Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy

Although electrochemical oxidation of simple organic molecules on metal catalysts is the basic ingredient of fuel cells, which have great technological potential as a renewable source of electrical energy, the detailed reaction mechanisms are in most cases not completely understood. Here, we investigate the ethanol-platinum interface in acidic aqueous solution using infrared-visible sum frequency generation (SFG) spectroscopy and theoretical calculations of vibrational spectra in order to identify the intermediates present during the electro-oxidation of ethanol. The complex vibrational spectrum in the fingerprint region imply on the coexistence of several adsorbates. Based on spectra in ultra-high-vacuum (UHV) and electrochemical environment from the literature and our density functional theory (DFT) calculations of vibrational spectra, new adsorbed intermediates, never before observed with conventional infrared (IR) spectroscopy, are proposed here: g2-acetaldehyde, g2-acetyl, ethylidyne, monodentate acetate, methoxy, tertiary methanol derivative, COH residue, g2-formaldehyde, mono and bidentate formate, CH3 and CH2 residues. In addition, we present new evidences for an ethoxy intermediate, a secondary ethanol derivative and an acetyl species, and we confirm the presence of previously observed adsorbates: a tertiary ethanol derivative, bidentate acetate, and COad. These results indicate that the platinum surface is much more reactive, and the reaction mechanism for ethanol electro-oxidation is considerably more complex than previously considered. This might be also true for many other molecule-catalyst systems.

Integration of spatial and temporal models to predict extreme water table depths

The objective of this work was to evaluate extreme water table depths in a watershed, using methods for geographical spatial data analysis. Groundwater spatio-temporal dynamics was evaluated in an outcrop of the Guarani Aquifer System. Water table depths were estimated from monitoring of water levels in 23 piezometers and time series modeling available from April 2004 to April 2011. For generation of spatial scenarios, geostatistical techniques were used, which incorporated into the prediction ancillary information related to the geomorphological patterns of the watershed, using a digital elevation model. This procedure improved estimates, due to the high correlation between water levels and elevation, and aggregated physical sense to predictions. The scenarios showed differences regarding the extreme levels - too deep or too shallow ones - and can subsidize water planning, efficient water use, and sustainable water management in the watershed.

Expansion of a subset of CD14(high)CD16(neg)CCR2(low/neg) monocytes functionally similar to myeloid-derived suppressor cells during SIV and HIV infection

Monocytes have been categorized in three main subpopulations based on CD14 and CD16 surface expression. Classical monocytes express the CD14(++)CD16(-) CCR2(+) phenotype and migrate to inflammatory sites by quickly responding to CCL2 signaling. Here, we identified and characterized the expansion of a novel monocyte subset during HIV and SIV infection, which were undistinguishable from classical monocytes, based on CD14 and CD16 expression, but expressed significantly lower surface CCR2. Transcriptome analysis of sorted cells demonstrated that the CCR2(low/neg) cells are a distinct subpopulation and express lower levels of inflammatory cytokines and activation markers than their CCR2(high) counterparts. They exhibited impaired phagocytosis and greatly diminished chemotaxis in response to CCL2 and CCL7. In addition, these monocytes are refractory to SIV infection and suppress CD8(+) T cell proliferation in vitro. These cells express higher levels of STAT3 and NOS2, suggesting a phenotype similar to monocytic myeloid-derived cells, which suppress expansion of CD8(+) T cells in vivo. They may reflect an antiproliferative response against the extreme immune activation observed during HIV and SIV infections. In addition, they may suppress antiviral responses and thus, have a role in AIDS pathogenesis. Antiretroviral therapy in infected macaque and human subjects caused this population to decline, suggesting that this atypical phenotype is linked to viral replication. J. Leukoc. Biol. 91: 803-816; 2012.

A large Cervidae Holocene accumulation in Eastern Brazil: an example of extreme taphonomical control in a cave environment

A remarkable cervid bone accumulation occurs at a single passage (named Cervid Passage; CP) at Lapa Nova, a maze cave in eastern Brazil. CP lies away from cave entrances, is a typical pitfall passage and contains bone remains of at least 121 cervids, besides few bats, peccaries and rodents remains. There is no evidence of water (or sediment) flow at the site and in general bones lack post depositional alterations and display anatomical proximity, suggesting that the majority of the remains found inside CP (mainly cervids) are due to animals that after entering the cave got trapped in the site. Observations suggest that two entrances could have provided access to cervids (and the few other animals, besides bats), either by falling inside the cave or by entering by their own free will. Once inside the cave, the maze pattern would make route finding difficult, and of all passage intersections, only the one leading to CP would result in a non-return situation, starving the animal to death. Radiocarbon dates suggest that animal entrapment occurred during at least 5 thousand years, during the Holocene. The reasons why mainly cervids were found are unknown but they are probably related to the biology of this group coupled with the fact that caves provide several specific taphonomic processes that may account for a strong bias in bone accumulation. Indeed, the frequent occurrence of Cervidae in both the fossil and sub-fossil record in Brazilian caves may be related to an overall high faunal abundance or may suggest that these animals were especially prone to enter caves, perhaps in search of nutrients (as cave saltpetre) or water.