Direct ab initio dynamics study of the reaction of C2(A3Πu) with CH4

The reaction of C₂(A³Π_u) with CH₄ has been investigated over a wide temperature range 200–3,000 K by direct ab initio dynamics method at the BMC‐CCSD//BB1K/6‐311+G(2d,2p) level of theory. The optimized geometries and frequencies of the stationary points are calculated at the BB1K/6‐311+G(2d,2p) level, and then the energy profiles of the reactions are refined using the BMC‐CCSD method. The activation barrier height for H‐abstraction reaction was calculated to be 4.44 kcal/mol in temperature range (337–605 K), and the electron transfer behavior was also analyzed by quasi‐restricted molecular orbital method in detail. The canonical variational transition‐state theory (CVT) with the small curvature tunneling (SCT) correction method is used to calculate the rate constants over a wide temperature range 200–3,000 K. The theoretical results shows that variational effect is to some extent large in lower temperature range, and small curvature and tunneling effect play important roles to the H‐atom abstraction only at lower temperatures. The CVT/SCT rate constants are in good agreement with the available experimental results. Our theoretical study is expected to provide a direct insight into the reaction mechanism and may be useful for estimating the kinetics of the title reaction over a wide temperature range where no experimental data are available so far. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Multilayer transfer printing on microreservoir-patterned substrate employing hydrophilic composite mold for selective immobilization of biomolecules

In this study, we introduce a hydrophilic composite mold with elasticity and moderate water permeability, suitable for transferring water-soluble polar molecules such as polyelectrolyte multilayer. This composite mold is constructed from two UV-curable polymers-Norland Optical Adhesives (NOA) 63, a urethane-related polymer, and poly(ethylene glycol) diacrylate (PEGDA). The mixture of inherently hard NOA 63 and hydrogel precursor, PEGDA, resulted in an optically transparent mold with some degree of elasticity and enhanced water permeability upon UV polymerization. Employing the NOA 63-PEGDA composite mold, a polyelectrolyte multilayer comprising alternate thin layers of poly(acrylic acid) (PAA) and poly(acrylamide) (PAAm) was transfer-printed onto arrays of microreservoir-patterned substrate to selectively prevent unwanted adsorption of biomolecules on the protruding surface. Antibody was immobilized selectively inside the microreservoirs where multilayer was not transferred, and a specific antibody binding reaction was detected inside the microreservoirs. Furthermore, the potential of this composite mold as a convenient tool for constructing a biosensor for detecting Escherichia coli (E. coli) O157:H7 was explored.     

Dynamic alignment of C2H4 investigated by using two linearly polarized femtosecond laser pulses

We have studied multielectron ionization and Coulomb explosion of C2H4 irradiated by 110 fs, 800 nm laser pulses at an intensity of approximately 10(15) W/cm2. Strong anisotropic angular distributions were observed for the atomic ions Cn+(n = 1-3). Based on the results of two crossed linearly polarized laser pulses, we conclude that such anisotropic angular distributions result from dynamic alignment, in which the rising edge of the laser pulses aligns the neutral C2H4 molecules along the laser polarization direction. The angular distribution of the exploding fragments, therefore, reflects the degree of the alignment of molecules before ionization. Using the same femtosecond laser with intensity below the ionization threshold, the alignment of C2H4 molecules was also observed.     

A Possible Reaction Channel from BrONO to BrNO2

A possible isomeriztion channel from BrONO( bromine nitrite) to BrNO2 (nitryl bromide) is predicted by means of MP2 and QCISD(T) (single-point) methods.The channel is a direct bromine abstraction reaction from BrONO molecule by NO2 in which the forward reaction barrier is 89.30 kJ/mol at final UQCISD(T)/6-311 G(2df)//UMP2/6-311G(d) level of theory with zero-point energies included,The result can explian the available experiments very well.     

New ON-OFF type Ca-selective fluoroionophore having boron-dipyrromethene fluorophores

A new fluorogenic ionophore has been prepared by conjugating calix[4]-crown-5 ether with boron-dipyrromethene fluorophore. The ionophore exhibited a pronounced selective ON-OFF type response toward Ca²⁺ ions over other physiologically important metal ions of Na⁺, K⁺, and Mg²⁺. The interaction with Ca²⁺ ions resulted in very efficient quenching of fluorescence at 507 nm excited by relatively long wavelength irradiation at 480 nm. The selectivity ratios toward Ca²⁺ ions over other tested physiologically important metal ions were larger than 180 in aqueous 95% MeOH solution.     

Graphene‐Assisted Room‐Temperature Synthesis of 2D Nanostructured Hybrid Electrode Materials: Dramatic Acceleration of the Formation Rate of 2D Metal Oxide Nanoplates Induced by Reduced Graphene Oxide Nanosheets

A new prompt room temperature synthetic route to 2D nanostructured metal oxide–graphene‐hybrid electrode materials can be developed by the application of colloidal reduced graphene oxide (RGO) nanosheets as an efficient reaction accelerator for the synthesis of δ‐MnO₂ 2D nanoplates. Whereas the synthesis of the 2D nanostructured δ‐MnO₂ at room temperature requires treating divalent manganese compounds with persulfate ions for at least 24 h, the addition of RGO nanosheet causes a dramatic shortening of synthesis time to 1 h, underscoring its effectiveness for the promotion of the formation of 2D nanostructured metal oxide. To the best of our knowledge, this is the first example of the accelerated synthesis of 2D nanostructured hybrid material induced by the RGO nanosheets. The observed acceleration of nanoplate formation upon the addition of RGO nanosheets is attributable to the enhancement of the oxidizing power of persulfate ions, the increase of the solubility of precursor MnCO₃, and the promoted crystal growth of δ‐MnO₂ 2D nanoplates. The resulting hybridization between RGO nanosheets and δ‐MnO₂ nanoplates is quite powerful not only in increasing the surface area of manganese oxide nanoplate but also in enhancing its electrochemical activity. Of prime importance is that the present δ‐MnO₂–RGO nanocomposites show much superior electrode performance over most of 2D nanostructured manganate systems including a similar porous assembly of RGO and layered MnO₂ nanosheets. This result underscores that the present RGO‐assisted solution‐based synthesis can provide a prompt and scalable method to produce nanostructured hybrid electrode materials.     

Fast and Selective Semihydrogenation of Alkynes by Palladium Nanoparticles Sandwiched in Metal–Organic Frameworks

The semihydrogenation of alkynes into alkenes rather than alkanes is of great importance in the chemical industry. Unfortunately, state‐of‐the‐art heterogeneous catalysts hardly achieve high turnover frequencies (TOFs) simultaneously with almost full conversion, excellent selectivity, and good stability. Here, we used metal–organic frameworks (MOFs) containing Zr metal nodes (“UiO”) with tunable wettability and electron‐withdrawing ability as activity accelerators for the semihydrogenation of alkynes catalyzed by sandwiched palladium nanoparticles (Pd NPs). Impressively, the porous hydrophobic UiO support not only leads to an enrichment of phenylacetylene around the Pd NPs but also renders the Pd surfaces more electron‐deficient, which leads to a remarkable catalysis performance, including an exceptionally high TOF of 13835 h^?1, 100 % phenylacetylene conversion 93.1 % selectivity towards styrene, and no activity decay after successive catalytic cycles. The strategy of using molecularly tailored supports is universal for boosting the selective semihydrogenation of various terminal and internal alkynes.     

Different elution modes and field programming in gravitational field-flow fractionation. Effect of channel angle

Gravitational field-flow fractionation (GrFFF) has been shown to be useful for separation and characterization of various types of micrometer-sized particles. It has been recognized however that GrFFF is less versatile than other members of FFF because the external field (Earth's gravity) in GrFFF is relatively weak and is not tunable (constant), which makes the force acting on the particles constant. A few approaches have been suggested to control the force acting on particles in GrFFF. They include (1) changing the angle between the Earth's gravitational field and the longitudinal axis of the channel, and (2) the use of carrier liquid having different densities. In the hyperlayer mode of GrFFF, the hydrodynamic lift force (HLF) also act on particles. The existence of HLF allows other means of changing the force acting on the particles in GrFFF. They include (1) the flow rate programming, or (2) the use of channels having non-constant cross-section. In this study, with polystyrene latex beads used as model particles, the channel angle was varied to study its effect on elution parameters (such as selectivity, band broadening and resolution) in the steric or in the hyperlayer mode of GrFFF. In addition, the effects of the channel thickness and the flow rate on the elution parameters were also investigated. It was found that, in the steric mode, the resolution decreases as the flow rate increases due to increased zone broadening despite of the increase in the selectivity. At a constant volumetric flow rate, both the zone broadening and the selectivity increase as the channel thickness increases, resulting in the net increase in the resolution. It was also found that the retention time decreases as the channel angle increases in both up- and down-flow positions. The zone broadening tends to increase almost linearly with the channel angle, while no particular trends were found in selectivity. As a result, the resolution decreases as the channel angle increases.     

Facile Solid‐Phase Organic Synthesis of 5‐Vinyl‐Substituted 1,2,4‐Oxadiazoles from Polymer‐Bound α‐Selenopropionic Acid

Cyclocondensation of polystyrene‐supported α‐selenopropionic acid with amidoximes in the presence of 1‐(3‐dimethylaminopropyl)‐3‐ethylcarbodiimide hydrochloride (EDC) followed by oxidative deselenation efficiently afforded 5‐vinyl 1,2,4‐oxadiazoles in good yield and purity with a facile work‐up procedure.