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Functional screening of metagenomic libraries is an important tool for the discovery of new molecules. The metabolic diversity of microorganisms enables survival in harsh environments and is related to the production of enzymes. In this study, we identified a protease-producing clone from a metagenomic library derived from mangrove sediment. The protease was purified by ammonium sulphate precipitation and gel filtration chromatography, with a yield of 77.27% and a specific activity of 8.57 U µg-1 . It had a molecular weight of approximately 70 kDa. MS/MS in ESI-Q-TOF revealed nine peptides similar to a peptidase of Bacillus safensis. The aligned partial sequence showed 47.48% identity and 82.74% similarity to the conserved domains of a glutamyl aminopeptidase from the human gut metagenome and 32.12% total coverage. The protease had an optimal pH of 8.5 and optimal activity at 60°C. At pH 9-12, its activity was greater than 80%. It had moderate thermotolerance and thermostability at temperatures of 40 and 50 °C. The KM and Vmax values were estimated to be 0.92 mg ml-1 , and 13.15 mmol min-1 for azocasein. Substrate specificity analysis showed that PR4A3 was active on gelatin, blood, egg yolk, and milk. These results support the potential use of PR4A3 in biotechnological applications.
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Proteínas de Bactérias/química , Proteínas de Bactérias/metabolismo , Endopeptidases/química , Endopeptidases/metabolismo , Sedimentos Geológicos/microbiologia , Metagenômica , Áreas Alagadas , Sequência de Aminoácidos , Bacillus/enzimologia , Proteínas de Bactérias/genética , Proteínas de Bactérias/isolamento & purificação , Biotecnologia , Brasil , Cromatografia em Gel , Endopeptidases/genética , Endopeptidases/isolamento & purificação , Ativação Enzimática , Ensaios Enzimáticos , Estabilidade Enzimática , Temperatura Alta , Concentração de Íons de Hidrogênio , Cinética , Metagenoma , Peso Molecular , Peptídeo Hidrolases/química , Peptídeo Hidrolases/genética , Peptídeo Hidrolases/isolamento & purificação , Sais , Alinhamento de Sequência , Especificidade por Substrato , Espectrometria de Massas em Tandem , TemperaturaRESUMO
The Fe(III) complexes Fe(5-Br-qsal)2Ni(dmit)2·solv with solv = CH2Cl2 (1) and (CH3)2CO (2) were synthesized, and their structural and magnetic properties were studied. While magnetization and Mössbauer spectroscopy data of 1 showed a gradual spin transition, compound 2 evidenced an abrupt transition with a thermal hysteresis of 13 K close to room temperature (T1/2 ↓ â¼273 K and T1/2 ↑ â¼286 K). A similar packing arrangement of segregated layers of cations and anions was found for 1 and 2. In both low-spin, LS, structures there are a large number of short intra- and interchain contacts. This number is lower in the high-spin, HS, phases, particularly in the case of 1. The significant loss of strong π-π interactions in the cationic chains and short contacts in the anionic chains in the HS structure of 1 leads to alternating strong and weak bonds between cations along the cationic chains and the formation of unconnected dimers along the anionic chains. This is consistent with a significant weakening of the extended interactions in 1. On the other hand, in the HS phase of 2 the 3D dimensionality of the short contacts observed in the LS phases is preserved. The effect of distinct solvent molecules on the intermolecular spacings explains the different spin crossover behaviors of the title compounds.
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This study investigated the effects of environmental temperature on repetitive box lifting (RBL) performance, associated stress hormone and creatine kinase (CK) responses. Ten healthy males performed two experimental trials in a random crossover design. The trials consisted of three 40 min (10 min sitting, 20 min standing, and 10 min RBL) circuits performed in either 23 °C or 38 °C followed by a 180 min seated recovery period in 23 °C. RBL performance (i.e., number of boxes lifted) was reduced (p ≤ 0.05) in 38 °C compared to the 23 °C trial. Physiological Strain Index was significantly different between trials (38 °C: 8.5 ± 1.1 versus 23 °C: 7.2 ± 0.7; p ≤ 0.01). Plasma testosterone was elevated (p ≤ 0.05) across both trials and then decreased at 60 min recovery, compared to pre-exercise (PRE) measures, but was higher (p ≤ 0.05) during the 38 °C trial. Plasma cortisol increased (p ≤ 0.05) at 60 min during both trials and remained elevated until 120 min in 23 °C, and until 60 min recovery in 38 °C. Serum CK was greater through 48 hr post compared to PRE values in both trials. Thus, 10 min RBL performance was reduced in 38 °C despite the 30-min rest periods between RBL intervals. Plasma testosterone and cortisol were generally higher during the 38 °C trial, suggesting a greater stress response. Additional research is needed to determine optimal work:rest cycles for maximizing work performance in thermally oppressive environments.
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Temperatura Corporal/fisiologia , Temperatura Alta , Remoção , Exposição Ocupacional/efeitos adversos , Estresse Fisiológico , Estudos Cross-Over , Humanos , Hidrocortisona/sangue , Masculino , Exposição Ocupacional/estatística & dados numéricos , Descanso , Testosterona/sangue , Trabalho , Adulto JovemRESUMO
When scanning a scene, the target of our search may be in plain sight and yet remain unperceived. Conversely, at other times the target may be perceived in the periphery prior to fixation. There is ample behavioral and neurophysiological evidence to suggest that in some constrained visual-search tasks, targets are detected prior to fixational eye movements. However, limited human data are available during unconstrained search to determine the time course of detection, the brain areas involved, and the neural correlates of failures to detect a foveated target. Here, we recorded and analyzed electroencephalographic (EEG) activity during free-viewing visual search, varying the task difficulty to compare neural signatures for detected and unreported ("missed") targets. When carefully controlled to remove eye-movement-related potentials, saccade-locked EEG shows that: (a) "Easy" targets may be detected as early as 150 ms prior to foveation, as indicated by a premotor potential associated with a button response; (b) object-discriminating occipital activity emerges during the saccade to target; and (c) success and failures to detect a target are accompanied by a modulation in alpha-band power over fronto-central areas as well as altered saccade dynamics. Taken together, these data suggest that target detection during free viewing can begin prior to and continue during a saccade, with failure or success in reporting a target possibly resulting from inhibition or activation of fronto-central processing areas associated with saccade control.
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Percepção de Forma/fisiologia , Movimentos Sacádicos/fisiologia , Córtex Visual/fisiologia , Vias Visuais/fisiologia , Adulto , Eletroencefalografia , Feminino , Humanos , MasculinoRESUMO
Single channel recordings were used to determine the effect of direct electrostatic interactions between sulfonate-coated gold nanoparticles and the constriction of the Staphylococcus aureus α-hemolysin protein channel on the ionic current amplitude. We provide evidence that Lys147 of α-hemolysin can interact with the sulfonate groups at the nanoparticle surface, and these interactions can reversibly block 100% of the residual ionic current. Lys147 is normally involved in a salt bridge with Glu111. The capture of a nanoparticle leads to a partial current block at neutral pH values, but protonation of Glu111 at pH 2.8 results in a full current block when the nanoparticle is captured. At pH 2.8, we suggest that Lys147 is free to engage in electrostatic interactions with sulfonates at the nanoparticle surface. To verify our results, we engineered a mutation in the α-hemolysin protein, where Glu111 is substituted by Ala (E111A), thus removing Glu111-Lys147 interactions and facilitating Lys147-sulfonate electrostatic interactions. This mutation leads to a 100% current block at pH 2.8 and a 92% block at pH 8.0, showing that electrostatic interactions are formed between the nanopore and the nanoparticle surface. Besides demonstrating the effect of electrostatic interactions on cross channel ionic current, this work offers a novel approach to controlling open and closed states of the α-hemolysin nanopore as a function of external gears.
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Ouro/química , Proteínas Hemolisinas/química , Lisina/química , Nanopartículas Metálicas/química , Nanoporos , Compostos de Sulfidrila/química , Concentração de Íons de Hidrogênio , Modelos Moleculares , Staphylococcus aureus/química , Propriedades de SuperfícieRESUMO
Twenty-eight Chagas disease patients (CD), 22 with the indeterminate clinical form (IND) and six with the cardiac or digestive form (CARD/DIG), were treated with benznidazole and underwent clinical and laboratorial analysis before (IND and CARD/DIG) and nine years after [patients after treatment (CDt), patients with the indeterminate clinical form at treatment onset (INDt) and with the cardiac or digestive form at treatment onset (CARD/DIGt)] treatment. The data demonstrate that 82.1% of CDt patients (23/28) remained clinically stable and 95.4% of the INDt (21/22) and 33.3% of the CARD/DIGt (2/6) patients showed unaltered physical and laboratorial examinations. The clinical evolution rate was 2%/year and was especially low in INDt patients (0.5%/year) relative to CARD/DIGt patients (7.4%/year). Positive haemoculture in treated patients was observed in 7.1% of the cases. None of the INDt (0/21) and 33.3% of the CARD/DIGt (2/6) patients displayed positive cultures. The PCR presented a positive rate significantly higher (85.2%, 23/27) than haemoculture and two samples from the same patient revealed the same result 57.7% of the patients. Conventional serology-ELISA on 16 paired samples remained positive in all individuals. Semi-quantitative ELISA highlighted significant decreases in reactivity, particularly in INDt relative to IND. Non-conventional serology-FC-ALTA-IgG, after treatment, showed positive results in all sera and 22 paired samples examined at seven and nine years after treatment, demonstrated significantly lower reactivity, particularly in INDt patients. This study was retrospective in nature, had a low number of samples and lacked an intrinsic control group, but the data corroborate other results found in the literature. The data also demonstrate that, even though a cure has not been detected in the none-treated patients, the benefits for clinical evolution were selectively observed in the group of INDt patients and did not occur for CARD/DIGt patients.
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Doença de Chagas/tratamento farmacológico , Nitroimidazóis/uso terapêutico , Tripanossomicidas/uso terapêutico , Trypanosoma cruzi/imunologia , Adolescente , Adulto , Anticorpos Antiprotozoários/sangue , Brasil , Cardiomiopatia Chagásica/tratamento farmacológico , Cardiomiopatia Chagásica/imunologia , Doença de Chagas/imunologia , Criança , Doença Crônica , Ensaio de Imunoadsorção Enzimática , Feminino , Humanos , Imunoglobulina G/imunologia , Masculino , Resultado do Tratamento , Adulto JovemRESUMO
Restricted contact with the external environment has allowed the development of microbial communities adapted to the oligotrophy of caves. However, nutrients can be transported to caves by drip water and affect the microbial communities inside the cave. To evaluate the influence of aromatic compounds carried by drip water on the microbial community, two limestone caves were selected in Brazil. Drip-water-saturated and unsaturated sediment, and dripping water itself, were collected from each cave and bacterial 16S rDNA amplicon sequencing and denaturing gradient gel electrophoresis (DGGE) of naphthalene dioxygenase (ndo) genes were performed. Energy-dispersive X-ray spectroscopy (EDX) and atomic absorption spectroscopy (AAS) were performed to evaluate inorganic nutrients, and GC was performed to estimate aromatic compounds in the samples. The high frequency of Sphingomonadaceae in drip water samples indicates the presence of aromatic hydrocarbon-degrading bacteria. This finding was consistent with the detection of naphthalene and acenaphthene and the presence of ndo genes in drip-water-related samples. The aromatic compounds, aromatic hydrocarbon-degrading bacteria and 16S rDNA sequencing indicate that aromatic compounds may be one of the sources of energy and carbon to the system and the drip-water-associated bacterial community contains several potentially aromatic hydrocarbon-degrading bacteria. To the best of our knowledge, this is the first work to present compelling evidence for the presence of aromatic hydrocarbon-degrading bacteria in cave drip water.
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The mineralogical composition of caves makes the environment ideal for inhabitation by microbes. However, the bacterial diversity in the cave ecosystem remains largely unexplored. In this paper, we described the bacterial community in an oxic chamber of the Sopradeira cave, an iron-rich limestone cave, in the semiarid region of Northeast Brazil. The microbial population in the cave samples was studied by 16S rDNA next-generation sequencing. A type of purple sulfur bacteria (PSB), Chromatiales, was found to be the most abundant in the sediment (57%), gravel-like (73%), and rock samples (96%). The predominant PSB detected were Ectothiorhodospiraceae, Chromatiaceae, and Woeseiaceae. We identified the PSB in a permanently aphotic zone, with no sulfur detected by energy-dispersive X-ray (EDX) spectroscopy. The absence of light prompted us to investigate for possible nitrogen fixing (nifH) and ammonia oxidizing (amoA) genes in the microbial samples. The nifH gene was found to be present in higher copy numbers than the bacterial-amoA and archaeal-amoA genes, and archaeal-amoA dominated the ammonia-oxidizing community. Although PSB dominated the bacterial community in the samples and may be related to both nitrogen-fixing and ammonia oxidizing bacteria, nitrogen-fixing associated gene was the most detected in those samples, especially in the rock. The present work demonstrates that this cave is an interesting hotspot for the study of ammonia-oxidizing archaea and aphotic PSB.
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The synthesis, structure, and magnetic properties of a novel oxalate-based bimetallic magnet obtained by using the chiral (S)-trimethyl-(1-phenyl-ethyl)-ammonium, ((S)-[PhCH(CH3)N(CH3)3](+)), cation as template is reported. This compound can be formulated as [(S)-[PhCH(CH3)N(CH3)3]][Mn(CH3CN)2/3Cr(ox)3] x (CH3CN)_(solvate), and it crystallizes in the chiral trigonal space group P3. It shows a distorted two-dimensional honeycomb structure formed by Mn(II) and Cr(III) ions connected through oxalate anions with [(S)-[PhCH(CH3)N(CH3)3](+) cations and solvent molecules intercalated between the oxalate layers. Two-thirds of the Mn(II) ions of the honeycomb anionic network are heptacoordinated. This compound behaves as a soft ferromagnet with an ordering temperature of 5.6 K.
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The ergogenic effects of caffeine on athletic performance have been shown in many studies, and its broad range of metabolic, hormonal, and physiologic effects has been recorded, as this review of the literature shows. However, few caffeine studies have been published to include cognitive and physiologic considerations for the athlete. The following practical recommendations consider the global effects of caffeine on the body: Lower doses can be as effective as higher doses during exercise performance without any negative coincidence; after a period of cessation, restarting caffeine intake at a low amount before performance can provide the same ergogenic effects as acute intake; caffeine can be taken gradually at low doses to avoid tolerance during the course of 3 or 4 days, just before intense training to sustain exercise intensity; and caffeine can improve cognitive aspects of performance, such as concentration, when an athlete has not slept well. Athletes and coaches also must consider how a person's body size, age, gender, previous use, level of tolerance, and the dose itself all influence the ergogenic effects of caffeine on sports performance.
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Desempenho Atlético , Cafeína/administração & dosagem , Desempenho Psicomotor/fisiologia , Esportes/fisiologia , Cafeína/efeitos adversos , Sistema Nervoso Central/efeitos dos fármacos , Medicina Baseada em Evidências , Feminino , Humanos , Masculino , Sistema Musculoesquelético/efeitos dos fármacos , Resistência Física , Fatores de Risco , Sensibilidade e Especificidade , Medicina EsportivaRESUMO
The systems biology approach has become an innovative tool when it comes to shedding light on the complex immune response underlying the development/maintenance of distinct clinical forms of Chagas disease. The goal of this study was to describe an integrative overview of Fc-γR expression, cytokine microenvironment and anti-Trypanosoma cruzi IgG interface in indeterminate-(IND) and cardiac-(CARD) patients. Data demonstrated that IND displayed an overall higher Fcγ-R expression (CD16; CD32; CD64) on neutrophils-(NEU), along with (CD16; CD64) on monocytes-(MON) as compared to CARD. Additionally, CARD presented an increased expression of CD32 in B-cells. While preserved frequency of IL-10-producing cells was observed in IND, decreased levels of IL-10+ phagocytes and enhanced TNF+ MON and NK-cells were observed in CARD. T. cruzi-antigen recall in vitro induces a general decrease of Fc-γR expression in Chagas disease patients, especially in CARD. Moreover, T. cruzi-antigen stimuli triggered a concomitant increase of IFN-γ+NEU/TNF+NK-cells and IL-10+MON/IL-10+B-cells in IND. Biomarker signatures further emphasized the contrasting Fc-γR expression and cytokine microenvironment observed in Chagas disease patients with distinct clinical forms. Up-regulation of Fc-γR expression (CD16 on NEU;MON;NK) was observed in IND, whereas a general decrease was reported for CARD. Moreover, while a mixed cytokine microenvironment (TNF; IL-10) was observed in IND, CARD presented a contrasting profile with up-regulation of TNF+NEU and IL-12+NEU. Integrative network analysis revealed a distinct assemblage of biomarkers, with CARD presenting a large number of negative internode connectivity in comparison with IND. The relevant gaps in Fc-γR expression and impaired regulatory cytokine microenvironment interfaced with the anti-T. cruzi IgG reactivity throughout an exacerbated negative connectivity may account for the development/maintenance of the clinical status of cardiac Chagas disease.
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INTRODUCTION: Authorities advise individuals to refrain from caffeine intake before or during exercise, especially when performed in the heat, due to potential fluid-electrolyte imbalances that exaggerate physiological strain. Yet, military personnel are often deployed to hot environments and must perform under sleep-deprived conditions where caffeine would be an ideal intervention strategy to enhance physical and cognitive performance. PURPOSE: To assess the effects of controlled chronic and acute caffeine ingestion on fluid-electrolyte, physiological and thermoregulatory responses during an exercise heat tolerance test (EHT). METHODS: Subjects were 59 active, college-aged males (mean +/- SE 21.6 +/- 0.4 yr, 177.9 +/- 0.8 cm, 75.4 +/- 1.0 kg, 11.1 +/- 0.7% body fat) who were randomized and stratified by age, bodyweight, and body composition into three groups. All subjects equilibrated caffeine intake at 3 mg x kg(-1) x d(-1) for days 1-6. On days 7-12, they consumed a treatment dose of either 0 (G0), 3 (G3), or 6 (G6) mg x kg(-1) x d(-1). Fluid-electrolyte and physiological measures were made on day 12, 1 h after caffeine intake, during the EHT (90 min walking, 1.56 m x s(-1), 5% grade; dry bulb temperature, 37.7 +/- 0.1 degree C; relative humidity, 56.3 -1.5%). RESULTS: There were no between-group differences (p > 0.05) in plasma, urinary, thermoregulatory, cardiovascular, and perceptual variables across time (pre- vs. post-EHT), although some of these variables increased significantly over time (p < 0.05). EHT time was significantly greater in G3 (86 +/- 2.0 min) vs. GO (75 +/- 3.3 min, p < 0.05). DISCUSSION: Acute caffeine ingestion, in chronically consuming subjects (3 and 6 mg x kg(-1) x d(-1)) did not alter fluid-electrolyte, exercise endurance or thermoregulatory responses during EHT when compared with G0.
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Regulação da Temperatura Corporal/efeitos dos fármacos , Cafeína/farmacologia , Exercício Físico/fisiologia , Temperatura Alta , Equilíbrio Hidroeletrolítico/efeitos dos fármacos , Adulto , Análise de Variância , Método Duplo-Cego , Transtornos de Estresse por Calor/prevenção & controle , Humanos , Masculino , Militares , Resistência Física/efeitos dos fármacosRESUMO
In this paper we present an experimental and theoretical study to investigate the electronic structures of [ML2]â» (M(III) = Cu, L = pdt and pds, pyrazine-2,3-dithiolate and -diselonate; M(III) = Au, L = pds) with the aim of elucidating the nature of the bonding and to establish the innocent-noninnocent character of the ligand in these complexes. Calculations based on DFT methods have been performed to obtain geometry optimizations, harmonic frequencies, IR intensities and Raman scattering activities. The experimental vibrational spectra are accurately reproduced by the calculations, which show that CC, CN, and CX (X = S, Se) vibrations are extensively mixed with other modes, and thus unsuitable to work as vibrational markers. Geometry optimization performed at the DFT level provides geometrical parameters in good agreement with the available structural data. The energetic sequence and nature of the redox-active molecular orbitals help to elucidate the observed electrochemical behaviour. Accordingly, the quasi-reversible redox couple for the reduction processes exhibited by [ML2]²â» (L = pdt and pds), that appears at negative values and depends both on the ligand and on the metal, is related to the LUMO which is a σ antibonding combination of the ligand orbitals (sulfur or selenium atoms) and the 3d(xy) (Cu) and 5d(xy) (Au) metal orbitals. The HOMO is a π-orbital with a b(2g) symmetry, predominantly ligand in character with a small contribution of the nd(xz) atomic orbitals in antibonding combination with chalcogen atom orbitals. The low energy of the metal d-orbitals compared to the ligand orbitals, due to the high effective nuclear charge of the metals, explains their small participation to this orbital. Thus in [ML2]â» the metals approach the oxidation state 3+ and the ligand a dichalcogenolate description and thus a prevalent innocent character. However the same ligand shows a noninnocent character in complexes with a different d8 metal such as Ni(II) whose d-orbitals lie at higher energies and mix at a higher extent with the ligand orbitals in the HOMO.
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Complexos de Coordenação/química , Metais/química , Pirazinas/química , Cobre/química , Ouro/química , Ligantes , Modelos Moleculares , Modelos Teóricos , Estrutura Molecular , Níquel/química , Oxirredução , Análise Espectral RamanRESUMO
A mathematical model is presented that describes the ionic transport across the cortical thick ascending limb (cTAL) of the Henle's loop, taking into account its tubular geometry. A comprehensive description of the cTAL is given for the first time in terms of potential, ion concentrations and ion fluxes along the tubule. For given ion concentrations at the entrance of the tubule, the model simulates steady-state profiles and allows the fitting of existing experimentally measured values at its exit. Moreover, the model expands the potentialities of experiments in situ and enables testing the effect of different perturbations induced by drugs or mutation-altering transport activity. One of the main insights given by this model is the increase of the lumenal electrical potential from the entrance to the exit of the tubule with a profile determined by the transepithelial electrical potential difference and by the chemical gradients along the lumen, both reflecting transepithelial salt transport. Furthermore, model and experimental results are consistent, showing that when the TAL is perfused at high rates with a diluted NaCl solution in relation to the bath, the transepithelial electrical potential difference increases from 6.7 to 23.0 mV and the potential difference across the basolateral barrier changes very little. The model predicts that the same static head is obtained independently of the NaCl concentration at the entrance of the tubule. A final important insight concerns the lowest reported NaCl concentrations (20-30 mM) at the exit of the tubule, which is controlled by a very tight epithelium, where the back-leak is substantially reduced.
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Alça do Néfron/fisiologia , Modelos Biológicos , Cloreto de Sódio/metabolismo , Equilíbrio Hidroeletrolítico/fisiologia , Animais , Transporte Biológico Ativo/fisiologia , Epitélio/fisiologia , Humanos , Potenciais da Membrana/fisiologiaRESUMO
This investigation determined if 3 levels of controlled caffeine consumption affected fluid-electrolyte balance and renal function differently. Healthy males (mean +/- standard deviation; age, 21.6 +/- 3.3 y) consumed 3 mg caffeine . kg(-1) . d(-1). on days 1 to 6 (equilibration phase). On days 7 to 11 (treatment phase), subjects consumed either 0 mg (C0; placebo; n= 20), 3 mg (C3; n = 20), or 6 mg (C6; n = 19) caffeine . kg(-1) . d(-1) in capsules, with no other dietary caffeine intake. The following variables were unaffected (P > 0.05) by different caffeine doses on days 1, 3, 6, 9, and 11 and were within normal clinical ranges: body mass, urine osmolality, urine specific gravity, urine color, 24-h urine volume, 24-h Na+ and K+ excretion, 24-h creatinine, blood urea nitrogen, serum Na+ and K+, serum osmolality, hematocrit, and total plasma protein. Therefore, C0, C3, and C6 exhibited no evidence of hypohydration. These findings question the widely accepted notion that caffeine consumption acts chronically as a diuretic.
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Água Corporal/efeitos dos fármacos , Cafeína/administração & dosagem , Estimulantes do Sistema Nervoso Central/administração & dosagem , Desidratação/induzido quimicamente , Rim/efeitos dos fármacos , Equilíbrio Hidroeletrolítico/efeitos dos fármacos , Adolescente , Adulto , Água Corporal/metabolismo , Cafeína/efeitos adversos , Cafeína/metabolismo , Estimulantes do Sistema Nervoso Central/efeitos adversos , Estimulantes do Sistema Nervoso Central/metabolismo , Relação Dose-Resposta a Droga , Método Duplo-Cego , Humanos , Rim/fisiologia , Testes de Função Renal , Masculino , Equilíbrio Hidroeletrolítico/fisiologiaRESUMO
Yeast strains from the genera Candida, Debaryomyces, Aureobasidium, Geotrichum, Pichia, Rhodotorula, Tremella, Hanseniaspora, and Cryptococcus were isolated from samples of a gold mine from liquid extraction circuit. These strains were tested for their ability to utilize acetonitrile at 12 mM as the sole nitrogen source. The yeasts that grew using acetonitrile at 12 mM were tested in the presence of acetonitrile, isobutyronitrile, methacrylnitrile, and propionitrile at concentrations of 12, 24, 48, 97, and 120 mM. One strain was selected for each nitrile and the concentration of nitrile in which the best growth occurred. Cryptococcus sp. strain UFMG-Y28 had a better growth on 120 mM propionitrile and 97 mM acetonitrile, Rhodotorula glutinis strain UFMG-Y5 on 48 mM methacrylnitrile, and Cryptococcus flavus strain UFMG-Y61 on 120 mM isobutyronitrile. The utilization of different nitriles and amides by yeast strains involves hydrolysis in a two-step reaction mediated by both inducible and intracellular nitrile hydratase and amidase.
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The deprotonated form of the ligands pyrazine-2,3-diselenol (pds) and pyrazine-2,3-dithiol (pdt) react with Cu(ClO(4))(2).6 H(2)O to form different Cu(III) complexes Na[Cu(III)(pds)(2)].2 H(2)O (1), Li[Cu(III)(pds)(2)].3 H(2)O (2), and Na[Cu(III)(pdt)(2)].2 H(2)O (4) depending on the countercation compound used as deprotonating agent (NaOH, LiOH). Two other Cu(III) complexes were obtained by replacement of the alkali metal cations with tetrabutylammonium (TBA(+)), namely, TBA[Cu(III)(pds)(2)] (3), and TBA[Cu(III)(pdt)(2)] (5). All complexes were characterized by (1)H and (13)C NMR and IR spectroscopy, electronic absorption, elemental analysis, cyclic voltammetry (CV), and X-ray crystallography. Electrical conductivity measurements on single crystals show that these salts exhibit insulating behavior. The crystal structure of these species revealed a lateral coordination capability of the N atoms of the pyrazine ring of both pds and pdt ligands towards the alkali metal ions, which leads to the build up of a net of coordinative bonds, hydrogen bonds, and contacts that result in the final 3D structure. Two parameters control the crystal engineering of the final 3D structures: the nature of the alkali metal countercation and the nature of the chalcogen atom (Se/S), which allow fine-tuning of complex 3D crystal lattice. Density functional calculations were performed on the [Cu(pds)(2)] and [Cu(pdt)(2)] systems to investigate the electronic structure of the complexes and understand their electronic and electrochemical behavior by studying the frontier molecular orbitals. This study also reveals whether the redox processes take place on the ligands or on the metal center, a question under continuous discussion in the literature.
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Álcalis/química , Cobre/química , Modelos Teóricos , Compostos Organometálicos/química , Cátions/química , Ligantes , Modelos Químicos , Compostos Organometálicos/síntese química , Pirazinas/síntese química , Pirazinas/química , EstereoisomerismoRESUMO
The deprotonated form of the pyrazine-2,3-diselenol (pds) ligand, pds(2-), reacts with Ni(II) inorganic salts to form the nickel compounds [Ni(II)(pds)(2)](nBu(4)N)(2) (1), [Ni(II)(pds)(2)]Na(2).2H(2)O (2), and [Ni(III)(pds)(2)](2)Na(2).4H(2)O (3), depending on the reaction conditions. They are characterized by NMR, EPR, UV-vis, and IR spectroscopies, elemental analysis, cyclic voltammetry, and X-ray crystallography. The crystal structure of compound 3 shows the formation of segregated stacks of Ni(pds)(2-) units, with a strong dimerization along the stacks. The stacked fashion of the crystal packing was expected since the supramolecular forces of the alkaline side coordination to the pyrazine moieties dominate, as happens in the recently reported analogous copper system [Cu(III)(pds)(2)]Na.2H(2)O. The structure of 2 further emphasizes the alkaline coordination as the dominating supramolecular event, and an orthogonal array of 2D layers is observed. The absence of alkaline cations in complex 1 is reflected in a crystal packing with isolated complex Ni(pds)(2)(2-) units. The dimerization found in the paramagnetic Ni(III) complex 3 promotes a very strong antiferromagnetic interaction, leading to a singlet ground state.