two murine cancer cell lines: mammary adenocarcinoma (LM3) and lung adenocarcinoma (LP07) and compared to cisplatin under the same experimental conditions.

3,5-Dimethyl-1-thiocarbamoylpyrazole and its Pd(II) complexes: Synthesis, spectral studies and antitumor activity

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

New palladium(II) complexes with pyrazole ligands Part I. Synthesis, spectral and thermal studies, and antitumor evaluation

The pyrazole ligand 3,5-dimethyl-4-iodopyrazole (HdmIPz) has been used to obtain a series of palladium(II) complexes (1-4) of the type [PdX(2)(HdmIPz)(2)] {X = Cl(-) (1); Br(-) (2); I(-) (3); SCN(-) (4)}. All compounds have been isolated, purified, and characterized by means of elemental analysis, IR spectroscopy, (1)H and (13)C{(1)H}-NMR experiments, differential thermal analysis (DTA), and thermogravimetry (TG). The TG/DTA curves showed that the compounds released ligands in the temperature range 137-605 A degrees C, yielding metallic palladium as final residue. The complexes and the ligand together with cisplatin have been tested in vitro by MTT assay for their cytotoxicity against two murine cancer cell lines: mammary adenocarcinoma (LM3) and lung adenocarcinoma (LP07).

O enigmático problema das gigantes ricas em Lítio e as perspectivas com o satélite Kepler

Lithium (Li) is a chemical element with atomic number 3 and it is among the lightest known elements in the universe. In general, the Lithium is found in the nature under the form of two stable isotopes, the 6Li and 7Li. This last one is the most dominant and responds for about 93% of the Li found in the Universe. Due to its fragileness this element is largely used in the astrophysics, especially in what refers to the understanding of the physical process that has occurred since the Big Bang going through the evolution of the galaxies and stars. In the primordial nucleosynthesis in the Big Bang moment (BBN), the theoretical calculation forecasts a Li production along with all the light elements such as Deuterium and Beryllium. To the Li the BNB theory reviews a primordial abundance of Log log ǫ(Li) =2.72 dex in a logarithmic scale related to the H. The abundance of Li found on the poor metal stars, or pop II stars type, is called as being the abundance of Li primordial and is the measure as being log ǫ(Li) =2.27 dex. In the ISM (Interstellar medium), that reflects the current value, the abundance of Lithium is log ǫ(Li) = 3.2 dex. This value has great importance for our comprehension on the chemical evolution of the galaxy. The process responsible for the increasing of the primordial value present in the Li is not clearly understood until nowadays. In fact there is a real contribution of Li from the giant stars of little mass and this contribution needs to be well streamed if we want to understand our galaxy. The main objection in this logical sequence is the appearing of some giant stars with little mass of G and K spectral types which atmosphere is highly enriched with Li. Such elevated values are exactly the opposite of what could happen with the typical abundance of giant low mass stars, where convective envelops pass through a mass deepening in which all the Li should be diluted and present abundances around log ǫ(Li) ∼1.4 dex following the model of stellar evolution. In the Literature three suggestions are found that try to reconcile the values of the abundance of Li theoretical and observed in these rich in Li giants, but any of them bring conclusive answers. In the present work, we propose a qualitative study of the evolutionary state of the rich in Li stars in the literature along with the recent discovery of the first star rich in Li observed by the Kepler Satellite. The main objective of this work is to promote a solid discussion about the evolutionary state based on the characteristic obtained from the seismic analysis of the object observed by Kepler. We used evolutionary traces and simulation done with the population synthesis code TRILEGAL intending to evaluate as precisely as possible the evolutionary state of the internal structure of these groups of stars. The results indicate a very short characteristic time when compared to the evolutionary scale related to the enrichment of these stars

Nitrogen content identification in crop plants using spectral reflectance and artificial neural networks

The accurate identification of the nitrogen content in crop plants is extremely important since it involves economic aspects and environmental impacts. Several experimental tests have been carried out to obtain characteristics and parameters associated with the health of plants and its growing. The nitrogen content identification involves a lot of nonlinear parametes and complexes mathematical models. This paper describes a novel approach for identification of nitrogen content thought spectral reflectance of plant leaves using artificial neural networks. The network acts as identifier of relationships among pH of soil, fertilizer treatment, spectral reflectance and nitrogen content in the plants. So, nitrogen content can be estimated and generalized from an input parameter set. This approach can be form the basis for development of an accurate real time nitrogen applicator.

Síntese e caracterização de compostos de coordenação homolépticos e heterolépticos com o ligante ácido kójico

The present work has as main objective to contribute to the coordination chemistry of the ligand kojic acid, with the synthesis and characterization of the homoleptic compounds [Al(kj)3], [Fe(kj)3], [Fe(kj)2], [Cu(kj)2] e [Ru(kj)3], and the new heteroleptic complexes, trans- K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2]. The obtained compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). The infrared results indicated the coordination of the bidentate ligand kojic acid, due to reductions in the values of the stretching frequencies of the carbonyl and double bonds, compared to the free ligand for all complexes obtained. The presence of new vibrational modes indicated the change of symmetry of the molecules in the new compounds synthesized. Additionally, the presence of vibrational modes assigned to metal-oxygen also contributed to confirm the ligand coordinating to the metal ions. Through this technique, was also possible to perform correlations of the numbers of vibrational modes, in the region 1400-900 cm-1 and the compounds geometry. The heteroleptic compounds exhibited υC≡N in 2065 and 2053 cm-1, respectively, for the trans-K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2], indicating coordination of the cyano ligand to metal ions FeII e RuII. Comparing the obtained values with literature data was possible to identify the complex isomerism as trans. In relation to the results of electronic spectroscopy, studies of pH variation of kojic acid provided information on the distribution of electron density in the molecule, showing characteristic spectral profile of kojic ion and its protonated form (Hkj, kojic acid), with two bands at 215 and 269 nm, or deprotonated (kj-), with bands at 226 and 315 nm. The electronic spectra obtained for all complexes in aqueous medium, in the ultraviolet region, exhibited variations of the energies assigned to kojic acid intraligand transitions while in the visible region, only transitions assigned to charge transfer of iron and ruthenium complex have been identified