Spectrophotometric study of binary and ternary systems involving metal ions and benzylidenepyruvates: Equilibria in aqueous solutions

The protonation of 4-dimethylaminobenzylidenepyruvate (DMBP) and 2-chloro-4-dimethylaminobenzylidenepyruvate (2-CI-DMBP) and their complex formation with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II) and Al(III) have been studied by potentiometric and spectrophotometric methods at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. The stability order found for 1 :1 complexes of both ligands is Al(III) > Cu(II) > Pb(II) > Ni(II) > Zn(II) > Co(II) > Cd(II) > Mn(II). The stability changes move in the same direction as the pKa of the ligands. The results are compared with literature values reported for metal ion pyruvate systems. Thermodynamic stabilities of ternary complexes formed in Cu(II)-B-L- systems, where B = 2,2′-bipyridyl (bipy), ethylenediamine or glycinate and L = DMBP or 2-CI-DMBP, were also determined. The Cu(bipy)L+ species are more stable than would be expected on purely statistical grounds. The importance of the :t system associated with bipy on the enhanced stability of its mixed ligand complexes is stressed. Analytical applications of the investigated ligands are outlined.

A study about the solutions of Schrödinger equation with an asymptotically linear potential

We determine the solutions of the Schrödinger equation for an asymptotically linear potential. Analytical solutions are obtained by superalgebra in quantum mechanics and we establish when these solutions are possible. Numerical solutions for the spectra are obtained by the shifted 1/N expansion method.

Study on transient ice formation of laminar flow inside externally supercooled rectangular duct

The transient process of solidification of laminar liquid flow (water) submitted to super-cooling was investigated both theoretically and experimentally. In this study an alternative analytical formulation and numerical approach were adopted resulting in the unsteady model with temperature dependent thermophysical properties in the solid region. The proposed model is based upon the fundamental equations of energy balance in the solid and liquid regions as well as across the solidification front. The basic equations and the associated boundary and initial conditions were made dimensionless by using the Landau transformation to immobilize the moving front and render the problem to a fixed plane type problem. A laminar velocity profile is admitted in the liquid domain and the resulting equations were discretized using the finite difference approach. The numerical predictions obtained were compared with the available results based on other models and concepts such as Neumann analytical model, the apparent thermal capacity model due to Bonacina and the conventional fixed grid energy model due to Goodrich. To obtain further comparisons and more validation of the model and the numerical solution, an experimental rig was constructed and instrumented permitting very well controlled experimental measurements. The numerical predictions were compared with the experimental results and the agreement was found satisfactory.

HPLC-EICD: An Useful Tool for the Pursuit of Novel Analytical Strategies for the Detection of Antioxidant Secondary Metabolites

Living cells are continuously exposed to a variety of challenges that exert oxidative stress and are directly related with senescence and the onset of various pathological conditions such as coronary heart disease, rheumatoid arthritis and cancer. Nevertheless, living organisms have developed a complex antioxidant network to counteract reactive species that are detrimental to life. With the aim of bio-prospecting plant species from the Brazilian Cerrado and Atlantic Forest, we have established a methodology to detect secondary antioxidant metabolites in crude extracts and fractions obtained from plant species. Combining HPLC with an electrochemical detector allowed us to detect micromolecules that showed antioxidant activities in Chimarrhis turbinata (DC) leaf extracts. Comparison with purified flavonoid standards led us to identify the compounds in their natural matrices giving valuable information on their antioxidant capacity.

Determination of acetonitrile and cyanide in rat blood: Application to an experimental study

Methods were developed for the analysis of acetonitrile and its metabolite cyanide in the blood of rats exposed to acetonitrile. Acetonitrile was analyzed by the headspace technique coupled to gas chromatography with detection by flame ionization, and cyanide was analyzed by high-performance liquid chromatography with fluorescence detection (λ ex = 418 nm and λ em = 460 nm) after derivatization of the ion with naphthalene 2,3-dicarboxyaldehyde and taurine. The quantitation limits of the methods for the analysis of acetonitrile and cyanide were 4.875 μg/mL and 0.025 μg/mL, respectively. The coefficients of variation of 10% or less obtained for intra- and interassay precision indicate the precision of these analytical methods and the systematic errors, all less than 5%, indicate that the methods are quite accurate. The methods were applied to an experimental study after the animals received acetonitrile at the doses of 2 mmol/kg or 5 mmol/kg.

A structural conformation study of aquatic humic acid

In the present work, aquatic humic substances (HS) were extracted by use of adsorbent XAD 8 and the acid humic fraction (AH) was separated throught acidification. After being purified by Hyphan resin and dialyze, the aquatic AH was characterized using Fourier-transform infrared spectroscopy and elemental analysis. The influence of the aquatic HA and electrolyte concentrations, pH and aquatic AH-metal complexation time on the conformation was investigated using UV/Vis spectroscopic studies, employing the equation suggested by Doty and Steiner. The results indicated that the acid humic flexible macromolecule assumes a condensed form at acid and alkaline pH. Other factors favoring condensed conformations are longer metal complexation time (ageing) and higher aquatic AH and electrolyte concentrations. Thus considering the strong influence of the investigated parameters in the structural conformation of the humic macromolecule, we conclude that studies using UV/Vis spectroscopy to estimate the concentration, aromaticity, humification degree of the aquatic AH and so on, require rigorous control over the experimental conditions employed to provide a correct interpretation of the analytical results. ©2006 Sociedade Brasileira de Química.

Monte Carlo and analytical calculation of lateral deflection of proton beams in homogeneous targets

Proton radiation therapy is a precise form of radiation therapy, but the avoidance of damage to critical normal tissues and the prevention of geographical tumor misses require accurate knowledge of the dose delivered to the patient and the verification of his position demand a precise imaging technique. In proton therapy facilities, the X-ray Computed Tomography (xCT) is the preferred technique for the planning treatment of patients. This situation has been changing nowadays with the development of proton accelerators for health care and the increase in the number of treated patients. In fact, protons could be more efficient than xCT for this task. One essential difficulty in pCT image reconstruction systems came from the scattering of the protons inside the target due to the numerous small-angle deflections by nuclear Coulomb fields. The purpose of this study is the comparison of an analytical formulation for the determination of beam lateral deflection, based on Molière's theory and Rutherford scattering with Monte Carlo calculations by SRIM 2008 and MCNPX codes. © 2010 American Institute of Physics.

The institutionality of gender in the State: new analytical perspectives

Includes bibliography

Comparative in vivo study of commercially pure Ti implants with surfaces modified by laser with and without silicate deposition: Biomechanical and scanning electron microscopy analysis

The purpose of this study was to evaluate commercially pure titanium implant surfaces modified by laser beam (LS) and LS associated with sodium silicate (SS) deposition, and compare them with machined surface (MS) and dual acid-etching surfaces (AS) modified. Topographic characterization was performed by scanning electron microscopy-X-ray energy dispersive spectroscopy (SEM-EDX), and by mean roughness measurement before surgery. Thirty rabbits received 60 implants in their right and left tibias. One implant of each surface in each tibia. The implants were removed by reverse torque for vivo biomechanical analysis at 30, 60, and 90 days postoperative. In addition, the surface of the implants removed at 30 days postoperative was analyzed by SEM-EDX. The topographic characterization showed differences between the analyzed surfaces, and the mean roughness values of LS and SS were statistically higher than AS and MS. At 30 days, values removal torque LS and SS groups showed a statistically significant difference (p < 0.05) when compared with MS and AS. At 60 days, groups LS and SS showed statistically significant difference (p < 0.05) when compared with MS. At 90 days, only group SS presented statistically higher (p < 0.05) in comparison with MS. The authors can conclude that physical chemistry properties and topographical of LS and SS implants increases bone-implant interaction and provides higher degree of osseointegration when compared with MS and AS. © 2012 Wiley Periodicals, Inc.

Analytical direct planetary perturbations on the orbital motion of satellites

An analytical expansion of the disturbing function arising from direct planetary perturbations on the motion of satellites is derived. As a Fourier series, it allows the investigation of the secular effects of these direct perturbations, as well as of every argument present in the perturbation. In particular, we construct an analytical model describing the evection resonance between the longitude of pericenter of the satellite orbit and the longitude of a planet, and study briefly its dynamic. The expansion developed in this paper is valid in the case of planar and circular planetary orbits, but not limited in eccentricity or inclination of the satellite orbit. © 2012 Springer Science+Business Media Dordrecht.

Development of an analytical method for the quantification of pfaffic acid in Brazilian ginseng (Hebanthe eriantha)

Hebanthe eriantha (Poir.) Pedersen (Amaranthaceae), which is known as Brazilian ginseng is widely used in folk medicine as an aphrodisiac and antidiabetic tonic. The anti-tumor activity, attributed to the pfaffic acid present in roots of H. eriantha, is responsible for the great interest in the commercialization of this species. In Brazil, the species H. eriantha is mainly used in commercial preparations, although other plants of the genus Pfaffia and Hebanthe have been marketed as Pfaffia paniculata or Brazilian ginseng. The pfaffic acid present in the roots is mainly conjugated with sugars (pfaffosides) and can be used as an active marker of H. eriantha, which helps to differentiate this species from others marketed as Brazilian ginseng. The main objective of this study was to develop and validate a liquid chromatographic method to quantify pfaffic acid in the roots of H. eriantha. The extraction and hydrolysis conditions were optimized using an univariate and experimental design, respectively, and the quantification of pfaffic acid by high performance liquid chromatography with diode-array detection (HPLC-DAD) was validated. This method was used to evaluate the pfaffic acid content in 30 different genotypes of the species from a germplasm collection. The content of pfaffic acid ranged from 0.97 to 4.29% (w/w) on a dry weight basis. © 2013 Elsevier B.V.

Role of Ca, Fe, Cu and Zn in breast cancer: Study by X-ray fluorescence techniques and immunohistochemical analysis

In recent years, several studies have shown that concentrations of trace elements are altered in neoplastic breast tissues. However, the microenvironment and metabolic changes caused by tumors are complex and still not completely understood. Under this aspect, the combination of different techniques to investigate the role of trace elements in promoting and/or maintaining a tumor is interesting once the combination of information obtained by analytical techniques and immunohistochemical assays, associated with clinicopathological data, may allow a better metabolic understanding of trace elements in breast cancer. In this work, the role of the trace elements Ca, Fe, Cu and Zn in neoplastic breast tissues was investigated by X-ray fluorescence (XRF) techniques and immunohistochemical assays. We determined concentrations of Ca, Fe, Cu and Zn in normal and neoplastic breast tissues using energy dispersive XRF, and these values were used to set the positive or negative expression of elements in normal and neoplastic tissues. These expressions were correlated with the spatial distributions of trace elements (evaluated by micro-XRF) and with immunoexpression of matrix metalloproteinases (MMPs), tissue inhibitors of MMPs and vascular endothelial growth factor. The results revealed that the expression of the trace elements Fe, Cu and vascular endothelial growth factor are related, indicating that higher levels of these elements can be associated with the angiogenic process in breast cancer. Also, associations between Ca, Zn and MMPs expression have been observed, possibly because of the fact that both metals are present in these proteins. © 2013 John Wiley & Sons, Ltd.

Ultrasound-assisted extraction of Na and K from swine feed and its application in a digestibility assay: A green analytical procedure

The study is aimed to evaluate the efficiency of ultrasound-assisted extraction (UAE) as a simple strategy focused on sample preparation for metal determination in biological samples. The extraction of sodium and potassium extraction was carried out from swine feed followed by determination of the concentration of these metals by flame atomic emission spectrometry (FAES). The experiment was performed to cover the study of the variables influencing the extraction process and its optimal conditions (sample mass, particle size, acid concentration, sonication time and ultrasound power); the determination of these analytical characteristics and method validation using certified reference material; and the analysis of pre-starter diets. The optimal conditions established conditions were as follows: mass: 100 mg, particle size:<60 μm, acid concentration: 0.10 mol L-1 HCl, sonication time: 50 s and ultrasound power: 102 W. The proposed method (UAE) was applied in digestibility assays of those nutrients present in different piglet pre-starter feeds and their results proved to be compatible with those obtained from mineralized samples (P < 0.05). The ultrasound extraction method was demonstrated to be an excellent alternative for handless sampling and operational costs and the method also has the advantage of does not generating toxic residues that may negatively affect human health and contaminate the environment. © 2013 Elsevier B.V. All rights reserved.

Electrochemical feasibility study of methyl parathion determination on graphite-modified basal plane pyrolytic graphite electrode

A low-cost electrochemical method was developed for the determination of trace-level of methyl parathion (MP) based on the properties of graphite-modified basal plane pyrolytic graphite electrode (graphite-bppg). A combination of graphite-bppg with square-wave voltammetric (SWV) analysis resulted in an original, sensitive and selective electrochemical method for determination of MP pesticide in drinking water. The electrode was constructed and the electrochemical behavior of MP was studied. Immobilization is achieved via film modification from dispersing graphite powder in deionized water and through pipeting a small volume onto the electrode surface allowing the solvent to volatilize. The strong affinity of the graphite modifier for the phosphorous group of the MP allowed the deposition of a significant amount of MP in less than 60 seconds. The cyclic voltammetric results indicate that the graphite-bppg electrode can enhance sensitivity in current intensity towards the quasi-reversible redox peaks of the products of the cathodic reduction of the nitro group at negative potential (peak I = 0.077 V and peak II = –0.062 V) and that the cathodic irreversible peak (peak III = –0.586 V) in comparison with bare bppg electrode and is also adsorption controlled process. Under optimized conditions, the concentration range and detection limit for MP pesticide are respectively 79.0 to 263.3 mmol L-1 and 3.00 mmol L-1. The proposed method was successfully applied to MP determination in drinking water and the performance of this electrochemical sensor has been evaluated in terms of analytical figures of merit.

Socio-demographic analysis of youth in the Caribbean- a three country case study

Many Caribbean youth are doing reasonably well. They live in loving and caring families, attend school and are involved in various social activities in their communities. The health and well-being of the children and youth1 in the Caribbean is, and has been, the centre of attention of many studies, meetings and policy directives set at the regional, subregional and national levels. Programmes have been put in place to address the basic needs of young children in the areas of health and education and to provide guidance and directives to youth and adolescents in the area of professional formation and transition to adulthood. Critical issues such as reproductive health and family planning combined with access to education and information on these topics have been promoted to some extent. And finally, the Caribbean is known for rather high school enrolment rates in primary education that hardly show any gender disparities. While the situation is still good for some, growing numbers of children and youth cannot cope anymore with the challenges experienced quite early in their lives. Absent parents, instable care-taking arrangements, violence and aggression subjected to at home, in schools and among their friends, lack of a perspective in schools and the labour-market, early sexual initiation and teenage pregnancies are some of those issues faced by a rising number of young persons in this part of the world. Emotional instability, psychological stress and increased violence are one of the key triggers for increased violence and involvement in crime exhibited by ever younger youth and children. Further, the region is grappling with rising drop-out rates in secondary education, declining quality schooling in the classrooms and increasing numbers of students who leave school without formal certification. Youth unemployment in the formal labour market is high and improving the quality of professional formation along with the provision of adequate employment opportunities would be critical to enable youth to complete consistently and effectively the transition into adulthood and to take advantage of the opportunities to develop and use their human capital in the process. On a rather general note, the region does not suffer from a shortage of policies and programmes to address the very specific needs of children and youth, but the prominent and severe lack of systematic analysis and monitoring of the situation of children, youth and young families in the Caribbean does not allow for targeted and efficient interventions that promise successful outcomes on the long term. In an effort to assist interested governments to fill this analytical gap, various initiatives are underway to enhance data collection and their systematic analysis2. Population and household censuses are conducted every decade and a variety of household surveys, such as surveys of living conditions, labour force surveys and special surveys focusing on particular sub-groups of the population are conducted, dependent on the resources available, to a varying degree in the countries of the region. One such example is the United Nations Children’s Fund (UNICEF)-funded Multi-Indicator Cluster Surveys (MICS) that assess the situation of children and youth in a country. Over the past years and at present, UNICEF has launched a series of surveys in a number of countries in the Caribbean3. But more needs to be done to ensure that the data available is analyzed to provide the empirical background information for evidence-based policy formulation and monitoring of the efficiency and effectiveness of the efforts undertaken.