Magnetically assisted gas-solid fluidization in a tapered vessel： Part I. Magnetization-LAST mode

This article presents further experimental results of the Magnetization-LAST mode in magnetically assisted gas-fluidized tapered beds, including external transverse magnetic field control of solid phase movement, central channel formation, spout depth and the pressure drop across the bed. Phase diagrams similar to those recently reported for the Magnetization-FIRST mode were also developed. Dimensional analysis based on ＂pressure transform＂ of the initial set of variables and involving the magnetic granular Bond number pertinent to particle aggregate formation was applied to develop the scaling relationships.     

A comparison of data reduction techniques for the aeroacoustic analysis of flow over a blunt flat plate

A large eddy simulation of flow over a forward-facing plate is performed and the resulting database analyzed with respect to sound radiation. Aeroacoustic analysis motivates an initial data compression comprising eduction of the zeroth-order spanwise Fourier mode. The space–time structure of this component of the flow is then analyzed using POD and DMD in order to probe both the energetics and dynamics of the sound-producing flow skeleton. Both data processing techniques educe flapping and shedding modes and identify a nonlinear interaction between the two. POD shows the flapping mode to be energetically unimportant, while DMD highlights its dynamic importance. The difference mode—vortex shedding modulated by flapping of the separation bubble—is found to be the most acoustically important feature of the flow.     

Direct fabrication of anatase TiO<Subscript>2</Subscript> hollow microspheres for applications in photocatalytic hydrogen evolution and lithium storage

Hollow titanium dioxide (TiO₂) microspheres were synthesized in one step by employing tetrabutyl orthotitanate (TBOT) as a precursor through a facile solvothermal method in the presence of NH₄HCO₃. XRD analysis indicated that anatase TiO₂ can be obtained directly without further annealing. TiO₂ hollow microspheres with diameters in the range of 1.0–4.0 μm were confirmed through SEM and TEM measurements. The specific surface area was measured to be 180 m² g^?1 according to the nitrogen adsorption–desorption isotherms. Superior photocatalytic performance and good lithium storage properties were achieved for resultant TiO₂ samples. The H₂ evolution rate of the optimal sample is about 0.66 mmol h^?1 after loaded with 1 wt.% Pt (20 mg samples). The reversible capacity remained 143 mAh g^?1 at a specific current of 300 mA g^?1 after 100 charge–discharge cycles. This work provides a facile strategy for the preparation of hollow titanium dioxide microspheres and demonstrates their promising photocatalytic H₂ evolution and the lithium storage properties.

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Graphical abstract Hollow titanium dioxide spheres are directly synthesized via a facile template-free solvothermal method with the presence of NH₄HCO₃ based on inside-out Ostwald ripening (see picture), and demonstrated both as a photocatalyst for water splitting and a promising anode material for lithium-ion batteries. Superior photocatalytic performance and excellent lithium storage properties are achieved for resultant TiO₂ hollow microspheres.

     

Effect of secondary structure on the thermodynamics and kinetics of PNA hybridization to DNA hairpins.

The binding of a series of PNA and DNA probes to a group of unusually stable DNA hairpins of the tetraloop motif has been observed using absorbance hypochromicity (ABS), circular dichroism (CD), and a colorimetric assay for PNA/DNA duplex detection. These results indicate that both stable PNA-DNA and DNA-DNA duplexes can be formed with these target hairpins, even when the melting temperatures for the resulting duplexes are up to 50 degrees C lower than that of the hairpin target. Both hairpin/single-stranded and hairpin/hairpin interactions are considered in the scope of these studies. Secondary structures in both target and probe molecules are shown to depress the melting temperatures and free energies of the probe-target duplexes. Kinetic analysis of hybridization yields reaction rates that are up to 160-fold slower than hybridization between two unstructured strands. The thermodynamic and kinetic obstacles to hybridization imposed by both target and probe secondary structure are significant concerns for the continued development of antisense agents and especially diagnostic probes.     

Efficiency considerations in the construction of interpolated potential energy surfaces for the calculation of quantum observables by diffusion Monte Carlo

A modified Shepard interpolation scheme is used to construct global potential energy surfaces (PES) in order to calculate quantum observables--vibrationally averaged internal coordinates, fully anharmonic zero-point energies and nuclear radial distribution functions--for a prototypical loosely bound molecular system, the water dimer. The efficiency of PES construction is examined with respect to (a) the method used to sample configurational space, (b) the method used to choose which points to add to the PES data set, and (c) the use of either a one- or two-part weight function. The most efficient method for constructing the PES is found to require a quantum sampling regime, a combination of both h-weight and rms methods for choosing data points and use of the two-part weight function in the interpolation. Using this regime, the quantum diffusion Monte Carlo zero-point energy converges to the exact result within addition of 50 data points. The vibrationally averaged O-O distance and O-O radial distribution function, however, converge more slowly and require addition of over 500 data points. The methods presented here are expected to be applicable to both other loosely bound complexes as well as tightly bound molecular species. When combined with high quality ab initio calculations, these methods should be able to accurately characterize the PES of such species.     

Enhanced fluorescence quenching in receptor-containing conjugated polymers: a calix[4]arene-containing poly(phenylene ethynylene)

A fluorescent poly(phenylene ethynylene) containing calix[4]arene-based receptor units has a sensitivity to quenching by the N-methylquinolinium ion that is over three times larger than that seen in a control polymer lacking calix[4]arenes.     

Linkage isomerism, structure, and reactivity studies of sulfenamide complexes of cobalt(III)

The S-bonded sulfenamide isomers have been prepared by the known reaction of hydroxylamine-O-sulfonate with (en)(2)Co(III) thiolate complexes of aminoethanethiol, cysteine, and penicillamine and the cis dithiolate formed by N,N'-ethylene-di-penicillamine (EDP) and Co(III). It is shown that the sulfenamides undergo linkage isomerization in alkaline solution to produce their respective N-bonded linkage isomers. The addition of acid yields the protonated N-bonded isomers. The structures of [(en)(2)Co(NH(2)S(CH(2))(2)NH(2))](2)(S(2)O(6))(3) and [Co((NH(2)S)(2)EDP)]Br have been determined by X-ray crystallography, and the pK(a) of [(en)(2)Co(NH(2)S(CH(2))(2)NH(2))](3+) has been determined by spectrophotometry. The pH dependencies of the kinetics of the linkage isomerization reactions have been studied and yield pK(a) values of the S-bonded isomers. The (en)(2)Co systems give only the acid-stable N,N' isomer at equilibrium, whereas the EDP complex gives a mixture of N,N' and N,S isomers at pH 7-9.     

Structures and reactivity of Zr(IV) chlorobenzene complexes

The synthesis, structures, and unusual reactivity of (C5R5)2ZrR'(ClPh)+ chlorobenzene complexes are described. The reaction of (C5R5)2ZrR'2 with [Ph3C][B(C6F5)4] in C6D5Cl affords [(C5R5)2ZrR'(ClC6D5)][B(C6F5)4] chlorobenzene complexes (1-d5, R' = CH2Ph and (C5R5)2 = (C5H5)2; 2a-d-d5, R' = Me and (C5R5)2 = rac-(1,2-ethylene(bis)indenyl) (2a), (C5H5)2 (2b), (C5H4Me)2 (2c), (C5Me5)2 (2d, C5Me5 = Cp*)). Complexes 1 and 2b,c are thermally robust but are converted to [{(C5R5)2Zr(mu-Cl)}2][B(C6F5)4]2 (4b,c) by a photochemical process in ClPh solution. In contrast, 2d undergoes facile thermal ortho-C-H activation to yield [Cp*2Zr(eta2-C,Cl-2-Cl-C6H4)][B(C6F5)4] (5), which slowly rearranges to [(eta4,eta1-C5Me5C6H4)Cp*ZrCl][B(C6F5)4] (6) via beta-Cl elimination and benzyne insertion into a Zr-CCp* bond. The higher thermal reactivity of 2d versus that of 1 and 2b,c is attributed to steric crowding associated with the Cp* ligands of 2d, which forces a ClPh ortho-hydrogen close to the Zr-Me group.     

Ruthenium-catalyzed [2 + 2] cycloadditions between 7-substituted norbornadienes and alkynes: an experimental and theoretical study

The ruthenium-catalyzed [2 + 2] cycloadditions of 7-substituted norbornadienes with an alkyne have been investigated. The cycloadditions were found to be highly regio- and stereoselective, giving only the anti-exo cycloadducts as the single regio- and stereoisomers in good yields. The results on the relative rate of different 7-substituted norbornadienes in the Ru-catalyzed [2 + 2] cycloadditions with an alkyne indicated that the reactivity of the alkene component decreases dramatically as the alkene becomes more electron deficient. Ab initio computational studies on the ruthenium-catalyzed [2 + 2] cycloadditions provided important information about the geometries and the arrangements of the four different groups on the Ru in the initial Ru-alkene-alkyne pi-complex, 14, and in the metallacyclopentene 15. Based on our computational studies, we also found that the first carbon-carbon bond formed in the [2 + 2] cycloaddition is between the C(5) of the alkene and the C(b) (the acetylenic carbon attached to the ester group) of the alkyne 8. Our computational studies on the potential energy profiles of the cycloadditions showed that the activation energy relative to the reactants for the oxidative addition step is in the range of 9.3-9.8 kcal/mol. The activation energy relative to the metallacyclopentene for the reductive elimination step is much higher than for the oxidative addition step (in the range of 25.9-27.6 kcal/mol).