Metallaaromaticity - a protean world

The nature of magnetically induced current densities (MICD) of metallabenzenes and related compounds has been examined with relativistic DFT calculations to assess the magnetic aromaticity of the molecules. The origin of the total MICD has been analyzed in terms of individual molecular orbital (MO) contributions. Our study reveals that the s-framework of the molecules always makes a diamagnetic contribution to the MICD. On the other hand, p-MOs and Craig–Möbius type p-MOs, i.e., MOs in which the dxy/dxz orbitals of the metal centers change the phase of the wave function akin to a Möbius twist, may not make a diatropic contribution. We have identified metallabenzenes with multiple magnetic aromaticities. In the case of iridabenzenes, s-MICD has been found to decrease dramatically from Ir(III) to Ir(V) systems. Furthermore, a brief examination of some recently synthesized metallapolycycles has shown that the metal center in a given ring can strongly modulate the aromaticity of neighboring rings. Finally, the finding that relatively minor perturbations in the ligand environment of the metal can substantially influence the aromaticity of metallabenzenes and related molecules underscores the protean character of metallaaromaticity and the need for even wider-ranging investigations. Considering the conflicts between magnetic response and ground-state aromaticity criteria (energetic, structural, and electronic criteria), we propose that the term aromatic be used for labeling a molecule if and only if all criteria confirm aromaticity. In other words, neither magnetic nor ground-state criteria are necessary and sufficient conditions for labeling a molecule aromatic

Ischaemic preconditioning of the liver before transplantation

Purpose: Assessment of the effect of a short ischaemic time prior to liver transplantation on the liver graft. Methods: White X Landrace pigs (N=10) were subjected to liver transplantation. Before being removed from the donor animal, the livers were randomised into two groups: group 1 - pre-procurement ischaemia (15 minutes' temporary arrest of portal venous and hepatic arterial inflow to the liver, followed by reperfusion of these vessels for a period of 15 minutes); group 2 - no prior inflow occlusion (control group). In group 1 a spleno-jugular bypass was established to prevent venous congestion, portal venous hypertension, intestinal oedema and bacterial translocation. The livers were perfused with Eurocollins solution (4oC), after which they were stored on ice for a period of 3 hours' cold ischaemic time. Hepatocellular injury was assessed according to liver cell function tests (aspartate aminotransferase, AST), biochemical indicators of reperfusion injury (malondialdehyde) and histopathology. Results: There was a significant rise of AST in both groups 1 hour after transplantation (from 51+27 IU/l to 357+152 IU/l in group 1 and from 29+10 IU/l to 359+198 IU/l in group 2). AST levels were marginally lower in group 1 at 2 and 4 hours after transplantation. There was also a rise in malondialdehyde levels in both groups at 5, 20, 40 and 60 minutes after transplantation. Levels of malondialdehyde were lower in the primed group at 5, 20 and 40 minutes, while the levels at 60 minutes after transplantation were comparable. Histological changes, as measured by vacuolisation, neutrophil infiltration and hepatic cell necrosis, were less in livers transplanted after ischaemic preconditioning, although the difference was not significant. Conclusions: Ischaemic preconditioning of the donor liver seems to decrease hepatocellular damage, reperfusion injury and histological changes in the liver after transplantation. Further studies with larger numbers are indicated

Hierarchy of piecewise non-linear maps with non-ergodicity behavior

We study the dynamics of hierarchy of piecewise maps generated by one-parameter families of trigonometric chaotic maps and one-parameter families of elliptic chaotic maps of $\mathbf{cn}$ and $\mathbf{sn}$ types, in detail. We calculate the Lyapunov exponent and Kolmogorov-Sinai entropy of the these maps with respect to control parameter. Non-ergodicity of these piecewise maps is proven analytically and investigated numerically . The invariant measure of these maps which are not equal to one or zero, appears to be characteristic of non-ergodicity behavior. A quantity of interest is the Kolmogorov-Sinai entropy, where for these maps are smaller than the sum of positive Lyapunov exponents and it confirms the non-ergodicity of the maps.Comment: 18 pages, 8 figure

Adding four-dimensional data assimilation by analysis nudging to the Model for Prediction Across Scales – Atmosphere (version 4.0)

The Model for Prediction Across Scales – Atmosphere (MPAS-A) has been modified to allow four-dimensional data assimilation (FDDA) by the nudging of temperature, humidity, and wind toward target values predefined on the MPAS-A computational mesh. The addition of nudging allows MPAS-A to be used as a global-scale meteorological driver for retrospective air quality modeling. The technique of analysis nudging developed for the Penn State/National Center for Atmospheric Research (NCAR) Mesoscale Model, and later applied in the Weather Research and Forecasting model, is implemented in MPAS-A with adaptations for its polygonal Voronoi mesh. Reference fields generated from 1°&thinsp; × &thinsp;1° National Centers for Environmental Prediction (NCEP) FNL (Final) Operational Global Analysis data were used to constrain MPAS-A simulations on a 92–25&thinsp;km variable-resolution mesh with refinement centered over the contiguous United States. Test simulations were conducted for January and July 2013 with and without FDDA, and compared to reference fields and near-surface meteorological observations. The results demonstrate that MPAS-A with analysis nudging has high fidelity to the reference data while still maintaining conservation of mass as in the unmodified model. The results also show that application of FDDA constrains model errors relative to 2&thinsp;m temperature, 2&thinsp;m water vapor mixing ratio, and 10&thinsp;m wind speed such that they continue to be at or below the magnitudes found at the start of each test period.</p

The permeability and selectivity of nanocomposite membrane of PEBAx 1657/PEI/SiO2 for separation of CO2, N2, O2, CH4 gases: A data set

The poly ether-block-amide (PEBAx)/Poly-ether-imide (PEI)/SiO2 nanocomposite membranes were fabricated using the solution casting method and utilized for separation of N2, O2, CH4, and CO2 gases. The effect of SiO2 nanoparticles loading on permeability and selectivity of gases using the nanocomposite membranes was tested. The data showed that the permeability of the gases increased with increasing SiO2 nanoparticle content. dBy adding SiO2 nanoparticles (10 wt%), the permeability of N2, O2, CH4, and CO2 gases elevated from 0.39, 1, 1.83 and 11.1 to 2.01, 1.95, 2.98 and 19.83 Barrer unit, respectively (at a pressure of 2 Bar). In contrast, with increasing SiO2 content the selectivity of the studied gases decreased. The morphology, crystallinity and the functional groups of the fabricated membranes were evaluated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) techniques. The data presented confirm the influence of the nanoparticles on the membrane structure and thus on the permeability and selectivity of the membranes

Strontium- and calcium-containing, titanium-stabilised phosphate-based glasses with prolonged degradation for orthopaedic tissue engineering.

Strontium- and calcium-releasing, titanium-stabilised phosphate-based glasses with a controlled degradation rate are currently under development for orthopaedic tissue engineering applications. Ca and/or Sr were incorporated at varying concentrations in quaternary phosphate-based glasses, in order to promote osteoinduction. Ti was incorporated at a fixed concentration in order to prolong degradation. Glasses of the general formula (P2O5)-(Na2O)-(TiO2)-(CaO)-(SrO) were prepared via the melt-quench technique. The materials were characterised by energy-dispersive X-ray spectroscopy, X-ray diffraction, (31)P magic angle spinning nuclear magnetic resonance, Fourier transform infrared spectroscopy, differential thermal analysis and density determination. The dissolution rate in distilled water was determined by measuring mass loss, ion release and pH change over a two-week period. In addition, the cytocompatibility and alkaline phosphatase activity of an osteoblast-like cell line cultured on the surface of glass discs was assessed. The glasses were shown to be amorphous and contained Q(1), Q(2) and Q(3) species. Fourier transform infrared spectroscopy revealed small changes in the glass structure as Ca was substituted with Sr and differential thermal analysis confirmed a decrease in crystallisation temperature with increasing Sr content. Degradation and ion release studies also showed that mass loss was positively correlated with Sr content. These results were attributed to the lower electronegativity of Sr in comparison to Ca favouring the formation of phosphate-based mineral phases. All compositions supported cell proliferation and survival and induced at least 2.3-fold alkaline phosphatase activity relative to the control. Glass containing 17.5 mol% Sr had 3.6-fold greater alkaline phosphatase activity than the control. The gradual release of Ca and Sr supported osteoinduction, indicating their potential suitability in orthopaedic tissue engineering applications

Waste sludge from shipping docks as a catalyst to remove amoxicillin in water with hydrogen peroxide and ultrasound

The waste sludge from shipping docks contains important elements that can be used as a catalyst after proper processing. The purpose of this study was to remove of amoxicillin (AMX) from the aquatic environment using waste sludge from shipping docks as catalyst in the presence of hydrogen peroxide/ultrasound waves. The catalyst was produced by treating waste sludge at 400 °C for 2 h. N2 adsorption, SEM, XRD, XRF, and FTIR techniques characterized the structural and physical properties of the catalyst. The BET-specific surface area of the catalyst reduced after AMX removal from 4.4 m2/g to 3.6 m2/g. To determine the optimal removal conditions, the parameters of the design of experiments were pH (5–9), contaminant concentration (5–100 mg/L), catalyst dosage (0.5–6 g/L), and concentration of hydrogen peroxide (10–100 mM). The maximum removal of AMX (98%) was obtained in the catalyst/hydrogen peroxide/ultrasound system at pH 5, catalyst dose of 4.5 g/L, H2O2 concentration of 50 mM, AMX concentration of 5 mg/L, and contact time of 60 min. The kinetics of removal of AMX from urine (k = 0.026 1/min), hospital wastewater (k = 0.021 1/min), and distilled water (k = 0.067 1/min) followed a first-order kinetic model (R2>0.91). The catalyst was reused up to 8 times and the AMX removal decreased to 45% in the last use. The byproducts and reaction pathway of AMX degradation were also investigated. The results clearly show that to achieve high pollutant removal rate the H2O2/ultrasound and catalyst/ultrasound synergy plays a key role