Breeder aggression does not predict current or future cooperative group formation in a cooperatively breeding bird.

In cooperatively breeding species, subordinates forgo reproduction to assist breeders in raising offspring. When cooperative breeding is facultative, breeders from the same population may differ in whether they are assisted by non-breeding helpers. Predation risk is a major source of nest failure and assistance during nest defense is often an overlooked, yet important, way helpers assist breeders. A breeder's aggressive response to a nest predator could have important implications for whether they form cooperatively breeding groups. We investigated the hypothesis that breeder aggression towards a nest predator is related to current and future helper recruitment. We tested the prediction that less aggressive breeders were more likely to form cooperative groups, which could occur if these breeders benefit from helper assistance during nest defense. We also considered the possibility that more aggressive breeders were more likely to form cooperative groups. We assessed the effects of partnerships and tested whether aggression exhibited by breeding partners was correlated. We conducted this work in the facultative, cooperatively breeding brown-headed nuthatch (Sitta pusilla). We measured breeder aggression in response to a taxidermy model of a nest predator to determine whether breeders' aggression correlated with their current or future helper recruitment. We found no evidence of a sex difference in aggression among breeders and aggression scores of breeding partners were not significantly correlated. Aggression scores for both breeding males and breeding females were unrelated to whether they formed cooperative groups in the current year. We followed most of the breeding males, though not breeding females, across years and found that breeding males' aggression scores were unrelated to helper recruitment the following year. Our results suggest that breeders' responses to nest predators are not related to cooperative group formation in this species and that males and females showed comparable levels of aggression towards a nest predator.

Amperometric detector for gas chromatography based on a silica sol-gel solid electrolyte.

An electrochemical cell comprising a silica sol-gel solid electrolyte, a working electrode that protrudes into a gas phase, and reference and counter electrodes that contact the solid electrolyte comprises an amperometric detector for gas chromatography. Under potentiostatic conditions, a current related to the concentration of an analyte in the gas phase is produced by its oxidation at the three-phase boundary among the sol-gel, working electrode, and the gas phase. The sol-gel is processed to contain an electrolyte that also serves as a humidistat to maintain a constant water activity even in the presence the gas chromatographic mobile phase. Response was demonstrated toward a diverse set of analytes, namely hydrogen, 1,2-ethandithiol, phenol, p-cresol, and thioanisole. Using flow injection amperometry of hydrogen with He as the carrier gas, 90% of the steady-state current was achieved in < 1s at a flow rate of 20mLmin-1. A separation of 1,2-ethandithiol, phenol, p-cresol, and thioanisole at a 2.2mLmin-1 flow rate was achieved with respective detection limits (k = 3 criterion) of 4, 1, 3, and 70 ppmv when the working electrode potential was 800mV.

Immobilization of nanobeads on a surface to control the size, shape and distribution of pores in electrochemically generated sol-gel films.

Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH3)3SiOCH3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm-3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH3)3SiOCH3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN)64- at scan rates above 5 mVs-1 yielded currents controlled primarily by linear diffusion. Below 5 mVs-1, convection rather than the expected factor, radial diffusion, apparently limited the current.

Phenotypic and Genotypic Characterization of Race TKTTF of Puccinia graminis f. sp. tritici that Caused a Wheat Stem Rust Epidemic in Southern Ethiopia in 2013-14.

A severe stem rust epidemic occurred in southern Ethiopia during November 2013 to January 2014, with yield losses close to 100% on the most widely grown wheat cultivar, 'Digalu'. Sixty-four stem rust samples collected from the regions were analyzed. A meteorological model for airborne spore dispersal was used to identify which regions were most likely to have been infected from postulated sites of initial infection. Based on the analyses of 106 single-pustule isolates derived from these samples, four races of Puccinia graminis f. sp. tritici were identified: TKTTF, TTKSK, RRTTF, and JRCQC. Race TKTTF was found to be the primary cause of the epidemic in the southeastern zones of Bale and Arsi. Isolates of race TKTTF were first identified in samples collected in early October 2013 from West Arsi. It was the sole or predominant race in 31 samples collected from Bale and Arsi zones after the stem rust epidemic was established. Race TTKSK was recovered from 15 samples from Bale and Arsi zones at low frequencies. Genotyping indicated that isolates of race TKTTF belongs to a genetic lineage that is different from the Ug99 race group and is composed of two distinct genetic types. Results from evaluation of selected germplasm indicated that some cultivars and breeding lines resistant to the Ug99 race group are susceptible to race TKTTF. Appearance of race TKTTF and the ensuing epidemic underlines the continuing threats and challenges posed by stem rust not only in East Africa but also to wider-scale wheat production.

PtIr-WO3 nanostructured alloy for electrocatalytic oxidation of ethylene glycol and ethanol.

In this article, we characterized tungsten oxide-decorated carbon-supported PtIr nanoparticles and tested it for the electrooxidation reactions of ethylene glycol and ethanol. Phase and morphological evaluation of the proposed electrocatalytic materials are investigated employing various characterization techniques including X-ray diffraction (XRD) and transmission electron microscopy (TEM). Electrochemical diagnostic measurements such as cyclic voltammetry, chronoamperometry, and linear sweep voltammetry revealed that the tungsten oxide-modified PtIr/Vulcan nanoparticles have higher catalytic activity for ethylene glycol and ethanol electrooxidation than that of PtIr/Vulcan. A significant enhancement for electrooxidation of CO-adsorbate monolayers occurred in the presence of a transition metal oxide relative to that of pure PtIr/Vulcan electrocatalyst. The likely reasons for this are modification on the Pt center electronic structure and/or increasing the population of reactive oxo groups at the PtIr/Vulcan electrocatalytic interface in different potential regions.

Adaptation to ephemeral habitat may overcome natural barriers and severe habitat fragmentation in a fire-dependent species, the Bachman's Sparrow (Peucaea aestivalis).

Bachman's Sparrow (Peucaea aestivalis) is a fire-dependent species that has undergone range-wide population declines in recent decades. We examined genetic diversity in Bachman's Sparrows to determine whether natural barriers have led to distinct population units and to assess the effect of anthropogenic habitat loss and fragmentation. Genetic diversity was examined across the geographic range by genotyping 226 individuals at 18 microsatellite loci and sequencing 48 individuals at mitochondrial and nuclear genes. Multiple analyses consistently demonstrated little genetic structure and high levels of genetic variation, suggesting that populations are panmictic. Based on these genetic data, separate management units/subspecies designations or translocations to promote gene flow among fragmented populations do not appear to be necessary. Panmixia in Bachman's Sparrow may be a consequence of an historical range expansion and retraction. Alternatively, high vagility in Bachman's Sparrow may be an adaptation to the ephemeral, fire-mediated habitat that this species prefers. In recent times, high vagility also appears to have offset inbreeding and loss of genetic diversity in highly fragmented habitat.

Assembly of crosslinked oxo-cyanoruthenate and zirconium oxide bilayers: Application in electrocatalytic films based on organically modified silica with templated pores.

Electrochemical deposition of crosslinked oxo-cyanoruthenate, Ru-O/CN-O, from a mixture of RuCl3 and K4Ru(CN)6 is known to yield a film on glassy carbon that promotes oxidations by a combination of electron and oxygen transfer. Layer-by-layer (LbL) deposition of this species and of a film formed by cycling of the electrode potential in a ZrO2 solution systematically increases the number of catalytically active sites of the Ru-O/CN-O on the electrode. The evaluation of the electrocatalytic activity was by cyclic voltammetric oxidation of cysteine at pH 2. Plots of the anodic peak current vs. the square root of scan rate were indicative of linear diffusion control of this oxidation, even in the absence of ZrO2, but the slopes of these linear plots increased with bilayer number, n, of (ZrO2 | Ru-O/CN-O) n . The latter observation is hypothesized to be due to an increased number of active sites for a given geometric electrode area, but proof required further study. To optimize utilization of the catalyst and to provide a size-exclusion characteristic to the electrode, the study was extended to LbL deposition of the composite in 50-nm pores of an organically modified silica film deposited by electrochemically assisted sol-gel processing using surface-bound poly(styrene sulfonate) nanospheres as a templating agent.

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids.

Modification of electrodes with nm-scale organically modified silica films with pores diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano crosslinks or gold nanoparticles protected by dirhodium-substituted phosophomolybdate (AuNP-Rh2PMo11), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. 10-nm pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH3)3SiOCH3 sol. 50-nm pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH3)3SiOCH3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)63- and Ru(NH3)63+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh2PMo11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.

Development of an automated on-line electrochemical chlorite ion sensor.

A sensor system for the automatic, in-line, determination of chlorite ion is reported. Electroanalytical measurements were performed in electrolyte-free liquids by using an electrochemical probe (EC), which enables in-line detection in high-resistance media such as disinfected water. Cyclic voltammetry scan rate studies suggest that the current arising from the oxidation of chlorite ion at an EC probe is mass-transfer limited. By coupling FIA with an EC probe amperometric cell, automated analysis was achieved. This sensor is intended to fulfill the daily monitoring requirements of the EPA DBP regulations for chlorite ion. Detection limits of 0.02-0.13 mg/L were attained, which is about one order of magnitude below the MRDL. The sensor showed no faradaic signal for perchlorate, chlorate, or nitrate. The lifetime and stability of the sensor were investigated by measuring calibration curves over time under constant-flow conditions. Detection limits of <0.1 mg/L were repeatedly achieved over a period of three weeks.

Preparation and Electrocatalytic Application of Composites Containing Gold Nanoparticles Protected with Rhodium-Substituted Polyoxometalates.

Substitution of a metal center of phosphomolybdate, PMo(12)O(40) (3-) (PMo(12)), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh(2)PMo(11) is demonstrated. The AuNP-Rh(2)PMo(11) mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh(2)PMo(11). At GC|APTES|AuNP-Rh(2)PMo(11), cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo(11) in the range -0.2 to 0.6 vs (Ag/AgCl)/V and the reversible Rh(II,III) couple at 1.0 vs (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC|Rh(2)PMo(11), and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and Rh(II). To stabilize AuNP-Rh(2)PMo(11) on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol-gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10(-8) mol dm(-3).

Oxidation and flow-injection amperometric determination of 5-hydroxytryptophan at an electrode modified by electrochemically assisted deposition of a sol-gel film with templated nanoscale pores.

The oxidation of 5-hydroxytryptophan (5-HTPP) yielded a passivating polymeric film at an indium tin oxide (ITO) electrode. Coating ITO with a nanoscale sol-gel film with a mesoporous structure was shown to change the pathway of the chemical reaction coupled to the electron transfer. The sol-gel film was deposited by an electrochemically assisted process, and the mesoporosity was imparted by including generation-4 poly(amidoamine) dendrimer in the precursor solution. The dendrimer was removed subsequently with an atmospheric oxygen plasma. This electrode remained active during cyclic voltammetry and controlled potential electrolysis of 5-HTPP, which was attributed to dimer, rather than polymer, formation from the oxidation product. Mass spectrometry confirmed this hypothesis. The anodic current was limited by the electron-transfer kinetics. Modification of the sol-gel film by inclusion of cobalt hexacyanoferrate, which catalyzes the oxidation, resulted in a diffusion-limited current. Determination of 5-HTPP by flow-injection amperometry had a detection limit of 17nM.

Detection of ozone gas using gold nanoislands and surface plasmon resonance.

Gold nanoislands interact with gaseous ozone to produce a surface plasmon resonance shift, similarly to the interaction of ozone and gold nanoparticles in water. Gold nanoislands are produced by sputtering, which significantly simplifies the synthesis and produces controlled size for the gold nanoislands. The shift of surface plasmon resonance peak was monitored while gold nanoislands were exposed to variable concentration of gaseous ozone. The shift was then correlated with ozone concentration. Our current results indicate sensing gaseous ozone at concentration of as low as 20 microg/L is achievable. Gold nanoislands were reversed to their original wavelength and were able to cycle between the wavelengths as ozone was introduced and removed. Potentially, this system can be useful as a sensor that identifies the presence of ozone at low part-per-billion concentrations of ozone in gaseous media.

Landscape Features and Panthers in Florida.

We used a geographic information system (GIS) to document spatial associations of Florida panthers, land cover, and other geographical features. Panther radio locations (n = 14,548) occurred in hardwood hammock, mixed hardwood swamp, and cypress swamp in greater proportion than in randomly positioned points (n = 8500). Panther radio locations occurred less frequently in agricultural, barren, and shrub and brush land cover. Panther home ranges consisted of a combination of preferred and avoided cover types, including freshwater marsh, cypress swamp, hardwood swamp, and agricultural land. These cover types accounted for 62% of the area in panther home ranges. We used correlation and discriminant function analyses to assess the potential importance of 20 landscape features. These panther locations were effectively distinguished from random points using four landscape variables: (1) the size of a contiguous patch of preferred land cover; (2) the proximity to preferred land cover; (3) the diversity of three preferred cover types within a window 120 × 120 m, and (4) the matrix within which preferred cover types occurred. Eighty-three percent of the panther locations and 81.9% of the random points were correctly classified based on a linear model constructed using these four variables. Large, contiguous areas of preferred land-cover types were especially important because 96% of all panther locations occurred within 90 m of preferred land cover. The average preferred forest patch size that was used by these panthers was 20,816 ha, and a regression equation suggests that patches larger than 500 ha are important. Maps of panther habitat suitability were developed using coefficients derived from discriminant analysis. Large areas of suitable land cover that are heavily used by panthers occur on private ranches covering 3606 km2 . Conservation of preferred habitat on these private lands is essential to maintaining a free-ranging population of panthers in southwest Florida. Características del paisaje y las panteras en Florida.

Resumen: Utilizamos un Sistema de Información Geográfico (SIG) para documentar las asociaciones espaciales de las panteras de Florida, cobertura de la tierra y otras características geográficas. La localización de las panteras (n = 14,548) se dió en mayor proporción en colinas de bosques de madera dura, humedales mixtos de madera dura y humedales de ciprés, que en puntos situados al azar (n = 8500). La localización de las panteras ocurrió con menor frecuencia en tierras yermas, y áreas con cobertura agrcola, arbustiva y de matorrales. Las áreas de distribución nativas a la pantera consistieron en una combinación de los tipos de cobertura preferidos y eludidos incluyendo pantanos de agua dulce, humedales de ciprés, humedales con árboles de madera dura y tierras agrícolas. Estos tipos de cobertura abarcaron el 62% del área de distribucion nativa de la pantera. Utilizamos correlación y análisis de funciones discriminantes para determinar la importancia potencial de 20 características del paisaje. Estos sitios caracteristicos para la pantera fueron diferenciados eficientemente de puntos al azar, utilizando cuatro variables del paisaje: (1) el tamaño de un parche continguo de la cobertura preferida; (2) la proximidad a una cobertura preferida; (3) la diversidad de tres tipos de cobertura preferida dentro de una ventana de 120 × 120 m y (4) la matriz dentro de la cual se dan los tipos preferidos de cobertura. Un 83% de los sitios de la pantera y un 81.9% de los puntos al azar fueron correctamecnte clasificados en base a un modelo lineal construído utilizando estas cuatro variables. Resultaron especialmente importantes áreas extensas y contínuas de los tipos de cobertura preferidos, ya que el 96% de todos los sitios con panteras se encontraron dentro de los 90 m de la cobertura preferida. El tamaño promedio de los parches del bosque preferido que fue utilizado por estas panteras fue de 20,816 ha y una ecuaciónde regresión sugiere que los parches de más de 500 ha son importantes. Los mapas de aptitud del hábitat para la pantera fueron desarrollados utilizando coeficientes derivados del análisis de funciones discriminantes. Extensas áreas con cobertura propicia, que son intensamente utilizadas por las panteras, se encuentran en ranchos privados cubriendo 3,60 km2 . La conservación de los hábitas preferidos en estas tierras privadas resulta escencial para mantener una población de panteras libres en el sudoeste de Florida.