Exposure and risk assessment in occupational exposure to fungi: aspects to consider in highly contaminated settings

Although a clear correlation between levels of fungi in the air and health impacts has not been shown in epidemiological studies, fungi must be regarded as potential occupational health hazards. Fungi can have an impact on human health in four different ways: (1) they can infect humans, (2) they may act as allergens, (3) they can be toxigenic, or (4) they may cause inflammatory reactions. Fungi of concern in occupational hygiene are mostly non-pathogenic or facultative pathogenic (opportunistic) species, but are relevant as allergens and mycotoxins producers. It is known that the exclusive use of conventional methods for fungal quantification (fungal culture) may underestimate the results due to different reasons. The incubation temperature chosen will not be the most suitable for every fungal species, resulting in the inhibition of some species and the favouring of others. Differences in fungi growth rates may also result in data underestimation, since the fungal species with higher growth rates may inhibit others species’ growth. Finally, underestimated data can result from non-viable fungal particles that may have been collected or fungal species that do not grow in the culture media used, although these species may have clinical relevance in the context. Due to these constraints occupational exposure assessment, in setings with high fungal contamination levels, should follow these steps: Apply conventional methods to obtain fungal load information (air and surfaces) regarding the most critical scenario previously selected; Guideline comparation aplying or legal requirements or suggested limits by scientific and/or technical organizations. We should also compare our results with others from the same setting (if there is any); Select the most suitable indicators for each setting and apply conventional-culture methods and also molecular tools. These methodology will ensure a more real characterization of fungal burden in each setting and, consequently, permits to identify further measures regarding assessment of fungal metabolites, and also a more adequate workers health surveillance. The methodology applied to characterize fungal burden in several occupational environments, focused in Aspergillus spp. prevalence, will be present and discussed.

Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: Z-ray absorption spectroscopy studies and biological applications

[CoCl(-Cl)(Hpz(Ph))(3)](2) (1) and [CoCl2(Hpz(Ph))(4)] (2) were obtained by reaction of CoCl2 with HC(pz(Ph))(3) and Hpz(Ph), respectively (Hpz(Ph)=3-phenylpyrazole). The compounds were isolated as air-stable solids and fully characterized by IR and far-IR spectroscopy, MS(ESI+/-), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single-crystal X-ray diffraction. Electrochemical studies showed that 1 and 2 undergo single-electron irreversible (CoCoIII)-Co-II oxidations and (CoCoI)-Co-II reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H2O2). Insitu X-ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox-1 and Ox-2, respectively) are analogous and contain a Co-III site. Complex 2 showed low invitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.