Ion Pairing in Aqueous Metal Sulfates and Platinum Group Metal Ammonium Solutions

The structure and dynamics of ions and ion pairs in solution play an integral part in several biological and chemical processes. Historically the calculation of ion pair association constants from computer simulations has been complicated due to the difficulty in validating metal ion force fields for solution simulations. In this thesis a force field for divalent metal ions in metal sulfate solutions (i.e. Mg2+SO4 2-, Ca2+SO4 2-, Mn2+SO4 2-, Fe2+SO4 2-, Co2+SO4 2-, Ni2+SO4 2-, Cu2+SO4 2- and Zn2+SO4 2-) important in physical and biophysical experiments is produced. Potential of mean force calculations are used to provide ion pair free energy profiles and free energy perturbation calculations are used to calibrate the potential of mean force (PMF) from which association constants for ion pairs can be produced for these metal sulfate solutions. The calibrated free energy profiles result in calculated association constants that are in excellent agreement with available experimental data where available. Consequently the force field has been shown to be accurate for simulations of biophysical and physical systems. Furthermore the method, proposed in this thesis, for calibrating PMFs and calculating detailed association constants from those curves can most likely be used for complex systems that have previously been computationally inaccessible. Next a detailed account of solvation structures and the nature of ion pair formation mechanisms for important metal sulfates in aqueous media are presented. Radial and spatial distribution functions calculated for several ion pair species reveal that the transition from free ions to contact ion pairs involves the loss of between one to two water molecules from the cation depending on the cation size. This is correlated with the experimental hydration numbers calculated for metal sulfate electrolyte solutions at several concentrations using density and ultrasonic velocity measurements. These experiments reveal a decrease in hydration number with an increase in concentration, which can be attributed to the formation of ion pairs. A more complex metal system is the industrially important platinum group metal (PGM) chloro-anion one. Their industrial importance relates to the search for a Green Chemistry Process for the separation of PGM chloro complexes that have been extracted from the mined ore into an acidic aqueous media. This requires a PGM separation process in water. Here an understanding of the hydration structure about the iii PGM chloro-anion complexes and the role that ammonium counter-ions play in disrupting that solvent structure when ammonium PGM salts are formed, is critical in the process design. To this end a solution force field, inclusive of the majority of PGM chloro-anion complexes (i.e. (Y)2[PtCl4]2-, (Y)2[PdCl4]2-, (Y)2[PtCl6]2-, (Y)2[PdCl6]2-, (Y)2[IrCl6]2-, (Y)2[OsCl6]2-, (Y)2[RuCl6]2-, (Y)3[IrCl6]3-, (Y)3[RhCl6]3- and (Y)3[RuCl6]3- , where Y = NH4 +) arising in acidic aqueous media, parameterised from experimental and quantum mechanically derived properties, was developed. Nanosecond atomistic molecular dynamics simulations were then performed for the PGM chloro-anion complexes. Analysis of the solvation structure using radial and spatial distribution functions revealed two distinct solvent structures corresponding to the square planar and octahedral species. The formation of ion pairs disrupts the solvent structure where the hydration shells about the bivalent hexachlorometallates are more affected compared with the trivalent hexachlorometallates and these first shell waters in turn are more affected than those in the bivalent tetrachlorometallates. Finally to inform the design of a separation process transport properties such as diffusion coefficients, ion hydration numbers and water residence times for the PGM chloro-anion complexes were calculated. It is observed that the diffusion rates of PGM chloro-anion complexes are strongly correlated to their ion hydration numbers as calculated by Voronoi tessellation of the simulation cell, such that a larger hydration shell volume results in a slower PGM chloro-anion diffusion rate

Ionic liquid-based strategy for predicting protein aggregation propensity and thermodynamic stability

Novel drug candidates are continuously being developed to combat the most life-threatening diseases; however, many promising protein therapeutics are dropped from the pipeline. During biological and industrial processes, protein therapeutics are exposed to various stresses such as fluctuations in temperature, solvent pH, and ionic strength. These can lead to enhanced protein aggregation propensity, one of the greatest challenges in drug development. Recently, ionic liquids (ILs), in particular, biocompatible choline chloride ([Cho]Cl)-based ILs, have been used to hinder stress-induced protein conformational changes. Herein, we develop an IL-based strategy to predict protein aggregation propensity and thermodynamic stability. We examine three key variables influencing protein misfolding: pH, ionic strength, and temperature. Using dynamic light scattering, zeta potential, and variable temperature circular dichroism measurements, we systematically evaluate the structural, thermal, and thermodynamic stability of fresh immunoglobin G4 (IgG4) antibody in water and 10, 30, and 50 wt % [Cho]Cl. Additionally, we conduct molecular dynamics simulations to examine IgG4 aggregation propensity in each system and the relative favorability of different [Cho]Cl-IgG4 packing interactions. We re-evaluate each system following 365 days of storage at 4 °C and demonstrate how to predict the thermodynamic properties and protein aggregation propensity over extended storage, even under stress conditions. We find that increasing [Cho]Cl concentration reduced IgG4 aggregation propensity both fresh and following 365 days of storage and demonstrate the potential of using our predictive IL-based strategy and formulations to radically increase protein stability and storage

Interferometric Mapping of Magnetic fields: NGC2071IR

We present polarization maps of NGC2071IR from thermal dust emission at 1.3 mm and from CO J=$2 \to 1$ line emission. The observations were obtained using the Berkeley-Illinois-Maryland Association array in the period 2002-2004. We detected dust and line polarized emission from NGC2071IR that we used to constrain the morphology of the magnetic field. From CO J=$2 \to 1$ polarized emission we found evidence for a magnetic field in the powerful bipolar outflow present in this region. We calculated a visual extinction $A_{\rm{v}} \approx 26$ mag from our dust observations. This result, when compared with early single dish work, seems to show that dust grains emit polarized radiation efficiently at higher densities than previously thought. Mechanical alignment by the outflow is proposed to explain the polarization pattern observed in NGC2071IR, which is consistent with the observed flattening in this source.Comment: 17 pages, 4 Figures, Accepted for publication in Ap

Chief Executive Officers in United States Hospitals: A Reexamination of Workforce Demographics and Educational Issues

The United States Bureau of Labor Statistics (BLS) reports the “employment of medical and health services mangers is expected to grow by 22 percent from 2010-2020.”The BLS notes this is substantially faster than the national average for other occupations. Information from this report finds its way into popular media, news shows, and other information outlets which increases the number of prospective applicants to College and University Healthcare Management programs. In 2007, the authors conducted a survey of chief executive officers (CEO) in United States hospitals that sought to identify educational and demographic information of individuals holding top management positions in US Healthcare institutions. The survey was repeated in 2012, at the 5-year interval, to determine if CEO information had changed

A Mini-Study of Employee Turnover in US Hospitals

A mini-study was conducted to collect self-reported employee turnover rates in U.S. hospitals. The results indicate many hospitals are struggling with high employee turnover rates. Wide-spread variances in ratings were observed across hospitals which may be due to lack of consistency in how they each calculate their employee turnover. This makes benchmarking for the purposes of performance improvement challenging

Succession Planning: Trends Regarding the Perspectives of Chief Executive Officers in United States Hospitals

A study was conducted to revisit the perceptions of chief executive officers (CEOs) in United States (U.S.) hospitals regarding the origin of leadership and how they felt about internally developed successors versus externally recruited successors. Furthermore, the study sought to understand how this group of executives utilizes the succession planning process, what factors impact successor identification, what positions are applicable for succession planning activities, and who is ultimately held responsible for leadership continuity within the hospital industry. The results of this 2012 study were compared to a previous study conducted in 2007 to determine if the perceptions had changed over time

Hydroclimatic changes in the British Isles through the Last-Glacial-Interglacial Transition:Multiproxy reconstructions from the Vale of Pickering, NE England

European paleoenvironmental records through the Last Glacial-Interglacial Transition (LGIT; ca 16-8 cal ka BP) record a series of climatic events occurring over decadal to multi-centennial timescales. Changes in components of the climatic system other than temperature (e.g. hydrology) through the LGIT are relatively poorly understood however, and further records of hydroclimatic changes are required in order to develop a more complete understanding on the phasing of environmental and anthropogenic responses in Europe to abrupt climate change. Here, we present a multiproxy palaeoenvironmental record (macroscale and microscale sedimentology, macrofossils, and carbonate stable isotopes) from a palaeolake sequence in the Vale of Pickering (VoP), NE England, which enables the reconstruction of hydroclimatic changes constrained by a radiocarbon-based chronology. Relative lake-level changes in the VoP occurred in close association (although not necessarily in phase) to threshold shifts across abrupt climate change transitions, most notably lowering during cooling intervals of the LGIT (∼GI-1d, ∼GI-1b, and ∼GS-1). This reflects more arid hydroclimates associated with these cooling episodes in the British Isles. Comparisons to hydrological records elsewhere in Europe show a latitudinal bifurcation, with Northern Europe (50–60°N) becoming more arid (humid), and Southern Europe (40–50°N) becoming more humid (arid) in response to these cooling (warming) intervals. We attribute these bifurcating signals to the relative positions of the Atlantic storm tracks, sea-ice margin, and North Atlantic Polar Front (NAPF) during the climatic events of the LGIT

A selected ion flow tube study of the reactions of gas-phase cations with PSCl3

A selected ion flow tube was used to investigate the positive ion chemistry of thiophosphoryl chloride, PSCl$_3$. Rate coefficients and ion product branching ratios have been determined at room temperature for reactions with nineteen cations ; H$_3$O$^+$, CF$_3^+$, CF$^+$, NO$^+$, NO$_2^+$, SF$_2^+$, SF$^+$, CF$_2^+$, O$_2^+$, H$_2$O$^+$, N$_2$O$^+$, O$^+$, CO$_2^+$, CO$^+$, N$^+$, N$_2^+$, Ar$^+$, F$^+$ and Ne$^+$ (in order of increasing recombination energy). Complementary data described in the previous paper have been obtained for this molecule via the observation of threshold photoelectron photoion coincidences. For ions whose recombination energies are in the range 10-22 eV, comparisons are made between the product ion branching rations of PSCl$_3$ from photoionisation and from ion-molecule reactions. In most instances, the data from the two experiments are well correlated, suggesting that long-range charge transfer is the dominant mechanism for these ion-molecule reactions ; the agreement is particularly good for the atomic ions Ar$^+$, F$^+$ and Ne$^+$. Some reactions (e.g. O$_2^+$ + PSCl$_3$), however, exhibit significant differences; short-range charge transfer must then be occurring following the formation of an ion-molecule complex. For ions whose recombination energies are less than 10 eV (i.e. H$_3$O$^+$, CF$_3^+$, CF$^+$ and NO$^+$), reactions can only occur via a chemical process in which bonds are broken and formed, because the recombination energy of the cation is less than the ionisation energy of PSCl$_3$

Stratospheric processes: Observations and interpretation

Explaining the observed ozone trends discussed in an earlier update and predicting future trends requires an understanding of the stratospheric processes that affect ozone. Stratospheric processes occur on both large and small spatial scales and over both long and short periods of time. Because these diverse processes interact with each other, only in rare cases can individual processes be studied by direct observation. Generally the cause and effect relationships for ozone changes were established by comparisons between observations and model simulations. Increasingly, these comparisons rely on the developing, observed relationships among trace gases and dynamical quantities to initialize and constrain the simulations. The goal of this discussion of stratospheric processes is to describe the causes for the observed ozone trends as they are currently understood. At present, we understand with considerable confidence the stratospheric processes responsible for the Antarctic ozone hole but are only beginning to understand the causes of the ozone trends at middle latitudes. Even though the causes of the ozone trends at middle latitudes were not clearly determined, it is likely that they, just as those over Antarctica, involved chlorine and bromine chemistry that was enhanced by heterogeneous processes. This discussion generally presents only an update of the observations that have occurred for stratospheric processes since the last assessment (World Meteorological Organization (WMO), 1990), and is not a complete review of all the new information about stratospheric processes. It begins with an update of the previous assessment of polar stratospheres (WMO, 1990), followed by a discussion on the possible causes for the ozone trends at middle latitudes and on the effects of bromine and of volcanoes