Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

A Ni⁰‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its Ni^II precursor. It retained chloride in the square‐planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni⁰ complex rapidly activated ammonia at room temperature, in a ligand‐assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent‐dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non‐innocent behavior of the NHC ligand.     

The backus-gilbert method revisited: background,implementation and examples

The paper deals with the Backus-Gilbert or averaging kernel inversion of linear integral equations. The theoretical background of the method is developed: it is shown that the method leads to a sequence of linear pointwise estimates, which are asymptotically unbiased when no error is present. Anumerical implementation is given. Finally, the algorithm is applied to numerical differentiation, Laplace transform inversion and to a geophysical inverseproblem arising in electromagnetic sounding.     

Nanocomposites based on crosslinked polyacrylic latex/silver nanoparticles for waterborne high‐performance antibacterial coatings

Functional polymer/AgNPs nanocomposites have been prepared. Silver nanoparticles (NPs) were synthesized to which polyacrylamide, PAAm, was covalently bound. PAAm was synthesized via a RAFT reaction and carried thiol and carboxylic acid end groups. Thiol was used to bind the polymer to the metal surface and carboxyl for further reactions. The AgNPs were used in a post‐crosslinking reaction with a separately synthesized poly(butyl acrylate‐co‐methyl methacrylate)/polyglycidyl methacrylate core/shell latex bearing epoxy functional groups. Dynamic mechanical analysis showed that the functional AgNPs effectively crosslinked the latex polymer, and that the final product had excellent mechanical strength. Antibacterial tests revealed that the nanocomposite films had strong antibacterial activity against all types of the bacteria and the immobilization of silver NPs by crosslinking retarded the release of silver in comparison to the uncrosslinked ones. With the presented method, it is possible to obtain ductile antibacterial nanocomposites to be used as waterborne functional coatings. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1435–1447     

CE and asymmetrical flow‐field flow fractionation studies of polymer interactions with surfaces and solutes reveal conformation changes of polymers

Amphiphilic diblock copolymers consisting of a hydrophobic core containing a polymerized ionic liquid and an outer shell composed of poly(N‐isoprolylacrylamide) were investigated by capillary electrophoresis and asymmetrical flow‐field flow fractionation. The polymerized ionic liquid comprised poly(2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate) with a constant block length (n = 24), while the length of the poly(N‐isoprolylacrylamide) block varied (n = 14; 26; 59; 88). Possible adsorption of the block copolymer on the fused silica capillary, due to alterations in the polymeric conformation upon a change in the temperature (25 and 45 °C), was initially studied. For comparison, the effect of temperature on the copolymer conformation/hydrodynamic size was determined with the aid of asymmetrical flow‐field flow fractionation and light scattering. To get more information about the hydrophilic/hydrophobic properties of the synthesized block copolymers, they were used as a pseudostationary phase in electrokinetic chromatography for the separation of some model compounds, that is, benzoates and steroids. Of particular interest was to find out whether a change in the length or concentration of the poly(N‐isoprolylacrylamide) block would affect the separation of the model compounds. Overall, our results show that capillary electrophoresis and asymmetrical flow‐field flow fractionation are suitable methods for characterizing conformational changes of such diblock copolymers.     

A novel method to prepare water dispersible poly(benzimidazobenzophenanthroline) (BBL) by partial substitution of chain ends with poly(ethylene oxide)

Poly(benzimidazobenzophenanthroline) (BBL) was prepared according to literature method and modified with poly(ethylene oxide) in a one pot synthesis. After precipitation in aqueous sodium carbonate solution and subsequent purification, aqueous dispersions were prepared by ultrasonication. Particle sizes in the dispersions ranged from few tens of nanometers to several micrometers and most of the particles had sizes of 50–250 nm. Further studies indicated that the colloidal stability is a combined result of steric stabilization caused by excluded volume interactions of PEO chains on particle surface and electrostatic stabilization by the dissociated carboxylic acid groups on the particle surface. The product could be processed into uniform films 20–30 nm in thickness by spin coating onto gold-plated silicon substrates having aminethiol monolayer as the top most layer.     

Pine Needles (Pinus Sylvestris) as a Bioindicator of Sulphur and Heavy Metal Deposition in the Area Around a Pulp and Paper Mill Complex at Kemi,Northern Finland

Abstract

The determination of sulphur and heavy metals in plants is an integral part of many environmental studies. Pine needles (Pinus Sylvestris) have proved to be suitable air quality indicators for pollutants, especially for sulphur. This study was carried out in the vicinity of Kemi, a town situated on the Gulf of Bothnia in northern Finland. An industrial complex comprising two pulp and paper mills is located in the centre of the area. Scots pine (Pinus Sylvestris) needles were collected from 29 sampling sites. The samples were dried, homogenized and digested with nitric acid. The concentrations of the elements S, Fe, Zn, Ca, V, and Pb were determined by ICP-AES. According to our results pine needles (Pinus sylvestris) appear to be an ideal bioindicator and sampling material for identifying and assessing atmospheric sulphur pollution derived from pulp and paper mills and can complement the information provided by plant mapping studies around pulp and paper mills.     

Multi-objective optimization by technical laws and heuristics

Common design principles apply to design of mechanical and biological machine structures. Most of the main properties of machines and creatures are determined by programmed genetics. These determine the geometry, material selection, functioning of machines and biological creatures and the fitness for service. The present approach of innovation and optimum design is based on basic mechanics with fuzzy goal formulations and heuristics, like axiomatic design. These models are combined synergistically to formulate the desired properties of the machines. First, engineering mechanics and heuristics are shown to have a finalistic guidance on the conceptual design of optimal fluid conveying channels consisting of a branch and a closing device. Then a multi-objective algorithm is tested in an industrial case study design of a preloaded screw fastened flange plate and it is shown to be a reliable tool for testing and innovating new solutions. The goals and constraints are modellled consistently by the same goal function form. The joints have to be reliable against risks of separation, relaxation, fatigue and creep fracture due to pressure differences. Compared to conventional results it gives nearly the same technical and safety functions even at half the cost. This approach is useful for optimizing new concepts and also existing machine designs showing possibilities for notable cost savings.     

Probing surface plasmons by bare V-shaped tips: modeling by geometrical optics and rigorous diffraction theory

Optical Review - We consider probing inhomogeneous waves in the near fields of metallic nanostructures with the aid of a dielectric V-shaped wedge connected to a waveguide. A geometrical model...     

Analysis of the photon–photon resonance influence on the direct modulation bandwidth of dual-longitudinal-mode distributed feedback lasers

The paper explores the possibilities to extend the direct modulation bandwidth in dual-longitudinal-mode distributed feedback lasers by exploiting the photon–photon resonance induced by the interaction of the two modes in the laser cavity. The effects on the direct amplitude modulation and on the direct modulation of the difference frequency between the two modes are analyzed using simulation and experimental results. When the photon–photon resonance, which occurs at the difference frequency between the two modes, is properly placed at a higher frequency than the carrier-photon resonance, the small-signal amplitude modulation (AM) bandwidth of the laser can be significantly increased. However, both simulations and experiments point out that a high small-signal AM bandwidth does not lead to a high large-signal AM bandwidth if the small-signal modulation response has significant variations across the modulation bandwidth. The paper shows that a high large-signal AM bandwidth is obtained when the two modes are significantly unbalanced, whereas a high-bandwidth difference frequency modulation can be best detected when the two modes are balanced and the DC bias is properly chosen.