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: 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: 〈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: 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.

Description: We examine in detail a one-year global reanalysis of carbon monoxide (CO) that is based on joint assimilation of conventional meteorological observations and Measurement of Pollution in The Troposphere (MOPITT) multispectral CO retrievals in the Community Earth System Model (CESM). Our focus is to assess the impact to the chemical system when CO distribution is constrained in a coupled full chemistry-climate model like CESM. To do this, we first evaluate the joint reanalysis (MOPITT Reanalysis) against four sets of independent observations and compare its performance against a reanalysis with no MOPITT assimilation (Control Run). We then investigate the CO burden and chemical response with the aid of tagged sectoral CO tracers. We estimate the total tropospheric CO burden in 2002 (from ensemble mean and spread) to be 371 ±12% Tg for MOPITT Reanalysis and 291 ± 9 % Tg for Control Run. Our multi-species analysis of this difference suggests that: a) direct emissions of CO and hydrocarbons are too low in the inventory used in this study; and b) chemical oxidation, transport, and deposition processes are not accurately and consistently represented in the model. Increases in CO led to net reduction of OH and subsequent longer lifetime of CH 4 (Control Run: 8.7 years versus MOPITT Reanalysis: 9.3 years). Yet, at the same time, this increase led to 5-10% enhancement of northern hemisphere O 3 and overall photochemical activity via HO X recycling. Such nonlinear effects further complicate the attribution to uncertainties in direct emissions alone. This has implications to chemistry-climate modeling and inversion studies of longer-lived species.

Description: [1]  Validation results are reported for the MOPITT (Measurements of Pollution in the Troposphere) “Version 5” (V5) product for tropospheric carbon monoxide (CO) and are compared to results for the “Version 4” product. The V5 retrieval algorithm introduces (1) a method for reducing retrieval bias drift associated with long-term instrumental degradation, (2) a more exact representation of the effects of random errors in the radiances and, for the first time, (3) the use of MOPITT's near-infrared (NIR) radiances to complement the thermal-infrared (TIR) radiances. Exploiting TIR and NIR radiances together facilitates retrievals of CO in the lowermost troposphere. V5 retrieval products based (1) solely on TIR measurements, (2) solely on NIR measurements and (3) on both TIR and NIR measurements are separately validated and analyzed. Actual retrieved CO profiles and total columns are compared with equivalent retrievals based on in-situ measurements from (1) routine NOAA aircraft sampling mainly over North America and (2) the “HIAPER Pole to Pole Observations” (HIPPO) field campaign. Particular attention is focused on the long-term stability and geographical uniformity of the retrieval errors. Results for the retrieved total column clearly indicate reduced temporal bias drift in the V5 products compared to the V4 product, and do not exhibit a positive bias in the Southern Hemisphere which is evident in the V4 product.

Description: Studies of sensory capacities in past life forms have offered new insights into their adaptations and lifeways. Audition is particularly amenable to study in fossils because it is strongly related to physical properties that can be approached through their skeletal structures. We have studied the anatomy of the outer and middle ear in the early hominin taxa Australopithecus africanus and Paranthropus robustus and estimated their auditory capacities. Compared with chimpanzees, the early hominin taxa are derived toward modern humans in their slightly shorter and wider external auditory canal, smaller tympanic membrane, and lower malleus/incus lever ratio, but they remain primitive in the small size of their stapes footplate. Compared with chimpanzees, both early hominin taxa show a heightened sensitivity to frequencies between 1.5 and 3.5 kHz and an occupied band of maximum sensitivity that is shifted toward slightly higher frequencies. The results have implications for sensory ecology and communication, and suggest that the early hominin auditory pattern may have facilitated an increased emphasis on short-range vocal communication in open habitats.