Intra-annular cyclophane diamines as proton sponges: a computational study

Gas-phase proton affinities of cyclophanes containing intra-annular amino groups were calculated using density functional theory (DFT) at the B3LYP/6-31+G^∗∗//B3LYP/6-31G^∗ level. They are higher in magnitude as those for proton sponges such as 1,8-bisaminonaphthalene, however, they are slightly weaker bases than 1,8-bis(dimethylamino)naphthalene. The high basicity of the cyclophane diamines is attributed mainly to their structural flexibility, which allows them to maximize the hydrogen bond strength in the cations by achieving N-H?N linearity, while strain relief upon protonation is less important. Another contributing factor is the stabilizing interaction of the added proton with adjacent phenyl π systems of the cyclophanes. Barriers for proton transfer between the nitrogen atoms of the diamine cations are also reported.     

Superior diffusion kinetics and electrochemical properties of α/β–type NaMn0.89Co0.11O2 as cathode for sodium-ion batteries

Journal of Solid State Electrochemistry - Sodium-ion batteries have emerged as an exciting alternative to commercially dominant lithium-ion batteries for electric vehicles and other applications....     

Supramolecular Arrangement and DFT analysis of Zinc(II) Schiff Bases: An Insight towards the Influence of Compartmental Ligands on Binding Interaction with Protein

We report, for the first time, a detailed crystallographic study of the supramolecular arrangement for a set of zinc(II) Schiff base complexes containing the ligand 2,6-bis((E)-((2-(dimethylamino)ethyl)imino)methyl)-4-R-phenol], where R=methyl/tert-butyl/chloro. The supramolecular study acts as a pre-screening tool for selecting the compartmental ligand R of the Schiff base for effective binding with a targeted protein, bovine serum albumin (BSA). The most stable hexagonal arrangement of the complex [Zn − Me] (R=Me) stabilises the ligand with the highest FMO energy gap (ΔE=4.22 eV) and lowest number of conformations during binding with BSA. In contrast, formation of unstable 3D columnar vertebra for [Zn − Cl] (R=Cl) tend to activate the system with lowest FMO gap (3.75 eV) with highest spontaneity factor in molecular docking. Molecular docking analyses reported in terms of 2D LigPlot+ identified site A, a cleft of domains IB, IIIA and IIIB, as the most probable protein binding site of BSA. Arg144, Glu424, Ser428, Ile455 and Lys114 form the most probable interactions irrespective of the type of compartmental ligands R of the Schiff base whereas Arg185, Glu519, His145, Ile522 act as the differentiating residues with ΔG=−7.3 kcal mol⁻¹.     

Chemistry of azoimidazoles. Synthesis,spectral characterization and redox studies of N(1)-benzyl-2-(arylazo)imidazolepalladium(II)chloride

Arylazoimidazoles (2) are N,N-chelating ligands. The polymerization trend of the azolate system is restricted via N(1)-benzylation. The parent molecules (2), N(1)-benzylated products (3) and palladium complexes (4) were made by standard methods. The ligands (3) and complexes (4) are new. They have been characterized by elemental analysis, i.r., u.v.-vis. and high resolution 1H-n.m.r. spectral data. Redox studies were carried out by cyclic voltammetry. On complexation, azo reduction is shifted anodically.     

Phytosynthesis of Silver Nanoparticles Using Walnut (Juglans regia) Bark with Characterization of the Antibacterial Activity against Streptococcus mutans

A green method using Juglans regia bark extract was used to synthesize silver nanoparticles at room temperature with monitoring by absorption spectroscopy. The size and shape of the synthesized nanoparticles were characterized by infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, high-resolution transmission electron microscopy, and small-angle X-ray scattering. The average particle size was from 10 to 30?nm. Gas chromatography–mass spectrometry (GC–MS) was used for the separation, identification, and quantification of components of the plant extracts. A possible mechanism for the synthesis of nanoparticles was elucidated based on the GC–MS results. The synthesized silver nanoparticles showed effective inhibition against Streptococcus mutans, which is the main causative agent for dental caries. The nanoparticles also showed promising antibiofilm activity by inhibiting the glucosyltransferase enzyme.     

Ruthenium (II) Catalyzed C(sp2)−H Bond Alkenylation of 2-Arylbenzo[d]oxazole and 2-Arylbenzo[d]thiazole with Unactivated Olefins

Functionalization of the bio-relevant heterocycles 2-arylbenzo[d]oxazole and 2-arylbenzo[d]thiazole has been achieved through Ru(II)-catalyzed alkenylation with unactivated olefins leading to selective formation of the mono-alkenylated products. This approach has a broad substrate scope with respect to the coupling partners, affords high yields, and works for gram scale synthesis using a readily available Ru-based catalyst. Mechanistic studies reveal a C−H activation pathway for the dehydrogenative coupling leading to the alkenylation. However, the results of the ESI-MS-guided deuterium kinetic isotope effect studies indicate that the C−H activation stage may not be the rate-determining step of the reaction. The use of a radical scavenging agent such as TEMPO did not show any detrimental effect on the reaction outcome, eliminating the possibility of the involvement of a free-radical pathway.     

Chaos in the delay logistic equation with discontinuous delays

This paper analyzes a delay logistic equation which models a feedback control problem. Interval map associated to the system is derived. By calculating Lyapunov exponent, we indicate stable orbit and chaotic phenomenon respectively. The results are verified through computer simulation. We identify the parameter which controls the dynamics.     

Two-warehouse production model for deteriorating inventory items with stock-dependent demand under inflation over a random planning horizon

This paper develops a production-inventory model for a deteriorating item with stock-dependent demand under two storage facilities over a random planning horizon, which is assumed to follow exponential distribution with known parameter. The effects of learning in set-up, production, selling and reduced selling is incorporated. Different inflation rates for various inventory costs and time value of money are also considered. A hybrid genetic algorithm is designed to solve the optimization problem which is hard to solve with existing algorithms due to the complexity of the decision variable. To illustrate the model and to show the effectiveness of the proposed approach a numerical example is provided. A sensitivity analysis of the optimal solution with respect to the parameters of the system is carried out.     

Birnbaum‐Saunders distribution: A review of models,analysis, and applications

Birnbaum and Saunders introduced a two‐parameter lifetime distribution to model the fatigue life of a metal, subject to cyclic stress. Since then, extensive work has been done on this model providing different interpretations, constructions, generalizations, inferential methods, and extensions to bivariate, multivariate, and matrix‐variate cases. More than 200 papers and one research monograph have already appeared describing all these aspects and developments. In this paper, we provide a detailed review of all these developments and, at the same time, indicate several open problems that could be considered for further research.