Leptodactylus bufonius

Number of Pages: 22Integrative BiologyGeological Science

Infrared laser stark spectroscopy of the OH···CH3OH complex isolated in superfluid helium droplets

The elimination of volatile organic compounds (VOCs) from the atmosphere is initiated by reactions with OH, NO$_{3}$ and O$_{3}$.footnote{Atkinson, R.; Arey, J., Chem. Rev. 2003, 103, 4605-4638.}$^{,}$footnote{Mellouki, A.; Le Bras, G.; Sidebottom, H., Chem. Rev. 2003, 103, 5077-5096.} For oxygenated VOCs, such as alcohols, ketones, ethers, etc., reactions occur nearly exclusively with the hydroxyl radical. Furthermore, the potential energy surfaces associated with reactions between OH and oxygenated VOCs generally feature a pre-reactive complex, stabilized by hydrogen bonding, which results in rate constants that exhibit large negative temperature dependencies.footnote{Smith, I. W. M.; Ravishankara, A. R., J. Phys. Chem. A 2002, 106, 4798-4807} This was explicitly demonstrated recently for the OH + methanol (MeOH) reaction, where the rate constant increased by nearly two orders of magnitude when the temperature decreased from 200 K to below 70 K, highlighting the potential impact of this reaction in the interstellar medium (ISM).footnote{Shannon, R. J.; Blitz, M. A.; Goddard, A.; Heard, D. E., Nat. Chem. 2013, 5, 745-749.}$^{,}$footnote{Martin, J. C. G.; Caravan, R. L.; Blitz, M. A.; Heard, D. E.; Plane, J. M. C., J. Phys. Chem. A 2014, 118, 2693-2701.} In this study, we trap this postulated pre-reactive complex formed between OH and MeOH using He nanodroplet isolation (HENDI) techniques, and probe this species using a combination of mass spectrometry and infrared laser Stark spectroscopy

Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)

Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H2O and OH–D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm−1 to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. University of Georgia; Estados UnidosFil: Brice, Joseph T.. University of Georgia; Estados UnidosFil: Leavitt, Christopher M.. University of Georgia; Estados UnidosFil: Liang, Tao. University of Georgia; Estados UnidosFil: Raston, Paul L.. James Madison University. Department of Chemistry and Biochemistry; Estados UnidosFil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Douberly, Gary E.. University of Georgia; Estados Unido

Addition of H_2O and O_2 to Acetone and Dimethylsulfoxide Ligated Uranyl(V) Dioxocations

Gas-phase complexes of the formula [UO_2(lig)]^+ (lig = acetone (aco) or dimethylsulfoxide (dmso)) were generated by electrospray ionization (ESI) and studied by tandem ion-trap mass spectrometry to determine the general effect of ligand charge donation on the reactivity of UO_2^+ with respect to water and dioxygen. The original hypothesis that addition of O_2 is enhanced by strong σ-donor ligands bound to UO_2^+ is supported by results from competitive collision-induced dissociation (CID) experiments, which show near exclusive loss of H_2O from [UO_2(dmso)(H_2O)(O_2)]^+, whereas both H_2O and O_2 are eliminated from the corresponding [UO_2(aco)(H_2O)(O_2)]^+ species. Ligand-addition reaction rates were investigated by monitoring precursor and product ion intensities as a function of ion storage time in the ion-trap mass spectrometer: these experiments suggest that the association of dioxygen to the UO_2^+ complex is enhanced when the more basic dmso ligand was coordinated to the metal complex. Conversely, addition of H_2O is favored for the analogous complex ion that contains an aco ligand. Experimental rate measurements are supported by density function theory calculations of relative energies, which show stronger bonds between UO_2^+ and O_2 when dmso is the coordinating ligand, whereas bonds to H_2O are stronger for the aco complex

Calibration of a common shortwave multispectral camera system for quantitative agricultural applications

Unmanned aerial systems (UAS) for collecting multispectral imagery of agricultural fields are becoming more affordable and accessible. However, there is need to validate calibration of sensors on these systems when using them for quantitative analyses such as evapotranspiration, and other modeling for agricultural applications. The results of laboratory testing of a MicaSense (Seattle, WA, USA) RedEdge™ 3 multispectral camera and MicaSense Downwelling Light Sensor (irradiance sensor) system using a calibrated integrating sphere were presented. Responses of the camera and irradiance sensor were linear over many light levels and became non-linear at light levels below expected real-world, field conditions. Simple linear corrections should suffice for most light conditions encountered during the growing season. Using an irradiance sensor or similar system may not properly account for light variability in cloudy or partly cloudy conditions as also identified by others. A simple stand for aiding in reference panel imagining was also described, which may facilitate repetitive, consistent reference panel imaging

The Macroscopic Rate of Nucleic Acid Translocation by Hepatitis C virus Helicase NS3h is Dependent on Both the Sugar and Base Moieties

The NS3 helicase (NS3h) of hepatitis C virus (HCV) is a 3′ to 5′ SF2 RNA and DNA helicase that is essential for the replication of HCV. We have examined the kinetic mechanism of translocation of NS3h along single-stranded nucleic acid with bases rU, dU and dT and have found that the macroscopic rate of translocation is dependent upon both the base and sugar moieties of the nucleic acid, with approximate macroscopic translocation rates of 3 nt/s (oligo-dT), 35 nt/s (oligo-dU), and 42 nt/s (oligo-rU), respectively. We found a strong correlation between the macroscopic translocation rates and the binding affinity of the translocating NS3h protein to the respective substrates such that weaker affinity corresponded to faster translocation. The values of K0.5 for NS3h translocation at a saturating ATP concentration are: (3.3 ± 0.4) μM nucleotide (poly-dT), (27 ± 2) μM nucleotide (poly-dU), and (36 ± 2) μM nucleotide (poly-rU). Furthermore, the results of isothermal titration of NS3h with these oligonucleotides suggest that differences in TΔS° are the principal source of the differences in the affinity of NS3h binding to these substrates. Interestingly, despite the differences in macroscopic translocation rates and binding affinities, the ATP coupling stoichiometry for NS3h translocation was identical for all three substrates, ~0.5 ATP molecules consumed per nucleotide translocated. This similar periodicity of ATP consumption implies a similar mechanism for NS3h translocation along RNA and DNA substrates

Natural climate solutions

Our thanks for inputs by L. Almond, A. Baccini, A. Bowman, S. CookPatton, J. Evans, K. Holl, R. Lalasz, A. Nassikas, M. Spalding, M. Wolosin, and expert elicitation respondents. Our thanks for datasets developed by the Hansen lab and the NESCent grasslands working group (C. Lehmann, D. Griffith, T. M. Anderson, D. J. Beerling, W. Bond, E. Denton, E. Edwards, E. Forrestel, D. Fox, W. Hoffmann, R. Hyde, T. Kluyver, L. Mucina, B. Passey, S. Pau, J. Ratnam, N. Salamin, B. Santini, K. Simpson, M. Smith, B. Spriggs, C. Still, C. Strömberg, and C. P. Osborne). This study was made possible by funding from the Doris Duke Charitable Foundation. Woodbury was supported in part by USDA-NIFA Project 2011-67003-30205 Data deposition: A global spatial dataset of reforestation opportunities has been deposited on Zenodo (https://zenodo.org/record/883444). This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1710465114/-/DCSupplemental.Peer reviewedPublisher PD

Clinical impairment in premanifest and early Huntington's disease is associated with regionally specific atrophy.

TRACK-HD is a multicentre longitudinal observational study investigating the use of clinical assessments and 3-Tesla magnetic resonance imaging as potential biomarkers for future therapeutic trials in Huntington's disease (HD). The cross-sectional data from this large well-characterized dataset provide the opportunity to improve our knowledge of how the underlying neuropathology of HD may contribute to the clinical manifestations of the disease across the spectrum of premanifest (PreHD) and early HD. Two hundred and thirty nine gene-positive subjects (120 PreHD and 119 early HD) from the TRACK-HD study were included. Using voxel-based morphometry (VBM), grey and white matter volumes were correlated with performance in four domains: quantitative motor (tongue force, metronome tapping, and gait); oculomotor [anti-saccade error rate (ASE)]; cognition (negative emotion recognition, spot the change and the University of Pennsylvania smell identification test) and neuropsychiatric measures (apathy, affect and irritability). After adjusting for estimated disease severity, regionally specific associations between structural loss and task performance were found (familywise error corrected, P < 0.05); impairment in tongue force, metronome tapping and ASE were all associated with striatal loss. Additionally, tongue force deficits and ASE were associated with volume reduction in the occipital lobe. Impaired recognition of negative emotions was associated with volumetric reductions in the precuneus and cuneus. Our study reveals specific associations between atrophy and decline in a range of clinical modalities, demonstrating the utility of VBM correlation analysis for investigating these relationships in HD