Magnetic, thermal and spectral characterization of 2,6-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 2,6-dimethoxybenzoic acid anion with ions of Co(II), Ni(II), and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies, and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have following colours: pink for Co(II), green for Ni(II), and blue for Cu(II) compounds. The carboxylate group binds as monodentate, and bidentate bridging and chelating ligands. On heating in air to 1173 K the complexes decompose in four, three or two steps. At first, they dehydrate in one or two steps to anhydrous salts, that next decompose to oxides of the respective metals. The solubility of the investigated dimethoxybenzoates in water at 293 K is of the order of 10-2 mol/dm3. Their magnetic moments were determined in the temperature range of 76-303 K. The results reveal the compounds of Co(II) and Ni(II) to be high-spin complexes and that of Cu(II) to form dimer.

Magnetic, thermal and spectral properties of Ni(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

Complexes of Ni(II) 2,3-, 3,5- and 2,6-dimethoxybenzoates have been synthesized, their physico-chemical properties have been compared and the influence of the position of -OCH3 substituent on their properties investigated. The analysed compounds are crystalline, hydrated salts with green colour. The carboxylate ions show a bidentate chelating or bridging coordination modes. The thermal stabilities of Ni(II) dimethoxybenzoates were investigated in air in the range of 293-1173 K. The complexes decompose in three steps, yelding the NiO as the final product of decomposition. Their solubilities in water at 293 K are in the order of 10-2-10-4 mol×dm-3. The magnetic susceptibilities for the analysed dimethoxybenzoates of Ni(II) were measured over the range of 76-303 K and the magnetic moments were calculated. The results reveal that the complexes are the high-spin ones and the ligands form the weak electrostatic field in the octahedral coordination sphere of the central Ni(II) ion. The various position -OCH3 groups in benzene ring cause the different steric, mesomeric and inductive effects on the electron density in benzene ring.

Magnetic, thermal and spectral behaviour of 3-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Physico-chemical properties of 3-chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II) were synthesized and studied. The complexes were obtained as mono- and dihydrates with a metal ion to ligand ratio of 1 : 2. All analysed 3-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II) and blue for Cu(II) complexes. Their thermal decomposition was studied in the range of 293 ­ 523 K, because it was found that on heating in air above 523 K 3-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10-4 ­ 10-2 mol / dm³. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 3-chloro-2-nitrobenzoates experimentally determined at 76 ­ 303 K change from 3.67µB to 4.61µB for Co(II) complex, from 2.15µB to 2.87µB for Ni(II) 3-chloro-2-nitrobenzoate and from 0.26µB to 1.39µB for Cu(II) complex. 3-Chloro-2-nitrobenzoates of Co(II) and Ni(II) follow the Curie-Weiss law. Complex of Cu(II) forms dimer.

Magnetic, thermal and spectral characterization of 2,4-dimethoxybenzoates of Mn(II), Co(II) and Cu(II)

2,4 - Dimethoxybenzoates of Mn(II), Co(II) and Cu(II) have been synthesized as hydrated or anyhydrous polycrystalline solids and characterized by elemental analysis, IR spectroscopy, magnetic studies and X-ray diffraction measurements. They possess the following colours: Mn(II) - white, Co(II) - pink and Cu(II) - blue. The carboxylate groups bind as monodentate, or a symmetrical bidentate bridging ligands and tridentate. The thermal stabilities were determined in air at 293-1173K. When heated the hydrated complexes dehydrate to from anhydous salts which are decomposed to the oxides of respective metals. The magnetic susceptibilites of the 2,4-dimethoxybenzoates were measured over the range 76-303 K and their magnetic moments were calculated. The results reveal the complexes of Mn(II), Co(II) to be high-spin complexes and that of Cu(II) to form dimer.

Spatial and Spectral Separability of Grasslands in the inner Turku Archipelago using Landsat Thematic Mapper Satellite Imagery

The present study investigates the spatial and spectral discrimination potential for grassland patches in the inner Turku Archipelago using Landsat Thematic Mapper satellite imagery. The spatial discrimination potential was computed through overlay analysis using official grassland parcel data and a hypothetical 30 m resolution satellite image capturing the site. It found that Landsat TM imagery’s ability to retrieve pure or near-pure pixels (90% purity or more) from grassland patches smaller than 1 hectare was limited to 13% success, compared to 52% success when upscaling the resolution to 10 x 10 m pixel size. Additionally, the perimeter/area patch metric is proposed as a predictor for the suitability of the spatial resolution of input imagery. Regression analysis showed that there is a strong negative correlation between a patch’s perimeter/area ratio and its pure pixel potential. The study goes on to characterise the spectral response and discrimination potential for the five main grassland types occurring in the study area: recreational grassland, traditional pasture, modern pasture, fodder production grassland and overgrown grassland. This was done through the construction of spectral response curves, a coincident spectral plot and a contingency matrix as well as by calculating the transformed divergence for the spectral signatures, all based on training samples from the TM imagery. Substantial differences in spectral discrimination potential between imagery from the beginning of the growing season and the middle of summer were found. This is because the spectral responses for these five grassland types converge as the peak of the growing season draws nearer. Recreational grassland shows a consistent discrimination advantage over other grassland types, whereas modern pasture is most easily confused. Traditional pasture land, perhaps the most biologically valuable grassland type, can be spectrally discriminated from other grassland types with satisfactory success rates provided early growing season imagery is used.

Thermal and spectral properties of di-and trimethoxybenzoates of silver (I)

The complexes of silver(I) with 2,3-, 2,4-, 2,6-, 3,4-, 3,5-dimethoxy-, and 2,3,4- and 3,4,5-trimethoxybenzoic acid anions have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric and X-ray studies. Their solubility in water has been also determined at 293K. All analysed complexes were found to be crystalline, anhydrous compounds with low symmetry. The carboxylate groups act as bidentate or monodentate ligands. The thermal stability of compounds has been examined in air in temperature range of 293-1173K. The analysed complexes were found to be stable at room temperature and their solubilities in water at 293K to be in the order of 10-4 mol.dm-3.

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

In this work, a new mathematical equation correction approach for overcoming spectral and transport interferences was proposed. The proposal was applied to eliminate spectral interference caused by PO molecules at the 217.0005 nm Pb line, and the transport interference caused by variations in phosphoric acid concentrations. Correction may be necessary at 217.0005 nm to account for the contribution of PO, since Atotal217.0005 nm = A Pb217.0005 nm + A PO217.0005 nm. This may be easily done by measuring other PO wavelengths (e.g. 217.0458 nm) and calculating the relative contribution of PO absorbance (A PO) to the total absorbance (Atotal) at 217.0005 nm: A Pb217.0005 nm = Atotal217.0005 nm - A PO217.0005 nm = Atotal217.0005 nm - k (A PO217.0458 nm). The correction factor k is calculated from slopes of calibration curves built up for phosphorous (P) standard solutions measured at 217.0005 and 217.0458 nm, i.e. k = (slope217.0005 nm/slope217.0458 nm). For wavelength integrated absorbance of 3 pixels, sample aspiration rate of 5.0 ml min-1, analytical curves in the 0.1 - 1.0 mg L-1 Pb range with linearity better than 0.9990 were consistently obtained. Calibration curves for P at 217.0005 and 217.0458 nm with linearity better than 0.998 were obtained. Relative standard deviations (RSD) of measurements (n = 12) in the range of 1.4 - 4.3% and 2.0 - 6.0% without and with mathematical equation correction approach were obtained respectively. The limit of detection calculated to analytical line at 217.0005 nm was 10 µg L-1 Pb. Recoveries for Pb spikes were in the 97.5 - 100% and 105 - 230% intervals with and without mathematical equation correction approach, respectively.

Sequence diversity in the coat protein gene of Lettuce big-vein associated virus and Mirafiori lettuce big-vein virus infecting lettuce in Brazil

Lettuce big vein associated virus (LBVaV) and Mirafiori lettuce big vein virus (MLBVV) have been found in mixed infection in Brazil causing the lettuce big vein disease. Analysis of part of the coat protein (CP) gene of Brazilian isolates of LBVaV collected from lettuce, showed at least 93% amino acid sequence identity with other LBVaV isolates. Genetic diversity among MLBVV CP sequences was higher when compared to LBVaV CP sequences, with amino acid sequence identity ranging between 91% to 100%. Brazilian isolates of MLBVV belong to subgroup A, with one RsaI restriction site on the coat protein gene. There is no indication for a possible geografical origin for the Brazilian isolates of LBVaV and MLBVV.

Use of data mining and spectral profiles to differentiate condition after harvest of coffee plants

This study aimed at identifying different conditions of coffee plants after harvesting period, using data mining and spectral behavior profiles from Hyperion/EO1 sensor. The Hyperion image, with spatial resolution of 30 m, was acquired in August 28th, 2008, at the end of the coffee harvest season in the studied area. For pre-processing imaging, atmospheric and signal/noise effect corrections were carried out using Flaash and MNF (Minimum Noise Fraction Transform) algorithms, respectively. Spectral behavior profiles (38) of different coffee varieties were generated from 150 Hyperion bands. The spectral behavior profiles were analyzed by Expectation-Maximization (EM) algorithm considering 2; 3; 4 and 5 clusters. T-test with 5% of significance was used to verify the similarity among the wavelength cluster means. The results demonstrated that it is possible to separate five different clusters, which were comprised by different coffee crop conditions making possible to improve future intervention actions.

Detection of soybean planted areas through orbital images based on culture spectral dynamics

The soybean is important to the economy of Brazil, so the estimation of the planted area and the production with higher antecedence and reliability becomes essential. Techniques related to Remote Sensing may help to obtain this information at lower cost and less subjectivity in relation to traditional surveys. The aim of this study is to estimate the planted area with soybean culture in the crop of 2008/2009 in cities in the west of the state of Paraná, in Brazil, based on the spectral dynamics of the culture and through the use of the specific system of analysis for images of Landsat 5/TM satellite. The obtained results were satisfactory, because the classification supervised by Maximum Verisimilitude - MaxVer along with the techniques of the specific system of analysis for satellite images has allowed an estimate of soybean planted area (soybean mask), obtaining values ​​of the metrics of Global Accuracy with an average of 79.05% and Kappa Index over 63.50% in all cities. The monitoring of a reference area was of great importance for determining the vegetative phase in which the culture is more different from the other targets, facilitating the choice of training samples (ROIs) and avoiding misclassifications.

Influence of data acquisition geometry on soybean spectral response simulated by the prosail model

View angle and directional effects significantly affect reflectance and vegetation indices, especially when daily images collected by large field-of-view (FOV) sensors like the Moderate Resolution Imaging Spectroradiometer (MODIS) are used. In this study, the PROSAIL radiative transfer model was chosen to evaluate the impact of the geometry of data acquisition on soybean reflectance and two vegetation indices (Normalized Difference Vegetation Index - NDVI and Enhanced Vegetation Index -EVI) by varying biochemical and biophysical parameters of the crop. Input values for PROSAIL simulation were based on the literature and were adjusted by the comparison between simulated and real satellite soybean spectra acquired by the MODIS/Terra and hyperspectral Hyperion/Earth Observing-One (EO-1). Results showed that the influence of the view angle and view direction on reflectance was stronger with decreasing leaf area index (LAI) and chlorophyll concentration. Because of the greater dependence on the near-infrared reflectance, the EVI was much more sensitive to viewing geometry than NDVI presenting larger values in the backscattering direction. The contrary was observed for NDVI in the forward scattering direction. In relation to the LAI, NDVI was much more isotropic for closed soybean canopies than for incomplete canopies and a contrary behavior was verified for EVI.

Novel Regression Methods For Spectral Data

Singular Value Decomposition (SVD), Principal Component Analysis (PCA) and Multiple Linear Regression (MLR) are some of the mathematical pre- liminaries that are discussed prior to explaining PLS and PCR models. Both PLS and PCR are applied to real spectral data and their di erences and similarities are discussed in this thesis. The challenge lies in establishing the optimum number of components to be included in either of the models but this has been overcome by using various diagnostic tools suggested in this thesis. Correspondence analysis (CA) and PLS were applied to ecological data. The idea of CA was to correlate the macrophytes species and lakes. The di erences between PLS model for ecological data and PLS for spectral data are noted and explained in this thesis. i

Intrapartum hypoxia and power spectral analysis of fetal heart rate variability

Reliable detection of intrapartum fetal acidosis is crucial for preventing morbidity. Hypoxia-related changes of fetal heart rate variability (FHRV) are controlled by the autonomic nervous system. Subtle changes in FHRV that cannot be identified by inspection can be detected and quantified by power spectral analysis. Sympathetic activity relates to low-frequency FHRV and parasympathetic activity to both low- and high-frequency FHRV. The aim was to study whether intra partum fetal acidosis can be detected by analyzing spectral powers of FHRV, and whether spectral powers associate with hypoxia-induced changes in the fetal electrocardiogram and with the pH of fetal blood samples taken intrapartum. The FHRV of 817 R-R interval recordings, collected as a part of European multicenter studies, were analyzed. Acidosis was defined as cord pH ≤ 7.05 or scalp pH ≤ 7.20, and metabolic acidosis as cord pH ≤ 7.05 and base deficit ≥ 12 mmol/l. Intrapartum hypoxia increased the spectral powers of FHRV. As fetal acidosis deepened, FHRV decreased: fetuses with significant birth acidosis had, after an initial increase, a drop in spectral powers near delivery, suggesting a breakdown of fetal compensation. Furthermore, a change in excess of 30% of the low-to-high frequency ratio of FHRV was associated with fetal metabolic acidosis. The results suggest that a decrease in the spectral powers of FHRV signals concern for fetal wellbeing. A single measure alone cannot be used to reveal fetal hypoxia since the spectral powers vary widely intra-individually. With technical developments, continuous assessment of intra-individual changes in spectral powers of FHRV might aid in the detection of fetal compromise due to hypoxia.

Theoretical Analysis and Numerical Simulation of Spectral Radiative Properties of Combustion Gases in Oxy/Air-Fired Combustion Systems

Energy efficiency is one of the major objectives which should be achieved in order to implement the limited energy resources of the world in a sustainable way. Since radiative heat transfer is the dominant heat transfer mechanism in most of fossil fuel combustion systems, more accurate insight and models may cause improvement in the energy efficiency of the new designed combustion systems. The radiative properties of combustion gases are highly wavelength dependent. Better models for calculating the radiative properties of combustion gases are highly required in the modeling of large scale industrial combustion systems. With detailed knowledge of spectral radiative properties of gases, the modeling of combustion processes in the different applications can be more accurate. In order to propose a new method for effective non gray modeling of radiative heat transfer in combustion systems, different models for the spectral properties of gases including SNBM, EWBM, and WSGGM have been studied in this research. Using this detailed analysis of different approaches, the thesis presents new methods for gray and non gray radiative heat transfer modeling in homogeneous and inhomogeneous H2O–CO2 mixtures at atmospheric pressure. The proposed method is able to support the modeling of a wide range of combustion systems including the oxy-fired combustion scenario. The new methods are based on implementing some pre-obtained correlations for the total emissivity and band absorption coefficient of H2O–CO2 mixtures in different temperatures, gas compositions, and optical path lengths. They can be easily used within any commercial CFD software for radiative heat transfer modeling resulting in more accurate, simple, and fast calculations. The new methods were successfully used in CFD modeling by applying them to industrial scale backpass channel under oxy-fired conditions. The developed approaches are more accurate compared with other methods; moreover, they can provide complete explanation and detailed analysis of the radiation heat transfer in different systems under different combustion conditions. The methods were verified by applying them to some benchmarks, and they showed a good level of accuracy and computational speed compared to other methods. Furthermore, the implementation of the suggested banded approach in CFD software is very easy and straightforward.

Clonal study of avian Escherichia coli strains by fliC conserved-DNA-sequence regions analysis

The clonal relationship among avian Escherichia coli strains and their genetic proximity with human pathogenic E. coli, Salmonela enterica, Yersinia enterocolitica and Proteus mirabilis, was determined by the DNA sequencing of the conserved 5' and 3'regions fliC gene (flagellin encoded gene). Among 30 commensal avian E. coli strains and 49 pathogenic avian E. coli strains (APEC), 24 commensal and 39 APEC strains harbored fliC gene with fragments size varying from 670bp to 1,900bp. The comparative analysis of these regions allowed the construction of a dendrogram of similarity possessing two main clusters: one compounded mainly by APEC strains and by H-antigens from human E. coli, and another one compounded by commensal avian E. coli strains, S. enterica, and by other H-antigens from human E. coli. Overall, this work demonstrated that fliC conserved regions may be associated with pathogenic clones of APEC strains, and also shows a great similarity among APEC and H-antigens of E. coli strains isolated from humans. These data, can add evidence that APEC strains can exhibit a zoonotic risk.