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71.
A computational study on the thermodynamic properties of 13 beta-diketones is presented. The B3LYP//6-311+G(2d,2p)//B3LYP/6-31G(d) theoretical approach was employed to compute the O-H and C-H bond dissociation enthalpies and enthalpy of tautomerization and to estimate standard gas-phase enthalpies of formation for the radicals and for the parent molecules. The gas-phase enthalpies of formation for the neutral molecules are in excellent agreement with available experimental data, supporting the estimates made for the radicals. The latter are very important for the clarification of the thermochemistry of many beta-diketonato metal complexes previously reported in the literature. Importantly, when substituents R = -CHR' are attached to the beta-diketone's scaffold, C-H homolytic bond cleavage is always favored with respect to O-H bond scission.  相似文献   
72.
In this work, a microfluidic free-flow electrophoresis device, obtained by thermal toner transferring on glass substrate, is presented. A microdevice can be manufactured in only 1 h. The layout of the microdevice was designed in order to improve the fluidic and electrical characteristics. The separation channel is 8 microm deep and presents an internal volume of 1.42 microL. The deleterious electrolysis effects were overcome by using a system that isolates the electrolysis products from the separation channel. The Joule heating dissipation in the separation channel was found to be very efficient up to a current density of 8.83 mA/mm(2) that corresponds to a power dissipation per unit volume of running electrolyte of 172 mW/microL. Promising results were obtained in the evaluation of the microdevices for the separation of ionic dyes. The microfluidic device can be used for a continuous sample pretreatment step for micro total analysis system.  相似文献   
73.
A procedure for the determination of As in diesel, gasoline and naphtha at μg L−1 levels by GFAAS is proposed. Sample stabilization was achieved by the formation of three component solutions prepared by mixing appropriate volumes of the samples propan-1-ol and nitric acid aqueous solution. This mixture resulted in a one-phase medium, which was indefinitely stable. No changes in the analyte signals were observed over several days in spiked samples, proving long-term stabilization ability. The use of conventional (Pd) and permanent (Ir) modification was investigated and the former was preferred. Central composite design multivariate optimization defined the optimum microemulsion composition as well as the temperature program. In this way, calibration using aqueous analytical solutions was possible, since the same sensitivity was observed in the investigated microemulsion media and in 0.2% v/v HNO3. Coefficients of correlation larger than 0.999 and an As characteristic mass of 22 pg were observed. Recoveries (n=4) obtained from spiked samples were 98±4, 99±3 and 103±5%, and the limits of detection in the original samples were 1.8, 1.2 and 1.5 μg L−1 for diesel, gasoline and naphtha, respectively. Validation was performed by the analysis of a set of commercial samples by independent comparative procedures. No significant difference (Student’s t-test, p<0.05) was observed between comparative and proposed procedure results. The total determination cycle lasted 4 min for diesel and 3 min for gasoline and naphtha, equivalent to a sample throughput of 7 h−1 for diesel and 10 h−1 for gasoline and naphtha.  相似文献   
74.
The effect of EuCl3 on the aggregation processes of sodium dodecyl sulfate was investigated. Electrical conductivity data, combined with Eu(III) luminescence measurements, suggest that the formation of micelles involving EuCl3 and SDS occurs at low SDS concentration; the formation of these mixed aggregates was also monitored by light scattering, which indicates that the addition of EuCl3 to SDS concentration at values below the critical micelle concentration of the pure surfactant results in a much higher light scattering than that found just with SDS micelles. It was also found that the Eu(III)/DS- complexes are formed with a binding ratio which varies between 20 and 4, depending on the initial concentration of Eu(III). As the concentration increases, turbidity occurs initially, but solutions become clear subsequently. In contrast to the behavior of SDS in the presence of aluminum(III), no flocculation was observed. From the analysis of electrical conductivity data and comparison with other systems, it is suggested that growth of aggregates happens, probably with formation of nonspherical systems. At the highest concentrations these may involve just Eu(III) and DS- ions. The effect of temperature on the SDS micellization process was studied. The calculated free energy of SDS micellization is not dependent on the initial EuCl3 but is dependent on the final balance between the presence of counterions in solution (ionic strength) and the temperature.  相似文献   
75.
The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents.  相似文献   
76.
Pseudomonas aeruginosa PACL strain, isolated from oil-contaminated soil taken from a lagoon, was used to investigate the efficiency and magnitude of biosurfactant production, using different waste frying soybean oils, by submerged fermentation in stirred tank reactors of 6 and 10 l capacities. A complete factorial experimental design was used, with the goal of optimizing the aeration rate (0.5, 1.0, and 1.5 vvm) and agitation speed (300, 550, and 800 rpm). Aeration was identified as the primary variable affecting the process, with a maximum rhamnose concentration occurring at an aeration rate of 0.5 vvm. At optimum levels, a maximum rhamnose concentration of 3.3 g/l, an emulsification index of 100%, and a minimum surface tension of 26.0 dynes/cm were achieved. Under these conditions, the biosurfactant production derived from using a mixture of waste frying soybean oil (WFSO) as a carbon source was compared to production when non-used soybean oil (NUSO), or waste soybean oils used to fry specific foods, were used. NUSO produced the highest level of rhamnolipids, although the waste soybean oils also resulted in biosurfactant production of 75–90% of the maximum value. Under ideal conditions, the kinetic behavior and the modeling of the rhamnose production, nutrient consumption, and cellular growth were established. The resulting model predicted data points that corresponded well to the empirical information.  相似文献   
77.
The present study investigated the essential oil obtained from Campomanesia guazumifolia (Cambess.) O. Berg, an aromatic plant used in Brazilian folk medicine. The chemical composition was performed by GC×GC/qMS. The antioxidant and antimicrobial activities were evaluated by DPPH and BCB and, MIC assays, respectively. Sixty-eight compounds were identified in the oil, where the major compounds were bicyclogermacrene (15%), globulol (5%) and spathulenol (5%). Sesquiterpene hydrocarbons (29 compounds) and oxygenated sesquiterpenes (20 compounds) were the most representative classes of terpenes. DPPH (IC50 value 26.1 ± 0.5 μg/mL) and BCB (68.3 ± 1.5%) values indicated a significant antioxidant activity. The essential oil strongly inhibited Staphylococcus aureus (MIC 15 ± 0.1 μg/mL), Escherichia coli (MIC 25 ± 0.2 μg/mL) and Candida albicans (MIC 5 ± 0.1 μg/mL). The results give a deeper understanding of the chemical composition and report for the first time the antioxidant and antimicrobial potential of the C. guazumifolia essential oil.  相似文献   
78.
Thermodynamic properties of 3- and 4-phenoxyphenol have been determined by using a combination of calorimetric and effusion techniques as well as by high-level ab initio molecular orbital calculations. The standard (p° = 0.1 MPa) molar enthalpies of formation in the condensed and gas states, Δ(f)H(m)°(cr or l) and Δ(f)H(m)°(g), at T = 298.15 K, of 3- and 4-phenoxyphenol were derived from their energies of combustion in oxygen, measured by a static bomb calorimeter, and from the enthalpies of vaporization or sublimation derived respectively by Calvet microcalorimetry for the 3-phenoxyphenol and by Knudsen effusion technique for the 4-phenoxyphenol. The theoretically estimated gas-phase enthalpies of formation were calculated from high-level ab initio molecular orbital calculations at the G3(MP2)//B3LYP level of theory. Furthermore, this composite approach was also used to obtain information about the gas-phase acidities, gas-phase basicities, proton and electron affinities, adiabatic ionization enthalpies, and, finally, O?H bond dissociation enthalpies. The good agreement between the G3MP2B3-derived values and the experimental gas-phase enthalpies of formation for the 3- and 4-phenoxyphenol gives confidence to the estimate concerning the 2-phenoxyphenol isomer, which was not experimentally studied, and to the estimates concerning the radical and the anion. Additionally, the experimental values of gas-phase enthalpies of formation were also compared with estimates based on the empirical scheme developed by Cox.  相似文献   
79.
Polyaniline is a model molecular system in the study of conductive polymers. Ionic liquids, on the other hand, are becoming more and more a very convenient alternative for conventional organic solvents. The dissolution of polyaniline‐emeraldine base (PANI‐EB) in imidazolium ILs leads to its doping, as indicated by optical and resonance Raman spectroscopies. In this study, it is proposed that the interaction of PANI‐EB and imidazolium ILs involves the specific interaction of the quinoid moiety of the former with the imidazolium ring of the latter, an interpretation that is also based on N K‐edge XANES measurements of neat PANI‐EB, neat ILs, and of their solutions.

  相似文献   

80.
In this work, the mineral composition of fresh bovine milk obtained from the milk-producing areas of the Brazilian State of Sergipe was examined. A dry-ashed digestion method and the ICP OES technique were used for the quantification of mineral elements (e.g., Ca, Mg, K, Na, P, Sr and Zn) in 27 samples of milk collected from properties located in milk-producing areas around Nossa Senhora da Glória. The following ranges of values (% m/v) were obtained: 0.063 to 0.117 for Ca; 0.060 to 0.114 for P; 0.024 to 0.064 for Na; and 0.087 to 0.164 for K. The ranges of values (mg L− 1) for the other mineral elements were also found: 0.68 to 1.89 for Sr; 2.46 to 5.73 for Zn; and 54.2 to 109.9 for Mg. Additionally, the exploratory evaluation of the 27 milk samples was performed using principal component analysis (PCA) involving seven variables dealing with the effect of different management systems (conventional and organic) on milk composition. The results show that there are indeed differences between the mineral composition of milk from properties that use organic practices and those that use conventional management practices.  相似文献   
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