Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).     

One-pot Synthesis,Crystal Structures and Antimicrobial Activities of Two New 1,4-Disubstituted 1,2,3-Triazole-4-Carboxylates

Two new 1,4-disubstituted 1,2,3-triazoles-4-carboxylates were synthesized via click reaction. Compound 1a was synthesized by the interaction of 6-nitro-tetrazolo[1.5-a]-pyridine with ethyl propynoate at room temperature in the presence of Cu(OAc)2 as a catalyst and THF as solvent. Compound 1b was also synthesized by the same manner except that tert-butyl propionate, instead of ethyl propynoate, was used. The compounds were characterized by IR, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction analysis. Compound 1a(C10H9N5O4) crystallizes in the triclinic system, space group P1 with a = 5.0894(9), b = 8.9834(13), c = 13.089(2) ?, α= 83.041(7), β= 80.256(7), γ=87.296(8)°, V = 585.24(16)?3, Z = 2, Mr = 263.22, crystal size(mm) = 0.37 × 0.20 ×0.18,(I 2σ(I)) = 8557, 2493, 1229, Rint = 0.057. Compound 1b(C12H13N5O4) crystallizes in the monoclinic system, space group P21/c with a = 6.8854(5), b = 21.783(2), c = 9.3986(8) ?,β = 93.239(4)°, V = 1407.4(2)?3, Z = 4, Mr = 291.27, crystal size(mm) = 0.38 × 0.22 × 0.20,(I 2σ(I)) = 11842, 3172, 1866, Rint = 0.047. Antimicrobial assay results showed that the title compounds display excellent activities to different bacterial and fungal strains.     

Nano palladium supported on high‐surface‐area metal–organic framework MIL‐101: an efficient catalyst for Sonogashira coupling of aryl and heteroaryl bromides with alkynes

Palladium nanoparticle‐incorporated metal–organic framework MIL‐101 (Pd/MIL‐101) was successfully synthesized and characterized using X‐ray diffraction, nitrogen physisorption, X‐ray photoelectron, UV–visible and infrared spectroscopies, and transmission electron microscopy. The characterization techniques confirmed high porosity and high surface area of MIL‐101 and high stability of nano‐size palladium particles. Pd/MIL‐101 nanocomposite was investigated for the Sonogashira cross‐coupling reaction of aryl and heteroaryl bromides with various alkynes under copper‐free conditions. The reusability of the catalyst was tested for up to four cycles without any significant loss in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Simultaneous determination of cinnamaldehyde and its metabolite in rat tissues by gas chromatography–mass spectrometry

Cinnamaldehyde (CA), an active ingredient isolated from the traditional Chinese medicine Cortex Cinnamomi, has a wide range of bioactivities. To clarify the distribution characteristics of CA, a selective and sensitive method utilizing gas chromatography–mass spetrometry was initially developed for simultaneously determining the concentration of CA and its metabolite cinnamyl alcohol in rat tissues. Selected ion masses of m/z 131, 105 and 92 were chosen, and separation of the analytes was performed on a DB‐5 ms (30 m × 0.25 mm, 0.25 µm, thickness) capillary column by gas chromatography–mass spectrometry. The calibration curves demonstrated good linearity and reproducibility over the range of 20–2000 and 20–4000 ng/mL for various tissue samples. Recoveries ranged from 86.8 to 107.5%, while intra‐ and interday relative standard deviations were all <11.3%. The analysis method was successfully applied in tissue distribution studies for CA and cinnamyl alcohol. As CA and cinnamyl alcohol may inter‐convert to one another, simultaneous determination of both analytes provides a comparative and accurate data for tissue study. The concentrations of CA and cinnamyl alcohol remaining in spleen were the highest among the main organs, including heart, liver, spleen, lung, kidney and brain. In addition, there was no long‐term accumulation of CA in rat tissues. Copyright © 2014 John Wiley & Sons, Ltd.     

An approach of dynamic mesh adaptation for simulating 3‐dimensional unsteady moving‐immersed‐boundary flows

In this paper, we present an approach of dynamic mesh adaptation for simulating complex 3‐dimensional incompressible moving‐boundary flows by immersed boundary methods. Tetrahedral meshes are adapted by a hierarchical refining/coarsening algorithm. Regular refinement is accomplished by dividing 1 tetrahedron into 8 subcells, and irregular refinement is only for eliminating the hanging points. Merging the 8 subcells obtained by regular refinement, the mesh is coarsened. With hierarchical refining/coarsening, mesh adaptivity can be achieved by adjusting the mesh only 1 time for each adaptation period. The level difference between 2 neighboring cells never exceeds 1, and the geometrical quality of mesh does not degrade as the level of adaptive mesh increases. A predictor‐corrector scheme is introduced to eliminate the phase lag between adapted mesh and unsteady solution. The error caused by each solution transferring from the old mesh to the new adapted one is small because most of the nodes on the 2 meshes are coincident. An immersed boundary method named local domain‐free discretization is employed to solve the flow equations. Several numerical experiments have been conducted for 3‐dimensional incompressible moving‐boundary flows. By using the present approach, the number of mesh nodes is reduced greatly while the accuracy of solution can be preserved.     

Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms

The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐Co^II derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear Co^II center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered.     

Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study

We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.     

Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.