Proton transfer and esterification reactions in EMIMOAc-based acidic ionic liquids

Acetate-based ionic liquids (such as 1-ethyl-3-methylimidazolium acetate, EMIMOAc) have potential applications for CO2 absorption and electrochemical reduction, chemical separations and extractions, and Fischer esterification of alcohols, amines, and starch. Both strong and weak organic acids can be dissolved in EMIMOAc and yield interesting proton-rich acidic ionic liquid solutions. We have used GCMS vapor pressure measurements, spectroscopic methods, calorimetry, and viscosity/conductivity measurements to investigate the properties and reactions of various acids dissolved in EMIMOAc. Unique proton transfer and esterification reactions are observed in many of these acidic solutions with carboxylic acids or sulfonic acids as solutes. Some acids react with the acetate anion to produce acetic acid, which provides a measure of acid strength in ionic liquid solvents. In addition, we observed an esterification reaction that might involve the imidazolium cation and the acetate anion to yield methyl acetate

Half-life and spin of 60Mn^g

A value of 0.28 +/- 0.02 s has been deduced for the half-life of the ground state of 60Mn, in sharp contrast to the previously adopted value of 51 +/- 6 s. Access to the low-spin 60Mn ground state was accomplished via beta decay of the 0+ 60Cr parent nuclide. New, low-energy states in 60Mn have been identified from beta-delayed gamma-ray spectroscopy. The new, shorter half-life of 60Mn^g is not suggestive of isospin forbidden beta decay, and new spin and parity assignments of 1+ and 4+ have been adopted for the ground and isomeric beta-decaying states, respectively, of 60Mn.Comment: 13 pages, 5 figures, Accepted for publication in Phys. Rev.

Probing shell structure and shape changes in neutron-rich sulfur isotopes through transient-field g factor measurements on fast radioactive beams of 38S and 40S

The shell structure underlying shape changes in neutron-rich nuclei near N=28 has been investigated by a novel application of the transient field technique to measure the first-excited state g factors in 38S and 40S produced as fast radioactive beams. There is a fine balance between proton and neutron contributions to the magnetic moments in both nuclei. The g factor of deformed 40S does not resemble that of a conventional collective nucleus because spin contributions are more important than usual.Comment: 10 pages, 6 figures, accepted in PR

An evaluation of the epidemiology of medication discrepancies and clinical significance of medicines reconciliation in children admitted to hospital.

To determine the incidence of unintended medication discrepancies in paediatric patients at the time of hospital admission; evaluate the process of medicines reconciliation; assess the benefit of medicines reconciliation in preventing clinical harm

Shell structure underlying the evolution of quadrupole collectivity in S-38 and S-40 probed by transient-field g-factor measurements on fast radioactive beams

The shell structure underlying shape changes in neutron-rich nuclei between N=20 and N=28 has been investigated by a novel application of the transient field technique to measure the first-excited state g factors in S-38 and S-40 produced as fast radioactive beams. Details of the new methodology are presented. In both S-38 and S-40 there is a fine balance between the proton and neutron contributions to the magnetic moments. Shell model calculations which describe the level schemes and quadrupole properties of these nuclei also give a satisfactory explanation of the g factors. In S-38 the g factor is extremely sensitive to the occupation of the neutron p3/2 orbit above the N=28 shell gap as occupation of this orbit strongly affects the proton configuration. The g factor of deformed S-40 does not resemble that of a conventional collective nucleus because spin contributions are more important than usual.Comment: 10 pages, 36 figures, accepted for publication in Physical Review

Particle Number and Size Distributions (PNSD) from a Hybrid Electric Vehicle (HEV) over Laboratory and Real Driving Emission Tests

Particle number (PN) emissions from hybrid electric vehicles (HEV) during engine ignition and re-ignition events are an important but scarcely reported area. The objectives of the present work are to study the effects of drive cycle properties on the engine behaviour of a hybrid electric vehicle (HEV) and to investigate how this impacts the tailpipe PN emissions and their size distributions (PNSD). Worldwide harmonised light vehicles test cycle (WLTC) testing was conducted, as well as chassis dynamometer emission measurements over a realistic real driving emissions (RDE) speed pattern, using a Euro 5 Toyota Prius HEV with a Cambustion DMS500 sampling PN concentrations at the tailpipe. It is shown that the number of vehicle stops during a test cycle has a direct impact on the re-ignition activity for the HEV. 64 ± 3% of the total PN from WLTC testing was produced during engine re-ignition events while only 6 ± 1% was from stabilised engine operation. Similar proportions were observed for the RDE-style test cycle. The majority of engine reignition and destabilised activity, and hence PN emission, was during the low-speed sections of the drive cycles used. The average PNSD across cycle phases was different between cycles, due to the influence of dynamic properties on engine behaviour and hence the PN emission profile. The PNSD at the engine re-ignition and destabilised events had a merged wide peak with a maximum at 60 nm diameter and a shoulder at 12 nm diameter. The HEV had increased emissions of particles smaller than 23 nm under cold start, but similar overall PN emission values, compared to a warm start. The results of this work highlight the importance of controlling HEV PN emissions to limit human exposure to PN in urban environments where the majority of PN emissions occur. The sensitivity of HEV PN emission factors and PNSD to engine behaviour and, in turn, test cycle dynamic properties, is important to note when considering legislative test cycles, particularly with reference to the freedoms afforded by the RDE test cycle. The results also indicate that substantial improvements to air quality could be made by reducing the particle measurement protocol PN cut-off size to 10 nm

Proton Drip-Line Calculations and the Rp-process

One-proton and two-proton separation energies are calculated for proton-rich nuclei in the region $A=41-75$. The method is based on Skyrme Hartree-Fock calculations of Coulomb displacement energies of mirror nuclei in combination with the experimental masses of the neutron-rich nuclei. The implications for the proton drip line and the astrophysical rp-process are discussed. This is done within the framework of a detailed analysis of the sensitivity of rp process calculations in type I X-ray burst models on nuclear masses. We find that the remaining mass uncertainties, in particular for some nuclei with $N=Z$, still lead to large uncertainties in calculations of X-ray burst light curves. Further experimental or theoretical improvements of nuclear mass data are necessary before observed X-ray burst light curves can be used to obtain quantitative constraints on ignition conditions and neutron star properties. We identify a list of nuclei for which improved mass data would be most important.Comment: 20 pages, 9 figures, 2 table

Equivalence of switching linear systems by bisimulation

A general notion of hybrid bisimulation is proposed for the class of switching linear systems. Connections between the notions of bisimulation-based equivalence, state-space equivalence, algebraic and input–output equivalence are investigated. An algebraic characterization of hybrid bisimulation and an algorithmic procedure converging in a finite number of steps to the maximal hybrid bisimulation are derived. Hybrid state space reduction is performed by hybrid bisimulation between the hybrid system and itself. By specializing the results obtained on bisimulation, also characterizations of simulation and abstraction are derived. Connections between observability, bisimulation-based reduction and simulation-based abstraction are studied.\ud \u

Ancient bears provide insights into Pleistocene ice age refugia in Southeast Alaska

During the Late Pleistocene, major parts of North America were periodically covered by ice sheets. However, there are still questions about whether ice-free refugia were present in the Alexander Archipelago along the Southeast (SE) Alaska coast during the last glacial maximum (LGM). Numerous subfossils have been recovered from caves in SE Alaska, including American black (Ursus americanus) and brown (U. arctos) bears, which today are found in the Alexander Archipelago but are genetically distinct from mainland bear populations. Hence, these bear species offer an ideal system to investigate long-term occupation, potential refugial survival and lineage turnover. Here, we present genetic analyses based on 99 new complete mitochondrial genomes from ancient and modern brown and black bears spanning the last ~45,000 years. Black bears form two SE Alaskan subclades, one preglacial and another postglacial, that diverged \u3e100,000 years ago. All postglacial ancient brown bears are closely related to modern brown bears in the archipelago, while a single preglacial brown bear is found in a distantly related clade. A hiatus in the bear subfossil record around the LGM and the deep split of their pre-and postglacial subclades fail to support a hypothesis of continuous occupancy in SE Alaska throughout the LGM for either species. Our results are consistent with an absence of refugia along the SE Alaska coast, but indicate that vegetation quickly expanded after deglaciation, allowing bears to recolonize the area after a short-lived LGM peak