Solvay (Canada)

In this study the performance of the lithium (Li) anode is characterized in two alternative ionic liquid electrolytes: (i) a solution of 0.5 mol·kg-1of lithium bis- (fluorosulfonyl)imide (LiFSI) in trimethyl(isobutyl)- phosphonium FSI (P111i4FSI) and (ii) an equimolar mixture of these two salts, effectively an inorganic-organic mixture IL. We have investigated the formation of the solid electrolyte interphase (SEI) at the lithium electrode and its influence on the polarization potential, the electrode surface impedance and deposition morphologies. Lithium metal cycling is revealed to be significantly more stable in the electrolyte with high lithium salt concentration due to the creation of a more uniform SEI. Stable and effective cycling was demonstrated at high applied currents (up to 12 mA·cm-2) with large areal capacities being transferred with each polarization cycle (up to 6 mAh·cm-2at 50 °C). An average Coulombic efficiency of not less than 99.2% was demonstrated under these conditions and SEM observations of the cycled electrode surfaces show a uniform and compact deposit. Combined with spectroscopic characterization of the electrolyte and electrode surface, these observations indicate a role for the speciation and transport properties of these high concentration ionic liquid electrolytes in modifiying the physicochemical properties of the SEI which result in enhanced cycling performance of the Li metal electrode.

The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm–2, 3 mA h·cm–2, 50 °C). The main components detected by MAS NMR and XPS after several hundreds of cycles are LiF and breakdown products from the bis(fluorosulfonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol·kg–1 of Li salt in IL) and the highly concentrated (3.8 mol·kg–1 of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced tendency for dendrite formation.

BACKGROUND: Although the diagnosis of gastroesophageal reflux disease (GERD) is based primarily on symptoms experienced by a patient, relatively little attention has been paid to the development and validation of self-administered questionnaires specific to GERD symptoms. The present article presents the validation of the short, self-administered GERD Symptom Frequency Questionnaire (GSFQ). METHODS: Patients with GERD participating in a randomized clinical trial comparing pantoprazole and nizatidine were asked to complete the GSFQ together with validated instruments for measurement of health-related quality of life (Medical Outcome Study Short Form 12) and gastrointestinal symptoms (Gastrointestinal Symptom Rating Scale). Completion of the GSFQ, Medical Outcome Study Short Form 12 and Gastrointestinal Symptom Rating Scale took place upon entry into the trial (baseline) and during the trial (days 7 and 28). Endoscopy was performed at baseline and after 28 days. Cronbach alpha was used to assess the internal consistency of the questionnaire. The test-retest reliability of the GSFQ was examined by the intraclass correlation coefficient among the 36 patients with stable GERD symptoms between day 7 and day 28. Construct validity was assessed by comparing the GSFQ with previously validated instruments. Known group validity was determined by comparing GSFQ scores across groups of patients known to differ clinically. Responsiveness to change was assessed by the Guyatt's statistic. RESULTS: Two hundred twenty-one patients formed the study baseline group. The analysis demonstrated that the GSFQ questionnaire had excellent psychometric properties shown by the high internal consistency (Cronbach alpha 0.84); that the test-retest reliability was satisfactory (intraclass correlation coefficient 0.64); that there was good evidence that the GSFQ indeed measured what it was intended to measure (validity); and that the GSFQ was highly responsive to change (Guyatt's statistic 1.48). DISCUSSION: The GSFQ is a short, self-administered, easy to use, GERD-specific questionnaire which should be considered as a useful assessment tool in the evaluation of patients with GERD and in the assessment of treatment outcomes.

In this work, three ionic liquids with two different cations and two different anions: trimethyl propyl phosphonium bis-fluorosulfonyl imide (P1113FSI), trimethyl isobutyl phosphonium bis-fluorosulfonyl imide (P111i4FSI) and trimethyl isobutyl phosphonium bis-trifluoromethylsulfonyl imide (P111i4TFSI) have been characterized and evaluated as electrolytes in lithium ion half-cells. It is found that ionic liquids with FSI− anion have superior properties over their TFSI− counterparts and those with the smaller cation, P1113, have better conductivity and viscosity. The two ionic liquids with FSI anion, P1113FSI and P111i4FSI, are liquid at room temperature and show high conductivities and low viscosities, reaching 10.0 mS/cm and 30 cP at room temperature for P1113FSI. They also exhibit electrochemical windows higher than 5 V and thermal stability exceeding 300°C. Mixing the ionic liquids with 0.5 M LiPF6 increases viscosities, lowers conductivities but improves electrochemical cathodic stability. The electrolyte mixtures have been evaluated in graphite/Li half cells, Li/LiFePO4 and Li/LiMn1.5Ni0.5O4 at C/12 for 100 cycles and at different rates: C/6, C/3, C and 2C for rate capabilities. Battery testing shows that unlike their TFSI− counterparts both ionic liquids with FSI− anion perform well with graphite anode and LiFePO4 cathode but fail with the higher voltage LiMn1.5Ni0.5O4 cathode.

The mode of action of iron(III) uptake from sulfate solutions by the commercial extractant CYANEX®272, bis(2,4,4-trimethylpentyl)phosphinic acid, has been studied using conventional solvent extraction methods, together with 31P{1 H} NMR spectroscopy, electrospray ionisation mass spectrometry, and DFT calculations that have not previously been used to analyse the content of the ISOPAR M water-immiscible phase. The maximum Fe-loading recorded was 177% of the theoretical maximum, based on the formation of an Fe(III) complex [Fe(L)3] with a 1:3 molar ratio of Fe to phosphinate (L). Inductively coupled plasma optical emission spectroscopy (ICP-OES) indicates that sulfate or hydrogen sulfate ions are co-extracted in a 1:2 molar ratio with iron across the whole of the Fe-loading range, which helps to account for the loadings being greater than 100% of the theoretical value. 31P{1 H} NMR spectroscopy indicates that the limiting factor in Fe-loading is the availability of uncomplexed CYANEX®272 (sulfate is present in large excess). In contrast to the behaviour of Co(II) and Zn(II) extraction by CYANEX®272, there is no evidence for the formation of polymeric Fe(III) complexes and highly viscous solutions at high metal loadings. The identity of the extracted species is likely to be a polynuclear Fe(III) sulfate complex.

A combination of mass spectrometry, DFT calculations and 31 P{ 1 H} NMR spectroscopy has been used to define the mode of action of the commercial cobalt extractant, bis(2,4,4‐trimethylpentyl)phosphinic acid (CYANEX®272, L 1 H) in Co recovery. The nature of the Co II complexes formed in the water‐immiscible phase is determined largely by the propensity of phosphinates to form strong interligand H‐bonds in the outer coordination sphere and also to form stable µ 2 ‐Co–O–P–O–Co bridges. At low Co loading levels, the predominant species is the 4:1 complex, [Co( L 1 ·L 1 H) 2 ], in which coordinated neutral phosphinic acid ligands form strong H‐bonds to adjacent anionic phosphinates. At higher Co loading, oligomers such as [( L 1 ·L 1 H)Co( L 1 2 Co) n ( L 1 ·L 1 H)] are formed with µ 2 ‐phosphinate bridging, resulting in a substantial increase in the viscosity of the water‐immiscible phase. The presence of tris(2,4,4‐trimethylpentyl)phosphine oxide ( L 2 ) in the commercial formulation reduces the viscosity because its incorporation into oligomeric complexes such as [( L 2 )Co{ L 1 3 Co L 1 Co L 1 3 Co} m L 1 ] can terminate chains, resulting in a lower average molecular weight. The uptake of Zn by L 1 H shows a very similar dependence of viscosity on loading, and DOSY spectra and mass spectrometry demonstrate that higher molecular weight species are present at high Zn loading.

BACKGROUND: Upper gastrointestinal symptoms attributable to gastroesophageal reflux disease or peptic ulcer are common, but the outcome of proton pump inhibitor therapy in clinical practice is not well documented. AIM: To assess the range of upper gastrointestinal acid-related symptoms in clinical practice and the rapidity of their response to pantoprazole (40 mg daily), after seven days of therapy. METHODS: A total of 726 Canadian physicians (65.3% family physicians) recorded a working diagnosis and alarm features in eligible patients, who then recorded the severity of eight upper gastrointestinal symptoms in a daily symptom diary during the first week of therapy. RESULTS: Complete data were obtained from 2273 (37.3% male) of 3261 patients; physicians diagnosed reflux esophagitis alone (66.9%), peptic ulcer (9.7%), other upper gastrointestinal disorders (12.3%) and reflux esophagitis with another diagnosis (11.1%). Alarm features were common (29.6%), but a history of gastrointestinal blood loss was rare (less than 1%). Mean daytime heartburn scores decreased from 2.59 to 1.40, and epigastric pain scores decreased from 2.54 to 1.56 over the first week (P<0.00001); the proportions of patients who became symptom-free were 68.1% and 55.4%, respectively. Decreased mean symptom scores were also observed for acid regurgitation (2.21 to 1.35), bloating (2.47 to 1.57), nausea (2.03 to 1.36), slow digestion (2.51 to 1.56) and burping (2.56 to 1.69). The percentage of patients with severe or very severe symptoms decreased from 53.5% to 13.8% at day 7. The physician's initial diagnosis was not predictive of outcome. CONCLUSIONS: In a predominantly primary care population with upper gastrointestinal acid-related symptoms, proton pump inhibitor therapy produces prompt symptomatic relief in most patients. Potential alarm symptoms are common, and further research is required to determine the absolute risk of alarm symptoms and their implications for empirical therapy.

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ECO2FUME® (2% phosphine, 98% CO2 by weight) and VAPORPH3OS® (99.3% phosphine average by weight) are cylinderized gas formulations of phosphine that have achieved significant growth in commercial applications for the disinfestation of food and non-food commodities in the last two decades. The expansion in the global application of these two cylinderized phosphine fumigants is driven by increasing concern for safety, efficacy, unreacted powdered residue and disposal associated with aluminium phosphide tablets, which are promoted as alternatives to methyl bromide, and the concern of insect resistance to phosphine in both developed and developing countries. This paper describes recent developments in the global application of ECO2FUME® and VAPORPH3OS® in terms of commercial in-transit fumigation of grains and logs in ships, fumigation of export distiller’s dried grain with solubles (DDGS) in containers and shiphold, best practices in the management of phosphine resistance of insects in grains, and establishment and application of quarantine and preshipment (QPS) phosphine fumigation protocols for selected fresh fruits, vegetables, dried fruits and cut flowers as an alternative to methyl bromide. The growing issue of powdered residue from unspent aluminium phosphine tablets and the use of cylinderized phosphine as an effective solution are discussed.