Oligonuclear copper complexes of a bioinspired pyrazolate-bridging ligand: synthesis, structures, and equilibria in solution

The synthesis of a new bioinspired dinucleating ligand scaffold based on a bridging pyrazolate with appended bis[2-(1-methylimidazolyl)methyl]aminomethyl chelate arms is reported. This ligand forms very stable copper complexes, and a series of different species is present in solution depending on the pH. Interconversions between these solution species are tracked and characterized spectroscopically, and X-ray crystallographic structures of three distinct complexes that correspond to the species present in solution from acidic to basic pH have been determined. Overall, this provides a comprehensive picture of the copper coordination chemistry of the new ligand system. Alterations in the protonation state are accompanied by changes in nuclearity and pyrazolate binding, which cause pronounced changes in color and magnetic properties. Antiferromagnetic coupling between the copper(II) ions is switched on or off depending on the pyrazole binding mode.     

Speeding up chaos and limit cycles in evolutionary language and learning processes

Evolution of human language and learning processes have their foundation built on grammar that sets rules for construction of sentences and words. These forms of replicator–mutator (game dynamical with learning) dynamics remain however complex and sometime unpredictable because they involve children with some predispositions. In this paper, a system modeling evolutionary language and learning dynamics is investigated using the Crank–Nicholson numerical method together with the new differentiation with non‐singular kernel. Stability and convergence are comprehensively proven for the system. In order to seize the effects of the non‐singular kernel, an application to game dynamical with learning dynamics for a population with five languages is given together with numerical simulations. It happens that such dynamics, as functions of the learning accuracy μ, can exhibit unusual bifurcations and limit cycles followed by chaotic behaviors. This points out the existence of fickle and unpredictable variations of languages as time goes on, certainly due to the presence of learning errors. More interestingly, this chaos is shown to be dependent on the order of the non‐singular kernel derivative and speeds up as this derivative order decreases. Hence, can people use that order to control chaotic behaviors observed in game dynamical systems with learning! Copyright © 2016 John Wiley & Sons, Ltd.     

A Two‐in‐one Pincer Ligand and its Diiron(II) Complex Showing Spin State Switching in Solution through Reversible Ligand Exchange

A novel pyrazolate‐bridged ligand providing two {PNN} pincer‐type compartments has been synthesized. Its diiron(II) complex LFe₂(OTf)₃(CH₃CN) ( 1 ; Tf=triflate) features, in solid state, two bridging triflate ligands, with a terminal triflate and a MeCN ligand completing the octahedral coordination spheres of the two high‐spin metal ions. In MeCN solution, 1 is shown to undergo a sequential, reversible, and complete spin transition to the low‐spin state upon cooling. Detailed UV/Vis and ¹⁹F NMR spectroscopic studies as well as magnetic measurements have unraveled that spin state switching correlates with a rapid multistep triflate/MeCN ligand exchange equilibrium. The spin transition temperature can be continuously tuned by varying the triflate concentration in solution.     

Adsorption behavior of large plasmids on the anion-exchange methacrylate monolithic columns

The objective of this study was to investigate the behavior of large plasmids on the monolithic columns under binding and nonbinding conditions. The pressure drop measurements under nonbinding conditions demonstrated that the flow velocities under which plasmid passing monolith became hindered by the monolithic pore structure depended on the plasmid size as well as on the average monolith pore size; however, they were all very high exceeding the values encountered when applying CIM monolithic columns at their maximal flow rate. The impact of the ligand density and the salt concentration in loading buffer on binding capacity of the monolith for different sized plasmids was examined. For all plasmids the increase of dynamic binding capacity with the increase of salt concentration in the loading solution was observed reaching maximum of 7.1 mg/mL at 0.4M NaCl for 21 kbp, 12.0 mg/mL at 0.4 M NaCl for 39.4 kbp and 8.4 mg/mL at 0.5M NaCl for 62.1 kbp. Analysis of the pressure drop data measured on the monolithic column during plasmid loading revealed different patterns of plasmid binding to the surface, showing "car-parking problem" phenomena under certain conditions. In addition, layer thickness of adsorbed plasmid was estimated and at maximal dynamic binding capacity it matched calculated plasmid radius of gyration. Finally, it was found that the adsorbed plasmid layer acts similarly as the grafted layer responding to changes in solution's ionic strength as well as mobile phase flow rate and that the density of plasmid layer depends on the plasmid size and also loading conditions.     

Characterisation of methacrylate monoliths for bacteriophage purification

Binding of three different bacteriophages (phages), namely T7, lambda and M13 on methacrylate monoliths was investigated. Phage M13 exhibited the highest dynamic binding capacity of 4.5×10(13) pfu/mL while T7 and lambda showed capacity of 1×10(13) pfu/mL, all corresponding to values of around 1mg/mL. Interestingly, capacity for lambda phage was increased 5-fold by increasing NaCl concentration in a loaded sample from 0 to 0.2M while there was a constant capacity decrease for T7 and M13 phages. Under optimal conditions, recovery for all three phages approached 100%. Measurement of a pressure drop increase during loading enabled estimation of adsorbed phage layer thickness. At a maximal capacity it was calculated to be around 50 nm for T7 phage and 60 nm for lambda phage matching closely capside size thus indicating monolayer adsorption while 80 nm layer thickness was estimated for M13 phage showing its orientation along the pore.     

Accuracy analysis of simplified and rigorous numerical methods applied to binary nanopatterning gratings in non-paraxial domain

A set of simplified and rigorous electromagnetic vector theories is used for analyzing the transmittance characteristics of diffraction phase gratings. The scalar diffraction theory and the effective medium theory are validated with the exact results obtained via the rigorous coupled-wave theory and the finite-difference time-domain method. The effects of surface profile parameters and also the angle of incidence is demonstrated to be a limiting factor in the accuracy of these theories. Therefore, the error of both simplified theories is also analyzed in non-paraxial domain with the intention of establishing a specific range of validity for both simplified theories.     

A multiblock PLS‐based algorithm applied to a causal model in marketing

A modern approach to logistics allows it to be understood and used for its capacity to generate value, because value is managerially important as a strategic objective for any firm. In the present work a particular view of this approach is offered by providing a structural model where logistics service quality and sacrifices contribute to the formation of logistics value, but where service quality is also an important determinant of satisfaction. This combined approach, tested with multiblock partial least‐sqaures path modelling, in the particular setting of a business‐to‐business encounter, provides empirical support for a chain of effects between service quality–logistics value–satisfaction–loyalty without underestimating the important effect of service quality on satisfaction and satisfaction on loyalty in industrial settings. This proposed conceptual model of the relationship between customer loyalty and the various contributing factors to that loyalty is the main contribution in this paper. Copyright © 2012 John Wiley & Sons, Ltd.     

Every bordered Riemann surface is a complete proper curve in a ball

We prove that every bordered Riemann surface admits a complete proper holomorphic immersion into a ball of $\mathbb C ^2$ , and a complete proper holomorphic embedding into a ball of $\mathbb C ^3$ .     

Mesh deformation based on artificial neural networks

In the article a new mesh deformation algorithm based on artificial neural networks is introduced. This method is a point-to-point method, meaning that it does not use connectivity information for calculation of the mesh deformation. Two already known point-to-point methods, based on interpolation techniques, are also presented. In contrast to the two known interpolation methods, the new method does not require a summation over all boundary nodes for one displacement calculation. The consequence of this fact is a shorter computational time of mesh deformation, which is proven by different deformation tests. The quality of the deformed meshes with all three deformation methods was also compared. Finally, the generated and the deformed three-dimensional meshes were used in the computational fluid dynamics numerical analysis of a Francis water turbine. A comparison of the analysis results was made to prove the applicability of the new method in every day computation.