O?+?C2H4 potential energy surface: lowest-lying singlet at the multireference level

Extensive density functional theory (DFT) calculations have been performed to develop a force field for the classical molecular dynamics (MD) simulations of various azobenzene derivatives. Besides azobenzene, we focused on a thiolated azobenzene’s molecular rod (4′-{[(1,1′-biphenyl)-4-yl]diazenyl}-(1,1′-biphenyl)-4-thiol) that has been previously demonstrated to photoisomerize from trans to cis with high yields on surfaces. The developed force field is an extension of OPLS All Atoms, and key bonding parameters are parameterized to reproduce the potential energy profiles calculated by DFT. For each of the parameterized molecule, we propose three sets of parameters: one best suited for the trans configuration, one for the cis configuration, and finally, a set able to describe both at a satisfactory degree. The quality of the derived parameters is evaluated by comparing with structural and vibrational experimental data. The developed force field opens the way to the classical MD simulations of self-assembled monolayers (SAMs) of azobenzene’s molecular rods, as well as to the quantum mechanics/molecular mechanics study of photoisomerization in SAMs.     

Cyclometalated platinum(II) diimine complexes: synthetically tuning the photophysical and electrochemical properties

Presented is the synthesis of an array of 16 heteroleptic phosphorescent diimine complexes of platinum(II) with electronically diverse ligand spheres and their full spectroscopic, photophysical, and electrochemical characterization. The complexes were found to exhibit luminescence (480-500 nm) in deaerated solutions at room temperature from a long-lived (3)LC state (τ = 2-3 μs) that exhibits significant metal character perturbed by a low-lying (1)MLCT state. Interestingly, emission from a (3)MLCT state was not observed as is the case with many other polypyridine-based d-block complexes. Electrochemical intermediates proved stable as multiple reversible reductions between -1 and -2 V vs. SCE were noted during cyclic voltammetry experiments unveiling the potential of these luminophores for use in a variety of optoelectronic and solar energy conversion applications.     

Generation of candidate ligands for nicotinic acetylcholine receptors via in situ click chemistry with a soluble acetylcholine binding protein template

Nicotinic acetylcholine receptors (nAChRs), which are responsible for mediating key physiological functions, are ubiquitous in the central and peripheral nervous systems. As members of the Cys loop ligand-gated ion channel family, neuronal nAChRs are pentameric, composed of various permutations of α (α2 to α10) and β (β2 to β4) subunits forming functional heteromeric or homomeric receptors. Diversity in nAChR subunit composition complicates the development of selective ligands for specific subtypes, since the five binding sites reside at the subunit interfaces. The acetylcholine binding protein (AChBP), a soluble extracellular domain homologue secreted by mollusks, serves as a general structural surrogate for the nAChRs. In this work, homomeric AChBPs from Lymnaea and Aplysia snails were used as in situ templates for the generation of novel and potent ligands that selectively bind to these proteins. The cycloaddition reaction between building-block azides and alkynes to form stable 1,2,3-triazoles was used to generate the leads. The extent of triazole formation on the AChBP template correlated with the affinity of the triazole product for the nicotinic ligand binding site. Instead of the in situ protein-templated azide-alkyne cycloaddition reaction occurring at a localized, sequestered enzyme active center as previously shown, we demonstrate that the in situ reaction can take place at the subunit interfaces of an oligomeric protein and can thus be used as a tool for identifying novel candidate nAChR ligands. The crystal structure of one of the in situ-formed triazole-AChBP complexes shows binding poses and molecular determinants of interactions predicted from structures of known agonists and antagonists. Hence, the click chemistry approach with an in situ template of a receptor provides a novel synthetic avenue for generating candidate agonists and antagonists for ligand-gated ion channels.     

An Efficacious Target-Field Approach to Design Shim Coils for Halbach Magnet of Mobile NMR Sensors

The main magnetic fields of mobile nuclear magnetic resonance (NMR) magnets differ from those of conventional NMR and magnetic resonance imaging (MRI) magnets. In the Halbach magnet, the main field B ₀ is perpendicular to the longitudinal axis, the symmetry of the current distribution with respect to the symmetry of the magnetic field differs from that in conventional target-field applications, and the current distribution on the coil surface cannot be expressed in terms of periodic basis functions. To obtain the winding pattern of the coil, an efficacious target-field approach. The surface of a coil is divided into small discrete elements, where each element is represented by a magnetic dipole. From the stream function of the elements, the resultant magnetic field is calculated. The optimization strategy follows an objective function defined by the power dissipation or efficiency of the coil. This leads to the optimum stream function on the coil surface, whose contour lines define the winding patterns of the coil. This paper shows winding patterns designed of shim coils for Halbach magnet and illustrates the craft of a shim coil using flexible printed circuit board. The performance of the coils is verified by simulating the fields they produce over the sensitive volume.     

Identifying sources and processes controlling the sulphur cycle in the Canyon Creek watershed, Alberta, Canada

Sources and processes affecting the sulphur cycle in the Canyon Creek watershed in Alberta (Canada) were investigated. The catchment is important for water supply and recreational activities and is also a source of oil and natural gas. Water was collected from 10 locations along an 8?km stretch of Canyon Creek including three so-called sulphur pools, followed by the chemical and isotopic analyses on water and its major dissolved species. The δ(2)H and δ(18)O values of the water plotted near the regional meteoric water line, indicating a meteoric origin of the water and no contribution from deeper formation waters. Calcium, magnesium and bicarbonate were the dominant ions in the upstream portion of the watershed, whereas sulphate was the dominant anion in the water from the three sulphur pools. The isotopic composition of sulphate (δ(34)S and δ(18)O) revealed three major sulphate sources with distinct isotopic compositions throughout the catchment: (1) a combination of sulphate from soils and sulphide oxidation in the bedrock in the upper reaches of Canyon Creek; (2) sulphide oxidation in pyrite-rich shales in the lower reaches of Canyon Creek and (3) dissolution of Devonian anhydrite constituting the major sulphate source for the three sulphur pools in the central portion of the watershed. The presence of H(2)S in the sulphur pools with δ(34)S values ～30?‰ lower than those of sulphate further indicated the occurrence of bacterial (dissimilatory) sulphate reduction. This case study reveals that δ(34)S values of surface water systems can vary by more than 20?‰ over short geographic distances and that isotope analyses are an effective tool to identify sources and processes that govern the sulphur cycle in watersheds.     

Measurements of WW and WZ production in W + jets final states in pp collisions

We study WW and WZ production with ?νqq (?=e,μ) final states using data collected by the D0 detector at the Fermilab Tevatron Collider corresponding to 4.3 fb(-1) of integrated luminosity from pp collisions at sqrt[s]=1.96 TeV. Assuming the ratio between the production cross sections σ(WW) and σ(WZ) as predicted by the standard model, we measure the total WV (V=W,Z) cross section to be σ(WV)=19.6(-3.0)(+3.2) pb and reject the background-only hypothesis at a level of 7.9 standard deviations. We also use b-jet discrimination to separate the WZ component from the dominant WW component. Simultaneously fitting WW and WZ contributions, we measure σ(WW)=15.9(-3.2)(+3.7) pb and σ(WZ)=3.3(-3.3)(+4.1) pb, which is consistent with the standard model predictions.     

Signature of a type-a glass transition and intrinsic confinement effects in a binary glass-forming system

We study dynamically highly asymmetric binary mixtures comprised of small methyl tetrahydrofuran (MTHF) molecules and polystyrene. Combined use of dielectric spectroscopy, ^{2}H nuclear magnetic resonance, incoherent quasielastic neutron scattering, and depolarized dynamic light scattering allows us to selectively probe the dynamics of the components in a broad dynamic range. It turns out that the mixtures exhibit two glass transitions in a wide concentration range although being fully miscible on a macroscopic scale. In between both glass transition temperatures, the dynamics of the small molecules show strong confinement effects, e.g., a crossover from Vogel-Fulcher to Arrhenius behavior of the time constants. Moreover, the dynamical behavior of small molecules close to the slow matrix is consistent with mode coupling theory predictions for a type-A glass transition, which was expected from recent theoretical and simulation studies in comparable systems.