The determination of accurate dipole polarizabilities alpha and gamma for the noble gases

The static dipole polarizabilities alpha and gamma for the noble gases helium through xenon were determined using large flexible one-particle basis sets in conjunction with high-level treatments of electron correlation. The electron correlation methods include single and double excitation coupled-cluster theory (CCSD), an extension of CCSD that includes a perturbational estimate of connected triple excitations, CCSD(T), and second order perturbation theory (MP2). The computed alpha and gamma values are estimated to be accurate to within a few percent. Agreement with experimental data for the static hyperpolarizability gamma is good for neon and xenon, but for argon and krypton the differences are larger than the combined theoretical and experimental uncertainties. Based on our calculations, we suggest that the experimental value of gamma for argon is too low; adjusting this value would bring the experimental value of gamma for krypton into better agreement with our computed result. The MP2 values for the polarizabilities of neon, argon, krypton and zenon are in reasonabe agreement with the CCSD and CCSD(T) values, suggesting that this less expensive method may be useful in studies of polarizabilities for larger systems

Connected triple excitations in coupled-cluster calculations of hyperpolarizabilities: Neon

We have calculated the second hyperpolarizability gamma of neon using the CCSD(T) method. The accuracy of the CCSD(T) approach has been established by explicit comparison with the single, double and triple excitation coupled-cluster (CCSDT) method using extended basis sets that are known to be adequate for the description of gamma. Our best estimate for gamma(sub 0) of 110 +/- 3 a.u. is in good agreement with other recent theoretical values and with Shelton's recent experimental estimate of 108 +/- 2 a.u. Comparison of the MP2 and CCSD(T) hyperpolarizability values indicates that MP2 gives a very good description of the electron correlation contribution to gamma(sub 0). We have combined MP2 frequency-dependent corrections with the CCSD(T) gamma(sub 0) to yield values of gamma(-2 omega;omega,omega,0) and gamma(exp K)(-omega;omega,0,0)

Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance

Abstract. Oxidation flow reactors (OFR) are a promising complement to environmental chambers for investigating atmospheric oxidation processes and secondary aerosol formation. However, questions have been raised about how representative the chemistry within OFRs is of that in the troposphere. We investigate the fates of organic peroxy radicals (RO 2 ), which play a central role in atmospheric organic chemistry, in OFRs and environmental chambers by chemical kinetic modeling, and compare to a variety of ambient conditions to help define a range of atmospherically relevant OFR operating conditions. For most types of RO 2 , their bimolecular fates in OFRs are mainly RO 2 +HO 2 and RO 2 +NO, similar to chambers and atmospheric studies. For substituted primary RO 2 and acyl RO 2 , RO 2 +RO 2 can make a significant contribution to the fate of RO 2 in OFRs, chambers and the atmosphere, but RO 2 +RO 2 in OFRs is in general somewhat less important than in the atmosphere. At high NO, RO 2 +NO dominates RO 2 fate in OFRs, as in the atmosphere. At high UV lamp setting in OFRs, RO 2 +OH can be a major RO 2 fate and RO 2 isomerization can be negligible for common multifunctional RO 2 , both of which deviate from common atmospheric conditions. In the OFR254 operation mode (where OH is generated only from photolysis of added O 3 ), we cannot identify any conditions that can simultaneously avoid significant organic photolysis at 254 nm and lead to RO 2 lifetimes long enough (~ 10 s) to allow atmospherically relevant RO 2 isomerization. In the OFR185 mode (where OH is generated from reactions initiated by 185 nm photons), high relative humidity, low UV intensity and low precursor concentrations are recommended for atmospherically relevant gas-phase chemistry of both stable species and RO 2 . These conditions ensure minor or negligible RO 2 +OH and a relative importance of RO 2 isomerization in RO 2 fate in OFRs within ~ x2 of that in the atmosphere. Under these conditions, the photochemical age within OFR185 systems can reach a few equivalent days at most, encompassing the typical ages for maximum secondary organic aerosol (SOA) production. A small increase in OFR temperature may allow the relative importance of RO 2 isomerization to approach the ambient values. To study heterogeneous oxidation of SOA formed under atmospherically-relevant OFR conditions, a different UV source with higher intensity is needed after the SOA formation stage, which can be done with another reactor in series. Finally, we recommend evaluating the atmospheric relevance of RO 2 chemistry by always reporting measured and/or estimated OH, HO 2 , NO, NO 2 and OH reactivity (or at least precursor composition and concentration) in all chamber and flow reactor experiments. An easy-to-use RO 2 fate estimator program is included with this paper to facilitate investigation of this topic in future studies.</p

Using the South African Triage Scale for prehospital triage: a qualitative study

Background Triage is a critical component of prehospital emergency care. Effective triage of patients allows them to receive appropriate care and to judiciously use personnel and hospital resources. In many low-resource settings prehospital triage serves an additional role of determining the level of destination facility. In South Africa, the Western Cape Government innovatively implemented the South African Triage Scale (SATS) in the public Emergency Medical Services (EMS) service in 2012. The prehospital provider perspectives and experiences of using SATS in the field have not been previously studied. Methods In this qualitative study, focus group discussions with cohorts of basic, intermediate and advanced life support prehospital providers were conducted and transcribed. A content analysis using an inductive approach was used to code transcripts and identify themes. Results 15 EMS providers participated in three focus group discussions. Data saturation was reached and four major themes emerged from the qualitative analysis: Implementation and use of SATS; Effectiveness of SATS; Limitations of the discriminator; and Special EMS considerations. Participants overall felt that SATS was easy to use and allowed improved communication with hospital providers during patient handover. Participants, however, described many clinical cases when their clinical gestalt triaged the patient to a different clinical acuity than generated by SATS. Additionally, they stated many clinical discriminators were too subjective to effectively apply or covered too broad a range of clinical severity (e.g., ingestions). Participants provided examples of how the prehospital environment presents additional challenges to using SATS such as changing patient clinical conditions, transport times and social needs of patients. Conclusions Overall, participants felt that SATS was an effective tool in prehospital emergency care. However, they described many clinical scenarios where SATS was in conflict with their own assessment, the clinical care needs of the patient or the available prehospital and hospital resources. Many of the identified challenges to using SATS in the prehospital environment could be improved with small changes to SATS and provider re-training

Evolution of OH reactivity in NO-free volatile organic compound photooxidation investigated by the fully explicit GECKO-A model

OH reactivity (OHR) is an important control on the oxidative capacity in the atmosphere but remains poorly constrained in many environments, such as remote, rural, and urban atmospheres, as well as laboratory experiment setups under low-NO conditions. For an improved understanding of OHR, its evolution during oxidation of volatile organic compounds (VOCs) is a major aspect requiring better quantification. We use the fully explicit Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model to study the OHR evolution in the NO-free photooxidation of several VOCs, including decane (an alkane), m-xylene (an aromatic), and isoprene (an alkene). Oxidation progressively produces more saturated and functionalized species. Total organic OHR (including precursor and products, OHRVOC) first increases for decane (as functionalization increases OH rate coefficients) and m-xylene (as much more reactive oxygenated alkenes are formed). For isoprene, C=C&nbsp;bond consumption leads to a rapid drop in OHRVOC before significant production of the first main saturated multifunctional product, i.e., isoprene epoxydiol. The saturated multifunctional species in the oxidation of different precursors have similar average OHRVOC per C&nbsp;atom. The latter oxidation follows a similar course for different precursors, involving fragmentation of multifunctional species to eventual oxidation of C1 and C2 fragments to CO2, leading to a similar evolution of OHRVOC per C&nbsp;atom. An upper limit of the total OH consumption during complete oxidation to CO2 is roughly three per C&nbsp;atom. We also explore the trends in radical recycling ratios. We show that differences in the evolution of OHRVOC between the atmosphere and an environmental chamber, and between the atmosphere and an oxidation flow reactor (OFR), can be substantial, with the former being even larger, but these differences are often smaller than between precursors. The Teflon wall losses of oxygenated VOCs in chambers result in large deviations of OHRVOC from atmospheric conditions, especially for the oxidation of larger precursors, where multifunctional species may suffer substantial wall losses, resulting in significant underestimation of OHRVOC. For OFR, the deviations of OHRVOC evolution from the atmospheric case are mainly due to significant OHR contribution from RO2 and lack of efficient organic photolysis. The former can be avoided by lowering the UV lamp setting in OFR, while the latter is shown to be very difficult to avoid. However, the former may significantly offset the slowdown in fragmentation of multifunctional species due to lack of efficient organic photolysis. &nbsp;</p

The left frontal cortex supports reserve in aging by enhancing functional network efficiency

Background: Recent evidence from fMRI studies suggests that functional hubs, i.e. highly connected brain regions, are important for mental health. We found recently that global connectivity of a hub in the left frontal cortex (LFC-connectivity) is associated with relatively preserved memory abilities and higher levels of protective factors (education, IQ) in normal aging and Alzheimer’s disease. These results suggest that LFC-connectivity supports reserve capacity alleviating memory decline. An open question is, however, why LFC-connectivity is beneficial and supports memory function in the face of neurodegeneration. We hypothesized that higher LFCconnectivity is associated with enhanced efficiency in connected major networks involved in episodic memory. We further hypothesized that higher LFC-related network efficiency predicts higher memory abilities. Methods: We assessed fMRI during a face-name association learning task in 26 healthy cognitively normal elderly participants. Using beta-series correlation analysis, we computed task-related LFC-connectivity to key memory networks including the default-mode network (DMN) and dorsal attention network (DAN). Network efficiency within the DMN and DAN was estimated by the graph theoretical small-worldness statistic. We applied linear regression analyses in order to test the association between LFC-connectivity to the DMN/DAN and small-worldness of these networks. Mediation analysis was applied to test LFC-connectivity to the DMN and DAN as a mediator of the association between education and higher DMN and DAN smallworldness. Lastly, we tested network small-worldness as a predictor of memory performance. Results: We found that higher LFC-connectivity to the DMN and DAN during successful memory encoding and recognition was associated with higher small-worldness of those networks. Higher task-related LFC-connectivity mediated the association between education and higher small-worldness in the DMN and DAN. Further, higher small-worldness of these networks predicted better performance in the memory task. Conclusions: The current results suggest that higher education-related LFC-connectivity to key memory networks during a memory task is associated with higher network efficiency and thus enhanced reserve of memory abilities in aging

The H19/let-7 double-negative feedback loop contributes to glucose metabolism in muscle cells

The H19 lncRNA has been implicated in development and growth control and is associated with human genetic disorders and cancer. Acting as a molecular sponge, H19 inhibits microRNA (miRNA) let-7. Here we report that H19 is significantly decreased in muscle of human subjects with type-2 diabetes and insulin resistant rodents. This decrease leads to increased bioavailability of let-7, causing diminished expression of let-7 targets, which is recapitulated in vitro where H19 depletion results in impaired insulin signaling and decreased glucose uptake. Furthermore, acute hyperinsulinemia downregulates H19, a phenomenon that occurs through PI3K/AKT-dependent phosphorylation of the miRNA processing factor KSRP, which promotes biogenesis of let-7 and its mediated H19 destabilization. Our results reveal a previously undescribed double-negative feedback loop between sponge lncRNA and target miRNA that contributes to glucose regulation in muscle cell

Validity and reliability of the South African Triage Scale in prehospital providers

Background The South African Triage Scale (SATS) is a validated in-hospital triage tool that has been innovatively adopted for use in the prehospital setting by Western Cape Government (WCG) Emergency Medical Services (EMS) in South Africa. The performance of SATS by EMS providers has not been formally assessed. The study sought to assess the validity and reliability of SATS when used by WCG EMS prehospital providers for single-patient triage. Methods This is a prospective, assessment-based validation study among WCG EMS providers from March to September 2017 in Cape Town, South Africa. Participants completed an assessment containing 50 clinical vignettes by calculating the three components — triage early warning score (TEWS), discriminators (pre-defined clinical conditions), and a final SATS triage color. Responses were scored against gold standard answers. Validity was assessed by calculating over- and under-triage rates compared to gold standard. Inter-rater reliability was assessed by calculating agreement among EMS providers’ responses. Results A total of 102 EMS providers completed the assessment. The final SATS triage color was accurately determined in 56.5%, under-triaged in 29.5%, and over-triaged in 13.1% of vignette responses. TEWS was calculated correctly in 42.6% of vignettes, under-calculated in 45.0% and over-calculated in 10.9%. Discriminators were correctly identified in only 58.8% of vignettes. There was substantial inter-rater and gold standard agreement for both the TEWS component and final SATS color, but there was lower inter-rater agreement for clinical discriminators. Conclusion This is the first assessment of SATS as used by EMS providers for prehospital triage. We found that SATS generally under-performed as a triage tool, mainly due to the clinical discriminators. We found good inter-rater reliability, but poor validity. The under-triage rate of 30% was higher than previous reports from the in-hospital setting. The over-triage rate of 13% was acceptable. Further clinically-based and qualitative studies are needed. Trial registration Not applicable

Biomarkers in advanced larynx cancer

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102058/1/lary24245.pd