Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: a new one-dimensional indium selenide

A new organically templated indium selenide, [C6H16N2][In2Se3(Se2)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV–vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C6H16N2][In2Se3(Se2)] contains anionic chains of stoichiometry [In2Se3(Se2)]2−, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In2Se3(Se2)]2− chains, which consist of alternating four-membered [In2Se2] and five-membered [In2Se3] rings, contain perselenide (Se2)2− units. UV–vis diffuse reflectance spectroscopy indicates that [C6H16N2][In2Se3(Se2)] has a band gap of 2.23(1) eV

Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride.

Fungicide-resistance management tactics: impacts on Zymoseptoria tritici populations

Azoles and Succinate Dehydrogenase Inhibitors (SDHIs) are the main fungicides available for septoria tritici blotch control, causal agent Zymoseptoria tritici. Decline in azole sensitivity, in combination with European legislation, poses a threat to wheat production in Ireland. Azole fungicides select CYP51 mutations differentially; it was hypothesised that using combinations of azoles could be an effective anti-resistance tool. Naturally inoculated field experiments were carried out in order to understand the impacts of using combinations of azoles, epoxiconazole and metconazole, on azole sensitivity. Approximately 3700 isolates were isolated and their sensitivity to both azoles analysed. Findings showed that limiting the number of applications, by alternating each fungicide, slowed selection for reduced azole sensitivity. Limiting azole use by reducing doses did not reduce selection for decreased azole sensitivity. Although not complete, cross-resistance was observed between the two azoles, which will lead to general reduction in azole sensitivity. A sub-selection of isolates from each treatment at each location were analysed for changes in the CYP51 gene. Sequence analysis identified 49 combinations of mutations in the CYP51 gene, and three different inserts in the CYP51 promoter. Intragenic recombination also featured in these populations. Baseline studies of five new SDHIs were carried out on 209 naturally infected, non-SDHI-treated isolates. With the exception of fluopyram, cross-resistance was apparent between the SDHIs. Analysis of 2300 isolates found that when compared to the solo products, mixing the SDHI isopyrazam and the azole epoxiconazole increased epoxiconazole sensitivity, but had no apparent effect on isopyrazam sensitivity. SDHI resistance-conferring mutations were absent in the baseline and experimental isolates. As long as azoles are used, Z. tritici populations will continue to evolve towards resistance. Combining different modes-of-action, SDHIs and multi-sites, with azoles will relieve some of that selective pressure. To get the best out of available fungicides, they should be used in combination with host resistance and good crop management practices.

Increased frequency of extreme La Niña events under greenhouse warming

The El Niño/Southern Oscillation is Earth’s most prominent source of interannual climate variability, alternating irregularly between El Niño and La Niña, and resulting in global disruption of weather patterns, ecosystems, fisheries and agriculture1, 2, 3, 4, 5. The 1998–1999 extreme La Niña event that followed the 1997–1998 extreme El Niño event6 switched extreme El Niño-induced severe droughts to devastating floods in western Pacific countries, and vice versa in the southwestern United States4, 7. During extreme La Niña events, cold sea surface conditions develop in the central Pacific8, 9, creating an enhanced temperature gradient from the Maritime continent to the central Pacific. Recent studies have revealed robust changes in El Niño characteristics in response to simulated future greenhouse warming10, 11, 12, but how La Niña will change remains unclear. Here we present climate modelling evidence, from simulations conducted for the Coupled Model Intercomparison Project phase 5 (ref. 13), for a near doubling in the frequency of future extreme La Niña events, from one in every 23 years to one in every 13 years. This occurs because projected faster mean warming of the Maritime continent than the central Pacific, enhanced upper ocean vertical temperature gradients, and increased frequency of extreme El Niño events are conducive to development of the extreme La Niña events. Approximately 75% of the increase occurs in years following extreme El Niño events, thus projecting more frequent swings between opposite extremes from one year to the next.

Environmental agreements as a Hawk-Dove game with confirmed proposals

This paper aims at two different contributions to the literature on international environmental agreements. First, we model environmental agreements as a generic situation, characterized as a Hawk-Dove game with multiple asymmetric equilibria. Second, the article applies the theory on non-cooperative games with confirmed proposals, based on an alternating proposals bargaining protocol, as a way of overcoming the usual problems of coordination and bargaining failures in environmental agreement games, due to payoff asymmetry and equilibrium multiplicity.

Paleomagnetism of the Santa Fe Group, central Brazil: Implications for the late Paleozoic apparent polar wander path for South America

Paleomagnetic and rockmagnetic data are reported for the Floresta Formation (Santa Fe Group) of the Sanfranciscana Basin, central Brazil. This formation represents the Permo-Carboniferous glacial record of the basin and comprises the Brocoto (diamictites and flow diamictites), Brejo do Arroz (red sandstones and shales with dropstones and invertebrate trails), and Lavado (red sandstones) members, which crop out near the cities of Santa Fe de Minas and Canabrava, Minas Gerais State. Both Brejo do Arroz and Lavado members were sampled in the vicinities of the two localities. Alternating field and thermal demagnetizations of 268 samples from 76 sites revealed reversed components of magnetization in all samples in accordance with the Permo-Carboniferous Reversed Superchron. The magnetic carriers are magnetite and hematite with both minerals exhibiting the same magnetization component, suggesting a primary origin for the remanence. We use the high-quality paleomagnetic pole for the Santa Fe Group (330.9 degrees E 65.7 degrees S; N = 60; alpha(95) = 4.1 degrees; k = 21) in a revised late Carboniferous to early Triassic apparent polar wander path for South America. On the basis of this result it is shown that an early Permian Pangea A-type fit is possible if better determined paleomagnetic poles become available.

Columbia revisited: Paleomagnetic results from the 1790 Ma colider volcanics (SW Amazonian Craton, Brazil)

In an attempt to improve our understanding of the Paleoproterozoic geodynamic evolution, a paleomagnetic study was performed on 10 sites of acid volcanic rocks of the Colider Suite, southwestern Amazonian Craton. These rocks have a well-dated zircon U-Pb mean age of 1789 +/- 7 Ma. Alternating field and thermal demagnetization revealed northern (southern) directions with moderate to high upward (downward) inclinations. Rock magnetism experiments and magnetic mineralogy show that this characteristic magnetization is carried by Ti-poor magnetite or by hematite that replaces magnetite by late-magmatic cleuteric alteration. Both magnetite and hematite carry the same characteristic component. The mean direction (Dm = 183.0 degrees, Im = 53.5 degrees, N = 10, alpha(95) = 9.8 degrees, K = 25.2) yielded a paleomagnetic pole located at 298.8 degrees E, 63.3 degrees S (alpha(95) = 10.2 degrees, K = 23.6), which is classified with a quality factor Q = 5. Paleogeographic reconstructions using this pole and other reliable Paleoproterozoic poles suggest that Laurentia, Baltica, North China Craton and Amazonian Craton were located in laterally contiguous positions forming a large continental mass at 1790 Ma ago. This is reinforced by geological evidence which support the existence of the supercontinent Columbia in Paleoproterozoic times. (C) 2008 Elsevier B.V. All rights reserved.

Potamotrygon tigrina, a new species of freshwater stingray from the upper Amazon basin, closely related to Potamotrygon schroederi Fernandez-Yepez, 1958 (Chondrichthyes: Potamotrygonidae)

A new species of Neotropical freshwater stingray, family Potamotrygonidae, is described from the Rio Nanay in the upper Rio Amazonas basin of Peru. Potamotrygon tigrina, n. sp., is easily distinguished from all congeners by its conspicuous dorsal disc coloration, composed of bright yellow to orange vermiculations strongly interwoven with a dark-brown to deep-black background. Additional features that in combination diagnose P. tigrina, n. sp., include the presence of a single angular cartilage, low and not closely grouped dorsal tail spines, and coloration of tail composed of relatively wide and alternating bands of creamy white and dark brown to black. Potamotrygon tigrina is closely related to Potamotrygon schroederi Fernandez-Yepez, 1958, which occurs in the Rio Negro (Brazil) and Rio Orinoco (Venezuela, Colombia). Both species are very similar in proportions and counts, and share features hypothesized to be derived within Potamotrygonidae, related to their specific angular cartilage morphology, distal tail color, dorsal tail-spine pattern, and ventral lateral-line system. To further substantiate the description of P. tigrina, n. sp., we provide a redescription of P. schroederi based on material from the Rio Negro (Brazil) and Rio Orinoco (Venezuela). Specimens from the two basins differ in number of vertebral centra and slightly in size and frequency of rosettes on dorsal disc, distinctions that presently do not warrant their specific separation. Potamotrygon tigrina is frequently commercialized in the international aquarium trade but virtually nothing is known of its biology or conservation status.

Synthesis of biodegradable polyhydroxyalcanoate copolymer from a renewable source by alternate feeding

Polyhydroxyalcanoates copolymers with 3-hydroxybutirate (3HB) and 3-hydroxyvalerate (3HV) co-monomers, P3(HB-co-x%HV), were produced in fed-batch culture by Ralstonia eutropha DSM428 using fructose as a single carbon source in the first step and adding propionic acid in the second step by alternating feeding. Polymer yield was 0.18 g/L with a content of 24 mol% of the 3HV fraction determined by H-1 NMR. NMR measurements indicated that the polymer obtained is isotactic. The copolymer attained 35% of crystallinity according to X-ray diffraction measurements, and two (020) planes were observed. Thermal behavior presented melting temperature at 154 degrees C and the crystallization temperature was 65 degrees C. A glass transition temperature was observed at -10 degrees C. Average molecular weight measured by GPC was 4.9 x 10(5) Dalton. Isothermal radial growth rates of spherulites of P3(HB-co-24%HV) were studied. All experimental facts and the analysis of the sequence distribution of diads and triads of 3HB and 3HV units led to the conclusion that it is not a completely statistical random copolymer once it contains different types of segments. POLYM.

Strategies to Optimize Biosensors Based on Impedance Spectroscopy to Detect Phytic Acid Using Layer-by-Layer Films

Impedance spectroscopy has been proven a powerful tool for reaching high sensitivity in sensor arrays made with nanostructured films in the so-called electronic tongue systems, whose distinguishing ability may be enhanced with sensing units capable of molecular recognition. In this study we show that for optimized sensors and bio-sensors the dielectric relaxation processes involved in impedance measurements should also be considered, in addition to an adequate choice of sensing materials. We used sensing units made from layer-by-layer (LbL) films with alternating layers of the polyeletrolytes, poly(allylamine) hydrochloride (PAH) and poly(vinyl sulfonate) (PVS), or LbL films of PAH alternated with layers of the enzyme phytase, all adsorbed on gold interdigitate electrodes. Surprisingly, the detection of phytic acid was as effective in the PVS/PAH sensing system as with the PAH/phytase system, in spite of the specific interactions of the latter. This was attributed to the dependence of the relaxation processes on nonspecific interactions such as electrostatic cross-linking and possibly on the distinct film architecture as the phytase layers were found to grow as columns on the LbL film, in contrast to the molecularly thin PAH/PVS films. Using projection techniques, we were able to detect phytic acid at the micromolar level with either of the sensing units in a data analysis procedure that allows for further optimization.

The gas flow rate increase obtained by an oscillating piezoelectric actuator on a micronozzle

Micronozzles with piezoelectric actuator were fabricated and investigated. The micronozzles were fabricated in glass substrates using a powder-blasting technique, and the actuator is a bimorph structure made from a piezoelectric polymer. The actuator was located at the nozzle outlet, and was driven in an oscillating mode by applying an alternating voltage across the actuator electrodes. With a pressure difference between inlet and outlet, the gas flow rate through the device was increased. This effect was quantified, and compared to a similar micronozzle with no actuator. The increase in the flow rate was defined as the gas flow through the micronozzle with actuator oscillating minus the gas flow without actuator, was found to depend on the inlet pressure, the pressure ratio, and the nozzle throat diameter. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis and characterization of glass-ceramic microspheres for thermotherapy

Glass microspheres containing radionuclides are used to treat liver cancer. A promising alternative therapy is being developed based on the magnetic hyperthermia which is related to the heat supplied by a magnetic material under an alternating current magnetic field. The advantage of this option is that most of killed cells are cancer cells which are more susceptible to the temperature raise. In the present work aluminum iron silicate glasses containing minor glass modifiers and nucleating agents were synthesized as irregular shape particles which were further transformed in microspheres by using a petrol liquefied gas-oxygen torch. The optimized processing parameters which lead to microspheres that give a response to the magnetic field were determined. The dissolution rate in water at 90 degrees C was determined to be 3 x 10(-8) g cm(-2) min(-1). The microsphere size distribution was determined by laser scattering. The crystalline phase responsible for the ferromagnetic response was identified as magnetite. Since this phase has a high saturation magnetization and high Curie temperature, it is potentially useful for biomedical applications. The hysteresis magnetic loop was measured for materials produced in different conditions, and some of them showed to be appropriated for thermotherapy. The ratio Fe(3+)/Fe(total) was determined by Mossbauer spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Weak antilocalization in HgTe quantum wells near a topological transition

The anomalous alternating magnetoresistivity in HgTe quantum wells with thicknesses of 5.8 and 8.3 nm, i.e., near the transition from the direct band spectrum to an inverted spectrum, has been revealed and analyzed. It has been shown that the revealed anomalous alternating magnetoresistivity in wells with an inverted spectrum is well described by the theory developed by S.V. Iordanskii et al. [JETP Lett. 60, 206 (1994)] and W. Knap et al. [Phys. Rev. B 53, 3912 (1996)]. A detailed comparison of the experimental data with the theory indicates the presence of only the cubic term in the spin splitting of the electronic spectrum. The applicability conditions of the mentioned theory are not satisfied in a well with a direct gap and, for this reason, such a certain conclusion is impossible. The results indicate the existence of a strong spin-orbit interaction in symmetric HgTe quantum wells near the topological transition.

Associating biosensing properties with the morphological structure of multilayers containing carbon nanotubes on field-effect devices

The control of molecular architecture provided by the layer-by-layer (LbL) technique has led to enhanced biosensors, in which advantageous features of distinct materials can be combined. Full optimization of biosensing performance, however, is only reached if the film morphology is suitable for the principle of detection of a specific biosensor. In this paper, we report a detailed morphology analysis of LbL films made with alternating layers of single-walled carbon nanotubes (SWNTs) and polyamidoamine (PAMAM) dendrimers, which were then covered with a layer of penicillinase (PEN). An optimized performance to detect penicillin G was obtained with 6-bilayer SWNT/PAMAM LbL films deposited on p-Si-SiO(2)-Ta(2)O(5) chips, used in biosensors based on a capacitive electrolyte-insulator-semiconductor (EIS) and a light-addressable potentiometric sensor (LAPS) structure, respectively. Field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) images indicated that the LbL films were porous, with a large surface area due to interconnection of SWNT into PAMAM layers. This morphology was instrumental for the adsorption of a larger quantity of PEN, with the resulting LbL film being highly stable. The experiments to detect penicillin were performed with constant-capacitance (Con Cap) and constant-current (CC) measurements for EIS and LAPS sensors, respectively, which revealed an enhanced detection signal and sensitivity of ca. 100 mV/decade for the field-effect sensors modified with the PAMAM/SWNT LbL film. It is concluded that controlling film morphology is essential for an enhanced performance of biosensors, not only in terms of sensitivity but also stability and response time. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Bose systems in spatially random or time-varying potentials

Bose systems, subject to the action of external random potentials, are considered. For describing the system properties, under the action of spatially random potentials of arbitrary strength, the stochastic mean-field approximation is employed. When the strength of disorder increases, the extended Bose-Einstein condensate fragments into spatially disconnected regions, forming a granular condensate. Increasing the strength of disorder even more transforms the granular condensate into the normal glass. The influence of time-dependent external potentials is also discussed. Fastly varying temporal potentials, to some extent, imitate the action of spatially random potentials. In particular, strong time-alternating potential can induce the appearance of a nonequilibrium granular condensate.