Synthesis and characterization of orthopalladated complexes containing tridentate C, N, O-oxazolones

The (Z)-4-aryliden-2-(2-acetoxyphenyl)-5(4H)oxazolones 1a-1c react with H2SO4 to give the corresponding (Z)-4-aryliden-2-(2-hydroxyphenyl)-5(4H)oxazolones 2a-2c.The molecular structures of 1c and 2a have been determined by X-ray diffraction methods, and show planar skeletons. Oxazolones 2a-2c are potential C, N, O-tridentate ligands towards transition metals, and their molecular design obeys to the search of a rigid environment around the metal. The reaction of Pd(OAc)2 with oxazolones 2a-2c (1:1 M ratio) in CF3CO2H or NCMe as solvents results in the synthesis of diverse complexes (3–7). As a function of the reaction conditions, two different bonding modes have been characterized: N, O-chelate in the dinuclear complexes Pd(¿2-N, O-2b, c)(µ -O2CCF3)]2 (3b, c), as a result of the N-coordination and deprotonation of the hydroxy group; and C, N, O-tridentate in mononuclear complexes Pd(¿ 3-C, N, O-2a, b)(L)] (L = CF3CO2H 4a, b; dmso-d6 5a, b; NCMe 6b; pyridine 7b), obtained after N-bonding, OH deprotonation and C–H bond activation. All complexes have been fully characterized by HRMS and NMR methods, showing the high stability of the C, N, O-tridentate bonding mode

Changes in Topsoil Properties after Centennial Scots Pine Afforestation in a European Beech Forest (NE Spain)

In this work, we studied the effects of centenary Scots pine (Pinus sylvestris L.) afforestation on topsoil properties conducted in a deforested area that was previously occupied by a natural European beech (Fagus sylvatica L.) forest. Organic layers and topsoil Ah mineral horizons (0–10 cm) were sampled in the Scots pine and European beech forests of Moncayo Natural Park (north-eastern Spain). The physical (stoniness, aggregate stability, and water repellency persistence and intensity), chemical (total organic C, total N, C/N, pH, and exchangeable Ca2+, Mg2+, Na+, K+, Al3+, and Fe3+), and physicochemical (cation exchange capacity) properties of soil were analyzed. Total organic C and N were also obtained for litter samples. The studied topsoils shared a series of common properties, such as a high stoniness and aggregate stability, very low base content, high cation exchange capacity, and extreme acidity. Soils that developed under the pinewood showed a higher soil water repellency intensity. However, K+ content was significantly higher in the beechwood soil. In both forest types, total organic C and N were similar in topsoil and litter (Hemimoder type), although C and N were pooled in different O-layers. Results indicate that pine afforestation in a deforested area was an adequate measure for soil protection since it did not show significant differences in the long term (ca. 100 years) compared to the nearby natural beech stands

Extruded scintillator for the Calorimetry applications

An extrusion line has been installed and successfully operated at FNAL (Fermi National Accelerator Laboratory) in collaboration with NICADD (Northern Illinois Center for Accelerator and Detector Development). This new Facility will serve to further develop and improve extruded plastic scintillator. Recently progress has been made in producing co-extruded plastic scintillator, thus increasing the potential HEP applications of this Facility. The current R&D work with extruded and co-extruded plastic scintillator for a potential ALICE upgrade, the ILC calorimetry program and the MINERvA experiment show the attractiveness of the chosen strategy for future experiments and calorimetry. We extensively discuss extruded and co-extruded plastic scintillator in calorimetry in synergy with new Solid State Photomultipliers. The characteristics of extruded and co-extruded plastic scintillator will be presented here as well as results with non-traditional photo read-ou

A Novel Use of Light Guides and Wavelength Shifting Plates for the Detection of Scintillation Photons in Large Liquid Argon Detectors

Scintillation light generated as charged particles traverse large liquid argon detectors adds valuable information to studies of weakly-interacting particles. This paper uses both laboratory measurements and cosmic ray data from the Blanche dewar facility at Fermilab to characterize the efficiency of the photon detector technology developed at Indiana University for the single phase far detector of DUNE. The efficiency of this technology was found to be 0.48% at the readout end when the detector components were characterized with laboratory measurements. A second determination of the efficiency using cosmic ray tracks is in reasonable agreement with the laboratory determination. The agreement of these two efficiency determinations supports the result that minimum ionizing muons generate ${\mathcal N}_{phot} = 40,000$ photons/MeV as they cross the LAr volume.Comment: Accepted version (without final editorial corrections

Fluorescence amplification of unsaturated oxazolones using palladium: photophysical and computational studies

Weakly fluorescent (Z)-4-arylidene-5-(4H)-oxazolones (1), ΦPL < 0.1%, containing a variety of conjugated aromatic fragments and/or charged arylidene moieties, have been orthopalladated by reaction with Pd(OAc)2. The resulting dinuclear complexes (2) have the oxazolone ligands bonded as a C^N-chelate, restricting intramolecular motions involving the oxazolone. From 2, a variety of mononuclear derivatives, such as [Pd(C^N-oxazolone)(O2CCF3)(py)] (3), [Pd(C^N-oxazolone)(py)2](ClO4) (4), [Pd(C^N-oxazolone)(Cl)(py)] (5), and [Pd(C^N-oxazolone)(X)(NHC)] (6, 7), have been prepared and fully characterized. Most of complexes 3–6 are strongly fluorescent in solution in the range of wavelengths from green to yellow, with values of ΦPL up to 28% (4h), which are among the highest values of quantum yield ever reported for organometallic Pd complexes with bidentate ligands. This means that the introduction of the Pd in the oxazolone scaffold produces in some cases an amplification of the fluorescence of several orders of magnitude from the free ligand 1 to complexes 3–6. Systematic variations of the substituents of the oxazolones and the ancillary ligands show that the wavelength of emission is tuned by the nature of the oxazolone, while the quantum yield is deeply influenced by the change of ligands. TD-DFT studies of complexes 3–6 show a direct correlation between the participation of the Pd orbitals in the HOMO and the loss of emission through non-radiative pathways. This model allows the understanding of the amplification of the fluorescence and the future rational design of new organopalladium systems with improved properties

The Hardness of Embedding Grids and Walls

The dichotomy conjecture for the parameterized embedding problem states that the problem of deciding whether a given graph $G$ from some class $K$ of "pattern graphs" can be embedded into a given graph $H$ (that is, is isomorphic to a subgraph of $H$) is fixed-parameter tractable if $K$ is a class of graphs of bounded tree width and $W[1]$-complete otherwise. Towards this conjecture, we prove that the embedding problem is $W[1]$-complete if $K$ is the class of all grids or the class of all walls

Application of Hamamatsu MPPC to T2K Neutrino Detectors

A special type of Hamamatsu MPPC, with a sensitive area of 1.3x1.3mm^2 containing 667 pixels with 50x50um^2 each, has been developed for the near neutrino detector in the T2K long baseline neutrino experiment. About 60 000 MPPCs will be used in total to read out the plastic scintillator detectors with wavelength shifting fibers. We report on the basic performance of MPPCs produced for T2K.Comment: Contribution to the proceedings of NDIP 2008, Aix-les-Bains, France, June 15-20, 200

Solving order constraints in logarithmic space.

We combine methods of order theory, finite model theory, and universal algebra to study, within the constraint satisfaction framework, the complexity of some well-known combinatorial problems connected with a finite poset. We identify some conditions on a poset which guarantee solvability of the problems in (deterministic, symmetric, or non-deterministic) logarithmic space. On the example of order constraints we study how a certain algebraic invariance property is related to solvability of a constraint satisfaction problem in non-deterministic logarithmic space

Muons tomography applied to geosciences and volcanology

Imaging the inner part of large geological targets is an important issue in geosciences with various applications. Dif- ferent approaches already exist (e.g. gravimetry, electrical tomography) that give access to a wide range of informations but with identified limitations or drawbacks (e.g. intrinsic ambiguity of the inverse problem, time consuming deployment of sensors over large distances). Here we present an alternative and complementary tomography method based on the measurement of the cosmic muons flux attenuation through the geological structures. We detail the basics of this muon tomography with a special emphasis on the photo-active detectors.Comment: Invited talk at the 6th conference on New Developments In Photodetection (NDIP'11), Lyon-France, July 4-8, 2011; Nuclear Instruments and Methods in Physics Research Section A, 201