Syntheses, crystal structures and properties of sterically congested heteroleptic complexes of group 10 metal ions with p-tolylsulfonyl dithiocarbimate and 1,2-bis (diphenylphosphino) ethane

Three novel heteroleptic complexes of the type cis- [ML(dppe)] [M = Ni(II), Pd(II), Pt(II); L = p-tolylsulfonyl dithiocarbimate; dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared and characterized. X-ray crystallography revealed the close proximity of one of the ortho phenyl protons of the dppe ligand to the metal in the Ni(II) complex showing existence of the less common C-H center dot center dot center dot Ni anagostic interactions observed for the first time in the dithio-phosphine mixed-ligand systems. The platinum complex showed a strong photoluminescence emission near visible region in CH(2)Cl(2) solution.

Inactivation of the antibacterial and cytotoxic properties of silver ions by biologically relevant compounds

There has been a recent surge in the use of silver as an antimicrobial agent in a wide range of domestic and clinical products, intended to prevent or treat bacterial infections and reduce bacterial colonization of surfaces. It has been reported that the antibacterial and cytotoxic properties of silver are affected by the assay conditions, particularly the type of growth media used in vitro. The toxicity of Ag+ to bacterial cells is comparable to that of human cells. We demonstrate that biologically relevant compounds such as glutathione, cysteine and human blood components significantly reduce the toxicity of silver ions to clinically relevant pathogenic bacteria and primary human dermal fibroblasts (skin cells). Bacteria are able to grow normally in the presence of silver nitrate at >20-fold the minimum inhibitory concentration (MIC) if Ag+ and thiols are added in a 1:1 ratio because the reaction of Ag+ with extracellular thiols prevents silver ions from interacting with cells. Extracellular thiols and human serum also significantly reduce the antimicrobial activity of silver wound dressings Aquacel-Ag (Convatec) and Acticoat (Smith & Nephew) to Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli in vitro. These results have important implications for the deployment of silver as an antimicrobial agent in environments exposed to biological tissue or secretions. Significant amounts of money and effort have been directed at the development of silver-coated medical devices (e.g. dressings, catheters, implants). We believe our findings are essential for the effective design and testing of antimicrobial silver coatings.

Energy and pitch-angle dispersions of LLBL/cusp ions seen at middle altitudes: predictions by the open magnetosphere model

Numerical simulations are presented of the ion distribution functions seen by middle-altitude spacecraft in the low-latitude boundary layer (LLBL) and cusp regions when reconnection is, or has recently been, taking place at the equatorial magnetopause. From the evolution of the distribution function with time elapsed since the field line was opened, both the observed energy/observation-time and pitch-angle/energy dispersions are well reproduced. Distribution functions showing a mixture of magnetosheath and magnetospheric ions, often thought to be a signature of the LLBL, are found on newly opened field lines as a natural consequence of the magnetopause effects on the ions and their flight times. In addition, it is shown that the extent of the source region of the magnetosheath ions that are detected by a satellite is a function of the sensitivity of the ion instrument . If the instrument one-count level is high (and/or solar-wind densities are low), the cusp ion precipitation detected comes from a localised region of the mid-latitude magnetopause (around the magnetic cusp), even though the reconnection takes place at the equatorial magnetopause. However, if the instrument sensitivity is high enough, then ions injected from a large segment of the dayside magnetosphere (in the relevant hemisphere) will be detected in the cusp. Ion precipitation classed as LLBL is shown to arise from the low-latitude magnetopause, irrespective of the instrument sensitivity. Adoption of threshold flux definitions has the same effect as instrument sensitivity in artificially restricting the apparent source region.

The characteristics of the magnetopause reconnection X-line deduced from low-altitude satellite observations of cusp ions

We present an analysis of a “quasi-steady” cusp ion dispersion signature observed at low altitudes. We reconstruct the field-parallel part of the Cowley-D ion distribution function, injected into the open LLBL in the vicinity of the reconnection X-line. From this we find the field-parallel magnetosheath flow at the X-line was only 20 ± 60 km s−1, placing the reconnection site close to the flow streamline which is perpendicular to the magnetosheath field. Using interplanetary data and assuming the subsolar magnetopause is in pressure balance, we derive a wealth of information about the X-line, including: the density, flow, magnetic field and Alfvén speed of the magnetosheath; the magnetic shear across the X-line; the de-Hoffman Teller speed with which field lines emerge from the X-line; the magnetospheric field; and the ion transmission factor across the magnetopause. The results indicate that some heating takes place near the X-line as the ions cross the magnetopause, and that sheath densities may be reduced in a plasma depletion layer. We also compute the reconnection rate. Despite its quasi-steady appearance on an ion spectrogram, this cusp is found to reveal a large pulse of enhanced reconnection rate.

A statistical study of large field-aligned flows of thermal ions at high-latitudes

A number of case studies of large, transient, field-aligned ion flows in the topside ionosphere at high-latitudes have been reported, showing that these events occur during periods of frictional heating and/or intense particle precipitation. This study examines the frequency of occurrence of such events for the altitude range 200–500 km, based on 3 years of incoherent scatter data. Correlations of the upgoing ion flux at 400 km with ion and electron temperatures at lower altitudes are presented, together with a discussion of possible mechanisms for the production of such large flows. The influence of low-altitude electron precipitation on the production of these events is also considered.

A new source of suprathermal O+ions near the dayside polar cap boundary

A new dayside source of O+ ions for the polar magnetosphere is described, and a statistical survey presented of upward flows of O+ ions using 2 years of data from the retarding ion mass spectrometer (RIMS) experiment on board DE 1, at geocentric distances below 3 RE and invariant latitudes above 40°. The flows are classified according to their spin angle distributions. It is believed that the spacecraft potential near perigee is generally less than +2 V, in which case the entire O+ population at energies below about 60 eV is sampled. Examples are given of field-aligned flow and of transversely accelerated “core” O+ ions; in the latter events a large fraction of the total O+ ion population has been transversely accelerated, and in some extreme cases all the observed ions (of all ion species) have been accelerated, and no residual cold population is observed (“toroidal” distributions). However, by far the most common type of O+ upflow seen by DE RIMS lies near the dayside polar cap boundary (particularly in the prenoon sector) and displays an asymmetric spin angle distribution. In such events the ions carry an upward heat flux, and strong upflow of all species is present (H+, He+, O+, O++, and N+ have all been observed with energies up to about 30 eV, but with the majority of ions below about 2 eV); hence, these have been termed upwelling ion events. The upwelling ions are embedded in larger regions of classical light ion polar wind and are persistently found under the following conditions: at geocentric distances greater than 1.4 RE; at all Kp in summer, but only at high Kp in winter. Low-energy conical ions (<30 eV) are only found near the equatorial edge of the events, the latitude of which moves equatorward with increasing Kp and is highly correlated with the location of field-aligned currents. The RIMS data are fully consistent with a “mass spectrometer effect,” whereby light ions and the more energetic O+ ions flow into the lobes and mantle and hence the far-tail plasma sheet, but lower-energy O+ is swept across the polar cap by the convection electric field, potentially acting as a source for the nightside auroral acceleration regions. The occurrence probability of upwelling ion events, as compared to those of low-altitude transversely accelerated core ions and of field-aligned flow, suggests this could be the dominant mechanism for supplying the nightside auroral acceleration region, and subsequently the ring current and near-earth plasma sheet, with ionospheric O+ ions. It is shown that the total rate of O+ outflow in upwelling ion events (greater than 10^25 s^{−1}) is sufficient for the region near the dayside polar cap boundary to be an important ionospheric heavy ion source.

Thermospheric Control of the Auroral Source of O+Ions for the Magnetosphere

Linear theory, model ion-density profiles and MSIS neutral thermospheric predictions are used to investigate the stability of the auroral, topside ionosphere to oxygen cyclotron waves: variations of the critical height, above which the plasma is unstable, with field-aligned current, thermal ion density and exospheric temperature are considered. In addition, probabilities are assessed that interactions with neutral atomic gases prevent O+ ions from escaping into the magnetosphere after they have been transversely accelerated by these waves. The two studies are combined to give a rough estimate of the total O+ escape flux as a function of the field-aligned current density for an assumed rise in the perpendicular ion temperature. Charge exchange with neutral oxygen, not hydrogen, is shown to be the principle limitation to the escape of O+ ions, which occurs when the waves are driven unstable down to low altitudes. It is found that the largest observed field-aligned current densities can heat a maximum of about 5×1014 O+ ions m−2 to a threshold above which they are subsequently able to escape into the magnetosphere in the following 500s. Averaged over this period, this would constitute a flux of 1012 m−2 s−1 and in steady-state the peak outflow would then be limited to about 1013 m−2 s−1 by frictional drag on thermal O+ at lower altitudes. Maximum escape is at low plasma density unless the O+ scale height is very large. The outflow decreases with decreasing field-aligned current density and, to a lesser extent, with increasing exospheric temperature. Upward flowing ion events are evaluated as a source of O+ ions for the magnetosphere and as an explanation of the observed solar cycle variation of ring current O+ abundance.

Ionospheric origin of magnetospheric O+ ions

Flows of thermal atomic oxygen (O+) ions are deduced from topside ionospheric plasma density profiles. The mean flux within most of the polar cap is of the order of 10^12 m^{−2} s^{−1}, a figure which is consistent with both theoretical and experimental estimates of the light ion polar wind at greater altitudes. Larger flows (up to 6 × 10^12 m^{−2} s^{−1}) are observed near the poleward edge of the night-side statistical auroral oval, a feature not reproduced in the light ion flux. The implication is one of a low altitude acceleration mechanism, acting upon the O+ ions at these latitudes and at heights above that at which the fluxes are observed. Such a process would enable ions to escape from the ionosphere because they do not exchange charge with neutral hydrogen. The observations are in general agreement with energetic O+ ions as previously observed in various parts of the magnetosphere.

Ions in the atmosphere

In Earth’s atmosphere, an ion is a cluster of molecules carrying an overall charge, known as a molecular cluster ion. Such cluster ions, with dimensions of approximately one nanometre, have usually been referred to as small ions, and their motion in air constitutes a small electric current. Large ions (or Langevin ions), by comparison, are physically larger (tens to hundreds of nm) and consequently electrically less mobile. Usage of the term “ion” to represent these molecular clusters originates from the early history of atmospheric electricity, which spans the discovery of the electron and the elucidation of the structure of matter. The distinction between large and small ions originates from distinguishing ions that could be accelerated by atmospheric electric fields (and therefore directly contribute to the conductivity of air), and those (the large ions) which were insufficiently electrically mobile to contribute to electrical conduction in air.

Determination of Very Slow Diffusion of Paramagnetic Ions by NMR Spectroscopy

In this paper, we propose a new method of measuring the very slow paramagnetic ion diffusion coefficient using a commercial high-resolution spectrometer. If there are distinct paramagnetic ions influencing the hydrogen nuclear magnetic relaxation time differently, their diffusion coefficients can be measured separately. A cylindrical phantom filled with Fricke xylenol gel solution and irradiated with gamma rays was used to validate the method. The Fricke xylenol gel solution was prepared with 270 Bloom porcine gelatin, the phantom was irradiated with gamma rays originated from a (60)Co source and a high-resolution 200 MHz nuclear magnetic resonance (NMR) spectrometer was used to obtain the phantom (1)H profile in the presence of a linear magnetic field gradient. By observing the temporal evolution of the phantom NMR profile, an apparent ferric ion diffusion coefficient of 0.50 mu m(2)/ms due to ferric ions diffusion was obtained. In any medical process where the ionizing radiation is used, the dose planning and the dose delivery are the key elements for the patient safety and success of treatment. These points become even more important in modern conformal radio therapy techniques, such as stereotactic radiosurgery, where the delivered dose in a single session of treatment can be an order of magnitude higher than the regular doses of radiotherapy. Several methods have been proposed to obtain the three-dimensional (3-D) dose distribution. Recently, we proposed an alternative method for the 3-D radiation dose mapping, where the ionizing radiation modifies the local relative concentration of Fe(2+)/Fe(3+) in a phantom containing Fricke gel and this variation is associated to the MR image intensity. The smearing of the intensity gradient is proportional to the diffusion coefficient of the Fe(3+) and Fe(2+) in the phantom. There are several methods for measurement of the ionic diffusion using NMR, however, they are applicable when the diffusion is not very slow.

Influence of heavy rare earth ions substitution on microstructure and magnetism of nanocrystalline magnetite

In this work we report results on the influence of heavy rare earth ions substitution on microstructure and magnetism of nanocrystalline magnetite. A series of Fe(2.85)RE(0.15)O(4) (RE = Gd, Dy, Ho, Tm and Yb) samples have been prepared by high energy ball milling. Structure/microstructure investigations of two selected samples Fe(2.85)Gd(0.15)O(4) and Fe(2.85)Tm(0.15)O(4), represent an extension of the previously published results on Fe(3)O(4)/gamma-Fe(2)O(3), Fe(2.85)Y(0.15)O(4) and Fe(2.55)In(0.45)O(4) [Z. Cvejic, S. Rakic, A. Kremenovic, B. Antic, C. Jovalekic. Ph. Colomban, Sol. State Sciences 8 (2006) 908], while magnetic characterization has been done for all the samples. Crystallite/particle size and strain determined by X-ray diffractometry and Transmission electron microscopy (TEM) confirmed the nanostructured nature of the mechanosynthesized materials. X-ray powder diffraction was used to analyze anisotropic line broadening effects through the Rietveld method. The size anisotropy was found to be small while strain anisotropy was large, indicating nonuniform distribution of deffects in the presence of Gd and Tm in the crystal structure. Superparamagnetic(SPM) behavior at room temperature was observed for all samples studied. The Y-substituted Fe(3)O(4) had the largest He and the lowest M(S). We discuss the changes in magnetic properties in relation to their magnetic anisotropy and microstructure. High field irreversibility (H>20kOe) in ZFC/FC magnetization versus temperature indicates the existence of high magnetocrystalline and/or strain induced anisotropy. (C) 2008 Elsevier B.V. All rights reserved.

Chromium ions phytoaccumulation by three floating aquatic macrophytes from a nutrient medium

In the present work, the trivalent and hexavalent chromium phytoaccumulation by three living free floating aquatic macrophytes Salvinia auriculata, Pistia stratiotes, and Eicchornia crassipes was investigated in greenhouse. These plants were grown in hydroponic solutions supplied with non-toxic Cr3+ and Cr6+ chromium concentrations, performing six collections of nutrient media and plants in time from a batch system. The total chromium concentrations into Cr-doped hydroponic media and dry roots and aerial parts were assayed, by using the Synchrotron radiation X-ray fluorescence technique. The aquatic plant-based chromium removal data were described by using a nonstructural kinetic model, obtaining different bioaccumulation rate, ranging from 0.015 to 0.837 1 mg(-1) d(-1). The Cr3+ removal efficiency was about 90%, 50%, and 90% for the E. crassipes, P. stratiotes, and S. auriculata, respectively; while it was rather different for Cr6+ one, with values about 50%, 70%, and 90% for the E. crassipes, P. stratiotes, and S. auriculata.

Investigation of AISI 1040 steel corrosion H(2)S solution containing chloride ions by digital image processing coupled with in electrochemical techniques

This paper presents a study of AISI 1040 steel corrosion in aqueous electrolyte of acetic acid buffer containing 3.1 and 31 x 10(-3) mol dm(-3) of Na(2)S in both the presence and absence of 3.5 wt.% NaCl. This investigation of steel corrosion was carried out using potential polarization, and open-circuit and in situ optical microscopy. The morphological analysis and classification of types of surface corrosion damage by digital image processing reveals grain boundary corrosion and shows a non-uniform sulfide film growth, which occurs preferentially over pearlitic grains through successive formation and dissolution of the film. (C) 2011 Elsevier Ltd. All rights reserved.