Kinetics and the mechanism of the thermal reaction between trifluoromethylhypofluorite and hexafluoropropene

The kinetics of the thermal reaction between CF₃OF and C₃F₆ have been investigated between 20 and 75°C. It is a homogeneous chain reaction of moderate length where the main product is a mixture of the two isomers 1-C₃F₇OCF₃ (68%) and 2-C₃F₇OCF₃ (32%). Equimolecular amounts of CF₃OOF₃ and C₆F₁₄ are formed in much smaller quantities. Inert gases and the reaction products have no influence on the reaction, whereas only small amounts of oxygen change the course of reaction and larger amounts produce explosions. The rate of reaction can be represented by eq. (I): The following mechanism explains the experimental results: Reaction (5) can be replaced by reactions (5a) and (5b), without changing the result: Reaction (4) is possibly a two-step reaction: For ∣CF₃ = ∣C₃F₆∣, ν_20°C = 36.8, ν_50°C = 24.0, and ν_70°C = 14.2.     

Enhancement of the antibiotic activity of aminoglycosides by extracts from Anadenanthera colubrine (Vell.) Brenan var. cebil against multi-drug resistant bacteria

The aim of this work was to evaluate the antimicrobial activity of ethanol (EEAC) and hexane (HFAC) extracts from the stem bark of Anadenanthera colubrina (Vell.) Brenan var. cebil alone or in combination with aminoglycosides against multi-drug resistant (MDR) bacteria. Minimal inhibitory concentrations (MICs) of the extracts were determined by using microdilution assay. For the evaluation of extracts as modulators of antibiotic resistance, MICs of neomycin and amikacin were determined in presence or absence of each compound at sub-inhibitory concentrations. Both EEAC and HFAC did not show antimicrobial activity against MDR strains tested. However, the addition of EEAC and HFAC enhanced the activity of neomycin and amikacin against Staphylococcus aureus SA10 strain. When the natural products were replaced by chlorpromazine, the same effect was observed. Anadenanthera colubrine var. cebil may be a source of phytochemicals able to potentiate the aminoglycoside activity against MDR S. aureus by the inhibition of efflux pump.     

Antioedematogenic activity,acetylcholinesterase inhibition and antimicrobial properties of Jacaranda oxyphylla

Jacaranda oxyphylla Cham. (Bignoniaceae) is a shrub found in the Brazilian cerrado and used in folk medicine to treat microbial infections. The aim of this study was to carry out a phytochemical screening and evaluate antioedematogenic, antimicrobial and antiacetylcholinesterase properties of J. oxyphylla crude extracts. All extracts analysed showed presence of terpenoids, which are potentially active chemical substances. A high AChE inhibitory activity for hexane extract from leaves and for the extracts from twigs was found. Ethanol extract from leaves of J. oxyphylla showed activity against Gram-positive (Staphylococcus aureus and Bacillus cereus) and Gram-negative (Escherichia coli) bacteria. This extract was also effective in inhibiting the stages of inflammation evaluated. Biological investigation and phytochemical screening of J. oxyphylla extracts provided additional evidence of its traditional medicinal value.     

Real‐time image‐content‐based beamline control for smart 4D X‐ray imaging

Real‐time processing of X‐ray image data acquired at synchrotron radiation facilities allows for smart high‐speed experiments. This includes workflows covering parameterized and image‐based feedback‐driven control up to the final storage of raw and processed data. Nevertheless, there is presently no system that supports an efficient construction of such experiment workflows in a scalable way. Thus, here an architecture based on a high‐level control system that manages low‐level data acquisition, data processing and device changes is described. This system is suitable for routine as well as prototypical experiments, and provides specialized building blocks to conduct four‐dimensional in situ, in vivo and operando tomography and laminography.     

Specific Heat Anomalies in Solids Described by a Multilevel Model

In the field of condensed matter physics, specific heat measurements can be considered as a pivotal experimental technique for characterizing the fundamental excitations involved in a certain phase transition. Indeed, phase transitions involving spin (de Souza et al. Phys. B Condens. Matter 404, 494 (2009) and Manna et al. Phys. Rev. Lett. 104, 016403 (2010)), charge (Pregelj et al. Phys. Rev. B 82, 144438 (2010)), lattice (Jesche et al. Phys. Rev. B 81, 134525 (2010)) (phonons) and orbital degrees of freedom, the interplay between ferromagnetism and superconductivity (Jesche et al. Phys. Rev. B 86, 020501 (2012)), Schottky-like anomalies in doped compounds (Lagos et al. Phys. C Supercond. 309, 170 (1998)), electronic levels in finite correlated systems (Macedo and Lagos J. Magn. Magn. Mater. 226, 105 (2001)), among other features, can be captured by means of high-resolution calorimetry. Furthermore, the entropy change associated with a first-order phase transition, no matter its nature, can be directly obtained upon integrating the specific heat over T, i.e., C(T)/T, in the temperature range of interest. Here, we report on a detailed analysis of the two-peak specific heat anomalies observed in several materials. Employing a simple multilevel model, varying the spacing between the energy levels Δ_i = (E_i?E₀) and the degeneracy of each energy level g_i, we derive the required conditions for the appearance of such anomalies. Our findings indicate that a ratio of \({\Delta }_{2}/{\Delta }_{1}\thickapprox \) 10 between the energy levels and a high degeneracy of one of the energy levels define the two-peaks regime in the specific heat. Our approach accurately matches recent experimental results. Furthermore, using a mean-field approach, we calculate the specific heat of a degenerate Schottky-like system undergoing a ferromagnetic (FM) phase transition. Our results reveal that as the degeneracy is increased the Schottky maximum in the specific heat becomes narrow while the peak associated with the FM transition remains unaffected.     

Biotreatment of High Strength Nitrate Waste Using Immobilized Preadapted Sludge

One of the major wastes generated by fertilizer, explosive, and nuclear industries are nitrate (as high as 1,000 ppm NO(3)N) whose removal before disposal has become a growing concern. In this study, an active denitrifying sludge was immobilized onto support materials like cloth and polyurethane foam and their denitrification efficiency on high nitrate wastes [1,000 ppm NO(3) (225 ppm NO(3)N), 5,000 ppm NO(3) (1,129 ppm NO(3)N), 7,500 ppm NO(3) (1,693 ppm NO(3) N)] was studied. Results showed complete degradation of the nitrate wastes (225 ppm NO(3)N, 1,129 ppm NO(3)N, and 1,693 ppm NO(3)N) without any accumulation of nitrite in a period of only 1, 4, and 10 h, respectively. Based on adhering and entrapment principle, an immobilization unit was developed using a combination of cloth and foam as well as both individually. This system used for treating such high nitrate wastes was found to be quite effective in waste water treatment, particularly in problems associated with solid-liquid separation. The batch column reactor was run in about 45 batches without any loss in activity or reactor stability.     

Evidence of change in the molecular organization of 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid solutions with the addition of water

Physico-chemical properties of ionic liquids like density, viscosity, conductivity, surface tension and excess molar volume are strongly dependent on their concentration in aqueous solutions. 1-n-Butyl-3-methylimidazolium tetrafluoroborate/water solutions, at 25 °C, shows two clearly distinguished behaviors, corresponding to a water-rich and a salt-rich region, with distinct physico-chemical properties. It is shown that [BMIm][BF₄] exhibits surfactant properties. The results obtained are discussed in terms of the interactions between cations and anions of the ionic liquid and the water molecule. IR studies show that the addition of water modifies the organization of the ionic liquid molecules. The data collection reported is helpful for a variety of different technological applications and in particular for electrochemical applications, as capacitors, batteries and fuel cells among others.     

Biomonitoring method for the simultaneous determination of cadmium and lead in whole blood by electrothermal atomic absorption spectrometry for assessment of environmental exposure

The aim of this work is to propose a biomonitoring method for the simultaneous determination of Cd and Pb in whole blood by simultaneous electrothermal atomic absorption spectrometry for assessment of environmental levels. A volume of 200 microL of whole blood was diluted in 500 microL of 0.2% (wv(-1)) Triton) X-100+2.0% (vv(-1)) HNO3. Trichloroacetic acid was added for protein precipitation and the supernatant analyzed. A mixture of 250 microg W+200 microg Rh as permanent and 2.0% (wv(-1)) NH4H2PO4 as co-injected modifiers were used. Characteristic masses and limits of detections (n=20, 3s) for Cd and Pb were 1.26 and 33 pg and 0.026 microg L(-1) and 0.65 microg L(-1), respectively. Repeatability ranged from 1.8 to 6.8% for Cd and 1.2 to 1.7% for Pb. The trueness of method was checked by the analysis of three Reference Materials: Lyphocheck Whole Blood Metals Control level 1 and Seronorm Trace Elements in Whole Blood levels 1 and 2. The found concentrations presented no statistical differences at the 95% confidence level. Blood samples from 40 volunteers without occupational exposure were analyzed and the concentrations ranged from 0.13 to 0.71 microg L(-1) (0.32+/-0.19 microg L(-1)) for Cd and 9.3 to 56.7 microg L(-1) (25.1+/-10.8 microgL(-1)) for Pb.