Special Issue 2: Uncertainties 2012

A time-resolved kinetic study of the reactions of ring-substituted cumyloxyl radicals (4-X-CumO•: X = OMe, t-Bu, Me, Cl, CF3) with methylferrocenes (MenFc: n = 2, 8, 10) has been carried out in acetonitrile solution. Evidence for an electron transfer (ET) process has been obtained for all radicals and an increase in reactivity has been observed on decreasing the oxidation potential of the ferrocene donor and on going from electron-releasing to electron-withdrawing ring substituents. Computations predict the formation of strongly bound π-stacked 4-X-CumO•/DcMFc complexes, characterized by intracomplex π−π distances around 4 Å. These findings point toward a (nonbonded) inner-sphere ET mechanism for the reactions of the 4-X-CumO•/MenFc couples

Insight into the chemoselective aromatic vs. side-chain hydroxylation of alkylaromatics with H2O2 catalyzed by a non-heme imine-based iron complex

The oxidation of a series of alkylaromatic compounds with H2O2 catalyzed by an imine-based non-heme iron complex prepared in situ by reaction of 2-picolylaldehyde, 2-picolylamine, and Fe(OTf)2 in a 2 : 2 : 1 ratio leads to a marked chemoselectivity for aromatic ring hydroxylation over side-chain oxidation. This selectivity is herein investigated in detail. Side-chain/ring oxygenated product ratio was found to increase upon decreasing the bond dissociation energy (BDE) of the benzylic C-H bond in line with expectation. Evidence for competitive reactions leading either to aromatic hydroxylation via electrophilic aromatic substitution or side-chain oxidation via benzylic hydrogen atom abstraction, promoted by a metal-based oxidant, has been provided by kinetic isotope effect analysis. This journal i

Perceptions of a group of elderly on the fact of not seeing the dentist regularly

Ainda existe no imaginário coletivo a ideia de que idosos não necessitam de assistência odontológica, pois são em sua maioria desdentados e usuários de dentaduras. Assim, a pergunta desta pesquisa é: Qual o motivo que faz com que muitos idosos não consultem regularmente o cirurgião-dentista? O objetivo foi levantar e analisar os motivos que fazem com que idosos cadastrados em uma Unidade de Saúde da Família não consultem regularmente o dentista. Trata-se de uma pesquisa descritiva exploratória de abordagem metodológica quanti-qualitativa realizada por meio de entrevistas domiciliares semiestruturadas aplicadas em 149 idosos cadastrados em uma Unidade de Saúde da Família na cidade de Ribeirão Preto,SP. Os dados foram analisados e sistematizados por meio da técnica da Análise de Conteúdo, e para a análise quantitativa foram realizadas análises bivariadas com associações significantes baseadas em valor de p<0,05. Houve associação estatisticamente significante entre visita ao dentista e idade (p=0,025), e observou-se que idosos com idades mais avançadas relataram ir menos ao dentista. Alguns dos motivos alegados foram: medo, dificuldade financeira, falta de tempo, além de falta de sintomatologia dolorosa nos dentes devido ao uso de dentaduras. Concluiu-se que os motivos alegados estão associados a aspectos sociais e culturais que devem ser analisados frente ao cuidado na atenção primária à saúde

Kinetic and Product Study of the S-oxidation vs HAT Chemoselectivity in Reactions Promoted by Nonheme Iron(IV)-oxo Complex/NHPI Mediator System

The chemoselectivity between S-oxidation and hydrogen atom transfer (HAT) from C−H bonds has been investigated in the oxidations of a series of aryl sulfides, alkyl aromatic compounds and benzylic alcohols promoted by the iron(IV)-oxo complex [(N4Py)FeIV(O)]2+ (N4Py: N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)-methylamine) either alone or in the presence of the N-hydroxyphthalimide (NHPI) mediator via kinetic and product studies. Kinetic analyses indicate a generally higher reactivity of [(N4Py)FeIV(O)]2+ for S-oxidation process while HAT is favored in the reactions promoted by phthalimide-N-oxyl radical (PINO) deriving from NHPI oxidation. Product analysis in intermolecular competitive oxidations confirms the kinetic results with sulfoxides obtained as major products in the oxidation promoted by [(N4Py)FeIV(O)]2+. Conversely, when NHPI is employed as a mediator, significant differences in terms of chemoselectivity are observed, and HAT-derived products are obtained in higher yields which translate into an inversion of selectivity in the case of the substrates containing activated C−H bonds like diphenylmethane, triphenylmethane and benzylic alcohols. A similar change of chemoselectivity is also observed in the oxidation of aromatic substrates containing both a sulfur atom and α to OH benzylic C−H bonds, with the sulfoxide product more abundant in the absence of NHPI and carbonyl products prevailing with the [(N4Py)FeIV(O)]2+/NHPI system

Shedding light on plant litter decomposition: Advances, implications and new directions in understanding the role of photodegradation

Litter decomposition contributes to one of the largest fluxes of carbon (C) in the terrestrial biosphere and is a primary control on nutrient cycling. The inability of models using climate and litter chemistry to predict decomposition in dry environments has stimulated investigation of non-traditional drivers of decomposition, including photodegradation, the abiotic decomposition of organic matter via exposure to solar radiation. Recent work in this developing field shows that photodegradation may substantially influence terrestrial C fluxes, including abiotic production of carbon dioxide, carbon monoxide and methane, especially in arid and semi-arid regions. Research has also produced contradictory results regarding controls on photodegradation. Here we summarize the state of knowledge about the role of photodegradation in litter decomposition and C cycling and investigate drivers of photodegradation across experiments using a meta-analysis. Overall, increasing litter exposure to solar radiation increased mass loss by 23% with large variation in photodegradation rates among and within ecosystems. This variation was tied to both litter and environmental characteristics. Photodegradation increased with litter C to nitrogen (N) ratio, but not with lignin content, suggesting that we do not yet fully understand the underlying mechanisms. Photodegradation also increased with factors that increased solar radiation exposure (latitude and litter area to mass ratio) and decreased with mean annual precipitation. The impact of photodegradation on C (and potentially N) cycling fundamentally reshapes our thinking of decomposition as a solely biological process and requires that we define the mechanisms driving photodegradation before we can accurately represent photodegradation in global C and N models. © 2012 US Government

Fragmentation reactions of radical cations

This paper summarizes most of the recent work by our group on the kinetic aspects of a variety of fragmentation reactions of radical cations involving the cleavage of C-H, O-H, C-C, and C-S bonds. In particular, the problems that have been addressed concern: (a) the carbon acidity/oxygen acidity dichotomy in the fragmentation of aryl- and thioarylalkanol radical cations; (b) the decarboxylation of aryl and thioarylacetic acid radical cations; (c) the structural factors influencing the rate of C-S bond cleavage in the radical cations of phenyl alkyl sulfides. The results presented and discussed have allowed us to recognize the important role played by the electron reorganization energy, associated with the intramolecular electron transfer from the scissile bond to the SOMO, with respect to the dynamics and mechanism of the fragmentation process in the radical cation. Copyright (c) 2006 John Wiley & Sons, Ltd