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681.
A thermodynamic analysis of methane oxidative reforming was carried out by Gibbs energy minimization (at constant pressure and temperature) and entropy maximization (at constant pressure and enthalpy) methods,to determine the equilibrium compositions and equilibrium temperatures,respectively.Both cases were treated as optimization problems (non-linear programming formulation).The GAMS 23.1 software and the CONOPT2 solver were used in the resolution of the proposed problems.The hydrogen and syngas production were favored at high temperatures and low pressures,and thus the oxygen to methane molar ratio (O 2 /CH 4) was the dominant factor to control the composition of the product formed.For O 2 /CH 4 molar ratios higher than 0.5,the oxidative reforming of methane presented autothermal behavior in the case of either utilizing O 2 or air as oxidant agent,but oxidation reaction with air possessed the advantage of avoiding peak temperatures in the system,due to change in the heat capacity of the system caused by the addition of nitrogen.The calculated results were compared with previously published experimental and simulated data with a good agreement between them. 相似文献
682.
Hossain Md Anawar Maria do Carmo Freitas Nuno Canha Isabel Dionísio Ho Manh Dung Catarina Galinha A. M. G. Pacheco 《Journal of Radioanalytical and Nuclear Chemistry》2012,294(3):377-381
Native plant species, lichens and tailings, sampled from a copper?Csulphide mining area located in southern?Ceastern Portugal, were analysed by neutron activation analysis (INAA) for determination of rare earth elements (REEs). Values of ??REEs and individual REEs concentration of tailing samples are higher than those of natural background concentrations. The higher values of REEs are found in modern slags and the mixture of oxidized gossan and sulphide disseminated country rocks when compared with the alluvial sediments contaminated by mine tailings. The total concentrations of light REEs are higher than those of heavy REEs in all tailing samples. Distribution patterns of PAAS-normalized REEs in mine tailings show slightly LREE enriched and flat HREE pattern with negative Eu anomaly. Lichens accumulated higher concentration of lanthanides than vascular plants. The elevated levels of REEs in lichen, native plant species and tailing samples reflect the contamination of REEs in S?o Domingos mining area. The Carlina corymbosa, Erica australis and Lavandula luisierra accumulated the higher amounts of La, Ce and other REEs than the other plant species grown in this mining area. 相似文献
683.
Juliano C.R. Freitas Túlio R. Couto Antônio A.S. Paulino João R. de Freitas Filho Ivani Malvestiti Roberta A. Oliveira Paulo H. Menezes 《Tetrahedron》2012,68(41):8645-8654
Catalytic amounts of tellurium(IV) tetrachloride were used to promote the O-glycosylation of 3,4,6-tri-O-acetyl-d-glucal to give the corresponding 2,3-unsaturated-O-glycosides. With simple alcohols, the desired compounds were obtained in good yields and excellent anomeric selectivity in a short reaction time using only 2 mol % of the catalyst. The application of the method in the synthesis of a small set of glycopyranosides with rigid or flexible linkers gave the corresponding α anomers as products in good yields. Further applications of some of the synthesized compounds in allylation reaction of aldehydes gave the corresponding homoallylic alcohols in good yields. 相似文献
684.
Baptista A Kato IT Prates RA Suzuki LC Raele MP Freitas AZ Ribeiro MS 《Photochemistry and photobiology》2012,88(3):584-589
In this study we developed a rat model of incipient caries to investigate the short-term effects of antimicrobial photodynamic therapy (aPDT) on oral microbiota regulation and demineralization arrestment. Twenty-nine male rats were submitted to caries induction. Early carious lesion was confirmed by optical coherence tomography (OCT) 5 days after experiment beginning in five animals. The remaining animals (n = 24) were randomly divided into two groups: control (n = 12), animals were untreated; and aPDT (n = 12), animals were treated with 100 μM of methylene blue for 5 min and irradiated by a light emitting diode at λ = 645 ± 30 nm, fluence rate of 480 mW cm(-2) and exposure time of 3 min. Bacterial burden was evaluated before, immediately after, 3, 7 and 10 days following treatment, and total number of microaerophilic bacteria was counted. OCT was also used to quantify teeth demineralization. A significant bacterial decrease of about 1.6 log was observed immediately after aPDT. Besides, bacterial load in aPDT group remained lower than control until 10 days post-treatment (P < 0.05) and variation of optical attenuation coefficient before and after aPDT was 15%, corroborating to caries arrestment. Put together, these findings suggest that aPDT was competent to reduce cariogenic bacteria and to avoid further mineral loss. 相似文献
685.
Continuous contact- and contamination-free ultrasonic emulsification-a useful tool for pharmaceutical development and production 总被引:1,自引:0,他引:1
A novel concept was developed here for the continuous, contact- and contamination-free treatment of fluid mixtures with ultrasound. It is based on exciting a steel jacket with an ultrasonic transducer, which transmitted the sound waves via pressurised water to a glass tube installed inside the jacket. Thus, no metallic particles can be emitted into the sonicated fluid, which is a common problem when a sonotrode and a fluid are in direct contact. Moreover, contamination of the fluid from the environment can be avoided, making the novel ultrasonic flow-through cell highly suitable for aseptic production of pharmaceutical preparations. As a model system, vegetable oil-in-water emulsions, fed into the cell as coarse pre-emulsions, were studied. The mean droplet diameter was decreased by two orders of magnitude yielding Sauter diameters of 0.5 microm and below with good repeatability. Increasing the residence time in the ultrasonic field and the sonication power both decreased the emulsion mean diameter. Furthermore, the ultrasonic flow-through cell was found to be well suited for the production of nanoparticles of biodegradable polymers by the emulsion-solvent extraction/ evaporation method. Here, perfectly spherical particles of a volume mean diameter of less than 0.5 microm could be prepared. In conclusion, this novel technology offers a pharmaceutically interesting platform for nanodroplet and nanoparticle production and is well suited for aseptic continuous processing. 相似文献
686.
Freitas AA Paulo L Maçanita AL Quina FH 《Langmuir : the ACS journal of surfaces and colloids》2006,22(19):7986-7993
The synthetic flavylium salt 4-carboxy-7-hydroxy-4'-methoxyflavylium chloride (CHMF) exhibits two acid-base equilibria in the range of pH 1-8 in both aqueous and micellar sodium dodecyl sulfate (SDS) solutions. The values of pK(a1) and pK(a2) for the cation-zwitterion (AH(2)(+) <--> Z + H(+)) and the zwitterion-base (Z <--> A(-) + H(+)) equilibria increase from 0.73 and 4.84 in water to 2.77 and 5.64 in SDS micelles, respectively. The kinetic study of the Z <--> A(-) + H(+) ground-state reactions in SDS points to the diffusion-controlled protonation of A(-) in the aqueous phase (k(p2w) = 4.2 x 10(10) M(-)(1) s(-)(1)) and in the micelle (k(p2m) = 2.3 x 10(11) M(-)(1) s(-)(1)). The deprotonation rate of Z did not significantly change upon going from water (k(d2) = 6.3 x 10(5) s(-)(1)) to SDS (k(d2) = 5.2 x 10(5) s(-)(1)), in contrast with the behavior of ordinary cationic flavylium salts, for which k(d2) strongly decreases in SDS micelles. These results suggest that deprotonation of the zwitterionic acid is not substantially perturbed by the micellar charge. Electronic excitation of the Z form of CHMF induces fast adiabatic deprotonation of the hydroxyl group of Z() (2.9 x 10(10) s(-)(1) in water and 8.4 x 10(9) s(-)(1) in 0.1 M SDS), followed by geminate recombination on the picosecond time scale. Interestingly, while recombination in water (k(rec) = 1.7 x 10(9) s(-)(1)) occurs preferentially at the carboxylate group, at the SDS micelle surface, recombination (k(rec) = 9.2 x 10(9) s(-)(1)) occurs at the hydroxyl group. The important conclusion is that proton mobility at the SDS micelle surface is substantially reduced with respect to the mobility in water, which implies that geminate recombination should be a general phenomenon in SDS micelles. 相似文献
687.
We define a sequence of real functions which coincide with Li'scoefficients at one and which allow us to extend Li's criterionfor the Riemann Hypothesis to yield a necessary and sufficientcondition for the existence of zero-free strips inside the criticalstrip 0 < R(z) < 1. We study some of the properties ofthese functions, including their oscillatory behaviour. 相似文献
688.
Experimental evidence have been suggesting that the toxicity of metals may involve inflammatory processes, with subsequent sustained overproduction of pro-oxidant reactive species, leading to indirect toxic effects, namely genotoxicity. Neutrophils, as important mediators of the innate defence systems, may have a hitherto not known role on these metal-induced adverse effects. Thus, the aim of the present study was to evaluate the putative activation of human neutrophils' oxidative burst by two groups of metals, the first group being able to undergo redox-cycling reactions (iron, copper, chromium and cobalt), whilst the primary route for the toxicity of the second group is not dependent on redox reactions (mercury and cadmium). The generation of reactive oxygen species (ROS) by metal-stimulated neutrophils was measured using the chemiluminometric probe luminol. Appropriate scavengers and metabolizing enzymes were subsequently used to identify the reactive species produced. The modulatory effects of metals on phorbol myristate acetate (PMA)-activated neutrophils were also studied. To evaluate the contribution of protein kinase C (PKC) on metal stimulatory effect, we used the specific inhibitor of PKC Gö6983. The obtained results showed that, in the present experimental conditions, only Cd (II) has the ability to stimulate the production of superoxide radical (O2−), hydrogen peroxide (H2O2), and hypochlorous acid (HOCl) in isolated human neutrophils. The same metal showed a synergistic effect with PMA. It was also demonstrated that Cd (II) induces neutrophils' oxidative burst mainly via activation of PKC, precluding a significant contribution of other cellular pathways for ROS generation mediated by this metal. These observations indicate that the sustained activation of human neutrophils may contribute for the long term adverse effects on human health mediated by Cd (II). 相似文献
689.
E. Andrade M. J. Madruga I. Bobos M. I. Paiva F. Maia A. Mateus R. Trindade M. C. Freitas M. A. Gonçalves 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(3):777-783
This paper describes the development of a separation method for americium from the effluents emanating from anion exchange
column, used for the recovery of plutonium from analytical waste solutions. The waste contained uranium, sodium, calcium and
iron as the major impurities as estimated by ICP-AES method. ~99% pure americium was obtained by three separation steps using
solvent extraction and extraction chromatography techniques. In the first step, uranium was quantitatively separated by giving
five contacts of equal volumes of 30% TBP in n-dodecane. Fe and Na were separated in the next step using 0.1 M TODGA + 0.5 M DHOA as the extractant. In the last step, Am
was separated from the co-extracted Ca (about 76%) using CMPO loaded extraction chromatographic column. The overall recovery
was >80% with decontamination factor (D.F.) from the impurities being >3000 while the purity of the product was 99%. 相似文献
690.
Soraya Alves de Morais Crislene Rodrigues da Silva Morais Petr?nio Filgueiras de Athayde Filho B. Freitas Lira Railda Shelsea Taveira Rocha do Nascimento 《Journal of Thermal Analysis and Calorimetry》2009,97(2):437-441
The mesoionic compounds are pentagonal heterocyclic betaines with their potential use mainly in the pharmacology field due
to the diversity of their biological activities. Their exceptional electric properties lead the compounds to be investigated
in the field such as the nonlinear optical devices. In this study, five mesoionic compounds of the 1,3-thiazole-5-thiolate
system had been synthesized from amino acids derived from glycine through 1,3-dipolar cycloaddition/cycloreversion reaction.
The compounds were characterized by the use of infrared spectrometry, thermogravimetry and differential scanning calorimetry
techniques. Thermal stability of each structure was determined and characterized by the kinetic study of the thermal decomposition
by non-isothermal thermogravimetry. The DSC curves for MI-1, MI-2, MI-3, MI-4, and MI-5 demonstrated their fusion and subsequent
decomposition with the exception of MI-3, which presented only decomposition stages. The kinetic models that better described
the thermal decomposition mechanism of the mesoionic compounds achieved by the non-isothermal methods were R1, R2 and R3 (based
on the geometric models). 相似文献