NO/H2S "crosstalk" Reactions. The Role of Thionitrites (SNO-) and Perthionitrites (SSNO-)

The redox chemistry of H2S with NO and other oxidants containing the NO group is discussed on a mechanistic basis because of the expanding interest in their biological relevance, with an eye open to the chemical differences of H2S and thiols RSH. We focus on the properties of two "crosstalk" intermediates, SNO- (thionitrite) and SSNO- (perthionitrite, nitrosodisulfide) based in the largely controversial status on their identity and chemistry in aqueous/nonaqueous media, en route to the final products N2O, NO2 -, NH2OH/NH3, and S8. Thionitrous acid, generated either in the direct reaction of NO + H2S or through the transnitrosation of RSNO's (nitrosothiols) with H2S at pH 7.4, is best described as a mixture of rapidly interconverting isomers, {(H)SNO}. It is reactive in different competitive modes, with a half-life of a few seconds at pH 7.4 for homolytic cleavage of the N-S bond, and could be deprotonated at pH values of up to ca. 10, giving SNO-, a less reactive species than {(H)SNO}. The latter mixture can also react with HS-, giving HNO and HS2 - (hydrogen disulfide), a S0(sulfane)-transfer reagent toward {(H)SNO}, leading to SSNO-, a moderately stable species that slowly decomposes in aqueous sulfide-containing solutions in the minute-hour time scale, depending on [O2]. The previous characterization of HSNO/SNO- and SSNO- is critically discussed based on the available chemical and spectroscopic evidence (mass spectrometry, UV-vis, 15N NMR, Fourier transform infrared), together with computational studies including quantum mechanics/molecular mechanics molecular dynamics simulations that provide a structural and UV-vis description of the solvatochromic properties of cis-SSNO- acting as an electron donor in water, alcohols, and aprotic acceptor solvents. In this way, SSNO- is confirmed as the elusive "yellow intermediate" (I412) emerging in the aqueous crosstalk reactions, in contrast with its assignment to polysulfides, HSn -. The analysis extends to the coordination abilities of {(H)SNO}, SNO-, and SSNO- into heme and nonheme iron centers, providing a basis for best unraveling their putative specific signaling roles.Fil: Marcolongo, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Venâncio, Mateus F.. Universidade Federal de Minas Gerais; BrasilFil: Rocha, Willian R.. Universidade Federal de Minas Gerais; BrasilFil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentin

Prostatic carcinomas with neuroendocrine differentiation diagnosed in needle biopsies, a morphologic study of 7 cases among 465 sequential biopsies in a tertiary cancer center

Purpose: Neuroendocrine carcinomas (NEC) of the prostate are rare, with only a few series hitherto reported. the objective of this study was to assess in a single institution the clinical and morphologic characteristics of neuroendocrine carcinomas diagnosed in needle core biopsies.Materials and Methods: the current study analyses seven cases diagnosed in needle biopsies at a large tertiary regional cancer center from Northeastern Brazil. Two pathologists reviewed specimens retrospectively, and demographic and morphologic characteristics were compared to 458 acinar tumors diagnosed in the same period.Results: There were five small cell carcinomas and two low-grade neuroendocrine carcinomas (carcinoid). NEC were associated with an acinar component in 5/7 cases and the Gleason score of the acinar component was always > 6. the number of cores involved in prostates with NEC was greater (65% compared to 24% of acinar tumors, p < 0.05). the mean PSA at diagnosis was 417.7 (range 5.7-1593, SD 218.3), compared to 100.5 (p = 0.1) of acinar tumors (range 0.3-8545, SD 22.7). Prostates harboring NEC were bigger (p < 0.001, mean volume 240 mL vs. 53 mL of acinar tumors). Treatment of NEC included palliative surgery, chemotherapy, and hormonal therapy.Conclusions: NEC of the prostate is rare and often associated with a high-grade acinar component. Prostates with NEC tend to be larger and involve a greater number of cores than acinar tumors. PSA at diagnosis does not seem to predict the presence of NE tumors in needle biopsy.Hosp Canc, Inst Canc Ceara, BR-60430230 Fortaleza, Ceara, BrazilEscola Paulista Med, BR-04023 São Paulo, BrazilEscola Paulista Med, BR-04023 São Paulo, BrazilWeb of Scienc

Electrochemical noise and impedance of Au electrode/electrolyte interfaces enabling extracellular detection of glioma cell populations

Microelectrode arrays (MEA) record extracellular local field potentials of cells adhered to the electrodes. A disadvantage is the limited signal-to-noise ratio. The state-of-the-art background noise level is about 10 μVpp. Furthermore, in MEAs low frequency events are filtered out. Here, we quantitatively analyze Au electrode/electrolyte interfaces with impedance spectroscopy and noise measurements. The equivalent circuit is the charge transfer resistance in parallel with a constant phase element that describes the double layer capacitance, in series with a spreading resistance. This equivalent circuit leads to a Maxwell-Wagner relaxation frequency, the value of which is determined as a function of electrode area and molarity of an aqueous KCl electrolyte solution. The electrochemical voltage and current noise is measured as a function of electrode area and frequency and follow unambiguously from the measured impedance. By using large area electrodes the noise floor can be as low as 0.3 μVpp. The resulting high sensitivity is demonstrated by the extracellular detection of C6 glioma cell populations. Their minute electrical activity can be clearly detected at a frequency below about 10 Hz, which shows that the methodology can be used to monitor slow cooperative biological signals in cell populations.</p

Secondary forest regeneration benefits old-growth specialist bats in a fragmented tropical landscape

Tropical forest loss and fragmentation are due to increase in coming decades. Understanding how matrix dynamics, especially secondary forest regrowth, can lessen fragmentation impacts is key to understanding species persistence in modified landscapes. Here, we use a whole-ecosystem fragmentation experiment to investigate how bat assemblages are influenced by the regeneration of the secondary forest matrix. We surveyed bats in continuous forest, forest fragments and secondary forest matrix habitats, similar to 15 and similar to 30 years after forest clearance, to investigate temporal changes in the occupancy and abundance of old-growth specialist and habitat generalist species. The regeneration of the second growth matrix had overall positive effects on the occupancy and abundance of specialists across all sampled habitats. Conversely, effects on generalist species were negligible for forest fragments and negative for secondary forest. Our results show that the conservation potential of secondary forests for reverting faunal declines in fragmented tropical landscapes increases with secondary forest age and that old-growth specialists, which are often of most conservation concern, are the greatest beneficiaries of secondary forest maturation. Our findings emphasize that the transposition of patterns of biodiversity persistence in island ecosystems to fragmented terrestrial settings can be hampered by the dynamic nature of human-dominated landscapes.Peer reviewe

World Press Photo 2012: the discursive construction of the Arab Spring

O presente artigo pretende analisar a forma como o fenómeno da Primavera Árabe foi retratado nas fotografias vencedoras do concurso World Press Photo em 2012. As fotografias jornalísticas, embora se apresentem como índices do real, condicionam frequentemente a percepção dos indivíduos e influenciam as suas práticas sociais. Também as fotografias vencedoras do World Press Photo, um dos concursos mais prestigiados de fotojornalismo, em 2012 não fogem ao construtivismo discursivo que molda a representação e a percepção dos acontecimentos. A partir da análise crítica do discurso, nomeadamente dos instrumentos teóricos da semiótica barthesiana e da semiótica social de Gunther Kress e Theo van Leeuwen, procurámos interpretar as 38 fotografias vencedoras do World Press Photo 2012, a fim de reflectirmos sobre o modo como contribuíram para a compreensão da Revolta Árabe e como despertaram o nosso interesse e a nossa imaginação para o desenrolar do conflito.ABSTRACT:This article aims to analyze how the Arab Spring phenomenon was represented in the award-winning photographs of the World Press Photo contest in 2012. Although news photographs are usually seen as indexes of the real, they often limit the perception of individuals and influence their social practices. Also the winning photographs in 2012 of the World Press Photo, one of the most prestigious photojournalism contests, do not escape the discursive constructivism that shapes the representation and perception of events. Drawing from critical discourse analysis, namely from the theoretical tools of barthesian semiotics and Gunther Kress’s and Theo van Leeuwen’s social semiotics, we sought to interpret the 38 award-winning photographs of the World Press Photo contest in 2012, in order to reflect on the way they have contributed to our understanding of the Arab Revolt and aroused our interest and imagination to the unfolding of the conflict.info:eu-repo/semantics/publishedVersio

Emergence of winner-takes-all connectivity paths in random nanowire networks

Nanowire networks are promising memristive architectures for neuromorphic applications due to their connectivity and neurosynaptic-like behaviours. Here, we demonstrate a self-similar scaling of the conductance of networks and the junctions that comprise them. We show this behavior is an emergent property of any junction-dominated network. A particular class of junctions naturally leads to the emergence of conductance plateaus and a “winner-takes-all” conducting path that spans the entire network, and which we show corresponds to the lowest-energy connectivity path. The memory stored in the conductance state is distributed across the network but encoded in specific connectivity pathways, similar to that found in biological systems. These results are expected to have important implications for development of neuromorphic devices based on reservoir computing

Different Assay Conditions for Detecting the Production and Release of Heat-Labile and Heat-Stable Toxins in Enterotoxigenic Escherichia coli Isolates

Enterotoxigenic Escherichia coli (ETEC) produce heat-labile (LT) and/or heat-stable enterotoxins (ST). Despite that, the mechanism of action of both toxins are well known, there is great controversy in the literature concerning the in vitro production and release of LT and, for ST, no major concerns have been discussed. Furthermore, the majority of published papers describe the use of only one or a few ETEC isolates to define the production and release of these toxins, which hinders the detection of ETEC by phenotypic approaches. Thus, the present study was undertaken to obtain a better understanding of ST and LT toxin production and release under laboratory conditions. Accordingly, a collection of 90 LT-, ST-, and ST/LT-producing ETEC isolates was used to determine a protocol for toxin production and release aimed at ETEC detection. for this, we used previously raised anti-LT antibodies and the anti-ST monoclonal and polyclonal antibodies described herein. the presence of bile salts and the use of certain antibiotics improved ETEC toxin production/release. Triton X-100, as chemical treatment, proved to be an alternative method for toxin release. Consequently, a common protocol that can increase the production and release of LT and ST toxins could facilitate and enhance the sensitivity of diagnostic tests for ETEC using the raised and described antibodies in the present work.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Butantan Inst, Bacteriol Lab, BR-05503900 São Paulo, BrazilSão Paulo Trop Med Inst, Seroepidemiol & Immunol Lab, BR-05403000 São Paulo, BrazilFleury Med & Hlth, BR-04344903 São Paulo, BrazilButantan Inst, Immunopathol Lab, BR-05503900 São Paulo, BrazilButantan Inst, Immunochem Lab, BR-05503900 São Paulo, BrazilAdolfo Lutz Inst, Bacteriol Sect, BR-01246000 São Paulo, BrazilUniversidade Federal de São Paulo, Escola Paulista Med, Dept Microbiol, BR-04923062 São Paulo, SP, BrazilUniversidade Federal de São Paulo, Escola Paulista Med, Dept Microbiol, BR-04923062 São Paulo, SP, BrazilWeb of Scienc

An electrical method to measure low-frequency collective and synchronized cell activity using extracellular electrodes

An electrical method to measure extracellular bioelectrical activity in vitro is presented. This method exploits the Helmholtz capacitive double-layer established at the electrode surface. Small extracellular voltage variations in the order of μVs induce through the double-layer capacitor a displacement current that is measured. This current is then enhanced by a gain factor proportional to the electrode capacitance. In addition, when measurements are carried out at low frequencies in current mode the electrode contribution to the noise can be minimized. The performance of the electrodes and the method is demonstrated using zebrafish hearts and glioma cell cultures. We propose that this electrical method is an ideal tool to measure in vitro slow and temporally synchronized events that are often involved in long range intracellular signaling.</p

Fermion correlators in non-abelian holographic superconductors

We consider fermion correlators in non-abelian holographic superconductors. The spectral function of the fermions exhibits several interesting features such as support in displaced Dirac cones and an asymmetric distribution of normal modes. These features are compared to similar ones observed in angle resolved photoemission experiments on high T_c superconductors. Along the way we elucidate some properties of p-wave superconductors in AdS_4 and discuss the construction of SO(4) superconductors.Comment: 49 pages, 11 figure