Dinámica de reacciones unimoleculares en fase gas: Desviaciones del comportamiento estadístico

The present review summarizes the most relevant results of our research group obtained recently in the field of unimolecular reaction dynamics. The following processes are specifically analyzed: the isomerization, dissociation and elimination in methyl nitrite, the fragmentation reactions of the mercaptomethyl cation, the C-CO dissociation in the acetyl and propionyl radicals, and the decomposition of vinyl fluoride. In all the cases, only state- or energy-selected systems are considered. Special emphasis is paid to the possibility of systems exhibiting non-statistical behavior.

Recuperação de metais de catalisadores mássicos e monometálicos

This work presents a study on the dissolution of some commercial monometallic and non-supported deactivated catalysts in HF + H2O2 mixtures (and, eventually, other media) under mild experimental conditions, after a previous oxidation step. The samples were neither crushed nor grinded. The best experimental conditions were dependent on the nature of the support and of the active phase. For example, the Pt/Al2O3 catalyst was dissolved in about 10 minutes, without agitation and heating; however, dissolution of the Pd/Al2O3, Ni/Al2O3, Ni/SiO2, Cu/Al2O3 and V2O5 samples required a temperature of 60 ºC and an agitation of 400 rpm. A careful addition of a NaOH solution allowed a quantitative precipitation of aluminium as criolite (Na3AlF6) or precipitation of Si as Na2SiF6; NaF was obtained as a by-product. As expected, processing of Pd/C, V2O5 and CuO.Cr2O3 samples was relatively simple. Metals recovery from catalysts reached a quantitative level in all samples studied; it is particularly interesting that platinum and palladium could be easily recovered in a single step process, thus separing them from aluminium.

Eletrodo íon-seletivo para determinação potenciométrica de alumínio(III) em meio de fluoreto

The construction and analytical evaluation of a coated graphite Al(III) ion-selective electrode, based on the ionic pair formed between the Al(F)n3-n anion and tricaprylylmethylammonium cation (Aliquat 336S) incorporated on a poly(vinylchloride) (PVC) matrix membrane are described. A thin membrane film of this ionic pair and dibutylphthalate (DBPh) in PVC was deposited directly on a cylindric graphite rod (2 cm length x 0.5 cm diameter) attached to the end of a glass tube using epoxy resin. The membrane solution was prepared by dissolving 40% (m/m) of PVC in 10 mL of tetrahydrofuran following addition of 45% (m/m) of DBPh and 15% (m/m) of the ionic pair. The effect of membrane composition, fluoride concentration, and several concomitants as potential interferences on the electrode response were investigated. The aluminium(III) ion-selective electrode showed a linear response ranging from 1.4 x 10-4 to 1.0 x 10-2 mol L-1, a detection limit of 4.0 x 10-5 mol L-1, aslope of -54.3±0.2mV dec-1 and a lifetime of more than 1 year (over 3000 determinations for each membrane). The slope indicates that the ion-selective electrode responds preferentially to the Al(F)4- species. Application of this electrode for the aluminium(III) determination in stomach anti-acid samples is reported.

O impacto industrial na composição química das águas subterrâneas com enfoque de consumo humano (Rio Grande, RS)

The alteration in the quality of groundwater in the industrial zone of Brazil's southernmost state was assessed by a hydrogeochemical study. In 70-85% of the studied area, fluoride, nitrate and phosphate in groundwater surpass the maximum limits for human consumption according to Brazilian environmental legislation. The chemical spectrum of contaminants and their spatial distribution show that fertilizer production processes are responsible for groundwater pollution. The natural conditions of the region are not favorable for minimal protection against infiltration of pollutants into the aquifer.

Processamento de pilhas Li/MnO2 usadas

This work presents two recycling processes for spent Li/MnO2 batteries. After removal of the solvent under vacuum the cathode + anode + electrolyte was submitted to one of the following procedures: (a) it was calcined (500 ºC, 5 h) and the calcined solid was submitted to solvent extraction with water in order to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Manganese was recovered as sulfate; (b) the solid was treated with potassium hydrogeno sulfate (500 ºC, 5 h). The solid was dissolved in water and the resulting solution was added dropwise to sodium hydroxide. Manganese was recovered as dioxide. The residual solution was treated with potassium fluoride in order to precipitate lithium fluoride.

Recuperação de cobalto e de lítio de baterias íon-lítio usadas

The "active mass" (cathode + anode + electrolyte) of spent Li-ion batteries was submitted to one of the following procedures: (a) it was calcined (500 ºC) and submitted to extraction with water to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Cobalt was recovered as sulfate; (b) the "active mass" was treated with potassium hydrogen sulfate (500 ºC) and dissolved in water. Cobalt was precipitated together with copper after addition of sodium hydroxide. Lithium was partially recovered as lithium fluoride. Co-processing of other battery components (aluminum and copper foils) affected negatively the behavior of the recovery procedures. Previous segregation of battery components is essential for an efficient and economical processing of the "active mass".

Teor de fluoretos em infusões de chá verde (Camellia sinensis)

The aim of this work was to study the influence of green tea consumption on fluoride ingestion. The extraction conditions of fluorides from green tea infusions were defined and nine brands of green tea available in Portugal were analyzed. The quantification of fluorides in the green tea was preceded by the implementation and validation of the potentiometric method (commercial fluoride selective electrode). The concentration of fluorides in the samples ranged from 0. 8 to 2. 0 mg L-1.

O ressurgimento da química de benzino com sililaril triflatos no contexto das reações de inserção em ligações sigma

In this paper we gathered articles concerning insertion reactions of arynes, exclusively generated from 2-(trimethylsilyl)aryl triflates in the presence of fluoride ions, in substrates bearing nucleophilic and electrophilic portions separated by sigma bonds. Accordingly, we stand out the great importance and versatility of such transformations in the preparation of highly functionalized aromatic systems, which are hardly synthesized in just one step for other methods.

Preparo de amostras de combustíveis fósseis por piroidrólise para a determinação de flúor e cloro

Pyrohydrolysis is proposed for fossil fuels sample preparation for further fluorine and chlorine determination. Samples were heated during 10 min at temperatures up to 1000 °C. Water vapor was passed through the reactor and the volatile products were condensed and collected in NH4OH solution. Fluoride was determined by potentiometry using an ion selective electrode (ISE) and Cl by ICP OES and DRC-ICP-MS. The results are in good agreement with certified values and the precision is better than 10% (n = 4). Sample preparation by means of pyrohydrolysis is relatively simple, whereas chlorine and fluorine can be determined at low concentrations.

Corrosion resistance improvement of titanium base alloys

The corrosion resistance of the new Ti-6Al-4V-1Zr alloy in comparison with ternary Ti-6Al-4V alloy in Ringer-Brown solution and artificial Carter-Brugirard saliva of different pH values was studied. In Ringer-Brown solution, the new alloy presented an improvement of all electrochemical parameters due to the alloying with Zr; also, impedance spectra revealed better protective properties of its passive layer. In Carter-Brugirard artificial saliva, an increase of the passive film thickness was proved. Fluoride ions had a slight negative influence on the corrosion and ion release rates, without to affect the very good stability of the new Ti-6Al-4V-1Zr alloy.

RESSONÂNCIA MAGNÉTICA NUCLEAR DE SUBSTÂNCIAS ORGANOFLUORADAS: UM DESAFIO NO ENSINO DE ESPECTROSCOPIA

Nuclear magnetic resonance is a technique that is widely used for elucidating and characterizing organic substances. Organofluorine substances have applications in many areas from drugs to liquid crystals, but their NMR spectra are often challenging due to fluoride coupling with other nuclei. For this reason, NMR spectra of this class of substances are not commonly covered in undergraduate and graduate chemistry courses and related fields. Thus, the aim of this work was the presentation and discussion of 1H, 13C, and 19F NMR spectra of eleven organofluorine substances which, in the case of 1H and 13C nuclei, showed classic patterns of first-order coupling and the effects of the fluorine nucleus in different chemical and magnetic environments. In addition, the observation of long distance coupling constants was possible through the use of apodization functions in the processing of the spectra. It is expected that the examples presented herein can be utilized and discussed in undergraduate and graduate NMR spectroscopy disciplines and thus improve the teaching and future research of organofluorine compounds.

MATERIAIS VÍTREOS E LUZ: PARTE 1

2015 is the Year of Light, according to UNESCO. Chemistry has a close relationship with light and one of the materials that allows such synergy is glass. Depending on the chemical composition of the glass, it is possible to achieve technological applications for the whole range of wavelengths extending from the region of the microwave to gamma rays. This diversity of applications opens a large range of research where chemistry, as a central science, overlaps the fields of physics, engineering, medicine, etc., generating a huge amount of knowledge and technological products used for humanity. This review article aimed at discussing some families of glasses, illustrating some applications. Due to the extension of the theme, and all points raised, we thought it would be good to divide the article into two parts. In the first part we focus on the properties of heavy metal oxide glasses, fluoride glasses and chalcogenide glasses. In the second part we emphasize the properties of glassy thin films prepared by sol-gel methodology and some applications, of both glasses as the films in photonics, and more attention was given to the nonlinear properties and uses of photonic fibers.

Flúor em chuva simulada: sintomatologia e efeitos sobre a estrutura foliar e o crescimento de plantas arbóreas

Os objetivos deste trabalho foram: caracterizar os efeitos do flúor em espécies arbóreas nativas, nos estádios de plântula e muda; identificar injúrias provocadas pelo flúor na estrutura da lâmina foliar da espécie mais sensível; fornecer subsídios para seleção de características a serem utilizadas na bioindicação e contribuir com informações sobre a resistência ou tolerância das plantas, visando ao reflorestamento de áreas impactadas pela chuva com flúor. As espécies analisadas foram Gallesia gorazema Moq. (Phytolaccaceae), Genipa americana L. (Rubiaceae), Joannesia princeps Vell. (Euphorbiaceae), Peltophorum dubium (Spreng.) Taub. (Leguminosae, Caesalpinioideae) e Spondias dulcis Forst. f. (Anacardiaceae). Plântulas e mudas dessas espécies, provenientes do Parque Estadual do Rio Doce (MG), foram submetidas a 20 min diários de chuva com flúor (30 mg.L-1), por 10 dias consecutivos. Necroses apicais e marginais foram observadas em todas as espécies analisadas, logo após a primeira chuva simulada. S. dulcis, no estádio de muda, foi a espécie mais sensível ao flúor, pois apresentou extensas necroses com apenas dois dias de tratamento, enquanto que G. americana foi a espécie mais resistente. Nas mudas, as espécies que acumularam mais flúor foram também as que apresentaram maior sensibilidade a esse poluente; essa relação não foi verificada nas plântulas. A concentração de flúor utilizada promoveu alterações drásticas na lâmina foliar de S. dulcis com extensas áreas necrosadas, danificando toda a sua estrutura anatômica. A sensibilidade ao flúor observada em S. dulcis indica que essa espécie apresenta potencial para ser usada como bioindicadora. Entretanto, estudos detalhados serão necessários para a melhor caracterização das respostas de S. dulcis ao flúor visando a sua utilização em programas de biomonitoramento ambiental.

The calcium-dependent protease of Loxosceles gaucho venom acts preferentially upon red cell band 3 transmembrane protein

Eighty micrograms red blood cell (RBC) ghosts from patients who had previously exhibited the cutaneous form of loxoscelism (presenting localized dermonecrosis) and the viscerocutaneous form of loxoscelism (presenting dermonecrosis, hemoglobinuria, hematuria, and jaundice) and from controls were incubated with 2.5 µg crude Loxosceles gaucho venom in 5 mM phosphate buffer, pH 7.4, at 37ºC. Among all membrane proteins, quantitative proteolysis of the important integral transmembrane protein 3 increased with venom dose and with incubation time from 30 to 120 min, as demonstrated by gel densitometry. Similar quantitative data were obtained for RBC ghosts from patients and from control subjects, a fact that argues against the possibility of genetic factors favoring the hemolytic viscerocutaneous form. These data suggest that the clinical forms may be different types of the same disease, with the viscerocutaneous form being the result of large amounts of intravascularly injected venom and the superficial form being the result of in situ venom action. Since protein 3 is a housekeeping integral membrane protein, whose genetic deficiency leads to hemolytic anemia, it is reasonable to relate it to the hemolysis which occurs in the viscerocutaneous form of loxoscelism. The venom protease responsible for the process was not inhibited after 120-min incubation by 0.2 mM paramethylsulfonyl fluoride or by 0.2 mM N-ethylmaleimide but was inhibited by 25 mM ethylenediaminetetraacetic acid (a calcium-chelating agent) in 5 mM phosphate buffer at pH 7.4, which suggests that the enzyme is a calcium-dependent metalloprotease.

Protective effect of N-acetylcysteine against oxygen radical-mediated coronary artery injury

The present study investigated the protective effect of N-acetylcysteine (NAC) against oxygen radical-mediated coronary artery injury. Vascular contraction and relaxation were determined in canine coronary arteries immersed in Kreb's solution (95% O2-5% CO2), incubated or not with NAC (10 mM), and exposed to free radicals (FR) generated by xanthine oxidase (100 mU/ml) plus xanthine (0.1 mM). Rings not exposed to FR or NAC were used as controls. The arteries were contracted with 2.5 µM prostaglandin F2alpha. Subsequently, concentration-response curves for acetylcholine, calcium ionophore and sodium fluoride were obtained in the presence of 20 µM indomethacin. Concentration-response curves for bradykinin, calcium ionophore, sodium nitroprusside, and pinacidil were obtained in the presence of indomethacin plus Nomega-nitro-L-arginine (0.2 mM). The oxidative stress reduced the vascular contraction of arteries not exposed to NAC (3.93 ± 3.42 g), compared to control (8.56 ± 3.16 g) and to NAC group (9.07 ± 4.0 g). Additionally, in arteries not exposed to NAC the endothelium-dependent nitric oxide (NO)-dependent relaxation promoted by acetylcholine (1 nM to 10 µM) was also reduced (maximal relaxation of 52.1 ± 43.2%), compared to control (100%) and NAC group (97.0 ± 4.3%), as well as the NO/cyclooxygenase-independent receptor-dependent relaxation provoked by bradykinin (1 nM to 10 µM; maximal relaxation of 20.0 ± 21.2%), compared to control (100%) and NAC group (70.8 ± 20.0%). The endothelium-independent relaxation elicited by sodium nitroprusside (1 nM to 1 µM) and pinacidil (1 nM to 10 µM) was not affected. In conclusion, the vascular dysfunction caused by the oxidative stress, expressed as reduction of the endothelium-dependent relaxation and of the vascular smooth muscle contraction, was prevented by NAC.