A convenient route to 1,3-diynes using ligand-free Cadiot–Chodkiewicz coupling reaction at room temperature under aerobic conditions

In this study, we report a copper-catalyzed ligand-free Cadiot–Chodkiewicz coupling reaction. No additives or ligands are required for this Cu-catalyzed C(sp)–C(sp) coupling reaction of terminal alkynes with alkynyl halides. The low cost of copper catalyst, excellent yield of the products, suppression of side-products and mild reaction conditions are the major advantages of this protocol.     

Unramified cohomology and Witt groups of anisotropic Pfister quadrics

The unramified Witt group of an anisotropic conic over a field , with , defined by the form is known to be a quotient of the Witt group of and isomorphic to . We compute the unramified cohomology group , where is the three dimensional anisotropic quadric defined by the quadratic form over . We use these computations to study the unramified Witt group of .

     

Sonochemical synthesis and properties of nanoparticles of FeSbO4

A sonochemical method was employed to prepare reactive nanoparticles of FeSbO(4) at 300 °C, which is the lowest calcination temperature reported so far for preparing FeSbO(4). A systematic evolution of the FeSbO(4) phase formation as a function of temperature was monitored by in situ synchrotron X-ray measurements. The 300 and 450 °C calcined powders exhibited specific surface areas of 116 and 75 m(2)/g, respectively. The X-ray photoelectron spectra analysis confirmed the presence of mainly Fe(3+) and Sb(5+) in the calcined powder. The response of the fabricated sensors (using both 300 and 450 °C calcined powders) toward 1000 ppm and 1, 2, 4, and 8% hydrogen, respectively, has been monitored at various operating temperatures. The sensors fabricated using 300 °C calcined powder exhibited a response of 76% toward 4% H(2) gas at an operating temperature of 300 °C, while those fabricated using 450 °C calcined powder exhibited a higher response of 91% with a quick recovery toward 4% H(2) gas at 300 °C. The results confirmed that a higher calcination temperature was preferred to achieve better sensitivity and selectivity toward hydrogen in comparison to other reducing gases such as butane and methane. The experimental results confirmed that the sonochemical process can be easily used to prepare FeSbO(4) nanoparticles for various catalytic applications as demonstrated. Here, we project FeSbO(4) as a new class of material exhibiting high sensitivity toward a wide range of hydrogen gas. Such sensors that could detect high concentrations of hydrogen may find application in nuclear reactors where there will be a leakage of hydrogen.     

Hydrodynamics and energy consumption studies in a three-phase liquid circulating three-phase fluid bed contactor

The hydrodynamics and energy consumption have been studied in a cold flow, bubbling and turbulent, pressurized gas–liquid–solid three-phase fluidized bed (0.15 m ID × 1 m height) with concurrent gas–liquid up flow is proposed with the intention of increasing the gas hold up. The hydrodynamic behaviour is described and characterised by some specific gas and liquid velocities. Particles are easily fluidized and can be uniformly distributed over the whole height of the column. The effect of parameters like liquid flow rate, gas flow rate, particle loading, particle size, and solid density on gas hold up and effect of gas flow rate, solid density and particle size on solid hold up, energy consumption and minimum fluidization velocity has been studied. At the elevated pressures a superior method for better prediction of minimum fluidization velocity and terminal settling velocities has been adopted. The results have been interpreted with Bernoulli’s theorem and Richardson–Zaki equation. Based on the assumption of the gas and liquid as a pretend fluid, a simplification has been made to predict the particle terminal settling velocities. The Richardson–Zaki parameter n′ was compared with Renzo’s results. A correlation has been proposed with the experimental results for the three-phase fluidization.     

MHD flow and mass transfer of chemically reactive upper convected Maxwell fluid past porous surface

The magnetohydrodynamic (MHD) flow and mass transfer of an electrically conducting upper convected Maxwell (UCM) fluid at a porous surface are studied in the presence of a chemically reactive species. The governing nonlinear partial differential equations along with the appropriate boundary conditions are transformed into nonlinear ordinary differential equations and numerically solved by the Keller-box method. The effects of various physical parameters on the flow and mass transfer characteristics are graphically presented and discussed. It is observed that the order of the chemical reaction is to increase the thickness of the diffusion boundary layer. Also, the mass transfer rate strongly depends on the Schmidt number and the reaction rate parameter. Furthermore, available results in the literature are obtained as a special case.     

Highly non-planar dendritic porphyrin for pH sensing: observation of porphyrin monocation

Metal-free porphyrin-dendrimers provide a convenient platform for the construction of membrane-impermeable ratiometric probes for pH measurements in compartmentalized biological systems. In all previously reported molecules, electrostatic stabilization (shielding) of the core porphyrin by peripheral negative charges (carboxylates) was required to shift the intrinsically low porphyrin protonation pK(a)'s into the physiological pH range (pH 6-8). However, binding of metal cations (e.g., K(+), Na(+), Ca(2+), Mg(2+)) by the carboxylate groups on the dendrimer could affect the protonation behavior of such probes in biological environments. Here we present a dendritic pH nanoprobe based on a highly non-planar tetraaryltetracyclohexenoporphyrin (Ar(4)TCHP), whose intrinsic protonation pK(a)'s are significantly higher than those of regular tetraarylporphyrins, thereby eliminating the need for electrostatic core shielding. The porphyrin was modified with eight Newkome-type dendrons and PEGylated at the periphery, rendering a neutral water-soluble probe (TCHpH), suitable for measurements in the physiological pH range. The protonation of TCHpH could be followed by absorption (e.g., ε(Soret)(dication)～270,000 M(-1) cm(-1)) or by fluorescence. Unlike most tetraarylporphyrins, TCHpH is protonated in two distinct steps (pK(a)'s 7.8 and 6.0). In the region between the pK(a)'s, an intermediate species with a well-defined spectroscopic signature, presumably a TCHpH monocation, could be observed in the mixture. The performance of TCHpH was evaluated by pH gradient measurements in large unilamellar vesicles. The probe was retained inside the vesicles and did not pass through and/or interact with vesicle membranes, proving useful for quantification of proton transport across phospholipid bilayers. To interpret the protonation behavior of TCHpH we developed a model relating structural changes on the porphyrin macrocycle upon protonation to its basicity. The model was validated by density functional theory (DFT) calculations performed on a planar and non-planar porphyrin, making it possible to rationalize higher protonation pK(a)'s of non-planar porphyrins as well as the easier observation of their monocations.     

Synthesis and characterization of nickel(II) and copper(II) complexes of hexaaza macrocycle, 4-methyl-1,3,5,8,11,14-hexaazatricyclooctadecane

The Ni(II) and Cu(II) complexes of a new 14-membered hexaazamacrocycle, 4-methyl-1,3,6,8,11,14-hexaazatricyclooctadecane (PCHA) in which a methyl group is attached to the macrocyclic frame work has been synthesized by the one pot reaction of triethylenetetraamine, formaldehyde and 1,2-propanediamine in the presence of metal ion. The complexes have been characterized by spectroscopic, electrochemical and molar conductivity measurements. The Ni(II) complex exists in solution as a mixture of octahedral, high-spin and planar, low-spin species; the thermodynamic parameters for the spin interconversion depend on the cyclic nature of the ligand. The crystal structure of [Ni(PCHA)](ClO₄)₂ was determined by X-ray crystallography.     

Vibrational dynamics of amorphous beryllium hydride and lithium beryllium hydrides

The vibrational density of states of amorphous beryllium hydride (a-BeH2) and lithium beryllium hydrides have been studied using inelastic neutron scattering, infrared, and Raman spectroscopies. The positions of the symmetrical (120-180 meV) and antisymmetrical (200-260 meV) Be-H stretching modes and those of the H-Be-H bending mode (50-120 meV) have been determined and the results discussed and compared with recent theoretical calculations. With the addition of lithium to the beryllium hydride network, the vibrational bands are shifted to lower energies, indicating a less rigid network.     

Dielectric relaxation and ion transport in silver–boro-tellurite glasses

Glass systems of composition xAg₂SO₄–20Ag₂O–(80?x) [0.50 B₂O₃–0.50 TeO₂], where x = 5, 10, 15, 20, 25 and 30 mol% have been prepared by melt-quenching technique. Frequency- and temperature-dependent conductivity measurements have been carried out in the frequency range 10 Hz to 10 MHz and at a temperature range of 303–353 K, respectively. DC conductivities exhibit Arrhenius behavior over the entire temperature range with a single activation barrier. Addition of Ag₂SO₄ expands the glass network and, consequently, conductivity increases. This suggests that the structure and network expansion are the key parameters for enhancing conductivity. Impedance spectra of these glasses show a single semicircle, indicating one type of conduction. AC conductivity behavior of the glasses was analyzed using both single power law and Kolhrauh–William–Watts (KWW) stretched exponential relaxation function. The power law exponent (s) is temperature-dependent, while the stretched exponent (β) is insensitive to temperature. Scaling behavior has also been carried out using reduced plots of conductivity with frequency, which suggests the ion transport mechanism remains unaffected by temperature and composition.