Direct assembly of a metallodendrimer encompassing seven triruthenium clusters units

A general strategy for the assembly of dendrimeric metallo-cluster species based on tritopic trinuclear ruthenium acetate complexes is demonstrated. First, a central core consisting of a [Ru3O(CH3COO)(6)(TPEB)(3)]PF6 complex (G0), where TPEB is the tripodal 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene ligand, was synthesized and then reacted with the end-capping complex [Ru3O(CH3COO)(6)(py)(2)(MeOH)]PF6, thus composing the first generation shell of a dendrimer encompassing twenty-one ruthenium ions (G1). The core and dendrimeric complexes were characterized by elemental analysis, UV-Vis, H-1 NMR, ESI-MS spectrometry and Differential pulse voltammetry. All results were consistent with the structure of that multinuclear cationic dendrimeric species. The isotopologic profile of daughter fragments and the strength of the metal-ligand bonds were carefully investigated providing the fragmentation pathway for the metallo-dendrimer upon ESI-MS dissociation conditions. (C) 2012 Elsevier B.V. All rights reserved.

Evaluation of the biocide activity of phosphorylated and sulfophosphorylated resins

Phosphorylated poly(styrene-co-divinylbenzene) copolymers prepared by aromatic electrophilic substitution reaction with PCl3/AlCl3 were reacted with carbon dissulfite in order to introduce sulfophosphorylated groups into copolymers. These modifications were characterized by FTIR, elemental analysis, spectrophotometry, optical and scanning electron microscopy. The antibacterial activities of the phosphorylated and sulfophorylated copolymers were assessed against Escherichia coli ATCC25922 suspensions (10(3)-10(7) cells mL(-1)) using a column system. The unmodified copolymers did not have antibacterial activity against the E. coil suspensions but the phosphorylated and sulfophorylated copolymers showed significant bactericidal action for all E. coli concentrations. The sulfophosphorylated copolymers had higher antibacterial activity than the phosphorylated ones, mainly for high concentrations of E. coli cells. Published by Elsevier B.V.

Spectroscopic characterization and crystal structure of cis-Bis(N-(2-benzoyl)-N ',N '-diphenylthioureato-k O-2,S)nickel(II)

The title compound [Ni(C20H15N2OS)(2)] is prepared by the reaction of metal acetate with the corresponding acylthiourea derivative. The complex is characterized by elemental analysis, IR, H-1 and C-13 NMR, and its structure is determined by single crystal X-ray diffraction. The Ni(II) ion is coordinated by the S and O atoms of two N-benzoyl-N',N'-diphenylthiourea ligands in a slightly distorted square-planar coordination geometry. The two O and two S atoms are mutually cis to each other. The substance crystallizes triclinic (P-1 space group) with cell dimensions a = 10.7262(9) , b = 12.938(3) , c = 14.2085(12) , alpha = 74.650(4)A degrees, beta = 78.398(4)A degrees, gamma = 68.200(5)A degrees, and two formula units in the unit cell. The structure is very close to the related N-(2-furoyl) Ni complex reported previously.

Structural, Spectroscopic (NMR, IR, and Raman), and DFT Investigation of the Self-Assembled Nanostructure of Pravastatin-LDH (Layered Double Hydroxides) Systems

Layered double hydroxide (LDH) nanocontainers, suitable as carriers for anionic drugs, were intercalated with Pravastatin drug using magnesium-aluminum and zinc-aluminum in a M-II/Al molar ratio equal 2 and different Al3+/Pravastatin molar ratios. Postsynthesis treatments were used in order to increase the materials crystallinity. Hybrid materials were characterized by a set of physical chemical techniques: chemical elemental analysis, X-ray diffraction (XRD), mass coupled thermal analyses, vibrational infrared and Raman spectroscopies, and solid-state C-13 nuclear magnetic resonance (NMR). Results were interpreted in light of computational density functional theory (DFT) calculations performed for Sodium Pravastatin in order to assign the data obtained for the LDH intercalated materials. XRD peaks of LDH-Pravastatin material and the one-dimensional (1D) electron density map pointed out to a bilayer arrangement of Pravastatin in the interlayer region, where its associated carboxylate and vicinal hydroxyl groups are close to the positive LDH. The structural organization observed for the stacked assembly containing the unsymmetrical and bulky monoanion Pravastatin and LDH seems to be promoted by a self-assembling process, in which local interactions are maximized and chloride ion cointercalation is required. It is observed a high similarity among vibrational and C-13 NMR spectra of Na-Pravastatin and LDH-Pravastatin materials. Those features indicate that the intercalation preserves the drug structural integrity. Spectroscopic techniques corroborate the nature of the guest species and their arrangement between the inorganic layers. Changes related to carboxylate, alcohol, and olefinic moieties are observed in both vibrational Raman and C-13 NMR spectra after the drug intercalation. Thus, Pravastatin ions are forced to be arranged as head to tail through intermolecular hydrogen bonding between adjacent organic species. The thermal decomposition profile of the hybrid samples is distinct of that one observed for Na-Pravastatin salt, however, with no visible increase in the thermal behavior when the organic anion is sequestrated within LDH gap.

Crystal structure and spectroscopic properties of polymeric adducts of the tetra-mu-haloaspirinate-dicopper(II)

Eight new copper(II) complexes with halo-aspirinate anions have been synthesized: [Cu-2(Fasp)(4)(MeCN)(2)] center dot 2MeCN (1), [Cu-2(Clasp)(4)(MeCN)(2)]center dot 2MeCN (2), [Cu-2(Brasp)(4) (MeCn)(2)] center dot 2MeCn (3), {[Cu-2(Fasp)(4)(Pyrz)] center dot 2MeCN}(n) (4) {[Cu-2(Clasp)(4)(Pyrz)] center dot 2MeCN}(n) (5), [Cu-2(Brasp)(4)(Pyrz)](n) (6), [Cu-2(Clasp)(4)(4,4'-Bipy)](n) (7), and [Cu-2(Brasp)(4)(4,4'-Bipy)](n) (8) (Fasp: fluor-aspirinate; Clasp: chloro-aspirinate; Brasp: bromo-aspirinate; MeCN: acetonitrile; Pyrz: pyrazine; 4,4'-Bipy: 4,4'-bipyridine). The crystal structure of two 2 and 4 have been determined by X-ray diffraction methods. All compounds have been studied employing elemental analysis, IR, and UV-Visible spectroscopic techniques. The results have been compared with previous data reported for complexes with similar structures.

Structure and luminescent investigation of the Ln(III)-beta-diketonate complexes containing tertiary amides

The synthesis and photoluminescent properties of Ln(III)-thenoyltrifluoroacetonate and dibenzoylmethanate complexes (Ln = Eu(III) and Gd(III) ions) containing tertiary amides such as dimethylacetamide (DMA), dimethylformamide (DMF), and dimethylbenzamide (DMB) as neutral ligands are reported. The Ln complexes were characterized by elemental analysis, complexometric titration with EDTA, and infrared spectroscopy. Single-crystal X-ray structure data of the [Eu(DBM)(3).(DMA)] compound indicates that this complex crystallizes in the triclinic system, space group PT with the following cell parameters: a = 10.2580(3) angstrom, b = 10.3843(2) angstrom, c= 22.3517(5) angstrom, alpha = 78.906(2)degrees, beta = 78.049(2)degrees, lambda= 63.239(2)degrees, V= 2066.41(9) angstrom(3), and Z = 2. The coordination polyhedron for the Eu(III) complex may be described as an approximate C-2v distorted monocapped trigonal prism. The optical properties of the Eu(III) complexes were studied based on the intensity parameters and luminescence quantum yield (q). The values of the ohm(2) parameter of the Eu-DBM complexes are larger than those for the Eu-TTA complexes, indicating that the Eu(III) ion is in a more polarizable chemical environment in the former case. The geometries of the complexes have been optimized by using the Sparkle Model, and the results have been used to perform theoretical predictions of the ligand-to-metal energy transfer via direct and exchange Coulomb mechanisms. (C) 2012 Elsevier Ltd. All rights reserved.

Thiosaccharine disulfide: synthesis, crystal structure, spectroscopic characterization and theoretical study

The title compound, (thiosaccharine disulfide), bis[1,10dioxide-2,3-dihidro-1,2-benzoisothiazol]disulfide, (tsac)2 has been synthesized and fully characterized by UV–Visible, IR, Raman, 1H and 13C NMR spectroscopy elemental analysis and structural X-ray crystallography. A DFT theoretical study has been performed and good agreement between experimental and theoretical values of structural parameters and vibration frequencies have been achieved.

CRITICAL APPLICATIONS OF SW 846 US EPA METHODS TO EVALUATION OF MARINE SAMPLES QUALITY

Technical evaluation of analytical data is of extreme relevance considering it can be used for comparisons with environmental quality standards and decision-making as related to the management of disposal of dredged sediments and the evaluation of salt and brackish water quality in accordance with CONAMA 357/05 Resolution. It is, therefore, essential that the project manager discusses the environmental agency`s technical requirements with the laboratory contracted for the follow-up of the analysis underway and even with a view to possible re-analysis when anomalous data are identified. The main technical requirements are: (1) method quantitation limits (QLs) should fall below environmental standards; (2) analyses should be carried out in laboratories whose analytical scope is accredited by the National Institute of Metrology (INMETRO) or qualified or accepted by a licensing agency; (3) chain of custody should be provided in order to ensure sample traceability; (4) control charts should be provided to prove method performance; (5) certified reference material analysis or, if that is not available, matrix spike analysis, should be undertaken and (6) chromatograms should be included in the analytical report. Within this context and with a view to helping environmental managers in analytical report evaluation, this work has as objectives the discussion of the limitations of the application of SW 846 US EPA methods to marine samples, the consequences of having data based on method detection limits (MDL) and not sample quantitation limits (SQL), and present possible modifications of the principal method applied by laboratories in order to comply with environmental quality standards.

Synthesis Methodology Applied to a Tunable Patch Filter With Independent Frequency and Bandwidth Control

A new methodology for the synthesis of tunable patch filters is presented. The methodology helps the designer to perform a theoretical analysis of the filter through a coupling matrix that includes the effect of the tuning elements used to tune the filter. This general methodology accounts for any tuning parameter desired and was applied to the design of a tunable dual-mode patch filter with independent control of center frequency and bandwidth (BW). The bandpass filter uses a single triangular resonator with two etched slots that split the fundamental degenerate modes and form the filter passband. Varactor diodes assembled across the slots are used to vary the frequency of each degenerate fundamental mode independently, which is feasible due to the nature of the coupling scheme of the filter. The varactor diode model used in simulations, their assembling, the dc bias configuration, and measured results are presented. The theory results are compared to the simulations and to measurements showing a very good agreement and validating the proposed methodology. The fabricated filter presents an elliptic response with 20% of center frequency tuning range around 3.2 GHz and a fractional BW variation from 4% to 12% with low insertion loss and high power handling with a 1-dB compression point higher than +14.5 dB.

Performance of an electronic tongue during monitoring 2-rnethylisoborneol and geosmin in water samples

2-Methylisoborneol (MIB) and geosmin (GSM) are sub products from algae decomposition and, depending on their concentration, can be toxic: otherwise, they give unpleasant taste and odor to water. For water treatment companies it is important to constantly monitor their presence in the distributed water and avoid further costumer complaints. Lower-cost and easy-to-read instrumentation would be very promising in this regard. In this study, we evaluate the potentiality of an electronic tongue (ET) system based on non-specific polymeric sensors and impedance measurements in monitoring MIB and GSM in water samples. Principal component analysis (PCA) applied to the generated data matrix indicated that this ET was capable to perform with remarkable reproducibility the discrimination of these two contaminants in either distilled or tap water, in concentrations as low as 25 ng L-1. Nonetheless, this analysis methodology was rather qualitative and laborious, and the outputs it provided were greatly subjective. Also, data analysis based on PCA severely restricts automation of the measuring system or its use by non-specialized operators. To circumvent these drawbacks, a fuzzy controller was designed to quantitatively perform sample classification while providing outputs in simpler data charts. For instance, the ET along with the referred fuzzy controller performed with a 100% hit rate the quantification of MIB and GSM samples in distilled and tap water. The hit rate could be read directly from the plot. The lower cost of these polymeric sensors allied to the especial features of the fuzzy controller (easiness on programming and numerical outputs) provided initial requirements for developing an automated ET system to monitor odorant species in water production and distribution. (C) 2012 Elsevier B.V. All rights reserved.

Mapeamento de solos e da produtividade de plantações de Eucalyptus grandis, com uso de sistema de informação geográfica

Detailed environmental land characterization is essential for technical and financial planning, for both the scientific point of view and technological application. This work aimed at the physiographic and pedological characterization and eucalyptus productivity mapping at Itatinga Forest Sciences Experimental Station (southeastern Brazil), using geographic information systems in order to identify possible cause-effect relationships between forest productivity and soil attributes. The digital cartographic dataset was structured as follows: as primary source of data, aerial photograph and field survey were used and, as a secondary source, topographical, geological and land use occupation maps were used. For mapping wood productivity at age six (MAI6, Mean Annual Increment), inventory data of permanent plots (same species, provenance and age) were used, which were obtained from Eucalyptus grandis plantations. Using simple linear correlation and backward stepwise multiple regression analysis, the dependent variable (MAI) was related with physical and chemical characteristics of the soils. Two standards of contour curves were identified, one with close curves, narrow and surrounding the drainage network, in the steeper and lower altitude areas; the other, with spaced contour lines, in the areas of higher altitude and with plane relief. Six types of soils were characterized as being highly related to the physiographic patterns of the area: loamy sandy to sandy clayey Typic Hapludox (LVAd, 47.5%), clayey Rhodic Hapludox (LVd1, 33.4%), sandy clay Rhodic Hapludox (LVd2, 6%), clayey Rhodic Hapludox (LVdf, 9.1%), Entisols (G, 3.4%) and Fluvents soil (RY, 0.6%). There were large variations in wood productivity in the Eucalyptus grandis plantations, characterized in six classes, ranging from 26 to 52 m(3) ha(-1) yr(-1). These productivity changes were strictly related to soil mapping units. Through multiple regression analysis, we found that clay and organic matter contents were the attributes which most strongly explained the productivity differences.

Archaeofacies Analysis: Using Depositional Attributes to Identify Anthropic Processes of Deposition in a Monumental Shell Mound of Santa Catarina State, Southern Brazil

In the coast of Santa Catarina State (southern Brazil), a large population of monumental shell mounds characterizes a highly dynamic coastal setting. In this paper, sedimentary facies analysis was adapted for description, sampling, and interpretation of shell mound complex and repetitive archaeostratigraphic successions. Archaeofacies identification in the field, according to depositional attributes, is tested by contrasting field description with multi-element chemical analyses, total carbon and nitrogen determinations, and micromorphological descriptions. Two vertical sequences at the black deposit of Jabuticabeira II shell mound were studied and preliminary results showed that: (1) depositional attributes are a reliable base for archaeofacies identification in the field, (2) the formation process of this site involved a sequence of anthropic depositional processes, where burned refuse was redeposited over the shell mound following a ritual construction pattern, and (3) the black deposit includes a double palimpsest that refers to provenance and meaning of mound construction material. (C) 2009 Wiley Periodicals, Inc.

Comparative analysis of shell occupation by two southern populations of the hermit crab Loxopagurus loxochelis (Decapoda, Diogenidae)

The present study aimed to comparatively verify the relation between the hermit crabs and the shells they use in two populations of Loxopagurus loxochelis. Samples were collected monthly from July 2002 to June 2003, at Caraguatatuba and Ubatuba Bay, Sao Paulo, Brazil. The animals sampled had their sex identified, were weighed and measured; their shells were identified, measured and weighed, and their internal volume determined. To relate the hermit crab's characteristics and the shells' variables, principal component analysis (PCA) and a regression tree were used. According to the PCA analysis, the three gastropod shells most frequently used by L. loxochelis varied in size. The regression tree successfully explained the relationship between the hermit crab's characteristics and the internal volume of the inhabited shell. It can be inferred that the relationship between the morphometry of an individual hermit crab and its shell is not straightforward and it is impossible to explain only on the basis of direct correlations between the body's and the shell's attributes. Several factors (such as the morphometry and the availability of the shell, environmental conditions and inter- and intraspecific competition) interact and seem to be taken into consideration by the hermit crabs when they choose a shell, resulting in the diversified pattern of shell occupancy shown here and elsewhere.

Comparative analysis of shell occupation by two southern populations of the hermit crab Loxopagurus loxochelis (Decapoda, Diogenidae)

The present study aimed to comparatively verify the relation between the hermit crabs and the shells they use in two populations of Loxopagurus loxochelis. Samples were collected monthly from July 2002 to June 2003, at Caraguatatuba and Ubatuba Bay, São Paulo, Brazil. The animals sampled had their sex identified, were weighed and measured; their shells were identified, measured and weighed, and their internal volume determined. To relate the hermit crab's characteristics and the shells' variables, principal component analysis (PCA) and a regression tree were used. According to the PCA analysis, the three gastropod shells most frequently used by L. loxochelis varied in size. The regression tree successfully explained the relationship between the hermit crab's characteristics and the internal volume of the inhabited shell. It can be inferred that the relationship between the morphometry of an individual hermit crab and its shell is not straightforward and it is impossible to explain only on the basis of direct correlations between the body's and the shell's attributes. Several factors (such as the morphometry and the availability of the shell, environmental conditions and inter- and intraspecific competition) interact and seem to be taken into consideration by the hermit crabs when they choose a shell, resulting in the diversified pattern of shell occupancy shown here and elsewhere.