Quimiluminescência de peróxidos orgânicos: geração de estados eletronicamente excitados na decomposição de 1,2-dioxetanos

In this review article, we give a general introduction on the mechanisms involved in organic chemiluminescence, where three basic models for excited state formation are presented. The chemiluminescence properties of 1,2-dioxetanes - four membered ring peroxides - are briefly outlined in the second part. In the main part, the mechanisms involved in the decomposition of 1,2-dioxetanes and analogous peroxides are discussed: (i) the unimolecular decomposition of 1,2-dioxetanes; (ii) the electron transfer catalyzed decomposition of peroxides by an intermolecular CIEEL (Chemically Initiated Electron Exchange Luminescence) mechanism; (iii) 1,2-dioxetane decomposition catalyzed by an intramolecular electron transfer mechanism (intramolecular CIEEL). Special emphasis is given to the latter subject, where recent examples with potential analytical applications are presented.

Técnica para seleção de variáveis aplicada à separação de gases

This paper describes an experimental design technique, known as variables search, developed to expose the critical variables and screen out the irrelevant ones. It is easy to learn and use and clearly dissociates the main and interactions effects from each other. An example of air separation process by pressure swing adsorption was used to demonstrate how the variables search technique works. The phases of identification of the critical variables is shown, step by step,.

Tautomerism and Fragmentation of Biologically Active Hetero Atom (O, N)-Containing Acyclic and Cyclic Compounds Under Electron Ionization

In this thesis a total of 86 compounds containing the hetero atoms oxygen and nitrogen were studied under electron ionization mass spectrometry (EIMS). These compounds are biologically active and were synthesized by various research groups. The main attention of this study was paid on the fragmentations related to different tautomeric forms of 2- phenacylpyridines, 2-phenacylquinolines, 8-aryl-3,4-dioxo-2H,8H-6,7-dihydroimidazo- [2,1-c][1,2,4]triazines and aryl- and benzyl-substituted 2,3-dihydroimidazo[1,2-a]pyrimidine-5,7-(1H,6H)-diones. Also regio/stereospecific effects on fragmentations of pyrrolo- and isoindoloquinazolinones and naphthoxazine, naphthpyrrolo-oxazinone and naphthoxazino-benzoxazine derivatives were screened. Results were compared with NMR data, when available. The first part of thesis consists of theory and literature review of different types of tautomerism and fragmentation mechanisms in EIMS. The effects of tautomerism in biological systems are also briefly reviewed. In the second part of the thesis the own results of the author, based on six publications,are discussed. For 2-phenacylpyridines and 2-phenacylquinolines the correlation of different Hammett substituent constants to the relative abundances (RA) or total ion currents (% TIC) of selected ions were investigated. Although it was not possible to assign most of the ions formed unambiguously to the different tautomers, the linear fits of their RAs and % TICs can be related to changing contributions of different tautomeric forms. For dioxoimidazotriazines and imidazopyrimidinediones the effects of substituents were rather weak. The fragmentations were also found useful for obtaining structural information. Some stereoisomeric pairs of pyrrolo- and isoindoloquinazolines and regiomeric pairs of naphtoxazine derivatives showed clear differences in thir mass spectra. Some mechanisms are suggested for their fragmentations.

Aplicação de análise de componentes principais para verificação de atribuições de sinais nos espetros de RMN ¹H: o caso dos 3-aril (1,2,4)-oxadiazol-5-carboidrazida benzilidenos

The ¹H NMR data set of a series of 3-aryl (1,2,4)-oxadiazol-5-carbohydrazide benzylidene derivatives synthesized in our group was analyzed using the chemometric technique of principal component analysis (PCA). Using the original ¹H NMR data PCA allowed identifying some misassignments of the proton aromatic chemical shifts. As a consequence of this multivariate analysis, nuclear Overhauser difference experiments were performed to investigate the ambiguity of other assignments of the ortho and meta aromatic hydrogens for the compound with the bromine substituent. The effect of the 1,2,4-oxadiazol group as an electron acceptor, mainly for the hydrogens 12,13, has been highlighted.

Aplicação da cromatografia gasosa bidimensional abrangente com microdetector de captura de elétrons para determinação de agrotóxicos em sedimentos

Analysis of seven pesticides in sediments was successfully achieved using comprehensive two-dimensional gas chromatography with micro-electron capture detection, as it provided higher sensitivity and less matrix interference. Repeatability and intermediate precision of peak areas and heights were less than 4% and the recovery percentage for the analytes ranged from 52 to 115%. Instrumental LOD and LOQ were in the range of 0.60 to 2.31 μg L-1 and 1.83 to 5.62 μg L-1, respectively. Concentrations of 3.34 μg kg-1 (dry basis) for trifloxystrobin and azoxystrobin (below the LOQ) were found in a sediment sample.

Influence of initial CaO/SiO2 ratio on the hydration of rice husk ash-Ca(OH)2 and sugar cane bagasse ash-Ca(OH)2 pastes

This work presents the results of a study on the hydration of pastes containing calcium hydroxide and either rice husk ash (RHA) or sugar cane bagasse ash (SCBA) in various initial CaO/SiO2 molar ratios. The products of the reactions were characterized by thermal analyses X-ray diffraction, and scanning electron microscopy. In the case of the RHA pastes, the product was composed of CaO-SiO2-H2O (type I C-S-H) or CaO-SiO2-H2O (type II C-S-H) according to the CaO/SiO2 ratio of the mixture. In contrast, in the case of the SBCA pastes, the product was composed primarily of CaO-SiO2-H2O that differed from both the previous types; the product also contained inclusions of calcium aluminate hydrates.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

Comparison of some properties of Cu(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

The physico-chemical properties and thermal stability in air of Cu(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates were compared and the influence of the position of -OCH3 substituent on their thermal stability was investigated. The complexes are crystalline, hydrated salts with blue colour. The carboxylate ion is a bidentate chelating or bridging group. The thermal stability of analysed Cu(II) dimethoxybenzoates was studied in the temperature range of 293-1173 K. The positions of methoxy- groups in benzene ring influence the thermal properties of studied complexes. Their different thermal properties are markedly connected with the various influence of inductive, mesomeric and steric effects of -OCH3 substituent on the electron density in benzene ring. The magnetic susceptibilities of the complexes were measured over the range of 76-300 K and the magnetic moments were calculated. The results show that they form dimers.

Magnetic, thermal and spectral properties of Ni(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

Complexes of Ni(II) 2,3-, 3,5- and 2,6-dimethoxybenzoates have been synthesized, their physico-chemical properties have been compared and the influence of the position of -OCH3 substituent on their properties investigated. The analysed compounds are crystalline, hydrated salts with green colour. The carboxylate ions show a bidentate chelating or bridging coordination modes. The thermal stabilities of Ni(II) dimethoxybenzoates were investigated in air in the range of 293-1173 K. The complexes decompose in three steps, yelding the NiO as the final product of decomposition. Their solubilities in water at 293 K are in the order of 10-2-10-4 mol×dm-3. The magnetic susceptibilities for the analysed dimethoxybenzoates of Ni(II) were measured over the range of 76-303 K and the magnetic moments were calculated. The results reveal that the complexes are the high-spin ones and the ligands form the weak electrostatic field in the octahedral coordination sphere of the central Ni(II) ion. The various position -OCH3 groups in benzene ring cause the different steric, mesomeric and inductive effects on the electron density in benzene ring.

The Influence of Certain Processing Factors on the Durability of Yttrium Stabilized Zirconia Used As Dental Biomaterial

In dentistry, yttrium partially stabilized zirconia (ZrO2) has become one of the most attractive ceramic materials for prosthetic applications. The aim of this series of studies was to evaluate whether certain treatments used in the manufacturing process, such as sintering time, color shading or heat treatment of zirconia affect the material properties. Another aim was to evaluate the load-bearing capacity and marginal fit of manually copy-milled custom-made versus prefabricated commercially available zirconia implant abutments. Mechanical properties such as flexural strength and surface microhardness were determined for green-stage milled and sintered yttrium partially stabilized zirconia after different sintering time, coloring process and heat treatments. Scanning electron microscope (SEM) was used for analyzing the possible changes in surface structure of zirconia material after reduced sintering time, coloring and heat treatments. Possible phase change from the tetragonal to the monoclinic phase was evaluated by X-ray diffraction analysis (XRD). The load-bearing capacity of different implant abutments was measured and the fit between abutment and implant replica was examined with SEM. The results of these studies showed that the shorter sintering time or the thermocycling did not affect the strength or surface microhardness of zirconia. Coloring of zirconia decreased strength compared to un-colored control zirconia, and some of the colored zirconia specimens also showed a decrease in surface microhardness. Coloring also affected the dimensions of zirconia. Significantly decreased shrinkage was found for colored zirconia specimens during sintering. Heat treatment of zirconia did not seem to affect materials’ mechanical properties but when a thin coating of wash and glaze porcelain was fired on the tensile side of the disc the flexural strength decreased significantly. Furthermore, it was found that thermocycling increased the monoclinic phase on the surface of the zirconia. Color shading or heat treatment did not seem to affect phase transformation but small monoclinic peaks were detected on the surface of the heat treated specimens with a thin coating of wash and glaze porcelain on the opposite side. Custom-made zirconia abutments showed comparable load-bearing capacity to the prefabricated commercially available zirconia abutments. However, the fit of the custom-made abutments was less satisfactory than that of the commercially available abutments. These studies suggest that zirconia is a durable material and other treatments than color shading used in the manufacturing process of zirconia bulk material does not affect the material’s strength. The decrease in strength and dimensional changes after color shading needs to be taken into account when fabricating zirconia substructures for fixed dental prostheses. Manually copy-milled custom-made abutments have acceptable load-bearing capacity but the marginal accuracy has to be evaluated carefully.

Sobrevivência de Fusarium oxysporum f. sp. lycopersici Raça 2 submetido à técnica da solarização associada à incorporação de folhas de mandioca

A solarização combinada com a prévia adição de material orgânico propicia controle efetivo de diversos fungos de solo que de outra forma são de difícil erradicação, permitindo, também, redução do tempo de tratamento. O objetivo do trabalho foi avaliar o controle do fungo Fusarium oxysporum f. sp. lycopersici Raça 2, por meio da incorporação da parte aérea de mandioca brava (Manihot utilisima) e mandioca mansa (Manihot dulcis) seguido de solarização do solo. Foi realizado experimento de campo, onde incorporou-se 3 Kg/m² da parte aérea de mandioca brava e mandioca mansa, separadamente. O experimento constou de seis tratamentos (solarização + mandioca brava; solarização + mandioca mansa; solo solarizado; solo; mandioca brava e mandioca mansa). A sobrevivência do fungo foi avaliado por meio das estruturas de resistência em meio semi-seletivo de Komada, aos 7, 14, 21 e 28 dias do início do experimento. As temperaturas do solo foram monitoradas através de um coletor de dados Tipo CR23X (Campbell Scientific) e a quantificação dos gases (CO2 e O2) foi feita pelo equipamento analisador de gases (Testo 325-1). Nos tratamentos solarizados, a temperatura do solo e aprisionamento de CO2 foram maiores em relação à testemunha (solo) e aos tratamentos apenas com a incorporação de material vegetal. A associação da incorporação de mandioca, tanto a "brava" quanto a "mansa", com a solarização, proporcionou a inativação de F. oxysporum f.sp. lycopersici Raça 2, podendo atuar no controle da doença murcha de fusarium causada por este patógeno. Os demais tratamentos foram inócuos, permitindo a sobrevivência do fungo.

Densidade básica e variação dimensional de um híbrido clonal de Eucalyptus urophylla x Eucalyptus grandis

Espécies de rápido crescimento como as do gênero Eucalyptus apresentam sérios problemas durante as diversas fases de processamento de desdobro, secagem e beneficiamento. Assim, este trabalho objetivou estudar as propriedades físicas da madeira de um híbrido clonal de Eucalyptus urophylla x Eucalyptus grandis de duas idades, provenientes de regeneração florestal por talhadia simples e por reforma, em diferentes intensidades de desbaste, com diâmetros entre 28,0 e 30,0 cm. Os resultados indicaram que o extrato de maior idade com intervenção de dois desbastes (E2) apresentou os maiores valores médios da densidade básica ao longo do fuste e na direção medula-casca, além de menores contrações volumétricas médias e menor fator anisotrópico médio (1,66). Apesar de o extrato E1, com talhadia e 70 meses de idade, cujo fator anisotrópico médio foi igual a 1,92, ser próximo do extrato E3, em que foi realizada apenas uma reforma aos 70 meses de idade, com fator anisotrópico igual a 2,04 ao longo do fuste, o extrato E1 apresentou os menores resultados de densidade básica média e retratibilidade média na primeira tora em relação à segunda. O mesmo comportamento foi verificado na contração volumétrica. O coeficiente de anisotropia na tora 2 foi menor do que na tora 1, nos extratos E1 e E3.

Utilização de biomassa na secagem de produtos agrícolas via gaseificação com combustão adjacente dos gases produzidos

Este estudo determinou a viabilidade do uso de um gaseificador/combustor que utiliza tocos de eucalipto, resíduos de serraria, cavacos de lenha e sabugo de milho como combustível na secagem de produtos agrícolas. Utilizou-se o gaseificador desenvolvido por SILVA (1988) com modificações na câmara de gaseificação; área da grelha reduzida de 0,21 para 0,06 m²; adição de um revestimento envolvendo a parte superior do gaseificador, e foi colocado um registro tipo borboleta na saída da câmara de combustão. O ar aquecido no combustor foi enviado para um secador que possuía câmaras metálicas que eram removíveis, içadas por um sistema de roldanas, facilitando a homogeneização da secagem. Como teste do sistema, secou-se café com umidade inicial de 54,5% bu até 11,1 ± 1,6% bu, utilizando-se de cavacos de lenha. A temperatura do ar de secagem foi de 60 ºC, pressão estática do ar na saída do ventilador de 9 mmca e velocidade de 46,3 m³ min-1. Concluiu-se que o gaseificador, usando cavacos de eucalipto como combustível, consumiu entre 15,3 e18,8 kg h-1 de biomassa, que o equipamento é viável para a secagem de café despolpado e para outros produtos agrícolas, não o impregnando de fumaça ou outras partículas, geradas nas fornalhas de fogo direto, e que todos os combustíveis de biomassa testados são viáveis na utilização do sistema via gasificação com adjacente combustão dos gases gerados.

Ambiência aérea em alojamento de frangos de corte: poeira e gases

A qualidade do ar em ambientes de produção animal vem sendo referenciada como ponto de interesse em estudos de sistema de controle ambiental, focando tanto a saúde dos animais que vivem em total confinamento, quanto a dos trabalhadores. O objetivo do trabalho foi determinar a variação da qualidade da ambiência aérea em dois tipos de galpões criatórios de frangos de corte: convencional (Gc) e tipo túnel (Gt). Os valores de poeira total, em ambos os galpões, ofereceram condições adequadas às aves; entretanto, as concentrações de poeira respirável no ar estiveram acima do limite recomendado para humanos. A concentração de monóxido de carbono, na fase de aquecimento, esteve acima dos 10 ppm máximos recomendados, no período avaliado, sendo superior na época de frio no galpão Gt (30 ppm), comparada ao galpão Gc (18 ppm). Os picos de concentração de amônia no ar estiveram acima dos 20 ppm máximos recomendados às aves a partir do 20º dia de produção, em ambos os galpões, e na média diária, por período superior no galpão Gt (4h30), quando comparado ao Gc (2h45). Foram encontrados apenas traços de óxido nítrico e metano, enquanto a concentração de gás carbônico, avaliada em condições diurnas, atendeu aos limites máximos permitidos, tanto para aves quanto para o trabalhador.