Relaxation Dynamics of Pseudomonas aeruginosa Re^I(C)O_3(α-diimine)(HisX)^+ (X=83, 107, 109, 124, 126)Cu-^(II) Azurins

Photoinduced relaxation processes of five structurally characterized Pseudomonas aeruginosa Re^I(CO)_3(α-diimine)(HisX) (X = 83, 107, 109, 124, 126)Cu^(II) azurins have been investigated by time-resolved (ps−ns) IR spectroscopy and emission spectroscopy. Crystal structures reveal the presence of Re-azurin dimers and trimers that in two cases (X = 107, 124) involve van der Waals interactions between interdigitated diimine aromatic rings. Time-dependent emission anisotropy measurements confirm that the proteins aggregate in mM solutions (D2O, KPi buffer, pD = 7.1). Excited-state DFT calculations show that extensive charge redistribution in the ReI(CO)_3 → diimine ^3MLCT state occurs: excitation of this ^3MLCT state triggers several relaxation processes in Re-azurins whose kinetics strongly depend on the location of the metallolabel on the protein surface. Relaxation is manifested by dynamic blue shifts of excited-state ν(CO) IR bands that occur with triexponential kinetics: intramolecular vibrational redistribution together with vibrational and solvent relaxation give rise to subps, 2, and 8−20 ps components, while the ~10^2 ps kinetics are attributed to displacement (reorientation) of the Re^I(CO)_3(phen)(im) unit relative to the peptide chain, which optimizes Coulombic interactions of the Re^I excited-state electron density with solvated peptide groups. Evidence also suggests that additional segmental movements of Re-bearing β-strands occur without perturbing the reaction field or interactions with the peptide. Our work demonstrates that time-resolved IR spectroscopy and emission anisotropy of Re^I carbonyl−diimine complexes are powerful probes of molecular dynamics at or around the surfaces of proteins and protein−protein interfacial regions

Snowpack Relative Permittivity and Density Derived from Near-Coincident Lidar and Ground-Penetrating Radar

Depth-based and radar-based remote sensing methods (e.g., lidar, synthetic aperture radar) are promising approaches for remotely measuring snow water equivalent (SWE) at high spatial resolution. These approaches require snow density estimates, obtained from in-situ measurements or density models, to calculate SWE. However, in-situ measurements are operationally limited, and few density models have seen extensive evaluation. Here, we combine near-coincident, lidar-measured snow depths with ground-penetrating radar (GPR) two-way travel times (twt) of snowpack thickness to derive \u3e20 km of relative permittivity estimates from nine dry and two wet snow surveys at Grand Mesa, Cameron Pass, and Ranch Creek, Colorado. We tested three equations for converting dry snow relative permittivity to snow density and found the Kovacs et al. (1995) equation to yield the best comparison with in-situ measurements (RMSE = 54 kg m−3). Variogram analyses revealed a 19 m median correlation length for relative permittivity and snow density in dry snow, which increased to \u3e 30 m in wet conditions. We compared derived densities with estimated densities from several empirical models, the Snow Data Assimilation System (SNODAS), and the physically based iSnobal model. Estimated and derived densities were combined with snow depths and twt to evaluate density model performance within SWE remote sensing methods. The Jonas et al. (2009) empirical model yielded the most accurate SWE from lidar snow depths (RMSE = 51 mm), whereas SNODAS yielded the most accurate SWE from GPR twt (RMSE = 41 mm). Densities from both models generated SWE estimates within ±10% of derived SWE when SWE averaged \u3e 400 mm, however, model uncertainty increased to \u3e 20% when SWE averaged \u3c 300 mm. The development and refinement of density models, particularly in lower SWE conditions, is a high priority to fully realize the potential of SWE remote sensing methods

Observation of D⁰ Meson Decays to Π⁺π⁻μ⁺μ⁻ and K⁺K⁻μ⁺μ⁻ Final States

The first observation of the D⁰→π⁺π⁻μ⁺μ⁻ and D⁰→K⁺K⁻μ⁺μ⁻ decays is reported using a sample of proton-proton collisions collected by LHCb at a center-of-mass energy of 8 TeV, and corresponding to 2  fb⁻¹ of integrated luminosity. The corresponding branching fractions are measured using as normalization the decay D⁰→K⁻π⁺[μ⁺μ⁻][subscript ρ⁰/ω], where the two muons are consistent with coming from the decay of a ρ⁰ or ω meson. The results are B(D⁰→π⁺π⁻μ⁺μ⁻)=(9.64±0.48±0.51±0.97)×10⁻⁷ and B(D⁰→K⁺K⁻μ⁺μ⁻)=(1.54±0.27±0.09±0.16)×10⁻⁷, where the uncertainties are statistical, systematic, and due to the limited knowledge of the normalization branching fraction. The dependence of the branching fraction on the dimuon mass is also investigated

PRELIMINARY VEGETATION AND HYDROLOGIC ANALYSES FOR BINGHAM CIENEGA

This report is in two parts. The first part covers the ecological processes pertinent to the restoration of Bingham Cienega. The second part presents a subregional groundwater flow model for analyzing the water budget, stream and spring behavior, and water table configuration. Because of the sparsity of ecological and hydrologic data, both parts must be considered as preliminary studies.Research and development for this project was funded in part by the Arizona Chapter of the Nature Conservancy, the Pima County Flood Control District, and the Arizona Game and Fish Department through a Heritage Grant (193067). The views and conclusions reported are those of the Authors and not necessarily shared by the above Grantees. We would like to give thanks to Dave Gori of the Nature Conservancy and Julia Fonseca of the Pima County Flood Control District for their review efforts. Also thanks to Bob Mac Nish, G. Philip Guertin, and Kevin Lansey for their thoughtful comments on the document. And finally a special thanks to Kim Fox for tireless effort in the field.This title from the Hydrology & Water Resources Technical Reports collection is made available by the Department of Hydrology & Atmospheric Sciences and the University Libraries, University of Arizona. If you have questions about titles in this collection, please contact [email protected]

Effects of groundwater pumping on the sustainability of a mountain wetland complex, Yosemite National Park, California

Study Region: We analyzed the effects of groundwater pumping on a mountain wetland complex, Yosemite National Park, California, USA. Study Focus: Groundwater pumping from mountain meadows is common in many regions of the world. However, few quantitative analyses exist of the hydrologic or ecological effects of pumping. New Hydrological Insights for the Region: Daily hydraulic head and water table variations at sampling locations within 100 m of the pumping well were strongly correlated with the timing and duration of pumping. The effect of pumping varied by distance from the pumping well, depth of the water table when the pumping started, and that water year's snow water equivalent (SWE). Pumping in years with below average SWE and/or early melting snow pack, resulted in a water table decline to the base of the fen peat body by mid summer. Pumping in years with higher SWE and later melting snowpack, resulted in much less water level drawdown from the same pumping schedule. Predictive modeling scenarios showed that, even in a dry water year like 2004, distinct increases in fen water table elevation can be achieved with reductions in pumping. A high water table during summers following low snowpack water years had a more significant influence on vegetation composition than depth of water table in wet years or peat thickness, highlighting the impact of water level drawdown on vegetation. Keywords: Fen, Groundwater pumping, Modeling, Mountain meadow, Water table, Wetland

The Early Picosecond Photophysics of Ru(II) Polypyridyl Complexes: A Tale of Two Timescales

The early picosecond time scale excited-state dynamics of the paradigm tris(2,2'-bipyridyl)Ruthenium(II) ([Ru(bpy)3]2+) and related complexes have been examined by picosecond Kerr-gated time-resolved resonance Raman (ps-TR3) spectroscopy. The evolution of the signature Raman bands of the lowest thermally equilibrated excited (THEXI) state under two-color pump/probe conditions show that this state is not fully populated within several hundred femtoseconds as proposed previously but rather only within the first 20 ps following excitation. In addition to an emission observed within the instrument rise time (τ < 3 ps), the early picosecond dynamics are characterized by a rise in the intensity of the Raman marker bands of the THEXI-3MLCT state, a rise time which, within experimental uncertainty, is not influenced by either partial or complete ligand deuteriation or the presence of ligands other than bpy, as in the heteroleptic complexes [Ru(bpy)2(L1)]+ and [Ru(bpy)2(Hdcb)]+ (where H2dcb is 4,4'-dicarboxy-2,2'-bipyridine and L1 is 2,-(5'-phenyl-4'-[1,2,4]triazole-3'-yl)pyridine). Overall, although the results obtained in the present study are consistent with those obtained from examination of this paradigm complex on the femtosecond timescale, regarding initial formation of the vibrationally hot 3MLCT state by ISC from the singlet Franck-Condon state, the observation that the THEXI-3MLCT state reaches thermal equilibration over a much longer time period than previously suggested warrants a re-examination of views concerning the rapidity with which thermal equilibration of transition metal complex excited states takes place.