Cinética e mecanismo da reação de auto-oxidação de S(IV) catalisada por íons metálicos de transição

The oxidation process of sulfur (IV) species (SO2, HSO3- e SO32-) by oxygen, catalysed by trace metal ion and complexes, can play an important role in atmospheric, analytical and bioinorganic chemistry. An overview of the most important reactions in these fields is presented. A fascinating redox cycling of the metal ions and complexes during such autoxidation process was revealed by the combination of kinetics and coordination chemistry studies.

Elementos da dinâmica química ao nível da teoria variacional do estado de transição com correções interpoladas

In this article are presented some fundamental elements of the conventional and of the variational transition state theories which are needed to carried out calculations of semi-classical chemical dynamics. Some important bottlenecks in building reliable potential energy surfaces using electronic structure calculations are also discussed. It is put emphasis on the methodology of the variational transition state theory with interpolated corrections (VTST-IC), and its application in the calculations of the rate constants and of the kinetic isotope effect (KIE) of CH4 + Cl « CH3 + HCl reaction.

Constituintes químicos de Ottonia corcovadensis Miq. da floresta Amazônica: atribuição dos deslocamentos químicos dos átomos de hidrogênio e carbono

In an ethanolic extract of leaves of Ottonia corcovadensis (Piperaceae) were identified sixteen terpenoids of essential oil and the three flavonoids 3',4',5,5',7-pentamethoxyflavone (1), 3',4',5,7-tetramethoxyflavone (2) and 5-hydroxy-3',4',5',7-tetramethoxyflavone (3) and cafeic acid (4). Two amides (5 and 6) were isolated from an ethanolic extract of the roots. The structures were established by spectral analysis, meanly NMR (1D and 2D) and mass spectra. Extensive NMR analysis was also used to complete ¹H and 13C chemical shift assignments of the flavonoids and amides. The components of the essential oil were identified by computer library search, retention indices and visual interpretation of mass spectra.

Aplicação da calorimetria exploratória diferencial no estudo da cinética de transição alfa -> delta HMX

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) or octogen is a white crystalline substance which occurs in four polymorphous forms. It is used in a wide variety of military and industrial formulations owing to its suitable properties. Researchers have demonstrated the usefulness of this energetic material in explosive components. In the present work we apply differential scanning calorimetry (DSC) to measure the a ® d solid-solid phase transition energy of HMX. The results obtained by Kissinger's and Ozawa's methods were 487 and 495 kJ/mol, respectively.

Lesões em DNA induzidas pela autoxidação de S(IV) na presença de íons metálicos de transição

The oxidation of sulfite catalyzed by transition metal ions produces reactive oxysulfur species that can damage plasmid and isolated DNA in vitro. Among the four DNA bases, guanine is the most sensitive to one-electron oxidation promoted by the species formed in the autoxidation of sulfite (HSO5-, HO•, SO3•-, SO4•- and SO5•-) due to its low reduction potential and ability to bind transition metal ions capable to catalyze oxidative processes. Some oxidative DNA lesions are promutagenic and oxidative DNA damage is proposed to play a crucial role in certain human pathologies, including cancer.

Avaliação da concentração de alguns íons metálicos em diferentes espécies de líquens do cerrado Sul-Mato-Grossense

Concentrations of Fe, Mn, Co, Cr, Zn and Cu were determinated using flame atomic absorption spectrometry in nine lichen species of the Sul-Mato-Grossense cerrado. The average metal ion concentrations varied in the following ranges: Fe, 248.41-1568.01; Mn, 98.50-397.33; Co, 10.08-24.81; Cr, 18.24-44.26; Zn, 14.62-34.79 and Cu, 3.23-7.57 mg kg-1. Statistical analysis (Pearson and Cluster) applied to the metal ion concentrations indicated that the accumulation of these ions can be due to several anthropogenic sources including agricultural activities, mineral exploration, biomass burning, soil mineral composition and leather tanning processes by chromium.

Aporte atmosférico de amônio, nitrato e sulfato em área de floresta ombrófila densa montana na Serra dos Órgãos, RJ

Wet and dry (dust) deposition was measured in the Serra dos Órgãos National Park. VWM pH was 5.3. Non-sea-salt (nss) SO4(2-) comprised 97% of total SO4(2-). The molar ratio [2(nss-SO4(2-)) + NO3-]/[NH4+ + H+] was 1.1, suggesting that pH is predominantly controlled by H2SO4, HNO3, and NH3. Wet deposition of NH4+, NO3-, and nss-SO4(2-) was respectively 0.59, 0.25, and 0.30 kmol ha-1 yr-1. Assuming that dry deposition of N can comprise 30-50% of its total (dry + wet) deposition, the latter is estimated to be 1.2-1.7 kmol ha-1 yr-1 (17-24 kg N ha-1 yr-1).

Estudi de seguretat i salut del projecte de pavimentació de diferents sectors de la Floresta. Sant Cugat del Vallès

El E.S.S. té com a objectiu establir les bases tècniques per fixar els paràmetres de la prevenció de riscos professionals durant la realització dels treballs d’execució de les obres del Projecte objecte d’estudi, així com complir amb les obligacions que es desprenen de la Llei 31 / 1995 i del RD 1627 / 1997, amb la finalitat de facilitar el control i el seguiment dels compromisos adquirits al respecte per part dels Contractistes.

Estudi per a la millora de l’espai públic a diferents sectors urbanístics de La Floresta

El document fa una proposta de pavimentació a La Floresta, als sectors urbanístics de Casino, Turó del Sol, Carrer del Caqui, la Floresta Alta, Colònia Parés, Colònia Mirador-oest, Colònia Mirador-est, els Porters sud, Muntanyesa sud i Sector del Golf.L’àmbit d’actuació la xarxa local que comprèn la distribució veïnal amb el trànsit pacificat amb prioritat per a vianants, enxarxada inevitablement amb la xarxa local de camins que transcorre per l’entorn no urbanitzat i que enllaça diversos espais urbans com cases aïllades, corredors verds fonamentalment en l’àmbit del Parc Natural de Collserola, i parcs i jardins del àmbit urbà de La Floresta. Els carrers interiors en aquests sectors es plantegen amb les característiques de circulació restringida. Es pren com a criteri, fer els vials principals de doble direcció, mentre que per als vials secundaris s’estudia la possibilitat d’un únic carril de circulació i mantenir les dues direccions deixant espais de reserva (sobreamples) per a l’encreuament de dos vehicles, tot afegidament al fet d’aconseguir el major espai d’aparcament. Aquesta definició de sectors portara delimitar en el seu interior les denominades “zones 30” que permeten compatibilitzar altres usos (bicicletes,..). La formalització d’aquests espais fa que es presenti una oportunitat de millora de la qualitat urbana que a La Floresta en escasses ocasions s’ha donat.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Interação de átomos leves com clusters de metais de transição

Density Functional Theory (DFT) calculations on the interactions of small atoms (H, C, O, and S) on first-row transition metal clusters were performed. The results show that the adsorption site may vary between the metal surface and the edge of the cluster. The adsorption energies, adatom-nearest neighbor and adatom-metal plane distances were also determined. Finally, the authors present a discussion about the performance of these metals as anodes on solid oxide fuel cells. The results obtained agree with empirical data, indicating that the theoretical model used is adequate

Qualidade dos méis produzidos por Melipona fasciculata Smith da região do cerrado maranhense

The honey of Melipona fasciculata is few known in terms of composition, and therefore generally associated with the characteristics of the honey of Apis mellifera. This study contributes to the knowledge of the physico-chemical characteristics of honey of M. fasciculata of the municipalities of Barra do Corda, Jenipapo dos Vieiras, Fernando Falcão, Carolina and Riachão, in cerrado region from Maranhão. The parameters studied were: moisture, pH, acidity, reducing sugars, apparent sucrose, hydroxymethylfurfural, diastase activity, insoluble solids, ash and color. Some of the observed patterns may conform to the established for A. mellifera, but others must be accompanied by a specific legislation.

Influência da saponificação na determinação de carotenoides em maracujás do cerrado

This work describes the evaluation of the effect of saponification process in the carotenoid's content of three species of passion fruit. The results indicated the saponification of the extract was necessary to obtain cis-violaxanthin, trans-violaxanthin and β-cryptoxanthin hydrolyzed. These compounds were found in fruits of commercial P. edulis and yellow wild P. edulis. However, the extract saponification did not permitted to obtain free carotenes in fruits of wild purple P. edulis and P. setacea, and to trans-violaxanthin of P. cincinnata, therefore saponification was not indicated in the carotenoid analysis of these three accessions of passion fruit.

Fluxos de óxido nitroso em solos com cobertura de Floresta Ombrófila Densa Montana na Serra dos Órgãos, Rio de Janeiro

Soil fluxes of N2O were determined over one year in montane tropical rainforest of southeastern Brazil with average annual rainfall of 2.8 m. Annual mean (± standard deviation) and median N2O fluxes were 3.0 ± 1.4 and 2.7 µg N m-2 h-1, respectively, is 5-10 times lower than mean values reported in literature for tropical rainforest soils in the Amazon basin. N2O fluxes varied spatially and seasonally, were about twice as high during summer as in winter, and significantly influenced by both monthly precipitation and soil temperature.

Fósforo em cronossequência de cana-de-açúcar queimada no cerrado goiano: análise de ácidos húmicos por RMN de 31P

The aim of this study was to identify, with the use of 31P NMR spectroscopy, organic P species in humic acids (HA) in samples from Oxisol cultivated in chronosequence with sugar cane, pasture and Cerrado. The main forms of P-type found were orthophosphate, monoester-P (phosphate sugars) and P-diester (orthophosphate). The 31P NMR technique proved capable of identifying changes in the areas studied as a function of sugar cane burning time. In areas with 1 and 5 years of burnt cane, a decrease in recalcitrant organic P in humic acids indicated the need for use of P-humic substances for plant nutrition.