Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

Shear-induced lamellar ionic liquid-crystal foam

n a recent paper we reported an experimental study of two N-alkylimidazolium salts. These ionic compounds exhibit liquid crystalline behaviour with melting points above 50 degrees C in bulk. However, if they are sheared, a (possibly non-equilibrium) lamellar phase forms at room temperature. Upon shearing a thin film of the material between microscope slides, textures were observed that are strikingly similar to liquid (wet) foams. The images obtained from polarising optical microscopy (POM) were found to share many of the known quantitative properties of a two-dimensional foam coarsening process. Here we report an experimental study of this foam using a shearing system coupled with POM. The structure and evolution of the foam are investigated through the image analysis of time sequences of micrographs obtained for well-controlled sets of physical parameters (sample thickness, shear rate and temperature). In particular, we find that there is a threshold shear rate below which no foam can form. Above this threshold, a steady-state foam pattern is obtained where the mean cell area generally decreases with increasing shear rate. Furthermore, the steady-state internal cell angles and distribution of the cell number of sides deviate from their equilibrium (i.e. zero-shear) values.

Effective teaching and optimal experiences: possible link

ISME, Thessaloniki, 2012

Effective isotropic potential for dipolar hard spheres

A new effective isotropic potential is proposed for the dipolar hard-sphere fluid, on the basis of recent results by others for its angle-averaged radial distribution function. The new effective potential is shown to exhibit oscillations even for moderately high densities and moderately strong dipole moments, which are absent from earlier effective isotropic potentials. The validity and significance of this result are briefly discussed.

10 kVp rule – An anthropomorphic pelvis phantom imaging study using a CR system: impact on image quality and effective dose using AEC and manual mode

Purpose - This study aims to investigate the influence of tube potential (kVp) variation in relation to perceptual image quality and effective dose (E) for pelvis using automatic exposure control (AEC) and non-AEC in a Computed Radiography (CR) system. Methods and materials - To determine the effects of using AEC and non-AEC by applying the 10 kVp rule in two experiments using an anthropomorphic pelvis phantom. Images were acquired using 10 kVp increments (60–120 kVp) for both experiments. The first experiment, based on seven AEC combinations, produced 49 images. The mean mAs from each kVp increment were used as a baseline for the second experiment producing 35 images. A total of 84 images were produced and a panel of 5 experienced observers participated for the image scoring using the two alternative forced choice (2AFC) visual grading software. PCXMC software was used to estimate E. Results - A decrease in perceptual image quality as the kVp increases was observed both in non-AEC and AEC experiments, however no significant statistical differences (p > 0.05) were found. Image quality scores from all observers at 10 kVp increments for all mAs values using non-AEC mode demonstrates a better score up to 90 kVp. E results show a statistically significant decrease (p = 0.000) on the 75th quartile from 0.37 mSv at 60 kVp to 0.13 mSv at 120 kVp when applying the 10 kVp rule in non-AEC mode. Conclusion - Using the 10 kVp rule, no significant reduction in perceptual image quality is observed when increasing kVp whilst a marked and significant E reduction is observed.

Shear-induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.

How foam-like is the shear-induced lamellar phase of an ionic liquid crystal?

Philosophical Magazine Letters Volume 88, Issue 9-10, 2008 Special Issue: Solid and Liquid Foams. In commemoration of Manuel Amaral Fortes

10 kVp rule – An anthropomorphic pelvis phantom imaging study using a CR system: impact on image quality and effective dose using AEC and manual mode

Background - Pelvis and hip radiography are consistently found to be amongst the highest contributors to the collective effective dose (E) in all ten DOSE DATAMED countries in Europe, representing 2.8 to 9.4% of total collective dose (S) in the TOP 20 exams list. The level of image quality should provide all the diagnostic information in order not to jeopardise the diagnosis, but being able to provide the needed clinical information with the minimum dose. A recent study suggests further research to determine whether the “10 kVp rule” would have value for a range of examinations using Computed Radiography (CR) systems. As a “rule of thumb” increasing the kVp by 10 whilst halving the mAs is suggested to give a similar perceptual image quality when compared to the original exposure factors. Aims - In light of the 10kVp rule, this study aims to investigate the influence of tube potential (kVp) variation in relation to perceptual image quality and E for pelvis imaging using automatic exposure control (AEC) and non-AEC in a Computed Radiography (CR) system. Research questions - Does the 10kVp rule works for the pelvis in relation to image quality in a CR system? Does the image quality differs when the AEC is used instead of manual mode using the 10kVp rule and how this impacts on E?

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

The solvation and redox behaviour of mixed ligand COPPER(II) complexes of acetylacetonate and aromatic dimines in ionic liquids

The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.

A balance between image quality and effective dose in orbital X-ray screening for ferromagnetic IOFBs: a pilot study

Purpose: To investigate whether standard X-ray acquisition factors for orbital radiographs are suitable for the detection of ferromagnetic intra-ocular foreign bodies in patients undergoing MRI. Method: 35 observers, at varied levels of education in radiography, attending a European Dose Optimisation EURASMUS Summer School were asked to score 24 images of varying acquisition factors against a clinical standard (reference image) using two alternative forced choice. The observers were provided with 12 questions and a 5 point Likert scale. Statistical tests were used to validate the scale, and scale reliability was also measured. The images which scored equal to, or better than, the reference image (36) were ranked alongside their corresponding effective dose (E), the image with the lowest dose equal to or better than the reference is considered the new optimum acquisition factors. Results: Four images emerged as equal to, or better than, the reference in terms of image quality. The images were then ranked in order of E. Only one image that scored the same as the reference had a lower dose. The reference image had a mean E of 3.31μSv, the image that scored the same had an E of 1.8μSv. Conclusion: Against the current clinical standard exposure factors of 70kVp, 20mAs and the use of an anti- scatter grid, one image proved to have a lower E whilst maintaining the same level of image quality and lesion visibility. It is suggested that the new exposure factors should be 60kVp, 20mAs and still include the use of an anti-scatter grid.

A narrative review on the reduction of effective dose to a paediatric patient by using different combinations of kVp, mAs and additional filtration whilst maintaining image quality

This paper reviews the literature for lowering of dose to paediatric patients through use of exposure factors and additional filtration. Dose reference levels set by The International Commission on Radiological Protection (ICRP) will be considered. Guidance was put in place in 1996 requires updating to come into line with modern imaging equipment. There is a wide range of literature that specifies that grids should not be used on paediatric patients. Although much of the literature advocates additional filtration, contrasting views on the relative benefits of using aluminium or copper filtration, and their effects on dose reduction and image quality can vary. Changing kVp and mAs has an effect on the dose to the patient and image quality. Collimation protects adjacent structures whilst reducing scattered radiation.

Reducing effective dose to a paediatric phantom by using different combinations of kVp, mAs and additional filtration whilst maintaining image quality

Purpose: To determine whether using different combinations of kVp and mAs with additional filtration can reduce the effective dose to a paediatric phantom whilst maintaining diagnostic image quality. Methods: 27 images of a paediatric AP pelvis phantom were acquired with different kVp, mAs and additional copper filtration. Images were displayed on quality controlled monitors with dimmed lighting. Ten diagnostic radiographers (5 students and 5 experienced radiographers) had eye tests to assess visual acuity before rating the images. Each image was rated for visual image quality against a reference image using 2 alternative forced choice software using a 5-point Likert scale. Physical measures (SNR and CNR) were also taken to assess image quality. Results: Of the 27 images rated, 13 of them were of acceptable image quality and had a dose lower than the image with standard acquisition parameters. Two were produced without filtration, 6 with 0.1mm and 5 with 0.2mm copper filtration. Statistical analysis found that the inter-rater and intra-rater reliability was high. Discussion: It is possible to obtain an image of acceptable image quality with a dose that is lower than published guidelines. There are some areas of the study that could be improved. These include using a wider range of kVp and mAs to give an exact set of parameters to use. Conclusion: Additional filtration has been identified as amajor tool for reducing effective dose whilst maintaining acceptable image quality in a 5 year old phantom.

Preventable exposure in routine chest CT examinations: evaluation of effective dose beyond prescribed anatomical landmarks

Objective - Evaluate preventable exposure dose in routine chest CT examinations beyond prescribed anatomical landmarks and estimate extra dose delivered to the patient. Background/rationale - Recent technical advances have greatly increased the clinical applications of CT; developments in multidetector-row CT (MDCT) technology have occurred; the major disadvantage with the increased use of MDCT is associated radiation exposure.

10 kVp rule - An anthropomorphic pelvis phantom imaging study using a CR system: impact on image quality and effective dose using AEC and manual mode

Purpose: This study aims to investigate the influence of tube potential (kVp) variation in relation to perceptual image quality and effective dose for pelvis using automatic exposure control (AEC) and non-AEC in a computed radiography (CR) system. Methods and Materials: To determine the effects of using AEC and non-AEC by applying the 10 kVp rule in two experiments using an anthropomorphic pelvis phantom. Images were acquired using 10 kVp increments (60-120 kVp) for both experiments. The first experiment, based on seven AEC combinations, produced 49 images. The mean mAs from each kVp increment were used as a baseline for the second experiment producing 35 images. A total of 84 images were produced and a panel of 5 experienced observers participated for the image scoring using the 2 AFC visual grading software. PCXMC software was used to estimate the effective dose. Results: A decrease in perceptual image quality as the kVp increases was observed both in non-AEC and AEC experiments, however no significant statistical differences (p> 0.05) were found. Image quality scores from all observers at 10 kVp increments for all mAs values using non-AEC mode demonstrates a better score up to 90 kVp. Effective dose results show a statistical significant decrease (p=0.000) on the 75th quartile from 0.3 mSv at 60 kVp to 0.1 mSv at 120 kVp when applying the 10 kVp rule in non-AEC mode. Conclusion: No significant reduction in perceptual image quality is observed when increasing kVp whilst a marked and significant effective dose reduction is observed.