Stereocontrolled Synthesis of Vinyl Boronates and Vinyl Silanes via Atom‐Economical Ruthenium‐Catalyzed Alkene–Alkyne Coupling

The synthesis of vinyl boronates and vinyl silanes was achieved by employing a Ru‐catalyzed alkene–alkyne coupling reaction of allyl boronates or allyl silanes with various alkynes. The double bond geometry in the generated vinyl boronates can be remotely controlled by the juxtaposing boron‐ and silicon groups on the alkyne substrate. The synthetic utility of the coupling products has been demonstrated in a variety of synthetic transformations, including iterative cross‐coupling reactions, and a Chan‐Lam‐type allyloxylation followed by a Claisen rearrangement. A sequential one‐pot alkene‐alkyne‐coupling/allylation‐sequence with an aldehyde to deliver a highly complex α‐silyl‐β‐hydroxy olefin with a handle for further functionalization was also realized.     

Imprinted ZnO nanostructure-based electrochemical sensing of calcitonin: A clinical marker for medullary thyroid carcinoma

The present work describes an exciting method for the selective and sensitive determination of calcitonin in human blood serum samples. Adopting the surface molecular imprinting technique, a calcitonin-imprinted polymer was prepared on the surface of the zinc oxide nanostructure. Firstly, a biocompatible tyrosine derivative as a monomer was grafted onto the surface of zinc oxide nanostructure followed by their polymerization on vinyl functionalized electrode surface by activator regenerated by electron transfer–atom transfer radical polymerization (ARGET–ATRP) technique. Such sensor can predict the small change in the concentration of calcitonin in the human body and it may also consider to be as cost-effective, renewable, disposable, and reliable for clinical studies having no such cross-reactivity and matrix effect from real samples. The morphologies and properties of the proposed sensor were characterized by scanning electron microscopy, cyclic voltammetry, difference pulse voltammetry and chronocoulometry. The linear working range was found to be 9.99 ng L⁻¹ to 7.919 mg L⁻¹ and the detection limit as low as 3.09 ± 0.01 ng L⁻¹ (standard deviation for three replicate measurements) (S/N = 3).     

Spherical confinement of coulombic systems inside an impenetrable box: H atom and the Hulthén potential

The generalized pseudospectral method is used to study spherical confinement in two simple Coulombic systems: (i) well celebrated and heavily studied H atom (ii) relatively less explored Hulthén potential. In both instances, arbitrary cavity size as well as low and higher states are considered. Apart from bound state eigenvalues, eigenfunctions, expectation values, quite accurate estimates of the critical cage radius for H atom for all the 55 states corresponding to , are also examined. Some of the latter are better than previously reported values. Degeneracy and energy ordering under the isotropic confinement situation are discussed as well. The method produces consistently high‐quality results for both potentials for small as well as large cavity size. For the H atom, present results are comparable to best theoretical values, while for the latter, this work gives considerably better estimates than all existing work so far. © 2014 Wiley Periodicals, Inc.     

Application of Löwdin's canonical orthogonalization method to the Slater‐type orbital configuration‐interaction basis set

We apply Löwdin's canonical orthogonalization method to investigate the linearly dependent problem arising from the variational calculation of atomic systems using Slater‐type orbital configuration‐interaction (STO‐CI) basis functions. With a specific arithmetic precision used in numerical computations, the nonorthogonal STO‐CI basis is easily linearly dependent when the number of basis functions is sufficiently large. We show that Löwdin's canonical orthogonalization method can successfully overcome such problem and simultaneously reduce the dimension of basis set. This is illustrated first through an S‐wave model He atom, and then the real two‐electron atoms in both the ground and excited states. In all of these calculations, the variational bound state energies of the two‐electron systems are obtained in reasonably high accuracy using over‐redundant STO‐CI bases, however, without using extended high‐precision technique. © 2015 Wiley Periodicals, Inc.     

MOLSIM: A modular molecular simulation software

The modular software MOLSIM for all‐atom molecular and coarse‐grained simulations is presented with focus on the underlying concepts used. The software possesses four unique features: (1) it is an integrated software for molecular dynamic, Monte Carlo, and Brownian dynamics simulations; (2) simulated objects are constructed in a hierarchical fashion representing atoms, rigid molecules and colloids, flexible chains, hierarchical polymers, and cross‐linked networks; (3) long‐range interactions involving charges, dipoles and/or anisotropic dipole polarizabilities are handled either with the standard Ewald sum, the smooth particle mesh Ewald sum, or the reaction‐field technique; (4) statistical uncertainties are provided for all calculated observables. In addition, MOLSIM supports various statistical ensembles, and several types of simulation cells and boundary conditions are available. Intermolecular interactions comprise tabulated pairwise potentials for speed and uniformity and many‐body interactions involve anisotropic polarizabilities. Intramolecular interactions include bond, angle, and crosslink potentials. A very large set of analyses of static and dynamic properties is provided. The capability of MOLSIM can be extended by user‐providing routines controlling, for example, start conditions, intermolecular potentials, and analyses. An extensive set of case studies in the field of soft matter is presented covering colloids, polymers, and crosslinked networks. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.     

An investigation of the electron density of a Jahn–Teller‐distorted CrII cation: the crystal structure and charge density of hexakis(acetonitrile‐κN)chromium(II) bis(tetraphenylborate) acetonitrile disolvate

In the crystal structure of the title homoleptic Cr^II complex, [Cr(CH₃CN)₆](C₂₄H₂₀B)₂·CH₃CN, the [Cr(CH₃CN)₆]²⁺ cation is a high‐spin d⁴ complex with strong static, rather than dynamic, Jahn–Teller distortion. The electron density of the cation was determined by single‐crystal X‐ray refinements using aspherical structure factors from wavefunction calculations. The detailed picture of the electronic density allowed us to assess the extent and directionality of the Jahn–Teller distortion of the Cr^II cation away from idealized octahedral symmetry. The topological analysis of the aspherical d‐electron density about the Cr^II cation showed that there are significant valence charge concentrations along the axial Cr—N axes. Likewise, there were significant valence charge depletions about the Cr^II cation along the equatorial Cr—N bonds. These charge concentrations are in accordance with a Jahn–Teller‐distorted six‐coordinate complex.     

Structural study of a manganese(II) `picket‐fence' porphyrin complex

`Picket‐fence' porphyrin compounds are used in the investigation of interactions of hemes with dioxygen, carbon monoxide, nitric monoxide and imidazole ligands. (Cryptand‐222)potassium chlorido[meso‐tetra(α,α,α,α‐o‐pivalamidophenyl)porphyrinato]manganese tetrahydrofuran monosolvate (cryptand‐222 is 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane), [K(C₁₈H₃₆N₂O₆)][Mn(C₆₄H₆₄N₈O₄)Cl]·C₄H₈O or [K(222)][Mn(TpivPP)Cl]·THF [systematic name for TpivPP: 5,10,15,20‐tetrakis(2‐tert‐butanamidophenyl)porphyrin], is a five‐coordinate high‐spin manganese(II) picket‐fence porphyrin complex. It crystallizes with a potassium cation chelated inside a cryptand‐222 molecule; the average K—O and K—N distances are 2.83 (4) and 2.995 (13) Å, respectively. All four protecting tert‐butyl pickets of the porphyrin are ordered. The porphyrin plane is nearly planar, as indicated by the atomic displacements and the dihedral angles between the mean planes of the pyrrole rings and the 24‐atom mean plane. The axial chloride ligand is located inside the molecular cavity on the hindered porphyrin side and the Mn—Cl bond is tilted slightly off the normal to the porphyrin plane by 3.68 (2)°. The out‐of‐plane displacement of the metal centre relative to the 24‐atom mean plane (Δ₂₄) is 0.7013 (4) Å, indicating a noticeable porphyrin core doming.     

On molecular topological properties of hex‐derived networks

Topological indices are numerical parameters of a molecular graph, which characterize its topology and are usually graph invariant. In quantitative structure–activity relationship/quantitative structure–property relationship study, physico‐chemical properties and topological indices such as Randić, atom–bond connectivity (ABC), and geometric–arithmetic (GA) index are used to predict the bioactivity of chemical compounds. Graph theory has found a considerable use in this area of research. In this paper, we study hex‐derived networks HDN1(n) and HDN2(n), which are generated by hexagonal network of dimension n and derive analytical closed results of general Randić index R_α(G) for different values of α, for these networks of dimension n. We also compute the general first Zagreb, ABC, GA, ABC₄, and GA₅ indices for these hex‐derived networks for the first time and give closed formulae of these degree‐based indices for hex‐derived networks. Copyright © 2016 John Wiley & Sons, Ltd.     

Highly Efficient Oxygen Reduction Reaction Fe-N-C Cathode in Long-durable Direct Glycol Fuel Cells

The oxygen reduction reaction in direct glycol fuel cells heavily relies on noble metal-based electrocatalysts. In this work, novel Pt group metal-free catalysts based on porous Fe-N-C materials are successfully synthesized as catalysts with high activity and durability for the cathode oxygen reduction reaction (ORR). Through the encapsulation of NH₄SCN salt, the surface elements and pore structure of the catalyst are effectively changed, and the active sites of Fe effectively are increased. The half-wave potential of the best Fe-N-C catalyst was –0.02 V vs. Hg/HgO in an alkaline environment. The porous Fe-N-C catalyst possesses a large specific surface area(1158 m²/g) and shows good activity and tolerance to glycol. The direct glycol fuel cell with the Fe-N-C cathode achieved a maximum power density of 62.2 mW/cm² with 4 mol/L KOH and 4 mol/L glycol solution at 25 °C and maintained discharge for more than 250 h at a 50 A/cm² current density.