CO2 REDUCTION TO HYDROCARBONS AND OXYGENATES: FUNDAMENTALS, STRATEGIES AND CHALLENGES. The development of renewable energy sources (e.g., solar and wind) moves foward, the tendance for replacing fossil fuels increases. However, these technologies have as primary barriers to industrial processes’ efficiency and especially storage. Thus, CO2 reduction routes using these energy sources could chemically store part of the energy as fuels or chemicals, offering alternatives to current oil and gas industry. This process is inspired by photosynthesis, e.g., photochemical or electrochemical processes, using homogeneous or heterogeneous catalysts. Nevertheless, this reaction is thermodynamically unfavorable and has very slow kinetics, given the high stability of the CO2 molecule and the complexity of the redox reactions involved. Therefore, this review addresses this process’s kinetic and thermodynamic challenges, and the fundamental concepts of the photo(electro)chemical processes for CO2 reduction, besides presenting and discussing the materials with the potential to act as catalysts. The main reaction mechanisms and advances in the understanding of such processes are discussed, as well as future perspectives

RESUMO: A leucoencefalomalácia (LEM) é uma enfermidade que acomete equídeos causada pela ingestão de milho e seus derivados e feno contaminados pela micotoxina fumonisina, um metabólito do fungo Fusarium verticillioides (sinônimo para F. moniliforme). Os sinais clínicos apresentam início agudo e evolução rápida e são decorrentes de lesões encefálicas. O objetivo deste estudo é descrever os achados clínicos de 11 equídeos diagnosticados com LEM, incluindo a análise do líquido cefalorraquidiano (LCR). 91% dos animais afetados eram equinos e somente 9% (1/11) era asinino. A localização clínica das lesões era 64% (7/10) cerebrais, manifestadas por alterações no estado mental e comportamento e 36% (4/10) no tronco encefálico, manifestadas por incoordenação, desvio lateral de cabeça, nistagmo, hipoalgesia da face e dificuldade de apreensão, mastigação e deglutição de alimentos. Comparativamente, os achados post mortem revelaram que 82% (9/11) das lesões eram no cérebro e 18% (2/11) no tronco encefálico. Alterações no LCR, tais como xantocromia (43%, 3/7), hiperproteinorraquia (50%, 3/6) e pleocitose (43%, 3/7), foram observadas. Os animais afetados apresentaram sinais clínicos compatíveis com lesões encefálicas e/ou de tronco cerebral. O LCR de animais com LEM pode apresentar xantocromia, hiperproteinorraquia, e pleocitose, reforçando que esta doença deve ser incluída como diagnóstico diferencial de encefalomielites.

ABSTRACT: Equine leukoencephalomalacia (LEM) is a disease caused by the ingestion of food, especially corn, contaminated by fumonisin, a Fusarium verticillioides (synonymous with F. moniliforme) metabolite. The clinical signs of brain injuries have an acute onset and rapid evolution. This study aimed to describe the clinical findings in 11 animals diagnosed with LEM, including cerebrospinal fluid (CSF) analysis. Of these animals, 91% (10/11) were horses, and only 9% (1/11) were asinine. The clinical localization of the lesions was 64% (7/10) cerebral, manifested mainly by altered mental state and behavioral disturbance, and 36% (4/11) were brainstem lesions, manifested by incoordination, head tilt, nystagmus, facial hypoalgesia, difficulty in apprehension, chewing, and swallowing food. Postmortem findings revealed that 82% (9/11) of the lesions were in the cerebrum and 18% (2/11) in the brainstem. CSF findings, such as xanthochromia (43%, 3/7), hyperproteinorrachia (50%, 3/6), and pleocytosis (43%, 3/7) were observed. The affected animals showed neurological signs that were compatible with cerebral and/or brainstem injuries. The CSF from animals with LEM may present with xanthochromia, hyperproteinorrachia, and pleocytosis, reinforcing the fact that this disease should be included in the differential diagnosis of encephalomyelopathies.

Abstract Syzygium malaccense is popularly used to treat inflammation and pain-related ailments. The species was assessed regarding its antioxidant, antiglycant, anti-inflammatory, including anti-neuroinflammatory, and antinociceptive activities. Different models were employed to measure S. malaccense extract (ESM) antioxidant activity. The antiglycant activity was determined using the glucose-induced protein glycation model. LPS-induced neuroinflammation on murine BV-2 microglial cell line was used for anti-neuroinflammatory activity evaluation. The croton oil-induced ear edema test was accomplished to evaluate the in vivo anti-inflammatory activity. Acetic acid-induced writhing together with formalin-induced paw licking assays were performed to evaluate the antinociceptive potential. Finally, the chemical characterization was accomplished by a UHPLC-MS analysis. ESM presented relevant antioxidant and antiglycant activity. NO production by BV-2 cells was reduced, indicating the relevant neuroprotective activity. ESM significantly decreased the mice ear edema induced by croton oil and the nociceptive stimulus induced by acetic acid and formalin by central and peripheral mechanisms. The flavonoids myricitrin, myricetin and quercetin were identified and, as far as we know, the alkaloid reserpine was reported in the species for the first time. The antioxidant and antiglycant potential of ESM, may be related to the in vivo anti-inflammatory and antinociceptive effects, and to the in vitro neuroinflammation inhibition.

Abstract Cell cycle alterations are among the principle hallmarks of cancer. Consequently, the study of cell cycle regulators has emerged as an important topic in cancer research, particularly in relation to environmental exposure. Particulate matter and coal dust around coal mines have the potential to induce cell cycle alterations. Therefore, in the present study, we performed chemical analyses to identify the main compounds present in two mineral coal samples from Colombian mines and performed systems chemo-biology analysis to elucidate the interactions between these chemical compounds and proteins associated with the cell cycle. Our results highlight the role of oxidative stress generated by the exposure to the residues of coal extraction, such as major inorganic oxides (MIOs), inorganic elements (IEs) and polycyclic aromatic hydrocarbons (PAH) on DNA damage and alterations in the progression of the cell cycle (blockage and/or delay), as well as structural dysfunction in several proteins. In particular, IEs such as Cr, Ni, and S and PAHs such as benzo[a]pyrene may have influential roles in the regulation of the cell cycle through DNA damage and oxidative stress. In this process, cyclins, cyclin-dependent kinases, zinc finger proteins such as TP53, and protein kinases may play a central role.

Abstract This work evaluated the effect of grape juice, red wine and resveratrol in liver parameters of rats submitted to high-fat diet. Experimental model was conducted with groups of adult females Rattus norvegicus: control (CG); high-fat (HG); grape juice (JG); red wine (RW) and resveratrol solution (RG). The high-fat diet significantly altered hepatocytes and Kupffer cells in all treated groups. HG group presented severe steatosis followed hepatocyte ballooning and tissue damages. JG group minimized hepatic histological lesion caused by high-fat diet and WG group also induced steatosis and inflammation in hepatocytes, similar to HG. Still, resveratrol protected the tissue against fatty liver disease by reducing fat infiltration and inflammation, indicating possible therapeutic effects on the liver. Cell cycle analysis showed that HG promoted damage to the tissue, reducing the viable cell content and increasing apoptosis, even when associated with wine consumption or isolated resveratrol. However, JG protected the liver against cell damage generated by the diet. Consumption of grape juice, even associated with a high-fat diet, represents a promising protection of the liver against cellular damage, but red wine further affects the tissue, and resveratrol alone was able to reduce damage but did not minimize cellular damage to the liver.

Abstract Mangroves are ecosystems located in the transition zone between land and sea, characterized by periodic flooding that confer to its unique characteristics. Little is known about the transformation of nutrients that occur during the organic matter degradation in this system. In this study, we monitor the nitrogen transformations in soils from three mangroves with distinct levels of contamination using labeled 15NO3-. We also screened the mangroves metagenomes for the presence of genes that encode enzymes involved in denitrification (nirS, nirK, nosZ, norB and narG), anaerobic oxidation of ammonia (anammox) (hh, hao and hzo) and dissimilatory nitrate reduction to ammonium (DNRA) (nrfA). The transformations of 15NO3- indicated the balance of denitrification over anammox and DNRA in all three mangroves, with lower rates of processes in the mangrove affected by oil contamination. The metagenomic analysis detected 56 sequences related to denitrification, 19 with anammox and 6 with DNRA. Genes related with denitrification were phylogenetically distributed among several groups of bacteria (mainly Gammaproteobacteria). Anammox and DNRA related sequences were affiliated with Planctomycetes and Gammaproteobacteria, respectively. Thus, metagenomic and functional approaches supported the description of denitrification, anammox and DNRA rates in mangrove soils, and identified the major bacterial groups involved in these processes.

Resumo Objetivo Verificar a ocorrência de risco agregado à saúde cardiometabólica e musculoesquelética de adolescentes brasileiros no período de 2008/09 e 2013/14 e identificar se existem diferenças no risco entre os sexos e nesses períodos. Métodos Trata-se de um estudo epidemiológico de tendência com abordagem quantitativa, composto por uma amostra voluntária de adolescentes, de 16 estados brasileiros. Os dados foram extraídos da base de dados do Projeto Esporte Brasil. A aptidão física relacionada a saúde foi avaliada a partir de: índice de massa corporal, aptidão cardiorrespiratória, flexibilidade, e força/resistência abdominal. Para o tratamento estatístico foi utilizado análise descritiva, qui-quadrado e regressão Poisson log. Resultados Nos anos de 2008/09, 14,6% de jovens brasileiros apresentaram risco à saúde cardiometabólica agregada e 17,1% risco agregado dos indicadores musculoesqueléticos. Enquanto em 2013/14, os valores dos indicadores de risco foram, respectivamente 40,0% e 22,4%. Observou-se que nos anos de 2013/14 o risco à saúde cardiometabólica dos meninos era 2,51 vezes maior que em 2008/09. Já para as meninas o aumento desse risco foi de 3 vezes. No que se refere à saúde musculoesquelética, as meninas apresentaram risco de 2,21 de estar na zona de risco em 2013/14 em relação à 2008/09. Conclusão A ocorrência de risco agregado à saúde cardiometabólica e musculoesquelética de adolescentes brasileiros aumentou nos períodos de 2008/09 e 2013/14. Com relação ao sexo houve um aumento no risco cardiometabólico e musculoesquelético nas meninas entre esses períodos. Já para os meninos houve aumento apenas do risco cardiometabólico.

Abstract Objective To assess the occurrence of an aggregate risk to cardiometabolic and musculoskeletal health of Brazilian adolescents in the period 2008/09 and 2013/14 and to identify whether there are differences in risk between the genders and in these periods. Methods This was a trend epidemiological study with a quantitative approach, consisting of a voluntary sample of adolescents from 16 Brazilian states. Data were extracted from the database of Brazil Sports Project (Projeto Esporte Brasil). Health-related physical fitness was evaluated based on body mass index, cardiorespiratory fitness, flexibility, and abdominal strength/resistance. Descriptive analysis, chi-squared test, and Poisson log regression were used for the statistical treatment. Results In the years 2008/09, 14.6% of Brazilian youngsters showed an aggregate risk to cardiometabolic health and 17.1% an aggregate risk for musculoskeletal indicators, whereas in 2013/14, the values of the risk indicators were, respectively 40.0% and 22.4%. It was observed that, in the years 2013/14, the risk to the cardiometabolic health of boys was 2.51 times greater than in 2008/09, while for girls, a three-fold increase in risk was observed. Concerning musculoskeletal health, girls showed a 2.21 risk of being in the risk zone in 2013/14 when compared with 2008/09. Conclusion The occurrence of an aggregate risk to the cardiometabolic and musculoskeletal health of Brazilian adolescents increased in the 2008/09 and 2013/14 periods. Regarding gender, an increase in the cardiometabolic and musculoskeletal risk between these periods was observed in girls. As for boys, an increase was observed only in cardiometabolic risk.

Com esta investigação teve-se por objetivo verificar se os três provadores avaliados constituem o número mínimo de provadores para assegurar a credibilidade da análise sensorial da bebida do café, “prova de chávena”. Para isso, foram realizados quatro experimentos sob diferentes condições de café no estádio cereja: A (café Catuaí Vermelho em altitudes inferiores a 900 m), B (café Catuaí Amarelo em altitudes inferiores a 900 m), C (café Catuaí Vermelho em altitudes iguais e/ou superiores a 900 m) e D (café Catuaí Amarelo em altitudes iguais e/ou superiores a 900 m), em que analisaram-se as notas atribuídas a oito características sensoriais de diferentes amostras nas condições anteriores por três provadores Q-grader que adotaram as regras internacionais da metodologia do Cup of Excellence (CoE). Com base em estatísticas descritivas aplicadas às notas que os provadores atribuíram a oito características sensoriais de diferentes amostras de cafés Catuaí Vermelho e Amarelo, no estádio cereja, provenientes de altitudes inferiores e superiores a 900 m, concluiu-se que o facto mais importante não é a quantidade de provadores envolvidos, mas sim a fiabilidade das notas por eles atribuídas, sendo fiabilidade uma medida que está diretamente associada à homogeneidade do conjunto de notas atribuídas por diferentes provadores, dada a uma mesma condição de avaliação.

This research to determine the minimum amount of testers was made to ensure the reliability of the sensory analysis of the coffee beverages. It were analyzed the scores assigned by three Q-grader who adopted the international rules from the Cup of Excellence (CoE) methodology. Based on descriptive statistics of the scores the testers assigned to eight sensorial characteristics of different samples for Red and Yellow Catuaí coffees, at the ripe coffee cherry produced in altitudes below and above 900 meters, it was concluded that the most important fact is not on the number of testers involved, but rather on the reliability of the scores they assign. Therefore, the reliability is a measure directly related to the homogeneity for the set of scores assigned by different testers, given the same condition for the evaluation.

RESUMO Os agricultores envolvidos na colheita do tabaco estão regularmente expostos a grande quantidade de agroquímicos. Para determinar como esta exposição a pesticidas induz alterações genéticas nestes agricultores, amostras de sangue foram obtidas de 77 indivíduos expostos e de 60 indivíduos não expostos. O dano ao DNA foi analisado pelo Ensaio Cometa e pelo Teste de Micronúcleos (MN). A capacidade antioxidante foi avaliada pela atividade da enzima superóxido dismutase (SOD), e a influência do polimorfismo do gene PON1 foi usada como um biomarcador de susceptibilidade. O teor de elementos inorgânicos foi determinado nas amostras de sangue pela análise PIXE. Nossos resultados mostraram que a freqüência de danos, índice de danos, freqüência de MN e a atividade da SOD foram significativamente mais elevados no grupo exposto em relação ao não exposto. O gene PON1 demonstrou influenciar a frequência de MN observada no grupo exposto. As concentrações de elementos inorgânicos foram maiores no grupo exposto em relação ao não exposto. Neste estudo observamos que danos genéticos e alterações no balanço oxidativo foram induzidos pela exposição dos agricultores a misturas complexas de pesticidas na presença de componentes inorgânicos, e pelas quais a influência do genótipo foi evidente.

ABSTRACT Agricultural workers involved in the harvest of tobacco crops are regularly exposed to large quantities of pesticides. In order to determine how this exposure to pesticides induces genetic alterations in these workers, blood samples were obtained from 77 exposed individuals, as well as from 60 unexposed subjects. DNA damage was analyzed by the Comet assay and by the micronucleus (MN) test. The antioxidant profile was evaluated by activity of superoxide dismutase (SOD), and the polymorphism of gene PON1 was used as a susceptibility biomarker. The content of inorganic elements in the blood samples was determined by PIXE analysis. Our results demonstrated that the damage frequency, damage index, the MN frequency, and the SOD activity were significantly elevated in the exposed relative to the unexposed group. A modulation of the MN results for the PON1 gene was observed in the exposed group. The concentrations of inorganic elements in the exposed group were higher compared to those of the unexposed group. In this study, we observed that genetic damage, and change in oxidative balance were induced by the exposure of workers to complex mixtures of pesticides in the presence of inorganic compounds, whereby an influence of the genotype was evident.

Tobacco farmers are routinely exposed to complex mixtures of inorganic and organic chemicals present in tobacco leaves. In this study, we examined the genotoxicity of tobacco leaves in the snail Helix aspersa as a measure of the risk to human health. DNA damage was evaluated using the micronucleus test and the Comet assay and the concentration of cytochrome P450 enzymes was estimated. Two groups of snails were studied: one fed on tobacco leaves and one fed on lettuce (Lactuca sativa L) leaves (control group). All of the snails received leaves (tobacco and lettuce leaves were the only food provided) and water ad libitum. Hemolymph cells were collected after 0, 24, 48 and 72 h. The Comet assay and micronucleus test showed that exposure to tobacco leaves for different periods of time caused significant DNA damage. Inhibition of cytochrome P450 enzymes occurred only in the tobacco group. Chemical analysis indicated the presence of the alkaloid nicotine, coumarins, saponins, flavonoids and various metals. These results show that tobacco leaves are genotoxic in H. aspersa and inhibit cytochrome P450 activity, probably through the action of the complex chemical mixture present in the plant.

A cromatografia gasosa bidimensional abrangente acoplada à espectrometria de massas por tempo de vôo (CG×CG-EMTDV) foi aplicada para avaliar o efeito do CO2 sobre a distribuição dos n-alcanos, alcanos ramificados, alquenos e compostos oxigenados em produtos da reação de Fischer-Tropsch. Coeluições de material não resolvido observadas em CG convencional foram resolvidas por CG×CG-EMTDV.

Comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS) was applied to evaluate the CO2 effect on distribution of n-alkanes, branched alkanes, alkenes and oxygen-containing compounds in Fischer-Tropsch products. GC × GC-TOFMS was able to resolve the unresolved compounds observed in conventional GC.

Novos compósitos magnéticos anfifílicos foram preparados pelo crescimento de nanotubos e nanofibras de carbono contendo partículas magnéticas através de deposição química de vapor (CVD), utilizando etanol como fonte de carbono e lama vermelha (RM, subproduto do processo Bayer de produção de alumina) como suporte e catalisador. Monitoramento da reação CVD à temperatura programada (TPCVD), difração de raios X (XRD), espectroscopia Mössbauer, espectroscopia de energia dispersiva (EDS), espectroscopia Raman, termogravimetria (TG/DTA), análise elementar (CHN), determinação de área superficial (BET), microscopia eletrônica de varredura (SEM) e de transmissão (TEM) e medidas magnéticas mostraram que etanol reduz íons de ferro na RM para formar fases magnéticas, por exemplo Fe3O4 e Fe0, e depósitos de carbono (5-42 wt.%) na forma de nanotubos e nanofibras. A combinação de nanoestruturas hidrofóbicas de carbono com óxidos hidrofílicos de Al, Si e Ti presentes na lama vermelha produziu materiais anfifílicos com excelente interação com a interface água-óleo. Misturas de óleo de soja ou de decalina com água (completamente imiscíveis) foram emulsificadas facilmente na presença dos compósitos anfifílicos. Quando os compósitos foram adicionados a uma emulsão água-biodiesel estável, as partículas anfifílicas difundiram-se para a interface água- óleo. As partículas do compósito foram atraídas por ímãs e carregaram com elas as gotas de óleo, levando à completa desemulsificação e separação entre biodiesel e água.

New magnetic amphiphilic composites were prepared by the catalytic carbon vapor deposition (CVD) growth of carbon nanotubes and nanofibers using ethanol as carbon source and red mud waste (RM, a by-product of the Bayer process of alumina production) as catalyst and support. Temperature-programmed CVD (TPCVD), analyses by X-ray diffractometry (XRD), Mössbauer spectroscopy, energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy, thermogravimetry (TG/DTA), elemental analysis (CHN), superficial area determination (BET), scanning (SEM) and transmission (TEM) electron microscopies and magnetic measurements showed that ethanol reduces the iron ions in the red mud to form magnetic phases, e.g., Fe3O4 and Fe0, and carbon deposits (5-42 wt.%), particularly nanotubes and nanofibers. The combination of the hydrophobic carbon nanostructures with the hydrophilic Al, Si and Ti oxides present in the RM produced amphiphilic materials with excellent interaction with the water-oil interface. Soybean oil or decalin mixtures with water (completely immiscible) were easily emulsified in the presence of the amphiphilic composites. When the composites were added to stable biodiesel-water emulsions, the amphiphilic particles diffused to the interface oil-water. These composite particles were attracted by a magnet, carrying the oil droplets with them and leading to the complete demulsification and separation of the biodiesel from the water.

O objetivo deste estudo foi descrever um pseudo-surto de C. difficile em um hospital após a troca do método de detecção de toxina. Em fevereiro de 2002 houve dois casos de DACD e em março ocorreram sete casos, que coincidiram com a mudança de teste (que detectava apenas toxina A e passou a detectar toxinas A e B). Foi suspeitado que houvesse um surto e vigilância ativa e reforço educacional para os profissionais de saúde foi implantado. Um caso de DACD foi definido como um paciente com início abrupto de diarréia (> 3 episódios de fezes líquidas) e um teste positivo. Os casos foram classificados como de aquisição comunitária ou hospitalar. Foram colhidas fezes para cultura para C. difficile e os isolados foram tipados por AP-PCR. De março de 2002 a dezembro de 2003 houve 138 casos de DACD: 70% foram hospitalares e, entre os 30% de casos comunitários, a maioria (81%) foi de pacientes provenientes diretamente da comunidade (50% não tinham histórico de internação). Cinquenta e dois por cento dos casos de DCAD hospitalar e 94% de casos na admissão haviam utilizado antimicrobianos. A incidência de DCAD em pacientes internados foi de 3,3/100 pacientes e na admissão foi 6,1/1000 pacientes. Dezesseis isolados foram tipados e apresentaram 13 perfis diferentes. Em conclusão, o aumento de DACD no nosso estudo ocorreu por uma mudança de método diagnóstico e não devido a um surto como foi suspeitado inicialmente. A incidência em pacientes internados foi muito inferior ao que já foi relatado em surtos. Houve 13 perfis moleculares sugerindo que não ocorreu um surto. DACD foi, em grande parte, de aquisição comunitária.

The objective of this study was to describe a pseudo-outbreak of C. difficile in a hospital, following a change in the method used to detect the toxin. In February 2002, there were two cases of CDAD and in March 7 occurred, coinciding with a change of the test (from detection of toxin A to toxin A/B). An outbreak was suspected. Active surveillance and education of staff were started. A CDAD case was defined as a patient with acute onset of diarrhea (³ three episodes of liquid stools) and a positive stool test. They were classified as hospital or community-acquired. Stool samples were also collected for C. difficile culture and isolates were typed using AP-PCR. From March 2002 through December 2003 there were 138 cases of CDAD: 70% were hospital-acquired and among the 30% with CDAD present on admission, most (81%) came directly from the community (50% had no history of hospitalization). Fifty-two percent of hospital-acquired CDAD and 94% of cases on admission had already used antibiotics. The incidence of CDAD in hospitalized patients during surveillance was 3.3 per 1000 patient-admissions. The incidence of CDAD present on admission was 6.1/1000 patients. Sixteen isolates were typed and presented 13 different profiles. In conclusion, the CDAD increase in our study occurred due to change in diagnostic methods and not due to an outbreak, as suspected initially. The incidence in hospitalized patients was much lower than in reported outbreaks. There were 13 molecular types suggesting that an outbreak did not occur. CDAD was largely community-acquired.