Resumo em inglês This article reports on some basic and conceptual principles concerning electron transfer (ET) and/or intervalence transfer (IT) phenomena in inorganic mixed-valence systems.
Transferência de elétron inversa na quimiexcitação da reação peróxi-oxalato usando ativadores facilmente redutíveis/ Inverse electron transfer in peroxyoxalate chemiexcitation using easily reducible activators
Resumo em inglês Chemiluminescence properties of the peroxyoxalate reaction in the presence of activators bearing electron withdrawing substituents were studied, to evaluate the possible occurrence of an inverse electron transfer, from the peroxide intermediate to the activator, in its chemiexcitation step. Relative catalytic rate constants and singlet quantum yields were obtained for the peroxyoxalate reaction, using 9-chloro, 9,10-dichloro, 9-cyano and 9,10-dicyanoanthracenes as activat (mais) ors. The linear free-energy correlation of the relative rate constants with the activators' reduction potentials and the dependence of the quantum yields on the released energy confirm, for the first time, the occurrence of this inverse electron transfer.
Resumo em inglês Aromatic nitration is one of the most relevant class of reactions in organic chemistry. It has been intensively studied by both experimental, including works in the condensed as well as in the gas phase, and theoretical procedures. However, the published results do not seem to converge to an unique mechanism. Electrophilic substitution and electron transfer, in an exclusive way, are both proposed as the main mechanism for the reaction. We review these proposals and discuss the most recent findings.
Síntese, caracterização e estudos de transferencia de energia do complexo dimérico constituído por Zn e Mn porfirina/ Dimer derivative of Zn and Mn Porfirin: Synthesis, caracterization and energy transfer studies
Resumo em português Muitos compostos modelo contendo porfirinas têm sido preparados num esforço para entender o sistema de fotossíntese e os processos de aproveitamento de energia solar. Sistemas doadores-receptores contendo porfirinas têm sido freqüentemente estudados para testar várias descrições teóricas sobre transferência de elétrons. O estudo de parâmetros fotoquímicos e fotofísicos como a distância para transferência de energia, geometria molecular e a diferença de po (mais) tencial eletrônico, tem se mostrado importante para a definição da transferência eletrônica em porfirinas. Neste trabalho apresentamos a síntese, purificação e caracterização por espectroscopia UV/Vis, ¹H e 19F RMN, luminescência e tempos de vida de novos modelos moleculares de porfirinas, que permitam investigar esses parâmetros. Utilizou-se o dímero Zn,Mn(TPPF4)2pip e seus monômeros ZnTPPF4pipH e MnF5TPP. A caracterização do ZnMn(TPPF4)2pip, foi dificultada devido a presença de Mn+3, devido ao forte acoplamento dos orbitais dpi do manganês e o sistema pi da porfirina, que aumenta a interação manganês-porfirina mudando o espectro eletrônico UV/Vis e distorcendo os sinais de ¹H e 19F RMN do dímero. A presença de Mn+3 desloca E1/2 do anel porfirínico para valores mais negativos, o que resulta em reduções mais difíceis, impedindo a transferência de energia da Znporfirina para a Mnporfirina. Resumo em inglês Porphyrins have revealed that factors as the energy transfer distance, molecular geometry and the difference of electronic potential, are important in a well defined electronic transfer. Porphyrin- containing donor-acceptor systems have been usefully employed to test various theoretical descriptions of electron transfer. The objective of this paper consists on the synthesis, purification and characterization by UV/Vis spectroscopy, ¹H and 19F NMR, luminescence and lifeti (mais) me of new molecular models, allowing the investigation of energy transfer parameters. This study was accomplished using the dimer Zn,Mn(TPPF4)2pip and its monomers ZnTPPF4pipH and MnF5TPP. The dimer characterization, Zn,Mn(TPPF4)2pip, was difficult due to the presence of Mn3+. The strong overlap between dpi orbitals of manganese and the porphyrin pi system increases the interaction manganese-porphyrin in changing the UV/Vis electronic spectrum and distorting the ¹H and 19F NMR signals of dimer. The presence of Mn3+ shifts the reduction potential of E1/2 of the porphyrin ring to more negatives values, what results in more difficult reductions, disabling the transfer of energy from Zincporphyrin to Manganeseporphyrin.
Relação entre transferência de carga e as interações intermoleculares em complexos de hidrogênio heterocíclicos/ Relationship between charge transfer and intermolecular interactions in heterocyclic hydrogen-bonded complexes
Resumo em inglês Hydrogen-bonded complexes formed by the interaction of the heterocyclic molecules C2H4O and C2H5N with HF, HCN, HNC and C2H2 have been studied using density functional theory. The hydrogen bond strength has been analyzed through electron density charge transfer from the proton acceptor to the proton donor. The density charge transfer has been estimated using different methods such as Mulliken population analysis, CHELPG, GAPT and AIM. It has been shown that AIM-estimated (mais) charge transfer correlates very well with the hydrogen bond energy and the infrared bathochromic effect of the proton donor stretching frequencies.
Quimiluminescência de peróxidos orgânicos: geração de estados eletronicamente excitados na decomposição de 1,2-dioxetanos/ Chemiluminescence of cyclic organic peroxides: generation of electronically excited states in 1,2-dioxetane decomposition
Resumo em inglês 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-dioxetane (mais) s; (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.
Pilhas de combustíveis microbianas utilizadas na produção de eletricidade a partir de rejeitos orgânicos: uma perspectiva de futuro/ Microbial fuel cells used in the production of electricity from organic waste: a perspective of future
Resumo em inglês In this review is presented an innovative technology for use of animal and vegetable waste with high pollution levels in microbial fuel cell (MFC) as an alternative to waste remediation and simultaneously producing electricity and fertilizer for agriculture. A brief history of MFC, the studies about the electron transfer mechanisms, discussion of the biological nanowires in bacteria and the use of chemical mediators or carriers of electrons are explained. The factors infl (mais) uencing the performance of MFCs, the application in waste and sewage treatment and power generation are also discussed.
Resumo em inglês Copper selenide (berzelianite) films were prepared on the title substrates using the chemical bath deposition technique (CBD). Film composition was determined by energy dispersion of x-rays. The kinetics of film growth is parabolic and film adherence limits the film thickness. On titanium, copper selenide forms islands that do not completely cover the surface, unless the substrate is prepared with a tin oxide layer; film composition also depends on the titanium oxide laye (mais) r. On vitreous carbon, CBD and mechanical immobilization techniques lead to films with similar resistances for the electron transfer across the film/substrate interface. On gold, composition studies revealed that film composition is always the same if the pH is in the range from 8 to 12, in contrast to films prepared by an ion-ion combination route. On copper, a new procedure for obtaining copper selenide films as thick as 5 µm has been developed.
Formação de membranas planas celulósicas por espalhamento duplo para os processos de nanofiltração e osmose inversa/ Membranes for nanofiltration and reverse osmosis prepared by simultaneous casting of two polymer solutions
Resumo em português No presente trabalho é estudado o preparo de membranas anisotrópicas compostas, em uma única etapa, para os processos de NF e OI, através do espalhamento simultâneo de duas soluções poliméricas [acetato de celulose - AC/formamida/acetona (26,3/23,7/50 % p/p) e AC/poli(vinil pirrolidona) - PVP/N,N-dimetilformamida - DMF (15/10/75 % p/p)]. A precipitação das soluções, em água destilada, foi acompanhada por medidas de transmitância de luz. Estudou-se a influên (mais) cia das condições de preparo das membranas, na sua morfologia e nas suas propriedades de transporte (fluxo de permeado e retenção de solutos - Polietilenoglicol (PEG) para a NF e NaCl para a OI). Realizou-se também um tratamento térmico nas diferentes membranas produzidas. Os resultados mostraram que é possível obter membranas celulósicas com total aderência das diferentes camadas, a qual pode ser atribuída às condições de transferência de massa que retardam a precipitação na região próxima à interface das soluções espalhadas simultaneamente. Com relação aos testes de OI e NF, as membranas desenvolvidas apresentaram valores de fluxo permeado (7 - 465 L/h.m²) dentro da faixa das membranas comerciais, retenção salina (NaCl) entre 24-63 % e retenção do PEG entre 53-82 %, mostrando o potencial de aplicação destas membranas. Resumo em inglês The purpose of this work is to investigate the preparation of composite anisotropic membranes in a single stage, through the technique of simultaneous casting of two polymer solutions (cellulose acetate (CA)/acetone/formamide (26.3/50/23.7 % w/w) and CA/polyvinylpyrrolidone/dimethyl formamide (15/10/75 % w/w)). The precipitation of the solutions was followed using light transmission experiments. The effect of the exposition period precipitation bath on the membrane proper (mais) ties is also reported. All the membranes were characterized by scanning electron microscopy and by permeation experiments. The RO and NF experiments are carried out using 5,000 mug/g (ppm) of NaCl aqueous solution and 5 g/L of polyethyleneglycol (PEG), 6 KDa, aqueous solution, respectively. Moreover, to reduce defects in the upper layer, the membranes were immersed in a water bath at 90°C for 60 minutes. The membrane morphology analysis indicates that is possible to obtain complete adhesion of the two layers. This result is related to the mass transfer conditions, which should delay the precipitation in the regions near the polymer solutions interface. Regarding the performance of the membranes in RO and NF experiments, the permeate fluxes are comparable to those observed with commercial membranes (7--465 L/h.m²). The solute retention varied in the range of 24 to 63% for NaCl, and in the range of 53 to 82% for PEG. These results point out the potential of technical scale application of the double layer membranes.
Estudo da reatividade do estado excitado triplete de 1,4-diaza-9-fluorenonas frente a doadores de hidrogênio e de elétron/ The reactivity of the triplet excited state of 1,4-diaza-9-fluorenones towards hydrogen and electron donors
Resumo em inglês The effect of the introduction of nitrogen atoms upon the triplet excited state reactivity of 1,4-diaza-9-fluorenone (1) and 1,4-diaza-9-benz[b]fluorenone (2), in acetonitrile, was investigated employing the nanosecond laser flash photolysis technique. The intersystem crossing quantum yield (Φces) for 1 and 2 was determined using 9-fluorenone as a secondary standard (Φces= 0.48, in acetonitrile) and for both diazafluorenones a value of Φces= 0.28 was found. (mais) Quenching rate constants ranged from 8.17x10(4) L mol-1 s-1 (2-propanol) to 1.02x10(10) L mol-1 s-1 (DABCO) for 1,4-diaza-9-fluorenone and from 6.95x10(5) L mol-1 s-1 (2-propanol) to 5.94x10(9) L mol-1 s-1 (DABCO) for 1,4-diaza-9-benz[b]fluorenone, depending if the quenching process involves energy, hydrogen or electron transfer. A comparison between quenching rate constants for both diazaflurenones and the parent compound, i.e. 9-fluorenone, a ketone with lowest triple state of ππ* configuration, lead to the conclusion that the reactive triplet excited state for 1,4-diaza-9-fluorenone and 1,4-diaza-9-benz[b]fluorenone has ππ* configuration.
Estudo de efeito dos sais precursores sobre as propriedades eletrocatalíticas de eletrodos de Ti-SnO2/Sb preparados por decomposição térmica/ Study of the effect of precursor salts on the electrocatalytic properties of Ti-SnO2/Sb electrodes prepared by thermal decomposition
Resumo em inglês The physical and electrochemical properties of Ti-SnO2/Sb electrodes obtained by the thermal decomposition of solutions of the precursor salts SnCl2×2H2O/SbCl3 and SnSO4/Sb2(SO4)3 were investigated. The reversibility of the cyclic voltammetric response of the Fe(CN)6(4-)/Fe(CN)6(3-) redox couple was assessed using the obtained electrodes. Their catalytic activity for the oxygen-evolving reaction and maximum capacity for electronic transfer were also evaluated by potentia (mais) l and current linear scans in 0.5 mol L-1 H2SO4. Additionally, scanning electron microscopy analyses allowed the visualization of the morphology of the oxide films obtained. The best results were presented by the electrodes obtained from the chloride salt precursors.
Resumo em inglês The aim of this work is to describe the recent area that it has been developed for the construction of amperometric sensors, with the purpose to make possible a more effective electron transfer between enzyme and electrode. The advances reported in the literature will be described, such as enzymatic configurations that can be mimic using the chemistry of the artificial enzymes.
Resumo em inglês The Michael addition reaction has been reported as a conventional nucleophilic process. However, more recently, alternative mechanisms involving electron transfer between acceptor and donnor species have been proposed.