ALBERT

Description: The development of new methodologies to affect non– ortho -functionalization of arenes has emerged as a globally important arena for research, which is key to both fundamental studies and applied technologies. A range of simple arene feedstocks (namely, biphenyl, meta -terphenyl, para -terphenyl, 1,3,5-triphenylbenzene, and biphenylene) is transformed to hitherto unobtainable multi-iodoarenes via an s-block metal sodium magnesiate templated deprotonative approach. These iodoarenes have the potential to be used in a whole host of high-impact transformations, as precursors to key materials in the pharmaceutical, molecular electronic, and nanomaterials industries. To prove the concept, we transformed biphenyl to 3,5-bis( N -carbazolyl)-1,1'-biphenyl, a novel isomer of 4,4'-bis( N -carbazolyl)-1,1'-biphenyl (CPB), a compound which is currently widely used as a host material for organic light-emitting diodes.

Description: 〈p〉In organic microcavities, hybrid light-matter states can form with energies that differ from the bare molecular excitation energies by nearly 1 eV. A timely question, given the recent advances in the development of thermally activated delayed fluorescence materials, is whether strong light-matter coupling can be used to invert the ordering of singlet and triplet states and, in addition, enhance reverse intersystem crossing (RISC) rates. Here, we demonstrate a complete inversion of the singlet lower polariton and triplet excited states. We also unambiguously measure the RISC rate in strongly coupled organic microcavities and find that, regardless of the large energy level shifts, it is unchanged compared to films of the bare molecules. This observation is a consequence of slow RISC to the lower polariton due to the delocalized nature of the state across many molecules and an inability to compete with RISC to the dark exciton reservoir.〈/p〉

Description: Numerous climate change effects on biodiversity have been anticipated and documented, including extinctions, range shifts, phenological shifts, and breakdown of interactions in ecological communities, yet the relative balance of different climate drivers and their relationships to other agents of global change (for example, land use and land-use change) remains relatively poorly understood. This study integrated historical and current biodiversity data on distributions of 115 Mexican endemic bird species to document areas of concentrated gains and losses of species in local communities, and then related those changes to climate and land-use drivers. Of all drivers examined, at this relatively coarse spatial resolution, only temperature change had significant impacts on avifaunal turnover; neither precipitation change nor human impact on landscapes had detectable effects. This study, conducted across species’ geographic distributions, and covering all of Mexico, thanks to two large-scale biodiversity data sets, could discern relative importance of specific climatic drivers of biodiversity change.

Description: Backarc spreading center characteristics reflect interactions between plate-driven mantle advection and melting and slab-driven hydrous melting and buoyant upwelling in the mantle wedge. At the Fonualei Rift and Spreading Center (FRSC) in the Lau Basin spreading rates decrease from slow to ultraslow, providing an opportunity to examine crustal accretion as the plate-driven component is minimized. A new Lau Basin kinematic analysis predicts FRSC spreading rates of ~32-8 mm/yr southward, much slower than previous estimates of ~95-47 mm/yr. Here we examine FRSC morphology and geophysical characteristics as it approaches the Tofua arc volcanic front southward and spreading rates decrease, minimizing the plate-driven component of mantle advection and maximizing buoyant hydrous flux melting. Axial morphology changes abruptly from a deep, flat, faulted axis ~100 km away from the arc to a volcanic ridge that shoals and increases in relief southward. Within ~50 km of the arc at the south end, the volcanic ridge is abruptly replaced by isolated volcanic cones bisected by volcanic rift zones and surrounded by anomalously deep seafloor. These morphologic changes likely reflect along-axis focusing of mantle upwelling and melting similar to that seen at ultraslow mid-ocean ridges, causing the change in morphology from a segmented ridge to spaced axial cones. We propose that as opening rates slow and the ridge approaches the arc, more of the inherently three-dimensional pattern of hydrous flux melting and buoyant upwelling in the mantle wedge is expressed volcanically. With faster opening, two-dimensional plate-driven mantle advection dominates melt production, favoring ridges over point-source features.

Description: The study uses a Monte Carlo radiative transfer model to examine the sensitivity of the UV Erythemal radiation (UVER) enhancement to broken liquid water clouds of the cumulus and stratocumulus type. The model uses monochromatic radiation at 310 nm corresponding approximately to the peak of the product between irradiance and the erythemal curve. All scattering, absorption, extinction coefficients and spectral albedos are tuned to this wavelength. In order of importance, fractional cloud cover, the area of individual cloud patches and cloud thickness exert a strong influence on the enhancement, with smaller contributions from cloud optical depth, cloud base height and solar zenith angle. In order to produce realistic enhancements for our study area located in the Valencia region of Spain (39° 30’ N; 0° 25’W), measurements were obtained from a Landsat image of the region in combination with a spectral Fourier transform model. The Monte Carlo model, as applied to the Fourier transform cloud distribution, produced satisfactory results compared to one year of measured UVER enhancement for the study region provided fractional cloud cover was equal to or greater than 3/10. At smaller cloud fractions, the neglect of cloud patches less than 50 m x 50 m in area by the model created significant discrepancies.

Description: Abstract Preparatory mechanisms accompanying or leading to nucleation of larger earthquakes have been observed at both laboratory and field scales, but conditions favoring the occurrence of observable preparatory processes are still largely unknown. In particular, it remains a matter of debate why some earthquakes occur spontaneously without noticeable precursors as opposed to events that are preceded by an extended failure process. In this study, we have generated new high‐resolution seismicity catalogs framing the occurrence of 20 ML 〉 2.5 earthquakes at The Geysers geothermal field in California. To this end, a seismicity catalog of the 11 days framing each large event was created. We selected 20 sequences sampling different hypocentral depths and hydraulic conditions within the field. Seismic activity and magnitude frequency distributions displayed by the different earthquake sequences are correlated with their location within the reservoir. Sequences located in the northwestern part of the reservoir show overall increased seismic activity and low b values, while the southeastern part is dominated by decreased seismic activity and higher b values. Periods of high injection coincide with high b values and vice versa. These observations potentially reflect varying differential and mean stresses and damage of the reservoir rocks across the field. About 50% of analyzed sequences exhibit no change in seismicity rate in response to the large main event. However, we find complex waveforms at the onset of the main earthquake, suggesting that small ruptures spontaneously grow into or trigger larger events.

Description: 〈p〉Integrated antibiotic resistance (AR) surveillance is one of the objectives of the World Health Organization global action plan on antimicrobial resistance. Urban wastewater treatment plants (UWTPs) are among the most important receptors and sources of environmental AR. On the basis of the consistent observation of an increasing north-to-south clinical AR prevalence in Europe, this study compared the influent and final effluent of 12 UWTPs located in seven countries (Portugal, Spain, Ireland, Cyprus, Germany, Finland, and Norway). Using highly parallel quantitative polymerase chain reaction, we analyzed 229 resistance genes and 25 mobile genetic elements. This first trans-Europe surveillance showed that UWTP AR profiles mirror the AR gradient observed in clinics. Antibiotic use, environmental temperature, and UWTP size were important factors related with resistance persistence and spread in the environment. These results highlight the need to implement regular surveillance and control measures, which may need to be appropriate for the geographic regions.〈/p〉

Description: The urban population of South America has grown at 1.05% per year, greater urbanization increasing problems related to air pollution. In most large cities in South America, there has been no continuous long-term measurement of regulated pollutants. One exception is São Paulo, Brazil, where an air quality-monitoring network has been in place since the 1970s. In this paper, we used an air quality-based approach to determine pollutant trends for emissions of carbon monoxide (CO), nitrogen oxides (NO x ), ozone (O 3 ) and coarse particulate matter (PM 10 ), mostly from mobile sources, in the Metropolitan Region of São Paulo (MRSP) for the 2000–2013 period. Mobile sources included light-duty vehicles (LDVs, comprising gasoline- or ethanol-powered cars and motorcycles) and heavy-duty vehicles (HDVs, comprising diesel-powered trucks and buses). Pollutant concentrations for mobile source emissions were measured and correlated with fuel sales by the emission factors. Over the 2000–2013 period, concentrations of NO x , CO, and PM 10 decreased by 0.65, 0.37, and 0.71% month −1 , respectively, whereas sales of gasoline, ethanol, and diesel increased by 0.26, 1.96, and 0.38% month −1 , respectively. LDVs were the major mobile source of CO, whereas LDVs were the major source of NO x and PM 10 . Increases in fuel sales and in the corresponding traffic volume were partially offset by decreases in pollutant concentrations. Between 2000 and 2013, there was a sharp (−5 ppb month −1 ) decrease in the concentrations of LDV-emitted CO, together with (less dramatic) decreases in the concentrations of HDV-emitted NO x and PM 10 (−0.25 and −0.09 ppb month −1 , respectively). Variability was greater for HDV-emitted NO x and PM 10 (R = −0.47 and −0.41, respectively) than for LDV-emitted CO (R = −0.72). We draw the following conclusions: the observed concentrations of LDV-emitted CO decreased at a sharper rate than did those of HDV-emitted NO x and PM 10 ; mobile source contributions to O 3 formation varied significantly, LDVs making a greater contribution during the 2000–2008 period, whereas HDVs made a greater contribution during the 2009–2013 period; and decreases in NO x emissions resulted in increases in O 3 observations.

Description: We present a revised three-plate kinematic model for the Lau Basin, focusing on new interpretations of the geologic characteristics of the Niuafo‘ou microplate boundaries. It builds upon the three-plate model by Zellmer and Taylor [2001], while resolving some geologic discrepancies in that model. Along the southern branch of the Mangatolu Triple Junction and the Fonualei Rift and Spreading Center, which together form the Niuafo'ou-Tonga plate boundary, our model predicts slow to ultraslow opening rates (~32-8 mm/yr southward), consistent with axial morphology and magnetic profile modeling. Our interpretation of the seafloor magnetization pattern and flank morphology along the Central Lau Spreading Center (CLSC) indicates that opening rates along the Australia-Niuafo'ou boundary are higher than predicted in the previous model, thus compensating for slower rates along the Niuafo'ou-Tonga boundary. Lastly, we show geologic evidence that Peggy Ridge (PR), interpreted previously as an active transform fault and therefore a strong azimuthal constraint on Niuafo'ou plate motion, is inactive and that the active plate boundary is the adjacent Lau Extensional Transform Zone, extending from the CLSC to its intersection with the Northwest Lau Spreading Center. The removal of the PR azimuthal constraint allows us to determine an Euler pole for Australia-Niuafo'ou opening that satisfies three-plate closure criterion and develop a geologically consistent model of Lau Basin kinematics. While the final model focuses on constraining current plate velocities assuming rigid plate Eulerian rotations, the geologic analyses presented herein also provide insight into long term basin evolution, which appears to involve significant non-rigid plate kinematics.

Description: Liquid crystalline (LC) materials, such as actin or tubulin networks, are known to be capable of deforming the shape of cells. Here, elements of that behavior are reproduced in a synthetic system, namely, a giant vesicle suspended in a LC, which we view as a first step toward the preparation of active, anisotropic hybrid systems that mimic some of the functionality encountered in biological systems. To that end, we rely on a coupled particle-continuum representation of deformable networks in a nematic LC represented at the level of a Landau–de Gennes free energy functional. Our results indicate that, depending on its elastic properties, the LC is indeed able to deform the vesicle until it reaches an equilibrium, anisotropic shape. The magnitude of the deformation is determined by a balance of elastic and surface forces. For perpendicular anchoring at the vesicle, a Saturn ring defect forms along the equatorial plane, and the vesicle adopts a pancake-like, oblate shape. For degenerate planar anchoring at the vesicle, two boojum defects are formed at the poles of the vesicle, which adopts an elongated, spheroidal shape. During the deformation, the volume of the topological defects in the LC shrinks considerably as the curvature of the vesicle increases. These predictions are confirmed by our experimental observations of spindle-like shapes in experiments with giant unilamellar vesicles with planar anchoring. We find that the tension of the vesicle suppresses vesicle deformation, whereas anchoring strength and large elastic constants promote shape anisotropy.