RESUMO
In 2015, >50 million cubic meters of Fe mining tailings were released into the Doce River basin from the Fundão dam, raising the question of its consequences on the affected ecosystems. This study aimed to establish a mineralogical-(geo)chemical association of potentially toxic elements (PTEs) from Fe mining tailings from the Fundão dam, collected seven days after the failure, through a multidisciplinary approach combining assessment of the risk to human health, environmental geochemistry, and mineralogy. Thus, eleven tailings samples were collected with the support of the Brazilian Military Police Fire Department. Granulometry, magnetic measurements, optical microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and sequential chemical extraction of PTEs analyses were performed. Contamination indexes, assessment of risk to human health, and Pearson correlation were calculated using the results of sequential chemical extraction of PTEs. The predominance of goethite in Fe oxyhydroxide concentrates from the mud indicates that the major source of hematite may not be from tailings, but from pre-existing soils and sediments, and/or preferential dissolution of hematite in deep flooded zones of the tailings column of the Fundão dam. Moreover, the high correlation of most carcinogenic PTEs with their crystallographic variables indicates that goethite is the primary source of contaminants. Goethites from Fe mining tailings showed high specific surface area and Al-substitution, and due to their greater stability and reactivity, the impacts on PTE sorption phenomena and bioavailability may be maintained for long periods. However, their lower dissolution rate, and the consequent release of heavy metals would promote greater resilience for affected ecosystems, preventing significant PTE inputs under periodic reduction conditions. More specific studies, involving the crystallographic characteristics of Fe oxyhydroxides should be developed since they may provide another critical component of this set of complex and dynamic variables that interfere with the bioavailability of metals in ecosystems.
Assuntos
Compostos Férricos , Compostos de Ferro , Metais Pesados , Minerais , Poluentes Químicos da Água , Humanos , Ecossistema , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Metais Pesados/análise , Brasil , Rios/químicaRESUMO
BACKGROUND: Cachaça is the distilled beverage typical of Brazil and can be subjected to the aging process in wooden barrels. In addition to oak barrels, cachaça is also aged in barrels of different Brazilian native woods, resulting in a wide variety of its sensory characteristics. In this work, 172 cachaças aged in bálsamo, jequitibá, oak, and umburana barrels were analyzed by synchronous fluorescence spectroscopy and by the classification methods of principal component analysis and partial least squares discriminant analysis. Spectra were preprocessed by the first derivative by Savitzky-Golay smoothing, using a filter width and polynomial order determined through face-centered central composite designs. Multivariate analysis was realized using the spectra recorded at different wavelength differences, and models were compared by the classification errors in the test sets. RESULTS: The principal component analysis applied to the synchronous fluorescence spectra presented a tendency of separation by the wood used in the aging process, and the partial least squares discriminant analysis model constructed using the fluorescence spectra recorded at a wavelength difference of 30 nm provided better performance parameters (efficiency 91-97%, sensitivity 81-100%, and specificity 91-100%). CONCLUSION: Synchronous fluorescence spectroscopy offers a promising approach for the classification of cachaças aged in bálsamo, oak, jequitibá, and umburana barrels, and the discriminant model can be used for routine analysis as a screening method. © 2022 Society of Chemical Industry.
Assuntos
Bebidas Alcoólicas , Saccharum , Espectrometria de Fluorescência , Madeira , Bebidas Alcoólicas/análise , Análise Discriminante , Análise dos Mínimos Quadrados , Análise Multivariada , Análise de Componente Principal , Saccharum/química , Espectrometria de Fluorescência/métodos , Madeira/análise , Madeira/químicaRESUMO
Although cachaça and rum are distilled beverages obtained from the same raw material, they present differences in their chemical compositions. In this study, synchronous fluorescence spectroscopy was used combined with supervised classification models based on the partial least squares discriminant analysis to develop a rapid and low-cost model for discriminating between 50 cachaça and 40 rum samples. Partial least squares discriminant analysis models were constructed using synchronous fluorescence spectra recorded at wavelength differences of 10-100 nm. Initially, spectra were preprocessed by the first derivative with the Savitzky-Golay smoothing, and filter width and polynomial order were selected through face-centered central composite designs. For the construction and validation models, the spectra data were split into two datasets: the training and the test sets containing 60 (C, n = 33; R, n = 27) and 30 (C, n = 17; R, n = 13) samples, respectively. The best discrimination was achieved using fluorescence spectra recorded at wavelength difference 10 nm, allowing the discrimination of cachaça and rum with a classification efficiency of 98%. These results indicate that synchronous fluorescence spectroscopy offers a promising approach for the authentication of cachaças and rums.
Assuntos
Bebidas Alcoólicas , Bebidas Alcoólicas/análise , Análise Discriminante , Análise dos Mínimos Quadrados , Espectrometria de FluorescênciaRESUMO
Paracoccidioidomycosis (PCM) is the most prevalent systemic mycosis in Latin American countries. Amphotericin B, sulfonamides, and azoles may be used in the treatment of PCM. However, the high toxicity, prolonged course of treatment, and significant frequency of disease relapse compromise their use. Therefore, there is a need to seek new therapeutic options. We conducted tests with thiosemicarbazone of lapachol (TSC-lap) to determine the antifungal activity and phenotypic effects against several isolates of Paracoccidioides spp. In addition, we evaluated the toxicity against murine macrophages and the ability to enhance phagocytosis. Further, we verified that TSC-lap was active against yeasts but did not show any interaction with the drugs tested. The TSC-lap showed no toxicity at the concentration of 40 µg/ml in macrophages, and at 15.6 µg/ml it could increase the phagocytic index. We observed that this compound induced in vitro ultrastructural changes manifested as withered and broken cells beyond a disorganized cytoplasm with accumulation of granules. We did not observe indications of activity in the cell wall, although membrane damages were noted. We observed alterations in the membrane permeability, culminating in a significant increase in K+ efflux and a gradual loss of the cellular content with increase in the concentration of TSC-lap. In addition, we showed a significant reduction of ergosterol amount in the Pb18 membrane. These data reinforce the possible mechanism of action of this compound to be closely associated with ergosterol biosynthesis and reaffirms the antifungal potential of TSC-lap against Paracoccidioides spp.
Assuntos
Antifúngicos/farmacologia , Membrana Celular/efeitos dos fármacos , Naftoquinonas/farmacologia , Paracoccidioides/efeitos dos fármacos , Tiossemicarbazonas/farmacologia , Animais , Ergosterol/biossíntese , Macrófagos/efeitos dos fármacos , Masculino , Camundongos , Camundongos Endogâmicos BALB C , Testes de Sensibilidade Microbiana , Paracoccidioidomicose/tratamento farmacológico , Paracoccidioidomicose/microbiologia , Fagocitose/efeitos dos fármacosRESUMO
Human cryptococcosis can occur as a primary or opportunistic infection and develops as an acute, subacute, or chronic systemic infection involving different organs of the host. Given the limited therapeutic options and the occasional resistance to fluconazole, there is a need to develop novel drugs for the treatment of cryptococcosis. In this report, we describe promising thiazole compounds 1, 2, 3, and 4 and explore their possible modes of action against Cryptococcus To this end, we show evidence of interference in the Cryptococcus antioxidant system. The tested compounds exhibited MICs ranging from 0.25 to 2 µg/ml against Cryptococcus neoformans strains H99 and KN99α. Interestingly, the knockout strains for Cu oxidase and sarcosine oxidase were resistant to thiazoles. MIC values of thiazole compounds 1, 2, and 4 against these mutants were higher than for the parental strain. After the treatment of C. neoformans ATCC 24067 (or C. deneoformans) and C. gattii strain L27/01 (or C. deuterogattii) with thiazoles, we verified an increase in intracellular reactive oxygen species (ROS). Also, we verified the synergistic interactions among thiazoles and menadione, which generates superoxides, with fractional inhibitory concentrations (FICs) equal to 0.1874, 0.3024, 0.25, and 0.25 for the thiazole compounds 1, 2, 3, and 4, respectively. In addition, thiazoles exhibited antagonistic interactions with parasulphonatephenyl porphyrinato ferrate III (FeTPPS). Thus, in this work, we showed that the action of these thiazoles is related to an interference with the antioxidant system. These findings suggest that oxidative stress may be primarily related to the accumulation of superoxide radicals.
Assuntos
Antifúngicos/farmacologia , Criptococose/tratamento farmacológico , Cryptococcus gattii/efeitos dos fármacos , Cryptococcus neoformans/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Tiazóis/farmacologia , Farmacorresistência Fúngica , Humanos , Testes de Sensibilidade Microbiana , Oxirredutases/genética , Sarcosina Oxidase/genética , Vitamina K 3/metabolismoRESUMO
The antifungal effects of two eicosanoic acids, 2-amino-3,4-dihydroxy-2-25-(hydroxymethyl)-14-oxo-6,12-eicosenoic acid (compound 1) and myriocin (compound 2), isolated from Mycosphaerella sp. were evaluated against Cryptococcus neoformans and C. gattii. The compounds displayed antifungal activities against several isolates of C. neoformans and C. gattii, with minimal inhibitory concentration (MIC) values ranging from 0.49 to 7.82 µM for compound 1 and 0.48-1.95 µM for compound 2. In the checkerboard microtiter test, both compounds exhibited synergistic activity with amphotericin B against C. gattii. Ultrastructural analysis revealed several signs of damage in C. gattii and C. neoformans cells treated with compounds 1 and 2, including deformities in cell shape, depressions on the surface, and withered cells. The cells of C. gattii treated with compounds 1 and 2 showed less loss of cellular material in comparison to those treated with amphotericin B. The difference in cellular material loss increased in a test compound concentration-dependent manner. Consistent with this observation, compounds 1 and 2 were able to internalize propidium iodide (PI) in C. gattii cells. In addition, compound 2 induced the formation of several pseudohyphae, suggesting that it could reduce virulence in C. gattii cells. The study results show that these natural products led to membrane damage; however, this may not be the main target of action. These compounds have potential antifungal activity and could be useful in further studies for developing more effective combination therapies with amphotericin B and reducing side effects in patients.
Assuntos
Antifúngicos/farmacologia , Ascomicetos/química , Produtos Biológicos/farmacologia , Cryptococcus gattii/efeitos dos fármacos , Cryptococcus neoformans/efeitos dos fármacos , Ácidos Eicosanoicos/farmacologia , Endófitos/química , Anfotericina B/farmacologia , Antifúngicos/isolamento & purificação , Produtos Biológicos/isolamento & purificação , Membrana Celular/efeitos dos fármacos , Membrana Celular/ultraestrutura , Cryptococcus gattii/citologia , Cryptococcus neoformans/citologia , Sinergismo Farmacológico , Ácidos Eicosanoicos/isolamento & purificação , Testes de Sensibilidade MicrobianaRESUMO
A homologous series of beta-brominated porphyrins derived from meso-tetrakis(4-carbomethoxyphenyl)porphyrinatomanganese(III) chloride, i.e., Mn(III)(Br(x)TCMPP)Cl (x=0,2,4,6, and 8), was prepared and investigated as cytochrome P450 models. Hydroxylations of cyclohexane by iodosylbenzene (PhIO) and iodobenzene diacetate (PhI(OAc)(2)) in the presence or absence of water were carried out as P450 model reactions. The influence of the degree of beta-bromination of the macrocycle on the UV-vis spectra, the Mn(III)/Mn(II) reduction potential, and the catalytic properties of the Mn(III)(Br(x)TCMPP)Cl (x=0,2,4,6, and 8) series were examined. The catalytic efficiency does not correlate with the Mn(III)/Mn(II) reduction potential and shows a bell-shaped behavior, where the best results are achieved with the hexabrominated complex. Better hydroxylation yields were achieved by using PhI(OAc)(2) as oxygen donor, but at expenses of catalyst recovery; addition of water to this system resulted in a increase in the reaction rate. Recycling of the more oxidatively robust complexes Mn(III)(Br(6)TCMPP)Cl and Mn(III)(Br(8)TCMPP)Cl is feasible when using PhIO as oxygen donor. Selectivity and UV-vis data suggested that hydroxylation by both PhIO and PhI(OAc)(2) share closely related active species and mechanism. We also show that the Mn(III)/Mn(II) reduction potentials are inappropriate predictors of P450-type activity of Mn porphyrin-catalyzed oxidations.