Parallel factor analysis of 4.2K excitation-emission matrices for the direct determination of dibenzopyrene isomers in coal-tar samples with a cryogenic fiber optic probe coupled to a commercial spectrofluorimeter

Several studies have shown high concentrations of polycyclic aromatic hydrocarbons (PAHs) in living spaces and soil adjacent to parking lots sealed with coal-tar-based products. Recent attention has been paid to the presence of seven PAHs in coal-tar samples ? namely, benz[a]anthracene, benzo[k]-fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene, chrysene, dibenz[a,h]anthracene, and indeno[1,2,3-cd]pyrene ? and their association to significant increases in estimated excess lifetime cancer risk for nearby residents. Herein, we present an analytical approach to screen the presence of five highly toxic, high-molecular weight PAHs (HMW-PAHs) in coal-tar samples. These include dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, dibenzo[a,e]pyrene, dibnezo[a,h]pyrene and naphtho[2,3-a]pyrene. Their direct analysis ? no without chromatographic separation ? - in a reference coal-tar sample is made possible with the combination of excitation-emission matrices (EEMs) and parallel-factor analysis (PARAFAC). EEMs are recorded at 4.2 K with the aid of a cryogenic fiber optic probe and a commercial spectrofluorimeter. The simplicity of the experimental procedure and the excellent analytical figures of merit demonstrate the screening potential of this environmentally friendly approach for the routine analysis of numerous coal-tar samples.Fil: Moore, Anthony F. T.. University of Central Florida; Estados UnidosFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; ArgentinaFil: Barbosa, Fernando Jr.. Universidade de Sao Paulo; BrasilFil: Campiglia, Andres D.. University of Central Florida; Estados Unido

Reference concentrations for trace elements in urine for the Brazilian population based on q-ICP-MS with a simple dilute-and-shoot procedure

Biomonitoring of trace elements is of critical importance in human health assessment. However, trace element concentrations in biological fluids are affected by environmental and physiological parameters, and therefore considerable variations can occur between specific population subgroups. Brazil is a large country with large environmental diversity and with a limited knowledge of the reference values (baseline data) for trace elements in biological fluids. Atomic absorption spectrometry (AAS) and inductively coupled plasma emission spectrometry (ICP-OES) are still the dominant analytical techniques used for biomonitoring trace element analysis in clinical specimens. However, the use of ICP-MS is becoming more usual in clinical laboratory analysis. Then, we evaluated here a simple dilute-and-shoot method for sequential determination of Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl and U in urine by quadrupole inductively coupled plasma mass spectrometry (q-ICP-MS). Urine samples (500 µL) were accurately pipetted into conical tubes (15 mL) and diluted to 10 mL with a solution containing 0.5 % (v/v) HNO3 + 0.005% (v/v) Triton X-100. Diluted urine samples also contain rhodium, iridium and yttrium added as internal standards. After that, samples were directly analyzed by ICP-MS against matrix-matching calibration. Method detection limit (3s, n = 20) were in the ng L-1 range for all analytes. The method was applied to the analysis of 412 ordinary urine samples from Brazilian healthy and non-exposed subjects to establish reference values. Data validation was provided by the analysis of the standard reference material (SRM) 2670a toxic elements in urine (freeze-dried) (high and low levels) from the National Institute of Standards and Technology (NIST) and reference urine samples from the trace elements intercomparison program operated by the Institut National de Sante' Publique du Quebec, Canada.O biomonitoramento de elementos químicos é de extrema importância na avaliação da saúde humana. Entretanto, as concentrações dos elementos químicos nos fluidos biológicos são afetadas por parâmetros ambientais e fisiológicos e, consequentemente, consideráveis variações podem ocorrer entre subgrupos de populações específicas. O Brasil é um país com ampla diversidade ambiental e existe limitado conhecimento de valores de referência para elementos químicos em fluidos biológicos. A espectrometria de absorção atômica (AAS) e a espectrometria de emissão ótica com plasma acoplado indutivamente (ICP-OES) ainda são as técnicas analíticas mais comumente empregadas no biomonitoramento de elementos químicos em amostras clínicas. Entretanto, o uso da espectrometria de massas com plasma acoplado indutivamente (ICP-MS) está se tornando a cada dia mais comum nos laboratórios clínicos. Neste estudo, foi avaliado um método rápido envolvendo simples diluição da amostra para determinação de Al, Ba, Be, Cd, Co, Cu, Cs, Mn, Ni, Pb, Pt, Sb, Se, Sn, Tl e U em urina por ICP-MS. Amostras de urina (500 μL) foram pipetadas em frascos cônicos de 15 mL e diluídas para 10 mL com uma solução contendo 0,5 % (v/v) HNO3 + 0,005% (v/v) Triton X-100. Ródio, irídio e ítrio foram adicionados como padrões internos. Em seguida, as amostras foram diretamente analisadas por ICP-MS com calibração por ajuste de matriz. Os limites de detecção do método (3s, n = 20) foram da ordem de ng L-1 para todos os analitos em estudo. O método foi aplicado para a análise de 412 amostras de urina de brasileiros saudáveis e não expostos ambientalmente ou ocupacionalmente a metais para o estabelecimento de valores de referência na população brasileira. A validação dos resultados foi acompanhada pela análise de material de referência certificada de urina (SRM) 2670a proveniente do National Institute of Standards and Technology (NIST) e de materiais de referência provenientes do Institut National de Sante' Publique Du Quebec, no Canadá.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Association of Urinary and Blood Concentrations of Heavy Metals with Measures of Bone Mineral Density Loss: a Data Mining Approach with the Results from the National Health and Nutrition Examination Survey

Osteoporosis and its consequence of fragility fracture represent a major public health problem. Human exposure to heavy metals has received considerable attention over the last decades. However, little is known about the influence of co-exposure to multiple heavy metals on bone density. The present study aimed to examine the association between exposure to metals and bone mineral density (BMD) loss. Blood and urine concentrations of 20 chemical elements were selected from 3 cycles (2005–2010) NHANES (National Health and Nutrition Examination Survey), in which we included white women over 50 years of age and previously selected for BMD testing (N = 1892). The bone loss group was defined as participants having T-score < − 1.0, and the normal group was defined as participants having T-score ≥ − 1.0. We developed classification models based on support vector machines capable of determining which factors could best predict BMD loss. The model which included the five-best features-selected from the random forest were age, body mass index, urinary concentration of arsenic (As), cadmium (Cd), and tungsten (W), which have achieved high scores for accuracy (92.18%), sensitivity (90.50%), and specificity (93.35%). These data demonstrate the importance of these factors and metals to the classification since they alone were capable of generating a classification model with a high prediction of accuracy without requiring the other variables. In summary, our findings provide insight into the important, yet overlooked impact that arsenic, cadmium, and tungsten have on overall bone health

Oral exposure to methylmercury modifies the prostatic microenvironment in adult rats

Methylmercury (MeHg) is an environmental pollutant that is highly toxic to the central nervous system. As its effects on male reproductive system are poorly understood, this study was carried out to analyse the effects of MeHg on the rat prostate. To evaluate the MeHg toxicity on ventral prostate, three groups of adult male Wistar rats received oral doses of 0.5, 1.0 and 3.0mg/kg MeHg, respectively, on a daily basis for 14days. A fourth group was used as a control. The prostate weight was decreased in rats treated orally with 0.5mg/kg MeHg compared to controls. Also, Hg concentration increased significantly in the prostate after treatments. There were reductions in serum testosterone levels and androgen receptor immunoreactivity in animals receiving 3.0mgMeHg/kg. The stereological data showed changes in the prostatic epithelial, stromal and luminal compartments which varied according to the different doses. Histopathological alterations, such as chronic inflammation, stratified epithelial hyperplasia and epithelial inflammatory reactive atypia, were observed in the 0.5mg/kg MeHg-treated group. Epithelial atrophy was observed in the 3.0mg/kg MeHg-treated group. In conclusion, the MeHg affects prostatic homoeostasis resulting in histopathological changes that may be relevant in the pathogenesis of prostatic disease.Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2007/56458-4

Genetic variants in selenoprotein genes modulate biomarkers of selenium status in response to Brazil nut supplementation (the SU.BRA.NUT study)

This work was supported by Brazilian grants from São Paulo Research Foundation to JLSD (Fundação de Amparo à Pesquisa do Estado de São Paulo-FAPESP processes: 2011/17720-0 and 2015/10146-8). Funding source had no involvement in study design, collection, analysis and interpretation of data from the present research.Peer reviewedPostprin

Sequential closure of the abdominal wall with continuous fascia traction (using mesh or suture) and negative pressure therapy

The last decade was marked by a multiplication in the number of publications on (and usage of) the concept of damage control laparotomy, resulting in a growing number of patients left with an open abdomen (or peritoneostomy). Gigantic hernias are among the dreaded consequences of damage control and the impossibility of closing the abdomen during the initial hospital admission. To minimize this sequela, the literature has proposed many different strategies. In order to explore this topic, the Evidence-based Telemedicine - Trauma & Acute Care Surgery (EBT -TACS) conducted a literature review and critically appraised the most relevant articles on the topic. No commercially available systems for the closure of peritoneostomies were analyzed, except for negative pressure therapy. Three relevant and recently published studies on the sequential closure of the abdominal wall (with mesh or sutures) plus negative pressure therapy were appraised. For this appraisal 2 retrospective and one prospective study were included. The EBT-TACS meeting was attended by representatives of 6 Universities and following recommendations were generated: (1) the association of negative pressure therapy and continuous fascia traction with mesh or suture and adjusted periodically appears to be a viable surgical strategy to treat peritoneostomies. (2) the primary dynamic abdominal closure with sutures or mesh appears to be more efficient and economically sound than leaving the patient with a gigantic hernia to undergo complex repair at a later date. New studies including larger number of patients classified according to their different presentations and diseases are needed to better define the best surgical treatment for patients with peritoneostomies.Na última década multiplicaram-se as publicações e a utilização da cirurgia de controle de danos, resultando num número crescente de pacientes deixados com o abdome aberto (ou peritoneostomia). Uma das consequências nefastas do abdome aberto são as hérnias ventrais gigantes que resultam da impossibilidade de se fechar o abdome durante a internação hospitalar do paciente. Para minimizar esta sequela têm surgido na literatura diferentes tipos de abordagem. Para abordar este tópico, a reunião de revista Telemedicina Baseada em Evidência - Cirurgia do Trauma e Emergência (TBE-CiTE) optou por não analisar sistemas comerciais de fechamento abdominal dinâmico, com exceção da terapia de pressão negativa ou vácuo. O grupo fez uma avaliação crítica dirigida de três artigos mais relevantes publicados recentemente sobre fechamento sequencial da parede abdominal (com tela ou sutura) mais vácuo. Nesta avaliação foram incluídos dois estudos retrospectivos mais um estudo prospectivo. Baseados na análise crítica desses 3 estudos mais a discussão que contou com a participação de representantes de 6 Universidades e realizada via telemedicina, são feitas as seguintes recomendações: (1) a associação de terapia de pressão negativa com tração fascial constante mediada por tela ou sutura, ajustada periodicamente, parece ser uma ótima estratégia cirúrgica para o tratamento de peritoneostomias. (2) O fechamento abdominal primário dinâmico com sutura e mediada por tela parece ser mais econômico e eficiente do que deixar o paciente com uma hérnia gigante e planejar uma reconstrução complexa tardiamente. Novos estudos com grupos maiores de pacientes separados de acordo com as diferentes apresentações e doenças são necesários para definir qual o melhor método cirúrgico para o tratamento de peritoneostomias.858

Evaluation of inductively coupled plasma mass spectrometry for determining Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen samples using a simple sample dilution method

A simple and fast method for the determination of Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen by quadrupole inductively coupled plasma spectrometry (q-ICP-MS) is described. Prior to analysis, samples (200 µL) were diluted 1:50 in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid and directly analyzed by ICP-MS. The limits of detection of the method are 0.3, 0.03, 0.2, 0.04, 0.04, 0.03 and 0.03 µg L-1 for 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 82Se and 55Mn, respectively. For purposes of comparison and method validation, four ordinary bovine semen samples were directly analyzed by ICP-MS and by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GF AAS), with no statistical difference between the techniques at the 95% level when applying the t-test. Then, the proposed method was applied in the determinations of Ca, Cu, Fe, Mg, Mn, Se and Zn in collected samples of bovine semen from different breeds, which are used in reproduction programs and artificial insemination

Ising spin glass under continuous-distribution random magnetic fields: Tricritical points and instability lines

The effects of random magnetic fields are considered in an Ising spin-glass model defined in the limit of infinite-range interactions. The probability distribution for the random magnetic fields is a double Gaussian, which consists of two Gaussian distributions centered respectively, at $+H_{0}$ and $-H_{0}$, presenting the same width $\sigma$. It is argued that such a distribution is more appropriate for a theoretical description of real systems than its simpler particular two well-known limits, namely the single Gaussian distribution ($\sigma \gg H_{0}$), and the bimodal one ($\sigma = 0$). The model is investigated by means of the replica method, and phase diagrams are obtained within the replica-symmetric solution. Critical frontiers exhibiting tricritical points occur for different values of $\sigma$, with the possibility of two tricritical points along the same critical frontier. To our knowledge, it is the first time that such a behavior is verified for a spin-glass model in the presence of a continuous-distribution random field, which represents a typical situation of a real system. The stability of the replica-symmetric solution is analyzed, and the usual Almeida-Thouless instability is verified for low temperatures. It is verified that, the higher-temperature tricritical point always appears in the region of stability of the replica-symmetric solution; a condition involving the parameters $H_{0}$ and $\sigma$, for the occurrence of this tricritical point only, is obtained analytically. Some of our results are discussed in view of experimental measurements available in the literature.Comment: 23 pages, 8 figures, accept for publication in Phys. Rev.

Methylene Blue to Neonatal Septic Shock treatment in neonate pigs,

Objective: The authors design an animal model of neonatal sepsis to analyze the treatment of neonatal septic shock with Methylene Blue (MB) in a swine model. Methods: The study design included twenty male newborn pigs divided into four groups: 1) The control group; 2) The sepsis group (induced with lipopolysaccharide); 3) The MB group, and 4) The MB-treated sepsis group. Septic shock was defined as Blood Pressure (BP) dropping 20% below the baseline value. Continuous Blood Pressure (BP), Nitric Oxide (NO) levels, cyclic Guanosine Monophosphate (cGMP), malondialdehyde acid, base excess, lactate, arterial blood gases, hematocrit, and echocardiography were analyzed. Results: The BP of the sepsis group treated with MB showed a slight improvement in the first hour after treatment; however, a significant difference was not observed compared to the untreated sepsis group. Besides hemodynamic stability, the current study did not show symptomatic pulmonary hypertension, suggesting that MB was safe in neonates and children. An improvement in Base Excel (BE) levels after MB administration in septic animals may indicate a possible improvement in microcirculation. Conclusion: The MB improved biomarkers related to septic shock prognosis, although an improvement in the blood levels could not be detected. MB might be a beneficial drug for hemodynamic instability in infants