Stabilizing a Molecular Switch at Solid Surfaces: A Density-Functional Theory Study of Azobenzene at Cu(111), Ag(111), and Au(111)

We present a density-functional theory trend study addressing the binding of the trans-cis conformational switch azobenzene (C6H5-N=N-C6H5) at three coinage metal surfaces. From the reported detailed energetic, geometric, and electronic structure data we conclude that the governing factor for the molecule-surface interaction is a competition between covalent bonding of the central azo (-N=N-) bridge on the one hand and the surface interaction of the two closed-shell phenyl (-C6H5) rings on the other. With respect to this factor the cis conformer exhibits a more favorable gas-phase geometric structure and is thus more stabilized at the studied surfaces. With the overall binding still rather weak the relative stability of the two isomers is thereby reduced at Ag(111) and Au(111). This is significantly different at Cu(111), where the cis bonding is strong enough to even reverse the gas-phase energetic order at the level of the employed semi-local electronic exchange and correlation (xc) functional. While this actual reversal may well be affected by the deficiencies due to the approximate xc treatment, we critically discuss that the rationalization of the general effect of the surface on the meta-stable molecular states is quite robust. This should equally hold for the presented analysis of recent tip-manipulation and photo-excitation isomerization experiments from the view point of the derived bonding mechanism.Comment: 10 pages including 4 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): Characterizing the role of spacer groups

We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface chemical bond. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N=N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.Comment: 9 pages including 6 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Competitividad Sistémica

Competitividad Sistémic

Waterborne Toxoplasmosis, Northeastern Brazil

Two waterborne outbreaks of toxoplasmosis have been described recently in southern Brazil. We present data from a community-based study of pregnant women in northeastern Brazil. Consumption of homemade ice was the only variable associated with seropositivity (adjusted odds ratio, 3.1, 95% confidence interval, 1.53–6.24). Our results suggest water as a source of infection with Toxoplasma gondii

Creating Calibration Curves to Determine Shock Pressure in Clinopyroxene

Impact cratering is an important geological process that occurs on every rocky body in the solar system. It alters the texture and mineralogy of rocks via shock metamorphism. The peak shock pressures experienced by a rock are traditionally evaluated using qualitative optical methods however, quantitative methods do exist. One such method was developed by Uchizono et al., who used X-ray Diffraction (XRD) to measure lattice strain () in several artificially shocked olivine grains using XRD peak broadening as a function of tan , where is the diffraction angle. They plotted the values against the known peak shock pressures experienced by the olivine grains. Using this calibration curve, the precise shock pressure experienced by a grain of olivine can be determined using its measured value. Another method was developed by McCausland et al. and Izawa et al., who used in situ XRD to measure strain-related mosaicity (SRM) of olivine in several ordinary chondrites and enstatite in enstatite chondrites, respectively. They plotted these results against the shock stage estimates for these meteorites. Using these plots, meteorites can be assigned to shock stage bins by measuring the SRM of olivine and/or enstatite. Both methods are useful for evaluating shock metamorphism, however, they have limitations. Uchizono et al.s calibration curve has been successfully applied to martian meteorites, however it can only be applied to olivine-bearing rocks. McCausland et al.s and Izawa et al.s SRM method is uncalibrated and is limited to binning meteorites by shock stage. This work aims to expand on both methods by creating calibration curves for clinopyroxene (CPX): one for , similar to Uchizono et al.s calibration curve for olivine, and one for SRM. This will extend the application of shock calibration methods to a greater variety of rock types. Preliminary results are presented herein

Ruling out Stellar Companions and Resolving the Innermost Regions of Transitional Disks with the Keck Interferometer

With the Keck Interferometer, we have studied at 2 um the innermost regions of several nearby, young, dust depleted "transitional" disks. Our observations target five of the six clearest cases of transitional disks in the Taurus/Auriga star-forming region (DM Tau, GM Aur, LkCa 15, UX Tau A, and RY Tau) to explore the possibility that the depletion of optically thick dust from the inner disks is caused by stellar companions rather than the more typical planet-formation hypothesis. At the 99.7% confidence level, the observed visibilities exclude binaries with flux ratios of at least 0.05 and separations ranging from 2.5 to 30 mas (0.35 - 4 AU) over >= 94% of the area covered by our measurements. All targets but DM Tau show near-infrared excess in their SED higher than our companion flux ratio detection limits. While a companion has previously been detected in the candidate transitional disk system CoKu Tau/4, we can exclude similar mass companions as the typical origin for the clearing of inner dust in transitional disks and of the near-infrared excess emission. Unlike CoKu Tau/4, all our targets show some evidence of accretion. We find that all but one of the targets are clearly spatially resolved, and UX Tau A is marginally resolved. Our data is consistent with hot material on small scales (0.1 AU) inside of and separated from the cooler outer disk, consistent with the recent SED modeling. These observations support the notion that some transitional disks have radial gaps in their optically thick material, which could be an indication for planet formation in the habitable zone (~ a few AU) of a protoplanetary disk.Comment: 36 pages, 7 figures. Accepted for publication in Ap

A direct-to-drive neural data acquisition system

Driven by the increasing channel count of neural probes, there is much effort being directed to creating increasingly scalable electrophysiology data acquisition (DAQ) systems. However, all such systems still rely on personal computers for data storage, and thus are limited by the bandwidth and cost of the computers, especially as the scale of recording increases. Here we present a novel architecture in which a digital processor receives data from an analog-to-digital converter, and writes that data directly to hard drives, without the need for a personal computer to serve as an intermediary in the DAQ process. This minimalist architecture may support exceptionally high data throughput, without incurring costs to support unnecessary hardware and overhead associated with personal computers, thus facilitating scaling of electrophysiological recording in the future.National Institutes of Health (U.S.) (Grant 1DP1NS087724)National Institutes of Health (U.S.) (Grant 1R01DA029639)National Institutes of Health (U.S.) (Grant 1R01NS067199)National Institutes of Health (U.S.) (Grant 2R44NS070453)National Institutes of Health (U.S.) (Grant R43MH101943)New York Stem Cell FoundationPaul Allen FoundationMassachusetts Institute of Technology. Media LaboratoryGoogle (Firm)United States. Defense Advanced Research Projects Agency (HR0011-14-2-0004)Hertz Foundation (Myhrvold Family Fellowship

The Genome of the Epsilonproteobacterial Chemolithoautotroph Sulfurimonas dentrificans

Sulfur-oxidizing epsilonproteobacteria are common in a variety of sulfidogenic environments. These autotrophic and mixotrophic sulfur-oxidizing bacteria are believed to contribute substantially to the oxidative portion of the global sulfur cycle. In order to better understand the ecology and roles of sulfur-oxidizing epsilonproteobacteria, in particular those of the widespread genus Sulfurimonas, in biogeochemical cycles, the genome of Sulfurimonas denitrificans DSM1251 was sequenced. This genome has many features, including a larger size (2.2 Mbp), that suggest a greater degree of metabolic versatility or responsiveness to the environment than seen for most of the other sequenced epsilonproteobacteria. A branched electron transport chain is apparent, with genes encoding complexes for the oxidation of hydrogen, reduced sulfur compounds, and formate and the reduction of nitrate and oxygen. Genes are present for a complete, autotrophic reductive citric acid cycle. Many genes are present that could facilitate growth in the spatially and temporally heterogeneous sediment habitat from where Sulfurimonas denitrificans was originally isolated. Many resistance-nodulation-development family transporter genes (10 total) are present; of these, several are predicted to encode heavy metal efflux transporters. An elaborate arsenal of sensory and regulatory protein-encoding genes is in place, as are genes necessary to prevent and respond to oxidative stress

Biodiversity post-2020: Closing the gap between global targets and national-level implementation

National and local governments need to step up efforts to effectively implement the post-2020 global biodiversity framework of the Convention on Biological Diversity to halt and reverse worsening biodiversity trends. Drawing on recent advances in interdisciplinary biodiversity science, we propose a framework for improved implementation by national and subnational governments. First, the identification of actions and the promotion of ownership across stakeholders need to recognize the multiple values of biodiversity and account for remote responsibility. Second, cross-sectorial implementation and mainstreaming should adopt scalable and multifunctional ecosystem restoration approaches and target positive futures for nature and people. Third, assessment of progress and adaptive management can be informed by novel biodiversity monitoring and modeling approaches handling the multidimensionality of biodiversity change

Progress in upscaling Miscanthus biomass production for the European bio-economy with seed-based hybrids

Funded by UK's Biotechnology and Biological Sciences Research Council (BBSRC) Department for Environment, Food and Rural Affairs (DEFRA). Grant Number: LK0863 BBSRC strategic programme Grant on Energy Grasses & Bio-refining. Grant Number: BBS/E/W/10963A01 OPTIMISC. Grant Number: FP7-289159 WATBIO. Grant Number: FP7-311929 Innovate UK/BBSRC ‘MUST’. Grant Number: BB/N016149/1Peer reviewedPublisher PD