Bi(III)‐catalyzed C―S cross‐coupling reaction

A direct synthetic route for the C―S coupling of aryl halides with thiophenols is described. This method is tolerant to electron‐withdrawing and electron‐donating functional groups and also to the presence of functional groups in the ortho position of the aryl iodide or thiophenol. Aryl iodides are coupled with thiophenols without affecting the other functionalities present in the aryl ring. These reactions follow second‐order kinetics. Copyright © 2012 John Wiley & Sons, Ltd.     

Nonlinear model of the firefly flash

Nonlinear Dynamics - This paper investigates bursting dynamics of a Rayleigh oscillator with multiple-frequency slow excitations, in which two different bursting patterns related to the bistable...     

Electrohydrodynamic transport of non‐symmetric electrolyte through porous wall of a microtube

Transport of salt through the wall of porous microtube is relevant in various physiological microcirculation systems. Transport phenomena based modeling of such system is undertaken in the present study considering a combined driving force consisting of pressure gradient and external electric field. Transport of salt is modeled in two domains, in the flow conduit and in the pores of porous wall of the microtube. The solute transport in the microtube is presented by convective‐diffusive mass balance and it is solved using integral method under the framework of boundary layer analysis. The wall of the microtube is considered to be consisting of series of straight parallel cylindrical pores with charged inner surface. The solute transport through the pores is considered to be composed of diffusive, convective and electric potential gradient governed by Nernst‐Planck equation. Transport in the microtube and pores is coupled through the osmotic pressure model for the solvent and Donnan equilibrium distribution for the solute. The simulated results agree remarkably well with the experimental data conducted by in‐house experimental set up. The charge density of the porous wall is estimated through the minimization of errors involved between the experimental and simulated data for different operating conditions.     

Mapping the inhomogeneity of the U and Th distributions — using sample size concept in the field conditions

Indigenously fabricated portable gamma-ray spectrometer (PGRS) is used for the measurement of gamma activity of ²¹⁴Bi (1.76 MeV) and ²⁰⁸TI (2.62 MeV), under field conditions in Mohar area, Shivpuri Distt. (MP). The energies are discriminated by using a Nal (TI) crystal of size 1.75″ × 2″. PGRS used to map the primordial elemental distributions shows reversals of concentration of thorium and uranium (represented by radium group) in field and lab analysis in many samples, which is attributed to the inhomogenity of distribution of these elements in the area. The concept of difference in the volume of dish shaped field sample and the randomly picked up sample from the field grid point (400 gm in lab analysis) is utilized to interpret the inhomogenity of these elements. However interpretations are based on the assumption that these primordial elements (U, Th) are in secular equilibrium and the terrain has low topographic relief.      

Single laser exposure fabrication of diamond-like 3-dimensional photonic crystal microstructures using circularly polarized light

Phase tunable multi-level diffractive optical elements define an attractive approach for single laser exposure fabrication of 3-dimensional photonic crystal microstructures. The significant advantage of these multi-level diffractive optical elements over two-level diffractive optical elements is the flexibility of fabricating a wide range of 3-dimensional periodic structures by manipulating the relative phase of different diffracted beams. Here, phase tuning was applied to demonstrate fabrication of a hybrid 3-dimensional structure intermediate between previously reported diamond-like Woodpile-type structure of tetragonal symmetry and structure having body-centered-tetragonal lattice symmetry. Circularly polarized light was applied for the first time to balance the diffraction order efficiencies and improve the structural uniformity. Design guidelines are presented for generating diamond-like photonic crystal template that possesses complete photonic bandgap when inverted with high refractive index materials.     

Convergent Synthesis of Oligosaccharide Fragments Corresponding to the Cell Wall O‐Polysaccharide of Salmonella enterica O53

Conventional glycoconjugate vaccines are prepared with polysaccharides isolated from bacterial fermentation, an approach with some significant drawbacks such as handling of live bacterial strains, the presence of biological impurities, and inter‐batch variations in oligosaccharide epitope structure. However, it has been shown in many cases that a synthetic fragment of appropriate structure conjugated to a protein can be an effective vaccine that circumvents the shortcomings of using full‐length oligosaccharides. The development of synthetic strategies to prepare glycoconjugate derivatives against pathogenic bacterial strains is therefore of great interest. Oligosaccharide fragments corresponding to the repeat unit of the cell wall O‐antigen of Salmonella enterica strain O53 were synthesized in good yield. Sequential and block glycosylation strategies were used for the synthesis of the target compounds. A number of recently developed reaction conditions were used in the synthetic strategy. A one‐pot reaction scheme was also developed for the multiple glycosylation steps. The stereoselective outcomes of all glycosylation reactions were very good.     

Ligand Transformations and Efficient Proton/Water Reduction with Cobalt Catalysts Based on Pentadentate Pyridine‐Rich Environments

A series of cobalt complexes with pentadentate pyridine‐rich ligands is studied. An initial Co^II amine complex 1 is prone to aerial oxidation yielding a Co^III imine complex 2 that is further converted into an amide complex 4 in presence of adventitious water. Introduction of an N‐methyl protecting group to the ligand inhibits this oxidation and gives rise to the Co^II species 5 . Both the Co^III 4 and Co^II 5 show electrocatalytic H₂ generation in weakly acidic media as well as in water. Mechanisms of catalysis seem to involve the protonation of a Co^II? H species generated in situ.     

Generalization of coupled-cluster response theory to multireference expansion spaces: application of the coupled-cluster singles and doubles effective Hamiltonian

Employing separate cluster ansatz in time-independent and time-dependent wave-operators, coupled-cluster (CC) response theory is generalized to multireference (MR) expansion spaces. For state energies, this corresponds to the MR secular problem with an arbitrary similarity-transformed effective Hamiltonian, H˜=Ω⁻¹ HΩ. The effective Hamiltonian can be generated via size-extensive CC methods. Thus the states in MR linear response theory (MRLRT) maintain the usual CC core-extensive properties. We have used the Gelfand unitary group basis of the spin-adapted configurations to construct the matrix of H˜ in the MR excitation space. As a preliminary application, the CC singles and doubles effective Hamiltonian is applied to excitation and photoionization energies of the CH⁺ and N₂ molecules, and is compared with experimental results and results from other numerical procedures including conventional CC linear response theory (CC-LRT), MR and full configuration interaction (MRCI and FCI) methods. The numerical results indicate that MRLRT reproduces valence and external excited states quantitatively, combining the best features of CC-LRT and MRCI. Received: 2 July 1998 / Accepted: 28 August 1998 / Published online: 11 November 1998     

Development and applications of a relaxation-inducing cluster expansion theory for treating strong relaxation and differential correlation effects

We present in this paper a multi-reference coupled cluster (MRCC) formulation for energy differences which treats orbital relaxation and correlation effects on the same footing, by invoking a novel cluster ansatz of the valence portion of the wave operator Ω_v. Unlike in the traditional normal-ordered exponential representation of Ω_v, our new relaxation-inducing ansatz, represented symbolically as E _r(S), allows contractions between the spectator lines and also certain other special contractions. By an extensive theoretical analysis, taking as an example the case of one-hole model space (the IP problem), we demonstrate that our ansatz incorporates in a manifestly spin-free form the orbital relaxation to all orders. The traditional Thouless-type of exponential transformation via one-body excitations can induce the same effect, as is done in the valence-specific or the quasi-valence-specific MRCC formalisms, but they have to be done in the spin-orbital basis – making the spin adaptation of the problem a complicated exercise. In contrast, we use a spin-free representation of the cluster operators right from start, but expand the rank of the cluster operators by involving spectator orbitals to distinguish the various spin possibilities. The combinatorial factors entering the contracted power series in E _r(S) are chosen in such a way that they correspond to what we would have obtained if we had used a Thouless-like transformation to induce the orbital relaxation. Our working equations generally have only finite powers of the cluster operators S, resulting in a very compact formulation of the relaxation problem. Pilot numerical applications for the IP computations of HF and H₂O in the core, the inner valence and the outer valence regions show very good performance of the method vis-a-vis those obtained using the traditional normal ordered ansatz for Ω_v. The improvement in the core IP value is particularly impressive, although even for the valence regions there is an overall improvement of the IP values. Received: 3 August 1998 / Accepted: 30 September 1998 / Published online: 15 February 1999     

Correction to: Bis-chelates of nickel(II) and copper(II) with an O,S-donor piperazine ligand

Transition Metal Chemistry - After the publication of this article ‘Bis-chelates of nickel(II) and copper(II) with an O,S-donor piperazine ligand,’ it came to our attention that...