Application of chemometric methods in the evaluation of chemical and spectroscopic data on organic matter from Oxisols in sewage sludge applications

Chemometric methods can contribute to soil research by permitting the extraction of more information from the data. The aim of this work was to use Principal Component Analysis to evaluate data obtained through chemical and spectroscopic methods on the changes in the humification process of soil organic matter from two tropical soils after sewage sludge application. In this case, humic acids extracted from Typic Eutrorthox and Typic Haplorthox soils with and without sewage sludge application for 7 consecutive years were studied. The results obtained for all of the samples and methods showed two clusters: samples extracted from the two soil types. These expected results indicated the textural difference between the two soils was more significant than the differences between treatments (control and sewage sludge application) or between depths. In this case, an individual chemometric treatment was made for each type of soil. It was noted that the characterization of the humic acids extracted from soils with and without sewage sludge application after 7 consecutive years using several methods supplies important results about changes in the humification degree of soil organic matter, These important result obtained by Principal Component Analysis justify further research using these methods to characterize the changes in the humic acids extracted from sewage sludge-amended soils. (C) 2009 Elsevier B.V. All rights reserved.

A broad study of two new promising antimycobacterial drugs: Ag(I) and Au(I) complexes with 2-(2-thienyl)benzothiazole

Synthesis, characterization, DFT simulation and biological assays of two new metal complexes of 2-(2-thienyl)benzothiazole - BTT are reported. The complexes [Ag(BTT)(2)NO3] - AgBTT2 and [Au(BTT)Cl]center dot 1/2H(2)O - AuBTT were obtained by mixing the ligand with silver (I) nitrate or gold(I) chloride in methanolic solution. Characterization of the complexes were based on elemental (C, H, N and S), thermal (TG-DTA) analysis, C-13 and H-1 NMR, FT-IR and UV-Vis spectroscopic measurements, as well as the X-ray structure determination for AgBTT2. Spectroscopic data predicted by DFT calculations were in agreement with the experimental data for both complexes. The ligand BTT was synthesized by the condensation of 2-thiophenecarboxaldehyde and 2-aminothiophenol in a microwave furnace. AgBTT2 has a monomeric structure. Both complexes show a good activity against Mycobacterium tuberculosis. Free BIT shows low antitubercular activity. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis, X-ray structure and antimycobacterial activity of silver complexes with alpha-hydroxycarboxylic acids

In this paper, synthesis, characterization and antimycobacterial properties of a new water-soluble complex identified as silver-mandelate are described. Elemental and thermal analyses are consistent with the formula [Ag(C6H5C(OH)COO)](n). The polymeric structure was determined by single X-ray diffraction and the two-dimensional structure is based on the bis(carboxylate-O,O') dimer [Ag-O, 2.237(3), 2.222(3) angstrom]. The structure is extended along both the b and c axes through two oxygen atoms of a bidentate alpha-hydroxyl-carboxylate residue [Ag-OH(hydroxyl), 2.477(3) angstrom; Ag-O(carboxylate), 2.502(3) angstrom; O-Ag-O, 63.94(9)degrees]. A strong d(10)-d(10) interaction was observed between two silver atoms. The Ag...Ag distance is 2.8307(15) angstrom. The NMR C-13 spectrum in D2O shows that coordination of the ligand to Ag(l) occurs through the carboxylate group in solution. Potentiometric titration shows that only species with a molar metaHigand ratio of 2:2 are formed in aqueous solution. The mandelate complex and the silver-glycolate, silver-malate and silver-hydrogen-tartarate complexes were tested against three types of mycobacteria, Mycobacterium avium, Mycobacterium tuberculosis and Mycobacterium kansasii, and their minimal inhibitory concentration (MIC) values were determined. The results show that the four complexes are potential candidates for antiseptic or disinfectant drugs for discharged secretions of patients affected with tuberculosis. (c) 2006 Published by Elsevier B.V.

Modeling a system of phosphated cross-linked high amylose for controlled drug release. Part 1: Synthesis and polymer characterization

High amylose was cross-linked with sodium trimetaphosphate (STMP) using 2% and 4% solutions of NaOH at room temperature with reaction contact times of 0.5, 1, 2 and 4 h. The different polymers obtained were analyzed by FT IR, C-13 and P-31 solid state NMR, SEM and C, H and P elemental analysis. The results were used to propose a two-stage mechanism for phosphate incorporation, the first being kinetically controlled. (C) 2008 Elsevier Ltd. All rights reserved.

An Oligosilsesquioxane Cage Functionalized with Molybdenum(II) Organometallic Fragments

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

Micromorphology and spectroscopic characteristics of organic matter in waterlogged podzols of the upper Amazon basin

In waterlogged environments of the upper Amazon basin, organic matter is a major driver in the podzolisation of clay-depleted laterites, especially through its ability to weather clay minerals and chelate metals. Its structure in eight organic-rich samples collected at the margin and in the centre of the podzolic area of a soil sequence was investigated. The samples illustrate the main steps in the development of waterlogged podzols and belong either to eluviated topsoil A horizons or to illuviated subsoil Bhs, Bh and 2BCs horizons. Organic matter micromorphology was described, and the overall molecular structure of their clay size fractions was assessed using Fourier transform infrared (FTIR) spectroscopy and cross polarization/magic angle spinning (CP/MAS) C-13 nuclear magnetic resonance (NMR). Organic features of the horizons strongly vary both vertically and laterally in the sequence. Topsoil A horizons are dominated by organic residues juxtaposed to clean sands with a major aliphatic contribution. In the subsoil, numerous coatings, characteristic of illuviation processes, are observed in the following horizons: (i) At the margin and bottom parts of the podzolic area, dark brown organic compounds of low aromacity with abundant oxygen-containing groups accumulate in Bhs and 2BCs horizons. Their spectroscopic features agree with the observation of cracked coatings in 2BCs and the presence of organometallic complexes, whose abundance decreases towards low lying positions. (ii) By contrast, black organic compounds of high aromacity with few chelating functions accumulate as coatings and infills in the overlying sandy Bh horizon of well-expressed waterlogged podzols. (c) 2008 Elsevier B.V. All rights reserved.

Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part I

This work describes the synthesis, IR and (13)C CPMAS NMR spectroscopic as well the thermal characterization of the new dicarboxylate complexes [Pd(2)(ox)(2)(4,4'-bipy)]n (1), [Pd(2)(ox)(2)(bpe)](n) (2) and [Pd(2)(ox)(2)(pz)](n) (3) {ox = oxalate, bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane, pz = pyrazine}. TG experiments reveal that compounds 1-3 undergo thermal decomposition in three steps. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part II

The synthesis and thermal behavior of the new [Pd(fum)(bipy)] (n) center dot 2nH(2)O (1), [Pd(fum)(bpe)] (n) center dot nH(2)O (2) and [Pd(fum)(pz)] (n) center dot 3nH(2)O (3) {bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and (13)C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46-491 A degrees C. In all the cases, metallic palladium was identified as the final residue.

Evolution of rheological properties and local structure during gelation of siloxane-polymethylmethacrylate hybrid materials

Hybrid siloxane-polymethylmethacrylate (PMMA) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (polymer) phases were prepared by the sot gel process through hydrolysis and polycondensation of 3-(trimethoxysilyl)propylmethacrylate (TMSM) and polymerization of methylmethacrylate (MMA) using benzoyl peroxide (BPO) as initiator. The effect of MMA, BPO and water contents on the viscoelastic behaviour of these materials was analysed during gelation by dynamic rheological measurements. The changes in storage (G') and loss moduli (G), complex viscosity (eta*) and phase angle (6) were measured as a function of the reaction time showing the viscous character of the sot in the initial step of gelation and its progressive transformation to an elastic gel. This study was complemented by Si-29 and C-13 solid-state nuclear magnetic resonance (NMR/MAS) measurements of dried gel. The analysis of the experimental results shows that linear chains are formed in the initial step of the gelation followed by a growth of branched structures and formation of a three-dimensional network. Near the gel point this hybrid material demonstrates the typical scaling behaviour expected from percolation theory.

Anxiolytic effects of erythrinian alkaloids from Erythrina mulungu

One new erythrinian alkaloid derivative, (+)-11 alpha-hydroxyerythravine (1), and the known (+)-erythravine (2) and (+)-alpha-hydroxyerysotrine (3) were isolated from the flowers of Erythrina mulungu. Their structures were determined by spectroscopic/spectrometric data interpretation of H-1, C-13, and 2D NMR and MS experiments. The relative configuration was established by NOESY analysis, while the conformation adopted by these molecules was evaluated through molecular modeling studies and coupling constants obtained by NMR analysis. Furthermore, the anxiolytic effects of the E. mulungu aqueous alcoholic crude extract and of the purified alkaloids were evaluated using the elevated T-maze test.

Studies on the constituents of a Brazilian folk infusion. Isolation and structure elucidation of new triterpene saponins from Ilex amara leaves

The isolation of three new triterpene saponins 3beta-O-beta-D-glucopyranosyl-(1-->3)-alpha-L-2-O-acetylara-binopyranosylolean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (2), 3beta-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-O-arabinopyranosylurs-12-en-28-oic acid (3), and 3beta-O-beta-D-glucopyranosyl-(1-->2)-beta-D-O-galactopyranosylurs-12-en-28-oic acid (4) together with five known saponins and one flavonoid glycoside from the aqueous infusion of flex amara (Vellozo) Loes. leaves is reported. All structures were elucidated by spectroscopic methods, including the concerted application of one-dimensional (H-1, TOCSY, C-13, and C-13 DEPT NMR) and two-dimensional NMR techniques (DQF-COSY, HSQC, and HMBC).

Solid-state and solution structural study of acetylacetone-modified tin(IV) chloride used as a precursor of SnO2 nanoparticles prepared by a sol-gel route

The effect of addition of different amounts of acetylacetone (acacH) on the species formed at room temperature and after thermohydrolysis at 70 degreesC for 30 and 120 min of ethanolic SnCl4.5H(2)O solutions is followed by EXAFS spectroscopy at the Sn K-edge. We show that thermohydrolyzed solutions are a mixture of SnO2 nanoparticles and soluble tin polynuclear species. The complexation of the tin molecular precursors by acetylacetonate ligands is evidenced by H-1, C-13, and Sn-119 NMR spectroscopy and EXAFS for a acacH/Sn ratio higher than 2. Single crystals are isolated from solution and the structure, determined by X-ray diffraction, is built up from monomeric Cl-3(H2O)Sn(acac)-H2O units bridged together by hydrogen bonding. The acacH/Sn ratio in solution controls the polycondensation of the hydrolyzed species but not the crystallite size of the SnO2 nanoparticles (similar to2 nm). Because of the major presence of chelated tin mono- and dimeric complexes in solution for acacH/Sn > 2, the condensation is almost inhibited, meanwhile the decrease of amount of chelated complexes for the acacH/Sn < 2 gives rise to an increase of the number of nanoparticles.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

A laser-induced fluorescence spectroscopic study of organic matter in a Brazilian Oxisol under different tillage systems

Laser-induced fluorescence (LIF) spectroscopy has been proposed as new method for determining the degree of humification of organic matter (OM) in whole soils. It can be also used to analyze the OM in whole soils containing large amounts of paramagnetic materials, and which are neither feasible to Electron Paramagnetic Resonance (EPR) nor to C-13 Nuclear Magnetic Resonance (NMR) spectroscopy. In the present study, 3 LIF spectroscopy was used to investigate the OM in a Brazilian Oxisol containing high concentration of Fe+3. Soil samples were collected from two areas under conventional tillage (CT), two areas under no-till management (NT) and from a non-cultivated (NC) area under natural vegetation. The results of LIF spectroscopic analysis of the top layer (0-5 cm) of whole soils showed a less aromatic OM in the non-cultivated than in the cultivated soils. This is consistent with data corresponding to HA samples extracted from the same soils and analyzed by EPR, NMR and conventional fluorescence spectroscopy. The OM of whole soils at 5-10 and 10-20 cm depth was also characterized by LIF spectroscopy.Analysis of samples of NT and NC soils showed a higher OM aromatic content at depth. This is a consequence of the accumulation of plant residues at the soil surface in quantities that are too large for microorganisms to metabolize fully, thus, resulting in less aromatic or less hurnified humic substances. In deeper soil layers, the input of residues was lower and further decomposition of humic substances by microorganisms continued, and the aromaticity and degree of humification increased with soil depth. This data indicates that the gradient of humification of OM in the NT soil was similar to those observed in natural soils. Nevertheless, the degree of humification of the OM in the soils under no-till management varied less than that corresponding to non-cultivated soils. This may be because the former have been managed under these practices for only 5 years, in contrast to the continuous humification process occurring in the natural soils. on the other band, LIF spectroscopic analysis of the CT soils showed less pronounced changes or no change in the degree of humification with depth. This indicates that the ploughing and harrowing involved in CT lead to homogenization of the soil and thereby also of the degree of humification of OM throughout the profile. (c) 2006 Elsevier B.V. All rights reserved.