Beyond LLM in M-theory

The Lin, Lunin, Maldacena (LLM) ansatz in D = 11 supports two independent Killing directions when a general Killing spinor ansatz is considered. Here we show that these directions always commute, identify when the Killing spinors are charged, and show that both their inner product and resulting geometry are governed by two fundamental constants. In particular, setting one constant to zero leads to AdS7 x S4, setting the other to zero gives AdS4 x S7, while flat spacetime is recovered when both these constants are zero. Furthermore, when the constants are equal, the spacetime is either LLM, or it corresponds to the Kowalski-Glikman solution where the constants are simply the mass parameter.Comment: 1+30 pages, footnote adde

Transfer Hydrogenation of ortho-Hydroxybenzophenone Ketimines Catalysed by BINOL-derived Phosphoric Acid Occurs by a 14-Membered Bifunctional Transition Structure

Chiral BINOL-derived phosphoric acids catalyse the transfer hydrogenation of ketimines using Hantszch esters. In many cases the nitrogen on the imine binds to the catalyst through the catalyst hydroxyl group and the nucleophile forms a second hydrogen bond to the phosphoryl oxygen. DFT and ONIOM calculations show that the introduction of an ortho- hydroxyaryl group on the carbon atom of the ketimine leads the reaction to proceed through a 14-membered bifunctional mechanism. The transition states of these reactions involve both hydrogen bonding from the hydroxyl group on the imine and the nucleophile’s proton to the phosphate catalyst. This mechanistic pathway is lower in energy than the conventional route, consistent with the experimentally observed increased rates of reaction relative to imines that are not derived from ortho-hydroxybenzophenone. To complement the high-level calculations, an accessible qualitative model has been developed that predicts the correct sense of stereoinduction for all examples.We thank the EPSRC for funding

Selecting Chiral BINOL-derived Phosphoric Acid Catalysts: General Model to Identify Steric Features Essential For Enantioselectivity

Choosing the optimal catalyst for a new transformation is challenging because the ideal molecular requirements of the catalyst for one reaction do not always simply translate to another. Large groups at the 3,3' positions of the binaphthol rings are important for efficient stereoinduction but if they are too large this can lead to unusual or poor results. By applying a quantitative steric assessment of the substituents at the 3,3' positions of the binaphthol ring, we have systematically studied the effect of modulating this group on enantioselectivity for a wide range of reactions involving imines, and verified this analysis using ONIOM calculations. We have shown that in most reactions, the stereochemical outcome depends on both proximal and remote sterics. Summarising detailed calculations into a simple qualitative model identifies and explains the steric features required for high selectivity. This model is consistent with seventy-seven papers reporting reactions (over 1000 transformations in total), and provides a straightforward decision tree for selecting the best catalyst.We thank EPSRC for funding

The importance of comorbidity in analysing patient costs in Swedish primary care

BACKGROUND: The objective was to explore the usefulness of the morbidity risk adjustment system Adjusted Clinical Groups(® )(ACG), in comparison with age and gender, in explaining and estimating patient costs on an individual level in Swedish primary health care. Data were retrieved from two primary health care centres in southeastern Sweden. METHODS: A cross-sectional observational study. Data from electronic patient registers from the two centres were retrieved for 2001 and 2002, and patients were grouped into ACGs, expressing the individual combination of diagnoses and thus the comorbidity. Costs per patient were calculated for both years in both centres. Cost data from one centre were used to create ACG weights. These weights were then applied to patients at the other centre. Correlations between individual patient costs, age, gender and ACG weights were studied. Multiple linear regression analyses were performed in order to explain and estimate patient costs. RESULTS: The variation in individual patient costs was substantial within age groups as well as within ACG weight groups. About 37.7% of the individual patient costs could be explained by ACG weights, and age and gender added about 0.8%. The individual patient costs in 2001 estimated 22.0% of patient costs in 2002, whereas ACG weights estimated 14.3%. CONCLUSION: ACGs was an important factor in explaining and estimating individual patient costs in primary health care. Costs were explained to only a minor extent by age and gender. However, the usefulness of the ACG system appears to be sensitive to the accuracy of classification and coding of diagnoses by physicians

Computational and experimental study of aerosol dispersion in a ventilated room

For many respiratory diseases, a primary mode of transmission is inhalation via aerosols and droplets. The COVID-19 pandemic has accelerated studies of aerosol dispersion in indoor environments. Most studies of aerosol dispersion present computational fluid dynamics results, which rarely include detailed experimental verification, and many of the computations are complex, making them hard to scale to larger spaces. This study presents a comparison of computational simulations and measurements of aerosol dispersion within a typical ventilated classroom. Measurements were accomplished using a custom-built low-cost sensor network composed of 15 commercially available optical particle sizers, which provided size-resolved information about the number concentrations and temporal dynamics of 0.3–40 µm diameter particles. Measurement results are compared to the computed dispersal and loss rates from a steady-state Reynolds-Averaged Navier–Stokes k-epsilon model. The results show that a newly developed aerosol-transport-model can accurately simulate the dispersion of aerosols and faithfully predict measured aerosol concentrations at different locations and times. The computational model was developed with scalability in mind such that it may be adapted for larger spaces. The experiments highlight that the fraction of aerosol recycled in the ventilation system depends on the aerosol droplet size and cannot be predicted by the recycled-to-outside air ratio. Moreover, aerosol recirculation is not negligible, as some computational approaches assume. Both modeling and measurements show that, depending on the location within the room, the maximum aerosol concentration can be many times higher than the average concentration, increasing the risk of infection

Quantifying morbidities by Adjusted Clinical Group system for a Taiwan population: A nationwide analysis

<p>Abstract</p> <p>Background</p> <p>The Adjusted Clinical Group (ACG) system has been used in measuring an individual's and a population's morbidities. Although all required inputs for running the ACG system are readily available, patients' morbidities and their associations to health care utilizations have been rarely studied in Taiwan. Therefore, the objective of this study was using the ACG system to quantify morbidities for Taiwanese population and to examine their relationship to ambulatory utilizations and costs.</p> <p>Methods</p> <p>This secondary analysis examined claims data for ambulatory services provided to 2.71 million representative Taiwanese in 2002 and 2003. People were grouped by the ACG system according to age, gender, and all ambulatory diagnosis codes in a given year. The software collapses the full set of ACGs into six morbidity categories (Non-users, Healthy, Low-morbidity, Moderate-, High- and Very-high) termed Resource Utilization Bands (RUBs). Each ACG was assigned a relative weight (RW), which was calculated as the ratio of mean ambulatory cost for each ACG to that for the overall. The distribution of morbidities was compared between years 2002 and 2003. The consistency of the distributions of visits, costs, and RWs of each ACG were examined for a two-year period. The relationship between people's morbidities and their ambulatory utilizations and costs was assessed.</p> <p>Results</p> <p>Ninety-eight percent of the subjects were correctly assigned to ACGs. Except for non-users (7.9 ~ 8.3%), most subjects were assigned to ACGs of acute and minor diseases and ACGs of moderate-to-high-morbid chronic diseases. The distributions of ACG-based morbidities were highly consistent (r = 0.949, <it>p < 0.001</it>) between 2002 and 2003. The ACG-specific visits (r = 0.955, <it>p < 0.001</it>), costs (r = 0.966, <it>p < 0.001</it>) and RWs (r = 0.991, <it>p < 0.001</it>) were correlated across two years. People grouped to the high-morbid ACGs had more visits and costs than those grouped to the low-morbid ACGs. Forty-six percent of the total ambulatory costs were spent by eighteen percent of the population, who were grouped to the High- and Very-high-morbidity RUBs.</p> <p>Conclusion</p> <p>This study demonstrated the feasibility, validity, and reliability of using the ACG system to measure morbidities in a Taiwan population and to explain their associations with ambulatory utilizations and costs for the whole country.</p

Squirrelpox virus: assessing prevalence, transmission and environmental degradation

Red squirrels (Sciurus vulgaris) declined in Great Britain and Ireland during the last century, due to habitat loss and the introduction of grey squirrels (Sciurus carolinensis), which competitively exclude the red squirrel and act as a reservoir for squirrelpox virus (SQPV). The disease is generally fatal to red squirrels and their ecological replacement by grey squirrels is up to 25 times faster where the virus is present. We aimed to determine: (1) the seropositivity and prevalence of SQPV DNA in the invasive and native species at a regional scale; (2) possible SQPV transmission routes; and, (3) virus degradation rates under differing environmental conditions. Grey (n = 208) and red (n = 40) squirrel blood and tissues were sampled. Enzyme-linked immunosorbent assay (ELISA) and quantitative real-time polymerase chain reaction (qPCR) techniques established seropositivity and viral DNA presence, respectively. Overall 8% of squirrels sampled (both species combined) had evidence of SQPV DNA in their tissues and 22% were in possession of antibodies. SQPV prevalence in sampled red squirrels was 2.5%. Viral loads were typically low in grey squirrels by comparison to red squirrels. There was a trend for a greater number of positive samples in spring and summer than in winter. Possible transmission routes were identified through the presence of viral DNA in faeces (red squirrels only), urine and ectoparasites (both species). Virus degradation analyses suggested that, after 30 days of exposure to six combinations of environments, there were more intact virus particles in scabs kept in warm (25°C) and dry conditions than in cooler (5 and 15°C) or wet conditions. We conclude that SQPV is present at low prevalence in invasive grey squirrel populations with a lower prevalence in native red squirrels. Virus transmission could occur through urine especially during warm dry summer conditions but, more notably, via ectoparasites, which are shared by both species

Water diffusion in atmospherically relevant α-pinene secondary organic material

Secondary organic material (SOM) constitutes a large mass fraction of atmospheric aerosol particles. Understanding its impact on climate and air quality relies on accurate models of interactions with water vapour. Recent research shows that SOM can be highly viscous and can even behave mechanically like a solid, leading to suggestions that particles exist out of equilibrium with water vapour in the atmosphere. In order to quantify any kinetic limitation we need to know water diffusion coefficients for SOM, but this quantity has, until now, only been estimated and has not yet been measured. We have directly measured water diffusion coefficients in the water soluble fraction of α-pinene SOM between 240 and 280 K. Here we show that, although this material can behave mechanically like a solid, at 280 K water diffusion is not kinetically limited on timescales of 1 s for atmospheric-sized particles. However, diffusion slows as temperature decreases. We use our measured data to constrain a Vignes-type parameterisation, which we extend to lower temperatures to show that SOM can take hours to equilibrate with water vapour under very cold conditions. Our modelling for 100 nm particles predicts that under mid to upper tropospheric conditions radial inhomogeneities in water content produce a low viscosity surface region and more solid interior, with implications for heterogeneous chemistry and ice nucleation

The removal of thermally aged films of triacylglycerides by surfactant solutions

Thermal ageing of triacylglycerides (TAG) at high temperatures produces films which resist removal using aqueous surfactant solutions. We used a mass loss method to investigate the removal of thermally aged TAG films from hard surfaces using aqueous solutions of surfactants of different charge types. It was found that cationic surfactants are most effective at high pH, whereas anionics are most effective at low pH and a non-ionic surfactant is most effective at intermediate pH. We showed that the TAG film removal process occurs in several stages. In the first ‘‘lag phase’’ no TAG removal occurs; the surfactant first partitions into the thermally aged film. In the second stage, the TAG film containing surfactant was removed by solubilisation into micelles in the aqueous solution. The effects of pH and surfactant charge on the TAG removal process correlate with the effects of these variables on the extent of surfactant partitioning to the TAG film and on the maximum extent of TAG solubilisation within the micelles. Additionally, we showed how the TAG removal is enhanced by the addition of amphiphilic additives such as alcohols which act as co-surfactants. The study demonstrates that aqueous surfactant solutions provide a viable and more benign alternative to current methods for the removal of thermally aged TAG films

Comprehensive modeling study of ozonolysis of oleic acid aerosol based on real-time, online measurements of aerosol composition

The chemical composition of organic aerosols profoundly influences their atmospheric properties, but a detailed understanding of heterogeneous and in-particle reactivity is lacking. We present here a combined experimental and modeling study of the ozonolysis of oleic acid particles. An online mass spectrometry (MS) method, Extractive Electrospray Ionization (EESI), is used to follow the composition of the aerosol at a molecular level in real time; relative changes in the concentrations of both reactants and products are determined during aerosol aging. The results show evidence for multiple non-first-order reactions involving stabilized Criegee intermediates, including the formation of secondary ozonides and other oligomers. Offline liquid chromatography MS is used to confirm the online MS assignment of the monomeric and dimeric products. We explain the observed EESI-MS chemical composition changes, and chemical and physical data from previous studies, using a process-based aerosol chemistry simulation, the Pretty Good Aerosol Model (PG-AM). In particular, we extend previous studies of reactant loss by demonstrating success in reproducing the time dependence of product formation and the evolving particle size. This advance requires a comprehensive chemical scheme coupled to the partitioning of semivolatile products; relevant reaction and evaporation parameters have been refined using our new measurements in combination with PG-AM.This work was supported by the UK Natural Environment Research Council (NERC grant NE/I528277/1) and the European Research Council (ERC starting grant 279405 and the Atmospheric Chemistry Climate Interactions (ACCI) project, grant 267760). PTG thanks NCAS Climate for support