Selective recognition of fluoride and acetate by a newly designed ruthenium framework: experimental and theoretical investigations

An effective anion sensor, [Ru(II)(bpy)(2)(H(2)L(-))](+) (1(+)), based on a redox and photoactive {Ru(II)(bpy)(2)} moiety and a new ligand (H(3)L = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid), has been developed for selective recognition of fluoride (F(-)) and acetate (OAc(-)) ions. Crystal structures of the free ligand, H(3)L and [1](ClO(4)) reveal the existence of strong intramolecular and intermolecular hydrogen bonding interactions. The structure of [1](ClO(4)) shows that the benzimidazole N-H of H(2)L(-) is hydrogen bonded with the pendant carboxylate oxygen while the imidazole N-H remains free for possible hydrogen bonding interaction with the anions. The potential anion sensing features of 1(+) have been studied by different experimental and theoretical (DFT) investigations using a wide variety of anions, such as F(-), Cl(-), Br(-), I(-), HSO(4)(-), H(2)PO(4)(-), OAc(-) and SCN(-). Cyclic voltammetry and differential pulse voltammetry established that 1(+) is an excellent electrochemical sensor for the selective recognition of F(-) and OAc(-) anions. 1(+) is also found to be a selective colorimetric sensor for F(-) or OAc(-) anions where the MLCT band of the receptor at 498 nm is red shifted to 538 nm in the presence of one equivalent of F(-) or OAc(-) with a distinct change in colour from reddish-orange to pink. The binding constant between 1(+) and F(-) or OAc(-) has been determined to be logK = 7.61 or 7.88, respectively, based on spectrophotometric titration in CH(3)CN. The quenching of the emission band of 1(+) at 716 nm (λ(ex) = 440 nm, Φ = 0.01 at 298 K in CH(3)CN) in the presence of one equivalent of F(-) or OAc(-), as well as two distinct lifetimes of the quenched and unquenched forms of the receptor 1(+), makes it also a suitable fluorescence-based sensor. All the above experiments, in combination with (1)H NMR, suggest the formation of a 1:1 adduct between the receptor (1(+)) and the anion (F(-) or OAc(-)). The formation of 1:1 adduct {[1(+)·F(-)] or [1(+)·OAc(-)]} has been further evidenced by in situ ESI-MS(+) in CH(3)CN. Though the receptor, 1(+), is comprised of two N-H protons associated with the coordinated H(2)L(-) ligand, only the free imidazole N-H proton participates in the hydrogen bonding interactions with the incoming anions, while the intramolecularly hydrogen bonded benzimidazole N-H proton remains intact as evidenced by the crystal structure of the final product (1). The hydrogen bond mediated anion sensing mechanism, over the direct deprotonation pathway, in 1(+) has been further justified by a DFT study and subsequent NBO analysis.     

Dual function of rare earth doped nano Bi(2)O(3): white light emission and photocatalytic properties

Undoped Bi(2)O(3) and single and double doped Bi(2)O(3)?:?M (where M = Tb(3+) and Eu(3+)) nanophosphors were synthesized through a simple sonochemical process and characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), EDS, diffuse reflectance (DRS) and photoluminescence (PL) spectrophotometry. The TEM micrographs show that resultant nanoparticles have a rod-like shape. Energy transfer was observed from host to the dopant ions. Characteristic green emissions from Tb(3+) ions and red emissions from Eu(3+) ions were observed. Interestingly, the Commission International de l'Eclairage (CIE) coordinates of the double doped Bi(2)O(3)?:?Eu(3+)(0.8%)?:?Tb(3+)(1.2%) nanorods lie in the white light region of the chromaticity diagram and it has a quantum efficiency of 51%. The undoped Bi(2)O(3) showed a band gap of 3.98 eV which is red shifted to 3.81eV in the case of double doped Bi(2)O(3)?:?Eu(3+)(0.8%)?:?Tb(3+)(1.2%) nanorods. The photocatalytic activities of undoped nano Bi(2)O(3) and double doped nano Bi(2)O(3)?:?Eu(3+)(0.8%)?:?Tb(3+)(1.2%) were evaluated for the degradation of Rhodamine B under UV irradiation of 310 nm. The results showed that Bi(2)O(3)?:?Eu(3+)(0.8%)?:?Tb(3+)(1.2%) had better photocatalytic activity compared to undoped nano Bi(2)O(3). The evolution of CO(2) was realized and these results indicated the continuous mineralization of rhodamine B during the photocatalytic process. Thus double doped Bi(2)O(3)?:?Eu(3+)(0.8%)?:?Tb(3+)(1.2%) nanorods can be termed as a bifunctional material exhibiting both photocatalytic properties and white light emission.     

Glycomimetic ligands for the human asialoglycoprotein receptor

The asialoglycoprotein receptor (ASGPR) is a high-capacity galactose-binding receptor expressed on hepatocytes that binds its native substrates with low affinity. More potent ligands are of interest for hepatic delivery of therapeutic agents. We report several classes of galactosyl analogues with varied substitution at the anomeric, C2-, C5-, and C6-positions. Significant increases in binding affinity were noted for several trifluoromethylacetamide derivatives without covalent attachment to the protein. A variety of new ligands were obtained with affinity for ASGPR as good as or better than that of the parent N-acetylgalactosamine, showing that modification on either side of the key C3,C4-diol moiety is well tolerated, consistent with previous models of a shallow binding pocket. The galactosyl pyranose motif therefore offers many opportunities for the attachment of other functional units or payloads while retaining low-micromolar or better affinity for the ASGPR.     

Positronium annihilation in liquids in the framework of non-local interaction

In the bubble model of ortho positronium (o-Ps) annihilation in liquid the origin of the trapping of o-Ps is the electron-exchange repulsive interaction between the electron of o-Ps and the electron of the medium. The corresponding effective interaction is non-local in nature. However, in the prevalent bubble model, this effective interaction is usually treated as local (model) potential (sharp or smooth). In the present study, we have taken an approach to consider this trapping interaction as non-local in nature, which is included through a model separable non-local function to tackle the problem in analytically solvable manner. The analytical calculations show that this non-local interaction effectively acts as a gauge potential in the energy of the Ps atom in parameter (bubble radius) space. The computed bubble variables obtained using experimental Ps annihilation data are shown. A comparison between the present data with the calculated results using prevalent bubble model has been presented. Discussions have been made on the input parameter dependencies of the computed data.     

Classical Representation of a Quantum System at Equilibrium

A quantum system at equilibrium is represented by a corresponding classical system, chosen to reproduce the thermodynamic and structural properties. The objective is to develop a means for exploiting strong coupling classical methods (e.g., MD, integral equations, DFT) to describe quantum systems. The classical system has an effective temperature, local chemical potential, and pair interaction that are defined by requiring equivalence of the grand potential and its functional derivatives with respect to the external and pair potentials for the classical and quantum systems. Practical inversion of this mapping for the classical properties is effected via the hypernetted chain approximation, leading to representations as functionals of the quantum pair correlation function. As an illustration, the parameters of the classical system are determined approximately such that ideal gas and weak coupling RPA limits are preserved (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Interface biquadratic coupling and magnon scattering in exchange-biased ferromagnetic thin films grown on epitaxial FeF2

The magnetic anisotropy of ferromagnetic (FM) Ni, Co, and Fe polycrystalline thin films grown on antiferromagnetic (AF) FeF(2)(110) epitaxial layers was studied, as a function of temperature, using ferromagnetic resonance. In addition to an in-plane anisotropy in the FM induced by fluctuations in the AF short-range order, a perpendicular (biquadratic) magnetic anisotropy, with an out-of-plane component, was found which increased with decreasing temperature above the AF Neél temperature (T(N) = 78.4 K). This is a surprising result given that the AF's uniaxial anisotropy axis was in the plane of the sample, but is consistent with prior experimental and theoretical work. The resonance linewidth had a strong dependence on the direction of the external magnetic field with respect to in-plane FeF(2) crystallographic directions, consistent with interface magnon scattering due to defect-induced demagnetizing fields. Below T(N), the exchange bias field H(E) measured via FMR for the Ni sample was in good agreement with H(E) determined from magnetization measurements if the perpendicular out-of-plane anisotropy was taken into account. A low field resonance line normally observed at H ≈ 0, associated with domain formation during magnetization in ferromagnets, coincided with the exchange bias field for T < T(N), indicating domain formation with the in-plane FM magnetization perpendicular to the AF easy axis. Thus, biquadratic FM-AF coupling is important at temperatures below and above T(N).     

New precision limit on the strange vector form factors of the proton

The parity-violating cross-section asymmetry in the elastic scattering of polarized electrons from unpolarized protons has been measured at a four-momentum transfer squared Q2 = 0.624 GeV2 and beam energy E(b) = 3.48 GeV to be A(PV) = -23.80 ± 0.78(stat) ± 0.36(syst) parts per million. This result is consistent with zero contribution of strange quarks to the combination of electric and magnetic form factors G(E)(s) + 0.517G(M)(s) = 0.003 ± 0.010(stat) ± 0.004(syst) ± 0.009(ff), where the third error is due to the limits of precision on the electromagnetic form factors and radiative corrections. With this measurement, the world data on strange contributions to nucleon form factors are seen to be consistent with zero and not more than a few percent of the proton form factors.     

New measurements of high-momentum nucleons and short-range structures in nuclei

We present new measurements of electron scattering from high-momentum nucleons in nuclei. These data allow an improved determination of the strength of two-nucleon correlations for several nuclei, including light nuclei where clustering effects can, for the first time, be examined. The data also include the kinematic region where three-nucleon correlations are expected to dominate.     

Silver-Gold Nanocomposite Substrates for Metal-Enhanced Fluorescence: Ensemble and Single-Molecule Spectroscopic Studies

In recent years, there has been a growing interest in the studies involving the interactions of fluorophores with plasmonic nanostructures or nanoparticles. These interactions lead to several favorable effects such as increase in the fluorescence intensities, increased photostabilities, and reduced excited-state lifetimes that can be exploited to improve the capabilities of present fluorescence methodologies. In this regard, we report the use of newly developed silver-gold nanocomposite (Ag-Au-NC) structures as substrates for metal-enhanced fluorescence (MEF). The Ag-Au-NC substrates have been prepared by a one-step galvanic replacement reaction from thin silver films coated on glass slides. This approach is simple and suitable for the fabrication of MEF substrates with large area. We have observed about 15-fold enhancement in the fluorescence intensity of ATTO655 from ensemble fluorescence measurements using these substrates. The fluorescence enhancement on the Ag-Au-NC substrates is also accompanied by a reduction in the fluorescence lifetime of ATTO655, which is consistent with the fluorophore-plasmon coupling mechanism. Single-molecule fluorescence measurements have been performed to gain more insight into the metal-fluorophore interactions and to unravel the heterogeneity in the interaction of individual fluorophores with the fabricated substrates. The single-molecule studies are in good agreement with the ensemble measurements and show maximum enhancements of ~50-fold for molecules located in proximity to the "hotspots" on the substrates. In essence, the Ag-Au-NC substrates have a very good potential for various MEF applications.     

An iron catalyzed regioselective oxidation of terminal alkenes to aldehydes

Fe(BF(4))(2)·6H(2)O with pyridine-2,6-dicarboxylic acid and PhIO can efficiently catalyze the regioselective oxidation of terminal alkene derivatives to aldehydes under mild and benign reaction conditions.