Coordination Properties of Ionic Liquid-Mediated Chromium(II) and Copper(II) Chlorides and Their Complexes with Glucose

The structural and coordination properties of complexes formed upon the interaction of copper(II) and chromium(II) chlorides with diallrylimidazolium chloride (RMlm(+)Cl(-)) ionic liquids and glucose are studied by a combination of density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS). In the absence of the carbohydrate substrate, isolated mononuclear four-coordinated MeCl42- species (Me = Cu, Cr) dominate in the ionic liquid solution. The organic part of the ionic liquid does not directly interact with the metal centers. The interactions between the RMlm(+) cations and the anionic metal chloride complexes are limited to hydrogen bonding with the basic Cl- ligands and the overall electrostatic stabilization of the anionic metal complexes. Exchange of Cl ligands by a hydroxyl group of glucose is only favorable for CrCl42-. For Cu2+ complexes, the formation of hydrogen bonded complexes between CuCl42- and glucose is preferred. No preference for the coordination of metal chloride species to specific hydroxyl group of the carbohydrate is found. The formation of binuclear metal chloride complexes is also considered. The reactivity and selectivity patterns of the Lewis acid catalyzed reactions of glucose are discussed in the framework of the obtained results.

Magnetic properties of copper hexadecaphthalocyanine (F16CuPc) thin films and powders

The structural and magnetic properties of F16CuPc thin films and powder, including x-ray diffraction (XRD), superconducting quantum interference device (SQUID) magnetometry, and theoretical modelling of exchange interactions are reported. Analysis of XRD from films, with thickness ranging between 100 and 160 nm, deposited onto Kapton and a perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) interlayer shows that the stacking angle (defined in the text) of the film is independent of the thickness, but that the texture is modified by both film thickness and substrate chemistry. The SQUID measurements suggest that all samples are paramagnetic, a result that is confirmed by our theoretical modelling including density functional theory calculations of one-dimensional molecular chains and Green's function perturbation theory calculations for a molecular dimer. By investigating theoretically a range of different geometries, we predict that the maximum possible exchange interaction between F16CuPc molecules is twice as large as that in unfluorinated copper-phthalocyanine (CuPc). This difference arises from the smaller intermolecular spacing in F16CuPc. Our density functional theory calculation for isolated F16CuPc molecule also shows that the energy levels of Kohn-Sham orbitals are rigidly shifted similar to 1 eV lower in F16CuPc compared to CuPc without a significant modification of the intramolecular spin physics, and that therefore the two molecules provide a suitable platform for independently varying magnetism and charge transport. 

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

Influence of nanoclays on mechanical and barrier properties of hydrogenated acrylonitrile butadiene rubber nanocomposites

In this research, two different methods have been investigated for optimising the preparation of hydrogenated acrylonitrile butadiene rubber/clay nanocomposites. Commercially available organoclay (Cloisite 20A) has been considered for the preparation of rubber nanocomposites. A detailed analysis has been made to investigate the morphological structure and mechanical behaviour at room temperature and at elevated temperature. Also the influence of organoclays on permeability has been studied. Structural analysis indicates very good dispersion for a low loading of 5 parts per hundred (phr) amount of nanoclays. Significant improvements in mechanical properties have been observed with the addition of organoclays at both room and elevated temperatures. Even with the low level of addition of nanoclays, there was a remarkable reduction in permeability. © Institute of Materials, Minerals and Mining 2011.

Melt Processing and Properties of Polyamide 6/Graphene Nanoplatelet Composites

Graphene, due to its outstanding properties, has become the topic of much research activity in recent years. Much of that work has been on a laboratory scale however, if we are to introduce graphene into real product applications it is necessary to examine how the material behaves under industrial processing conditions. In this paper the melt processing of polyamide 6/graphene nanoplatelet composites via twin screw extrusion is investigated and structure–property relationships are examined for mechanical and electrical properties. Graphene nanoplatelets (GNPs) with two aspect ratios (700 and 1000) were used in order to examine the influence of particle dimensions on composite properties. It was found that the introduction of GNPs had a nucleating effect on polyamide 6 (PA6) crystallization and substantially increased crystallinity by up to 120% for a 20% loading in PA6. A small increase in crystallinity was observed when extruder screw speed increased from 50 rpm to 200 rpm which could be attributed to better dispersion and more nucleation sites for crystallization. A maximum enhancement of 412% in Young's modulus was achieved at 20 wt% loading of GNPs. This is the highest reported enhancement in modulus achieved to date for a melt mixed thermoplastic/GNPs composite. A further result of importance here is that the modulus continued to increase as the loading of GNPs increased even at 20 wt% loading and results are in excellent agreement with theoretical predictions for modulus enhancement. Electrical percolation was achieved between 10–15 wt% loading for both aspect ratios of GNPs with an increase in conductivity of approximately 6 orders of magnitude compared to the unfilled PA6.

Geotechnical monitoring using a combination of LIDAR, real-time dGPS, and electrical tomography to assess geotechnical risk of a coastal landslide.

The Antrim Coast Road stretching from the seaport of Larne in the East of Northern Ireland has a well-deserved reputation for being one of the most spectacular roads in Europe (Day, 2006). However the problematic geology; Jurassic Lias Clay and Triassic Mudstone overlain by Cretaceous Limestone and Tertiary Basalt, and environmental variables result in frequent instances of slope instability manifested in both shallow debris flows and occasional massive rotational movements, creating a geotechnical risk to this highway. This paper describes how a variety of techniques are being used to both assess instability and monitor movement of these active slopes near one site at Straidkilly Point, Glenarm. An in-depth understanding of the geology was obtained via boreholes, resistivity surveys and laboratory testing. Environmental variables recorded by an on-site weather station were correlated with measured pore water pressure and soil moisture infiltration data. Terrestrial LiDAR (TLS), with surveys carried out on a bi-monthly basis allowed for the generation of Digital Elevation Models (DEMs) of difference, highlighting areas of recent movement, accumulation and depletion. Morphology parameters were generated from the DEMs and include slope, curvature and multiple measures of roughness. Changes in the structure of the slope coupled with morphological parameters were characterised and linked to progressive failures from the temporal monitoring. In addition to TLS monitoring, Aerial LiDAR datasets were used for the spatio-morphological characterisation of the slope on a macro scale. A Differential Global Positioning System (dGPS) was also deployed on site to provide a real-time warning system for gross movements, which were also correlated with environmental conditions. Frequent electrical resistivity tomography (ERT) surveys were also implemented to provide a better understanding of long-term changes in soil moisture and help to define the complex geology. The paper describes how the data obtained via a diverse range of methods has been combined to facilitate a more informed management regime of geotechnical risk by the Northern Ireland Roads Service.