A model of fracture in reinforced concrete arches based on lumped damage mechanics

A simplified model of cracking and damage in RC circular elements is proposed. The model can be used for the structural assessment of arches and rings. The constitutive equations are based on lumped damage mechanics which is an adaptation of fracture and continuum damage mechanics to the theory of frames with plastic hinges. An arch element is assumed to be the assemblage of an elastic circular component and two inelastic hinges where the main inelastic effects, plastic yielding of the longitudinal reinforcement and concrete cracking, are concentrated. Deformations in the elastic part are assumed to be small but the model may include some geometrically nonlinear effects due to large displacements or rotations of the hinges. The numerical examples presented in the paper show that the model describes correctly the global behavior of two structures including the softening phase.     

Photochemical Properties of trans‐[Ru(NH3)4(bpa)(L)]2+ (L = py,isn, 4‐acpy or 4‐pic)

Photochemical reactions of ruthenium (II) complexes of type trans‐[Ru(NH₃)₄LL']²⁺, where L is a nitrogenous heterocyclic ligand, pyridine (py), isonicotinamide (isn), 4‐acetylpyridine (4‐acpy) or 4‐picoline (4‐pic), and L´ is a 1,2‐bis(4‐pyridyl)ethane (bpa) ligand, were studied with the purpose of evaluating the ligand exchange when, in solution, the complexes are irradiated at the wavelengths of 365, 436, 480 and 519 nm. The study revealed that at lower wavelengths, a labilization process is observed for py and 4‐pic ligands, even at low quantum yields, indicating the dependence of the photolabeling process on the wavelength. The study also reveals that for the filters of greater wavelength, the processes of photolabilization do not occur for any of the studied complexes. The study also shows that there are no photolization processes for the complexes obtained with the isn and 4‐acpy ligands, and it is therefore possible to classify them as nonreactive.     

Electrical,structural and thermal properties of new conductive blends (PANICG) based on polyaniline and cashew gum for organic electronic

Journal of Thermal Analysis and Calorimetry - The application of cashew gum, in particular the one which is abundant in northeastern Brazil, remains limited to the foods and pharmaceutics industry....     

Electrospray ionization mass spectrometric analysis of newly synthesized α,β‐unsaturated γ‐lactones fused to sugars

Knowledge of the fragmentation mechanisms of lactones and their behaviour under electrospray ionization (ESI) conditions can be extended to larger and more complex natural products that contain an α,β‐unsaturated γ‐lactone moiety in their structure. Moreover, little is known about the gas‐phase behaviour of α,β‐unsaturated γ‐lactones linked or fused to sugars. Therefore, five α,β‐unsaturated γ‐lactones (butenolides) fused to a pyranose ring, recently synthesized compounds with potential relevance regarding their biological properties, were investigated using ESI‐MS and ESI‐MS/MS in both positive and negative ion modes. Their fragmentation mechanisms and product ion structures were compared. It was observed that two isomers could be unambiguously distinguished in the negative ion mode by the fragmentation pathways of their deprotonated molecules as well as in the positive ion mode by the fragmentation pathways of either the protonated or the sodiated molecule. Fragmentation mechanisms are proposed taking into account the MS/MS data and semi‐empirical calculations using the PM6 Hamiltonean. The semi‐empirical calculations were also very useful in determining the most probable protonation and cationization sites. Copyright © 2010 John Wiley & Sons, Ltd.     

Radionuclide, Metal and Non-metal Levels in Percolated Water from Soils Fertilized with Phosphogypsum

Phosphogypsum (PG) is a by-product of the phosphate fertilizer industry, which is produced by precipitation during the wet process of phosphate rocks. While commercial uses, in agriculture and in manufacturing gypsum board and Portland cement, consume less than a few percent of this by-product, the vast majority is disposed of on land in gypsum. In Brazil, three main industries are responsible for the production and storage of about 5.5 × 10⁶ tons per year. PG may contain trace metals, non-metals, fluorides and natural radionuclides. Since, in Brazil, PG has been used for many years as soil amendment, it is important to know its availability, mainly in aquatic environments used for human consumption. In this case, more restrictive limits must be adopted. This work aimed to evaluate the mobility of metals in sand and clayey soils and, consequently, the contamination of drainage water through greenhouse-scale leaching and transport of toxic elements and radionuclides from soils fertilized with PG to crops. In general, it was observed that elemental concentrations were below the actual detection limit of the equipment for all conditions of interest, indicating a low mobility of the analyzed elements in the soil.     

Flavonoid–matrix cluster ions in MALDI mass spectrometry

The behaviour of 2,5‐dihydroxybenzoic acid (2,5‐DHB) matrix under matrix‐assisted laser desorption/ionisation (MALDI) conditions was investigated, and the formation of 2,5‐DHB cluster ions, mainly dehydrated 2,5‐DHB ions, is reported. Interestingly, in the mass spectra of this compound, besides dimers and trimers, protonated tetramers, pentamers, hexamers and heptamers were also found with significant abundance. The MALDI behaviour of four flavonoids, quercetin, myricetin, luteolin and kaempferol, using 2,5‐DHB as matrix, was also investigated. The mass spectra of the flavonoids studied revealed a number of flavonoid–2,5‐DHB cluster ions (mainly with the dehydrated 2,5‐DHB). The number of clusters formed is dependent on the structure of the analyte. For luteolin and kaempferol, in particular, evidence was found for the formation of cluster ions involving retro Diels Alder fragments and intact flavonoids molecules, as well as the corresponding protonated retro Diels Alder fragments with dehydrated DHB molecules. All ion compositions were attributed taking into account high accuracy mass measurements and tandem mass spectrometry experiments. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of hydroxylated polycyclic aromatic hydrocarbons in urine using comprehensive two-dimensional gas chromatography with a flame ionization detector

The determination of polycyclic aromatic hydrocarbon (PAH) metabolites in human urine is the method of choice for assessing exposure to carcinogenic compounds. The objective of this study was the development of a comprehensive two-dimensional gas chromatography (GC × GC) method using a flame ionisation detector (FID) to simultaneously determine 10 hydroxylated PAH. The method was based on enzymatic deconjugation, liquid–liquid extraction, and trimethylsilyl (TMS) derivatization of the analytes by microwave heating. Satisfactory separation was achieved. The coefficient of variance was 3.8–12.8%. LOD was 0.03–0.18 μg/L, and LOQ was 0.1–0.5 μg/L. The mean recovery was 76%. The method was applied to the analysis of urine from smokers and non-smokers.     

The Noncommutative Harmonic Oscillator Based on Symplectic Representation of Galilei Group

We study symplectic unitary representations for the Galilei group and derive the Schrödinger equation in phase space. Our formalism is based on the noncommutative structure of the star product. Guided by group theoretical concepts, we construct a physically consistent phase-space theory in which each state is described by a quasi-probability amplitude associated with the Wigner function. As applications, we derive the Wigner functions for the 3D harmonic oscillator and the noncommutative oscillator in phase space.     

Determination of cadmium, chromium and lead in marine sediment slurry samples by electrothermal atomic absorption spectrometry using permanent modifiers

A procedure for the determination of cadmium, chromium, and lead in marine sediment slurries by electrothermal atomic absorption spectrometry is proposed. Slurry was prepared by mixing 10 mg of ground sample with particle size smaller than 50 μm completed to the weight of 1.0 g with a 3% nitric acid and 10% hydrogen peroxide solution. The slurry was maintained homogeneous with an aquarium air pump. For cadmium, the best results were obtained using iridium permanent with optimum pyrolysis and atomization temperatures of 400 and 1300 °C, respectively, a characteristic mass, m_o (1% absorption), of 2.3 pg (recommended 1 pg). Without modifier use, zirconium, ruthenium, and rhodium m_o were 3.4, 4.1, 4.6, and 4.8 pg, respectively. For chromium, the most sensitive condition was obtained with zirconium permanent with optimum pyrolysis and atomization temperatures of 1500 and 2500 °C, m_o of 6.6 pg (recommended 5.5 pg); and without modifier use, rhodium, iridium, and ruthenium m_o were 5.3, 8.8, 8.8, and 8.9 pg, respectively. For lead, the best modifier was also zirconium, m_o of 8.3 pg for the optimum pyrolysis and atomization temperatures of 600 and 1400 °C, respectively, (recommended m_o of 9.0 pg). For iridium, ruthenium, without modifier, and rhodium, m_o were 14.7, 15.5, 16.5, and 16.5 pg, respectively. For all the modifiers selected in each case, the peaks were symmetrical with r² higher than 0.99. Being analyzed (n = 10), two marine sediment reference materials (PACS-2 and MESS-2 from NRCC), the determined values, μg l⁻¹, and certified values in brackets, were 2.17 ± 0.05 (2.11 ± 0.15) and 0.25 ± 0.03 (0.24 ± 0.01) for cadmium in PACS-2 and MESS-2, respectively. For chromium in PACS-2 and MESS-2 the values were 94.7 ± 5.6 (90.7 ± 4.6) and 102.3 ± 10.7 (106 ± 8), respectively. Finally, for lead in PACS-2 and MESS-2, the results obtained were 184 ± 7 (183 ± 8) and of 25.2 ± 0.40 (21.9 ± 1.2), respectively. For cadmium and lead in both samples and chromium in PACS-2, calibration was accomplished with aqueous calibration curves. For chromium in MESS-2, only with the standard addition technique results were in agreement with the certified ones. The limits of detection (k = 3, n = 10) obtained with the diluents were 0.1, 3.4, and 3.6 μg l⁻¹ for cadmium, chromium, and lead, respectively.     

Effects of low-level laser irradiation in ultrastructural morphology, and immunoexpression of VEGF and VEGFR-2 of rat masseter muscle

The present study evaluates by ultrastructural and immunohistochemical methods, the possible changes on muscular tissue affected by LLLI during a treatment, for example, in cases of temporomandibular joint disorders. Sixty male Wistar rats divided into 6 groups (n=10) received ten laser irradiations, with different energy densities (groups I-0; II-0.5; III-1.0; IV-2.5; V-5.0; and VI-20 J/cm(2)). Muscles were removed and processed for transmission electron microscopic and immunohistochemical (VEGF and VEGFR-2) analyses. Captured photomicrographs of immunohistochemistry and transmission electron microscopy were evaluated. It was observed in the irradiated muscles, mitochondria of different shapes and sizes, with increased plasticity evidenced by organelles in fusion, division and the presence of elongated structures with characteristics of mitochondria, proximity with the dilated sarcoplasmatic reticulum, suggesting organelles with large amounts of energy, and the presence of cytoplasmic protrusions in the capillaries with high dosages. All studied groups showed immunostainings for both markers (VEGF and VEGFR-2), but in general those who received higher doses also showed the markings more pronounced, suggesting dose-dependent biomodulation. It was concluded that the LLLI was able to modify the ultrastructural characteristics and immunohistochemical pattern of VEGF and VEGFR-2 in the masseter muscle of rats.