Simple method for determination of cocaine and main metabolites in urine by CE coupled to MS

in this work, a simple method for the simultaneous determination of cocaine (COC) and five COC metabolites (benzoylecgonine, cocaethylene (CET), anhydroecgonine, anhydroecgonine methyl ester and ecgonine methyl ester) in human urine using CE coupled to MS via electrospray ionization (CE-ESI-MS) was developed and validated. Formic acid at 1 mol/L concentration was used as electrolyte whereas formic acid at 0.05 mol/L concentration in 1:1 methanol:water composed the coaxial sheath liquid at the ESI nozzle. The developed method presented good linearity in the dynamic range from 250 ng/mL to 5000 ng/mL (coefficient of determination greater than 0.98 for all compounds). LODs (signal-to-noise ratio of 3) were 100 ng/mL for COC and CET and 250 ng/mL for the other studied metabolites whereas LOQ`s (signal-to-noise ratio of 10) were 250 ng/mL for COC and CET and 500 ng/mL for all other compounds. Intra-day precision and recovery tests estimated at three different concentration levels (500, 1500 and 5000 ng/mL) provided RSD lower than 10% (except anhydroecgonine, 18% RSD) and recoveries from 83-109% for all analytes. The method was successfully applied to real cases. For the positive urine samples, the presence of COC and its` metabolites was further confirmed by MS/MS experiments.

New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3

New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule.

SYNTHESIS, CHARACTERIZATION AND THERMAL ANALYSIS OF 1:1 AND 2:3 LANTHANIDE(III) CITRATES

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL center dot xH(2)O] and [Ln(2)(LH)(3)center dot 2H(2)O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C6O7H5)(3-) and LH for (C6O7H6)(2-). Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL center dot xH(2)O]. The compounds [Ln(2)LH(3)center dot 2H(2)O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C-2v symmetry for the coordination polyhedron of [LnL center dot xH(2)O] and C-4v for [Ln(2)(LH)(3)center dot 2H(2)O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.

CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-LaO(3) for low temperature water-gas shift reaction

This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-La(2)O(3) oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts` activities were tested in the forward WGSR, and the CuO/CeO(2) catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO(2) catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu and Cu(1+) species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst. (c) 2010 Elsevier B.V. All rights reserved.

Biodegradação de hidrocarbonetos aromáticos policíclicos: prospecção metagenômica e modelagem computacional 3-D de proteínas

Knowledge of the native prokaryotes in hazardous locations favors the application of biotechnology for bioremediation. Independent strategies for cultivation and metagenomics contribute to further microbiological knowledge, enabling studies with non-cultivable about the "native microbiological status and its potential role in bioremediation, for example, of polycyclic aromatic hydrocarbons (HPA's). Considering the biome mangrove interface fragile and critical bordering the ocean, this study characterizes the native microbiota mangrove potential biodegradability of HPA's using a biomarker for molecular detection and assessment of bacterial diversity by PCR in areas under the influence of oil companies in the Basin Petroleum Geology Potiguar (BPP). We chose PcaF, a metabolic enzyme, to be the molecular biomarker in a PCR-DGGE detection of prokaryotes that degrade HPA s. The PCR-DGGE fingerprints obtained from Paracuru-CE, Fortim-CE and Areia Branca-RN samples revealed the occurrence of fluctuations of microbial communities according to the sampling periods and in response to the impact of oil. In the analysis of microbial communities interference of the oil industry, in Areia Branca-RN and Paracuru-CE was observed that oil is a determinant of microbial diversity. Fortim-CE probably has no direct influence with the oil activity. In order to obtain data for better understanding the transport and biodegradation of HPA's, there were conducted in silico studies with modeling and simulation from obtaining 3-D models of proteins involved in the degradation of phenanthrene in the transport of HPA's and also getting the 3-D model of the enzyme PcaF used as molecular marker in this study. Were realized docking studies with substrates and products to a better understanding about the transport mechanism and catalysis of HPA s

TNF-alpha, H2O2 and NO response of peritoneal macrophages to Yersinia enterocolitica O : 3 derivatives

In this study, the effect of Yersinia derivatives on nitric oxide (NO), hydrogen peroxide (H2O2) and tumor necrosis factor-alpha (TNF-alpha) production by murine peritoneal macrophages was investigated. Addition of lipopolysaccharide (LPS) to the macrophage culture resulted in NO production that was dose dependent. on the other hand, bacterial cellular extract (CE) and Yersinia outer proteins (Yops) had no effect on NO production. The possible inhibitory effect of Yops on macrophage cultures stimulated with LPS was investigated. Yops partially inhibited NO production (67.4%) when compared with aminoguanidine. The effects of Yersinia derivatives on H2O2 production by macrophages were similar to those on NO production. LPS was the only derivative that stimulated H2O2 release in a dose-dependent manner. All Yersinia derivatives provoked the production of TNF-alpha, but LPS had the strongest effect, as observed for NO production. CE and Yops stimulated TNF-alpha production to a lesser extent than LPS. The results indicate the possibility that in vivo Yops may aid the evasion of the bacteria from the host defense mechanism by impairing the secretion of NO by macrophages. (C) 2003 Elsevier SAS. All rights reserved.

Thermal studies on solid 1,4-bis(3-carboxy-3-oxo-prop-1-enyl) benzene of lighter trivalent lanthanides

Solid-state compounds of general formula Ln(2)L(3)center dot nH(2)O, where L represents 1,4-bis(3-carboxy-3-oxo-prop-1-enyl)benzene and Ln = La, Ce, Pr, Nd, Sm, were synthesized. Complexometric titrations with EDTA, thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, elemental analysis and infrared spectroscopy have been employed to characterize and to study the thermal behavior of these compounds in dynamic air atmosphere. The results led to information about the composition, dehydration, crystallinity, and thermal decomposition of the synthesized compounds.

Estudo da imunoexpressão dos transportadores de glicose 1 e 3 em carcinomas epidermóides de lábio inferior e sua relação com parâmetros clínico-patológicos

The Epidermoid Carcinoma (EC) is the most common lesions located in the region of the head and neck and, despite advances in treatment modalities, the prognosis is still poor. The malignant cells show an increase in glucose uptake, process mediated by glucose transporters (GLUTs). Increased expression of GLUT 1 and GLUT 3 is related to the aggressive behavior of this lesion. The aim of this study was to evaluate, through immunohistochemistry, the expression of GLUTs 1 and 3 in EC of the lower lip. The sample consisted of 40 cases of EC of the lower lip, of which 20 had regional lymph node metastasis and the remaining 20 with absence of metastasis. The percentages of immunostained cells in front of tumor invasion and in the center of tumor were evaluated. These results were related to the presence and absence of lymph node metastasis, TNM classification and histological grading. The percentage of cytoplasmic/membranous expression of GLUT 1 ranged from 77.35% to 100%, while for GLUT 3 this value ranged from 0.79% to 100%. As for nuclear staining for GLUT 1, this percentage ranged from 0 to 0.42%, however. GLUT 3 showed only one case with nuclear staining. Despite the significant expression of tumor cells related to the proteins studied, we observed no statistically significant relationship between the variables and the antibodies analyzed, regardless of the region evaluated. However, there was a moderate positive correlation between cytoplasmic/membranous immunoexpressions of GLUT 1 in invasion front and in the tumor center (r = 0.679, p <0.001). Similarly, moderate positive correlation was found between the nuclear immunoexpressions of GLUT 1 in the invasion front and in the tumor center (r = 0.547, p <0.001). For GLUT 3, was also observed a moderate statistically significant positive correlation between cytoplasmic/membranous expression in tumor invasion front and in tumor center (r = 0.589, p <0.001). We also observed that the immunoreactivity for GLUT 1 was higher than GLUT 3 expression in invasion front (p <0.001) and tumor center (p <0.001). From these results, this study suggests that tumor hypoxia is a remarkable characteristic of the EC of the lower lip and GLUT 1 may be primarily responsible for glucose uptake into the interior of the malignant cells

Parâmetros de fonte de microterremotos em Cascavel-CE

In this dissertation it was studied the rupture characteristic of earthquakes of the Town of Cascavel CE, Northeastern Brazil. Located on the border of the Potiguar Basin, the Town of Cascavel is one of the most seismically active intraplate areas in the country. In this town, on November 20th, 1980 a 5,2mb earthquake occurred. This was the largest earthquake ever reported in Northeast Brazil. Studies of this region using instruments were possible after 1989, with several campaigns being done using seismographic networks. From the beginning of the monitoring to April 2008 more than 55,000 events were recorded. With the data collected by a network with six 3-components digital seismographic stations during the campaigns done from September 29th, 1997 to March 5th, 1998, estimates of source parameters were found fitting the displacement spectra in the frequency domain for each event. From the fitting of the displacement spectra it was possible to obtain the corner frequency ( ) c f and long period amplitude ( ) W0 . Source parameters were determined following Brune (1970) and Madariaga (1976) models. Twenty-one seismic events were analyzed (0.7 £ £ 2.1) b m in order to estimate the source dimension (r ), seismic moment ( ) M0 , static stress drop (Ds ), apparent stress ( ) a s , seismic energy ( ) S E and moment magnitude ( ) W M for each of the events. It was observed that the ratio between radiated seismic energy and moment seismic (apparent stress) increases with increasing moment and hence magnitude at the observed range. As suggested by Abercrombie (1995), also in this work there is a breakdown in the scaling for earthquakes with magnitudes smaller than three ( < 3.0) W M , so that the rupture physics is different for larger events. If this assumption is valid, the earthquakes analyzed in this work are not selfsimilar. Thus, larger events tend to radiated more energy per unit area than smaller ones.

Estudo sísmico no açude Tucunduba, Senador Sá, CE

The Tucunduba Dam, is west of Fortaleza, Ceará State. The seismic monitoring of the area, with an analogical station and seven digital stations, had beginning on June 11, 1997. The digital stations, operated from June to November 1997. The data collected in the period of digital monitoring was analyzed for determination of hypocenters, focal mechanisms, and shear-wave anisotropy analysis. For determination of hypocenters, it was possible to find an active zone of nearly 1 km in length, with depth between 4.5 and 5.2 km. A 60&#61616;AZ/88&#61616;SE fault plane was determined using the least-squares method and hypocenters of a selected set of 16 earthquakes recorded. Focal mechanisms were determined, in the composite fault plane solution, a strike-slip fault, trending nearly E-W, was found. Single fault plane solutions were obteined to some earthquakes presented mean values of 65&#61616; (azimuth), and 80&#61616; (dip). Shear-wave anisotropy was found in the data. Polarization directions and travel time delays, between S spliting waves, were determined. It was not possible to obtain any conclusion on the cause of the observed anisotropy. It is not clear if there is correlation between seismicity and mapped faults in the area, although the directions obtained starting from the hipocentros and focal mechanism are they are consistent with directions, observed in the area, photo, topographic and fractures directions observed in the area

Estudoda sismicidade na região de Sobral - CE em 2008

The town of Sobral is located at the northwest part of the Ceará State, 250 km away from its capital, Fortaleza. In January 2008, an intense seismic activity began near Sobral with one event with magnitude 4,2mb on May 21. Since the start of its seismic activity, all events were recorded by the SBBR station (located on EMBRAPA Caprinos Farm), which operates in the region since August 2007. After this event, monitoring the seismic activity was carried out with the deployment of a local three component digital seismographic network, from June 5, 2008 until September 24. Initially, this network was composed of six seismographic stations. Later additional five stations were deployed until August 26 2008. This local network detected approximately 2,800 earthquakes. In this study we analyzed 581 earthquakes recorded by at least three stations for hypocentral and focal mechanism determination, and to contribute to a better explanation of the seismicity which in this region. To determine the hypocenters, we used a half-space model, with vP = 6,00 km/s and vP/vS = 1,71. From the hypocentral determination, it was revealed an active seismic zone with depth ranging between 1 and 8 km, 6 km long in E - W direction. The determination of fault planes and focal mechanism was obtained using the programs FPFIT and PLAN, which allowed comparison between their respective results in order to obtain more accurate results. A set of 24 earthquakes were selected to determine fault using PLAN planes and focal mechanisms using FPFIT. With the aid of detailed map of hypocenters this set, it was possible to identify three structures. Therefore, the set of 24 earthquakes were divided into three subsets. The type of mechanism was predominantly strike-slip with a dextral direction. Although the region has two tectonic structures near the site of the study area: the Café- Ipueiras Fault (normal fault) and the Sobral-Pedro II Lineament (dextral strike-slip fault) it was not possible to correlate the seismicity founded with those structures

Expression of Ki-67 Antigen and Caspase-3 Protein in Benign Lesions and Esophageal Carcinoma

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

Sol-gel synthesis and characterization of Fe(2)O(3) center dot CeO(2) doped with Pr ceramic pigments

Undoped x center dot alpha-Fe(2)O(3) y center dot CeO(2) and doped with praseodymium ceramic pigments were obtained by the sol-gel method after heat treatment at 800 degrees C for 2 h. These pigments were characterized by XRD, nitrogen adsorption, scanning electron microscopy, ultraviolet-visible absorption spectroscopy and colorimetrical measurements. Red and brown colors with several tonalities were observed after changes with Ce and Pr concentration.

Prochloraz residue levels in ginger submitted to Sportak 450 CE postharvest treatment

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

Synthesis, characterization and thermal studies on solid state 3-methoxybenzoate of lighter trivalent lanthanides

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