Specific and reversible immobilization of proteins tagged to the affinity polypeptide C-LytA on functionalized graphite electrodes

We have developed a general method for the specific and reversible immobilization of proteins fused to the choline-binding module C-LytA on functionalized graphite electrodes. Graphite electrode surfaces were modified by diazonium chemistry to introduce carboxylic groups that were subsequently used to anchor mixed self-assembled monolayers consisting of N,N-diethylethylenediamine groups, acting as choline analogs, and ethanolamine groups as spacers. The ability of the prepared electrodes to specifically bind C-LytA-tagged recombinant proteins was tested with a C-LytA-β-galactosidase fusion protein. The binding, activity and stability of the immobilized protein was evaluated by electrochemically monitoring the formation of an electroactive product in the enzymatic hydrolysis of the synthetic substrate 4-aminophenyl β-D-galactopyranoside. The hybrid protein was immobilized in an specific and reversible way, while retaining the catalytic activity. Moreover, these functionalized electrodes were shown to be highly stable and reusable. The method developed here can be envisaged as a general, immobilization procedure on the protein biosensor field.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Impacto de las desigualdades de género en la mortalidad materna en Latinoamérica

Antecedentes/Objetivos: Pese a que los países Iberoamericanos han intentado desarrollar políticas de control de la mortalidad materna (MM), toda ella evitable; las cifras siguen siendo elevadas. La influencia de factores como el PIB está demostrada, pero mucho menos la influencia de otros factores como las desigualdades de género. Se pretende comparar como varía la mortalidad materna en los países iberoamericanos en función de su desigualdad de género, y en comparación con un grupo de países desarrollados, con énfasis en Ecuador en donde la MM es un grave problema. Métodos: Estudio transversal ecológico para el año 2012 que utiliza el país como unidad de análisis, sobre la relación del indicador compuesto de desigualdad de género (IDG: 0 igualdad y 1 desigualdad) y la mortalidad materna (MM) en los 19 países Iberoamericanos respecto a los países nórdicos, Canadá y España. Se recoge información sobre el índice de libertad y el Producto interior bruto (PIB). Fuentes de información: estadísticas de: Naciones Unidas, Comisión Económica para América Latina y el Caribe, OMS/OPS. Se realiza modelo de regresión lineal simple y múltiple para analizar la asociación entre las variables independientes IDG y la MM, controlando por PIB. Resultados: El rango del IDG de los países Iberoamericanos oscila entre Costa Rica 0,346 y Guatemala 0,539, mientras que Suecia es el país de mejor IDG (0,055). Ecuador se sitúa en el 9º lugar del IDG: 0,442 (IDG España: 0,119), y se sitúa en el 16º lugar al tener una MM de 110 x100.000 nacidos vivos. Se detecta una asociación entre la MM y el Índice de desigualdad de género r2 = 70,3% (p < 0,001), que se mantiene controlando por PIB r2 = 72% (p = 0,001). A mayor desigualdad de género mayor mortalidad materna. Dos de los componentes del IDG (fertilidad en adolescentes y mujeres con más educación que 2ª) se muestran asociados con el IDG, en el sentido de que a más fertilidad en adolescentes mayor MM -controlado por PIB: r2 = 68,3% (p = 0,005), y que a menos mujeres con más que la educación 2ª más MM (controlado por PIB: r2 = 60,8% (p = 0,05). Además, se detecta asociación entre la MM y el índice de libertad r2 = 34,2% (p = 0,002), que sube controlando por PIB r2 = 62,1% (p = 0,03). Conclusiones: La mortalidad materna en Latinoamérica en 2012 está en relación directa con las desigualdades de género, explicando buena parte de la variabilidad de la MM entre los países. La manera en que las sociedades se organizan mediante su toma de decisiones e implementación de sus políticas, son un importante factor de reducción de la MM, países como Ecuador, están desarrollando políticas en este campo, y deberían considerar una coordinación con las políticas de reducción de las desigualdades de género.

Production of methanol from CO2 electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution

In this study, we examine the performance of Cu2O and Cu2O/ZnO surfaces in a filter-press electrochemical cell for the continuous electroreduction of CO2 into methanol. The electrodes are prepared by airbrushing the metal particles onto a porous carbon paper and then are electrochemically characterized by cyclic voltammetry analyses. Particular emphasis is placed on evaluating and comparing the methanol production and Faradaic efficiencies at different loadings of Cu2O particles (0.5, 1 and 1.8 mg cm−2), Cu2O/ZnO weight ratios (1:0.5, 1:1 and 1:2) and electrolyte flow rates (1, 2 and 3 ml min−1 cm−2). The electrodes including ZnO in their catalytic surface were stable after 5 h, in contrast with Cu2O-deposited carbon papers that present strong deactivation with time. The maximum methanol formation rate and Faradaic efficiency for Cu2O/ZnO (1:1)-based electrodes, at an applied potential of −1.3 V vs. Ag/AgCl, were r = 3.17 × 10−5 mol m−2 s−1 and FE = 17.7 %, respectively. Consequently, the use of Cu2O–ZnO mixtures may be of application for the continuous electrochemical formation of methanol, although further research is still required in order to develop highly active, selective and stable catalysts the electroreduction of CO2 to methanol.

Entrevista com Duarte Cabral de Mello. Intelectual português aborda sua trajetória como crítico e acadêmico

Entrevista com o professor português Duarte Cabral de Mello abordando sua trajetória como crítico e acadêmico.

Exploring Multi-Component Superconducting Compounds by a High-Pressure Method and Ceramic Combinatorial Chemistry

In this short review, we provide some new insights into the material synthesis and characterization of modern multi-component superconducting oxides. Two different approaches such as the high-pressure, high-temperature method and ceramic combinatorial chemistry will be reported with application to several typical examples. First, we highlight the key role of the extreme conditions in the growth of Fe-based superconductors, where a careful control of the composition-structure relation is vital for understanding the microscopic physics. The availability of high-quality LnFeAsO (Ln = lanthanide) single crystals with substitution of O by F, Sm by Th, Fe by Co, and As by P allowed us to measure intrinsic and anisotropic superconducting properties such as Hc2, Jc. Furthermore, we demonstrate that combinatorial ceramic chemistry is an efficient way to search for new superconducting compounds. A single-sample synthesis concept based on multi-element ceramic mixtures can produce a variety of local products. Such a system needs local probe analyses and separation techniques to identify compounds of interest. We present the results obtained from random mixtures of Ca, Sr, Ba, La, Zr, Pb, Tl, Y, Bi, and Cu oxides reacted at different conditions. By adding Zr but removing Tl, Y, and Bi, the bulk state superconductivity got enhanced up to about 122 K.

Radiolarian-based paleotemperatures of ODP Site 177-1089 in the Atlantic Sector of the Southern Ocean

Two cores, Site 1089 (ODP Leg 177) and PS2821-1, recovered from the same location (40°56'S; 9°54'E) at the Subtropical Front (STF) in the Atlantic Sector of the Southern Ocean, provide a high-resolution climatic record, with an average temporal resolution of less than 600 yr. A multi-proxy approach was used to produce an age model for Core PS2821-1, and to correlate the two cores. Both cores document the last climatic cycle, from Marine Isotopic Stage 6 (MIS 6, ca. 160 kyr BP, ka) to present. Summer sea-surface temperatures (SSSTs) have been estimated, with a standard error of ca. +/-1.16°C, for the down core record by using Q-mode factor analysis (Imbrie and Kipp method). The paleotemperatures show a 7°C warming at Termination II (last interglacial, transition from MIS 6 to MIS 5). This transition from glacial to interglacial paleotemperatures (with maximum temperatures ca. 3°C warmer than present at the core location) occurs earlier than the corresponding shift in delta18O values for benthic foraminifera from the same core; this suggests a lead of Southern Ocean paleotemperature changes compared to the global ice-volume changes, as indicated by the benthic isotopic record. The climatic evolution of the record continues with a progressive temperature deterioration towards MIS 2. High-frequency, millennial-scale climatic instability has been documented for MIS 3 and part of MIS 4, with sudden temperature variations of almost the same magnitude as those observed at the transitions between glacial and interglacial times. These changes occur during the same time interval as the Dansgaard-Oeschger cycles recognized in the delta18Oice record of the GRIP and GISP ice cores from Greenland, and seem to be connected to rapid changes in the STF position in relation to the core location. Sudden cooling episodes ('Younger Dryas (YD)-type' and 'Antarctic Cold Reversal (ACR)-type' of events) have been recognized for both Termination I (ACR-I and YD-I events) and II (ACR-II and YD-II events), and imply that our core is located in an optimal position in order to record events triggered by phenomena occurring in both hemispheres. Spectral analysis of our SSST record displays strong analogies, particularly for high, sub-orbital frequencies, to equivalent records from Vostok (Antarctica) and from the Subtropical North Atlantic ocean. This implies that the climatic variability of widely separated areas (the Antarctic continent, the Subtropical North Atlantic, and the Subantarctic South Atlantic) can be strongly coupled and co-varying at millennial time scales (a few to 10-ka periods), and eventually induced by the same triggering mechanisms. Climatic variability has also been documented for supposedly warm and stable interglacial intervals (MIS 1 and 5), with several cold events which can be correlated to other Southern Ocean and North Atlantic sediment records.

(Table 1) Age determination of sediment core MD02-2589

Sortable silt mean grain sizes together with oxygen and carbon isotopic data produced on the benthic foraminiferal species Fontbotia wuellerstorfi are used to construct high-resolution records of near-bottom flow vigour and deep water ventilation at a core site MD02-2589 located at 2660 m water depth on the southern Agulhas Plateau. The results suggest that during glacial periods (marine oxygen isotope stages 2 and 6, MIS 2 and MIS 6, respectively), there was a persistent contribution of a well-ventilated water mass within the Atlantic to Indian oceanic gateway with a d13C signature similar to present-day Northern Component Water (NCW), e.g., North Atlantic Deep Water (NADW). The records of chemical ventilation and near-bottom flow vigor reflect changes in the advection of northern source waters and meridional variability in the location of the Antarctic Circumpolar Current and its associated fronts. We suggest that during Termination II (TII), changes in chemical ventilation are largely decoupled from near-bottom physical flow speeds. A mid-TII climate optimum is associated with a low-flow speed plateau concurrent with a period of increased ventilation shown in the benthic d13C of other Southern Ocean records but not in our benthic d13C of MD02-2589. The climate optimum is followed by a period of southern cooling around 128 ka coincident with a stronger influence of NCW to interglacial levels at around 124 ka. All proxy records show a near synchronous and rapid shift during the transition from MIS 5a-4 (73 ka). This large event is attributed to a rapid decrease in NADW influence and replacement over the Agulhas Plateau by southern source waters.

(Table) Radiocarbon datings of sediment core BLK-1 obtained from Barkol Lake, China

The Barkol Lake, as a closed inland lake, is located at the northeast Xinjiang in northwest China. A combination of geochemical indicators including d18O and d13C of carbonate, TOC, carbonate contents, as well as grain size proxies and magnetic susceptibility of sediments obtained from a newly recovered section at this lake, provides a high-resolution history of climatic change in the past 9400 years. Multi-indicators reflect that Holocene climatic change in the study region generally follows the Westerly Wind pattern of Holocene, and three climatic periods can be identified. Between 9400 and 7500 cal a B.P., climate was characterized by relatively drier and colder condition. From 7500 to 5800 cal a B.P., a relatively warmer and moister climate prevailed, but between 5800 and 3500 cal a B.P., climate shifted towards warmer and drier conditions. A relatively colder and wetter climate prevailed during 3500~1000 cal a B.P., then it changed towards cold and dry between 1000 and 500 cal a B.P.; after 500 cal a B.P., climate changed towards warm and dry conditions again. This study reflects that during the Middle Holocene (from ca 7000 to 3500 cal a B.P.), variations of carbonate d18O of sediments from several lakes in the northern Xinjiang were synchronous with that of Qinghai Lake, where was strongly influenced by the South Asian monsoon; however, after 3500 cal a B.P. this consistency was interrupted, possibly resulting from a re-domination of the Westerly Wind and the retreat of South Asian monsoon in the northern Xinjiang.

Distribution of clay minerals in surface sediments of the Eurasian Arctic Ocean

Clay-mineral distributions in the Arctic Ocean and the adjacent Eurasian shelf areas are discussed to identify source areas and transport pathways of terrigenous material in the Arctic Ocean. The main clay minerals in Eurasian Arctic Ocean sediments are illite and chlorite. Smectite and kaolinite occur in minor amounts in these sediments, but show strong variations in the shelf areas. These two minerals are therefore reliable in reconstructions of source areas of sediments from the Eurasian Arctic. The Kara Sea and the western part of the Laptev Sea are enriched in smectite, with highest values of up to 70% in the deltas of the Ob and Yenisey rivers. Illite is the dominant clay mineral in all the investigated sediments except for parts of the Kara Sea. The highest concentrations with more than 70% illite occur in the East Siberian Sea and around Svalbard. Chlorite represents the clay mineral with lowest concentration changes in the Eastern Arctic, ranging between 10 and 25%. The main source areas for kaolinite in the Eurasian Arctic are Mesozoic sedimentary rocks on Franz-Josef Land islands. Based on clay-mineral data, transport of the clay fraction via sea ice is of minor importance for the modern sedimentary budget in the Arctic basins.