Extraction of Scandium (III) from acidic solutions using organo-phosphoric acid reagents: A comparative study

Comparative and synergistic solvent extraction of Sc(III) using two phosphoric acidic reagents such as di-(2-ethyhexyl) phosphoric acid and 2,4,4,tri-methyl,pentyl-phosphinic acid was investigated. Slope analysis method suggests a cation exchange reaction of Sc(III) with both extractants at a molar ratio of extractant: Sc(III) = 2.5:1 at equilibrium pH< 1.5. The plot of log D vs. log [Extractant] yield the slope (n) value as low as 1.2-1.3 and as high as n=7 at low and high extrcatant concentration level, respectively. Extraction isotherm study predicted the need of 2 stages at A: O=1:4 and A: O=1:3 using 0.1 M D2EHPA and 0.1 M Cyanex 272, respectively. Stripping of Sc (III) was carried out at varied NaOH concentration to ascertain the optimum stripping condition for effective enrichment of metal. The predicted stripping condition (2)-stages with A: O=1:3 and 1:4 for D2EHPA and Cyanex 272, respectively) obtained from Mc-Cabe Thiele plot was further validated by 6-cycles CCS study. An actual leach solution of Mg-Sc alloy bearing 1.0 g/L of Sc (III), 2.5 g/L of Mg and 0.2 M HCl was subjected for selective separation of Sc at the optimum condition. The counter current simulation (CCS) study for both extraction and stripping of actual solution resulted quantitative separation of Sc with ∼12 fold enrichment. The organic phase before and after loading of Sc (III) along with the diluents was characterized by FTIR to ascertain the phase transportation of Sc (III)

Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues

Measurements of the proton NMR paramagnetic relaxation rates for several series of isostructural lanthanide(III) complexes have been performed in aqueous solution over the field range 1.0 to 16.5 Tesla. The field dependence has been modeled using Bloch–Redfield–Wangsness theory, allowing values for the electronic relaxation time, Tle and the magnetic susceptibility, μeff, to be estimated. Anomalous relaxation rate profiles were obtained, notably for erbium and thulium complexes of low symmetry 8-coordinate aza-phosphinate complexes. Such behaviour challenges accepted theory and can be interpreted in terms of changes in Tle values that are a function of the transient ligand field induced by solvent collision and vary considerably between Ln3+ ions, along with magnetic susceptibilities that deviate significantly from free-ion values

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

A kinetic study on hydrochloric acid leaching of nickel from Ni–Al2O3 spent catalyst

Hydrochloric acid leaching of nickel from spent Ni-Al2O3 catalyst (12.7% Ni, 39.2% Al and 0.68% Fe) has been investigated at a range of conditions by varying particle size (50-180μm), acid concentration (0.025-2M), pulp density (0.2-0.4%, w/v) and temperature (293-353K). Nickel was selectively leached from the catalyst, irrespective of the different conditions. Under the most suitable conditions (1M HCl, 323K, stirring at 500rpm, 50-71μm particle size), the extent of leaching of Ni and Al after 2h was 99.9% and 1%, respectively. The XRD pattern of the spent catalyst corresponded to crystalline α-Al2O3 along with elemental Ni. The peak due to elemental Ni was absent in the residue sample produced at the optimum leaching conditions, confirming the complete dissolution of Ni from the spent catalyst. The leaching results were well fitted with the shrinking core model with apparent activation energy of 17kJ/mol in the temperature range of 293-353K indicating a diffusion controlled reaction

Narrow-range optical pH sensors based on luminescent europium and terbium complexes immobilized in a sol gel glass

The metal-based emission of a series of luminescent europium and terbium complexes incorporating an aromatic chromophore is rendered pH-dependent either through perturbation of the aryl singlet or triplet energy or by modulating the degree of quenching of the lanthanide excited state. Systems exhibiting each of these pathways have been incorporated in thin-film sot gel matrixes and evaluated as pH sensors in static and flow analyses at constant ionic strength. pH-dependent intensity or ratiometric methods, for emission or excitation spectra, have been defined for lanthanide complexes incorporating substituted phenanthridine (pK(a)* from ca. 6.8 to 7.2) or 6- cyanophenanthridine-2-sulfonyl chromophores (pK(a) similar to 7.14 in human serum solution) (lambda (exc) 365 nm, phiH(2)O = 7.2%)

Critical analysis of the limitations of Bleaney's theory of magnetic anisotropy in paramagnetic lanthanide coordination complexes

The origins of the breakdown of Bleaney's theory of magnetic anisotropy are described, based on an analysis of eleven different complexes of the second half of the 4f elements that form isostructural series. An examination of the chemical shift and relaxation rate behaviour of resonances located at least four bonds away from the paramagnetic centre was undertaken, and correlated to theoretical predictions. The key limitations relate to comparability of ligand field splitting with spin–orbit coupling, variation in the position of the principal magnetic axis between Ln complexes and the importance of multipolar terms in describing lanthanide ligand field interactions

A New Paramagnetically Shifted Imaging Probe for MRI

Purpose: To develop and characterize a new paramagnetic contrast agent for molecular imaging by MRI. Methods: A contrast agent was developed for direct MRI detection through the paramagnetically shifted proton magnetic resonances of two chemically equivalent tert-butyl reporter groups within a dysprosium(III) complex. The complex was characterized in phantoms and imaged in physiologically intact mice at 7 Tesla (T) using three-dimensional (3D) gradient echo and spectroscopic imaging (MRSI) sequences to measure spatial distribution and signal frequency. Results: The reporter protons reside ∼6.5 Å from the paramagnetic center, resulting in fast T1 relaxation (T1 = 8 ms) and a large paramagnetic frequency shift exceeding 60 ppm. Fast relaxation allowed short scan repetition times with high excitation flip angle, resulting in high sensitivity. The large dipolar shift allowed direct frequency selective excitation and acquisition of the dysprosium(III) complex, independent of the tissue water signal. The biokinetics of the complex were followed in vivo with a temporal resolution of 62 s following a single, low-dose intravenous injection. The lower concentration limit for detection was ∼23 μM. Through MRSI, the temperature dependence of the paramagnetic shift (0.28 ppm.K−1) was exploited to examine tissue temperature variation. Conclusions: These data demonstrate a new MRI agent with the potential for physiological monitoring by MRI. Magn Reson Med 77:1307–1317, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited