The Vibrational Spectra of the Boron Halides and Their Molecular Complexes. Part 14. Ab Initio Studies of the Boron Trifluoride-Nitrous Acid Complex

A number of electron donor-acceptor complexes formed between boron trifluoride and nitrous acid have been studied, in order to ascertain which of the interacting monomers acts as the acid and which as the base.We have found four complexes in which electron donation occurs in the direction HONO → BF3. These complexes are bound through the hydroxyl O, the N and the nitrosyl O atoms, in decreasing order of strength of interaction, and in the last case two separate rotational isomers have been identified. The intermolecular structural parameters and the perturbations of the intramolecular bond lengths and angles are consistent with the trends in the interaction energies. The vibrational spectra have also been examined, and the wavenumber shifts and intensity ratios track with the energetic and structural data. The mechanism of complex formation in each case is donation of a lone pair of electrons on the N or O atoms into the &3960;* orbital of BF3, with back donation in the case of the complex bound through the nitrogen atom froma lone pair on one of the F atoms of BF3 into the σ*(OH) orbital of HONO. The total amounts of charge transferred vary, in general, with the strengths of interaction, while the charge density topologies and their properties confirm the conclusions derived from the other characteristics discussed.KEYWORDS Ab initio studies, molecular complexes, boron trifluoride, nitrous acid.Supplementary files attache

Binary Molecular Complexes and the Nature of Molecular Association

Asurvey is presented of the results of some ab initio calculations of the properties of a variety of binary  molecular complexes. The properties include the molecular structures, the interaction energies and the vibrational spectra. The interaction energies have been correlated with some physical properties of the interacting monomer species, and the changes in the values of the monomer structural parameters, and the vibrational wavenumber shifts occurring on complexation have been correlated with the interaction energies. The range of molecular complexes studied covers examples from the hydrogen-bonded, blue-shifting  hydrogenbonded, halogen-bonded and electron donor-acceptor types. Some generalizations concerning the nature of molecular association have been presented.KEYWORDS: Ab initio calculations, molecular complexes, molecular structures, interaction energies, vibrational spectra

The Vibrational Spectra of the Boron Halides and their Molecular Complexes. Part 8. Ab initio Studies of the Complexes of Boron Trifluoride with Water and Hydrogen Sulphide

The structures, interaction energies and vibrational spectra of the van derWaals complexes formed between boron trifluoride, as Lewis acid, and water and hydrogen sulphide, as Lewis bases, have been determined by means of ab initio calculations at the second-order level of Møller-Plesset perturbation theory, using a number of basis sets, including double- and triple-zeta, with polarization and diffuse functions.Two conformers, an eclipsed and a staggered species, have been examined for each complex. In the case of the boron  trifluoride-water complex, the spectra computed using the largest basis set have been compared with the spectra obtained experimentally in nitrogen, argon and neon matrices at cryogenic temperatures.KEYWORDS: Ab initio calculations, molecular complexes, boron trifluoride, water; hydrogen sulphide,  molecular structures, interaction energies, vibrational spectra

Methods of classification for women undergoing induction of labour: a systematic review and novel classification system

OBJECTIVE To develop and demonstrate the applicability of a classification system for induction of labour (IOL) that fulfils recognised classification system attributes for clinical, surveillance and research purposes. DESIGN Proof of concept. SETTING, POPULATION Applicability demonstrated in a population cohort of 909,702 maternities in New South Wales, Australia, 2002-2011. METHODS A multidisciplinary collaboration developed a classification system through a systematic literature review, development of a clinically logical model, and presentation to stakeholders for feedback and refinement. Classification factors included parity (nulliparous, parous), previous caesarean section (CS), gestational age (≤36, 37-38, 39-40, ≥41 weeks gestation), number (singleton, multiple) and presentation of the fetus (cephalic, non-cephalic). We determined: the size of each classification group, the contribution each group made to overall IOL rates, and within-group IOL rates (calculated as proportions of all maternities, all maternities excluding prelabour CS and of all continuing maternities). MAIN OUTCOME MEASURES Applicability of IOL classification using routinely collected obstetric data. RESULTS A 10 group classification system was developed. Of all maternities, 25.4% were induced. Nulliparous and parous women without a prior CS at 39-40 weeks gestation with a singleton cephalic-presenting fetus were the largest groups (21.2% and 24.5% respectively) and accounted for the highest proportion of all IOL (20.7% and 21.5% respectively). The highest within group IOL rates were for nullipara (53.8%) and multipara (45.5%) ≥41 weeks gestation. CONCLUSION We propose a classification system for IOL that has the attributes of simplicity and clarity, utilises information that is readily and reliably collected and reported, and enables standard characterisation of populations of women having an IOL.NHMRC 1021025, ARC FT12010006

Adolescents’ responses to the promotion and flavouring of e-cigarettes

Objectives The purpose of the study is to examine adolescents’ awareness of e-cigarette marketing and investigate the impact of e-cigarette flavour descriptors on perceptions of product harm and user image. Methods Data come from the 2014 Youth Tobacco Policy Survey, a cross-sectional in-home survey conducted with 11–16 year olds across the UK (n = 1205). Adolescents’ awareness of e-cigarette promotion, brands, and flavours was assessed. Perceptions of product harm, and likely user of four examples of e-cigarette flavours was also examined. Results Some participants had tried e-cigarettes (12 %) but regular use was low (2 %) and confined to adolescents who had also smoked tobacco. Most were aware of at least one promotional channel (82 %) and that e-cigarettes came in different flavours (69 %). Brand awareness was low. E-cigarettes were perceived as harmful (M = 3.54, SD = 1.19) but this was moderated by product flavours. Fruit and sweet flavours were perceived as more likely to be tried by young never smokers than adult smokers trying to quit (p < 0.001). Conclusions There is a need to monitor the impact of future market and regulatory change on youth uptake and perceptions of e-cigarettes

Analyzing Recent Coronary Heart Disease Mortality Trends in Tunisia between 1997 and 2009.

BACKGROUND: In Tunisia, Cardiovascular Diseases are the leading causes of death (30%), 70% of those are coronary heart disease (CHD) deaths and population studies have demonstrated that major risk factor levels are increasing. OBJECTIVE: To explain recent CHD trends in Tunisia between 1997 and 2009. METHODS: DATA SOURCES: Published and unpublished data were identified by extensive searches, complemented with specifically designed surveys. ANALYSIS: Data were integrated and analyzed using the previously validated IMPACT CHD policy model. Data items included: (i)number of CHD patients in specific groups (including acute coronary syndromes, congestive heart failure and chronic angina)(ii) uptake of specific medical and surgical treatments, and(iii) population trends in major cardiovascular risk factors (smoking, total cholesterol, systolic blood pressure (SBP), body mass index (BMI), diabetes and physical inactivity). RESULTS: CHD mortality rates increased by 11.8% for men and 23.8% for women, resulting in 680 additional CHD deaths in 2009 compared with the 1997 baseline, after adjusting for population change. Almost all (98%) of this rise was explained by risk factor increases, though men and women differed. A large rise in total cholesterol level in men (0.73 mmol/L) generated 440 additional deaths. In women, a fall (-0.43 mmol/L), apparently avoided about 95 deaths. For SBP a rise in men (4 mmHg) generated 270 additional deaths. In women, a 2 mmHg fall avoided 65 deaths. BMI and diabetes increased substantially resulting respectively in 105 and 75 additional deaths. Increased treatment uptake prevented about 450 deaths in 2009. The most important contributions came from secondary prevention following Acute Myocardial Infarction (AMI) (95 fewer deaths), initial AMI treatments (90), antihypertensive medications (80) and unstable angina (75). CONCLUSIONS: Recent trends in CHD mortality mainly reflected increases in major modifiable risk factors, notably SBP and cholesterol, BMI and diabetes. Current prevention strategies are mainly focused on treatments but should become more comprehensive

A robust SNP barcode for typing Mycobacterium tuberculosis complex strains

Strain-specific genomic diversity in the Mycobacterium tuberculosis complex (MTBC) is an important factor in pathogenesis that may affect virulence, transmissibility, host response and emergence of drug resistance. Several systems have been proposed to classify MTBC strains into distinct lineages and families. Here, we investigate single-nucleotide polymorphisms (SNPs) as robust (stable) markers of genetic variation for phylogenetic analysis. We identify ~92k SNP across a global collection of 1,601 genomes. The SNP-based phylogeny is consistent with the gold-standard regions of difference (RD) classification system. Of the ~7k strain-specific SNPs identified, 62 markers are proposed to discriminate known circulating strains. This SNP-based barcode is the first to cover all main lineages, and classifies a greater number of sublineages than current alternatives. It may be used to classify clinical isolates to evaluate tools to control the disease, including therapeutics and vaccines whose effectiveness may vary by strain type

Classical and semi-classical energy conditions

The standard energy conditions of classical general relativity are (mostly) linear in the stress-energy tensor, and have clear physical interpretations in terms of geodesic focussing, but suffer the significant drawback that they are often violated by semi-classical quantum effects. In contrast, it is possible to develop non-standard energy conditions that are intrinsically non-linear in the stress-energy tensor, and which exhibit much better well-controlled behaviour when semi-classical quantum effects are introduced, at the cost of a less direct applicability to geodesic focussing. In this article we will first review the standard energy conditions and their various limitations. (Including the connection to the Hawking--Ellis type I, II, III, and IV classification of stress-energy tensors). We shall then turn to the averaged, nonlinear, and semi-classical energy conditions, and see how much can be done once semi-classical quantum effects are included.Comment: V1: 25 pages. Draft chapter, on which the related chapter of the book "Wormholes, Warp Drives and Energy Conditions" (to be published by Springer), will be based. V2: typos fixed. V3: small typo fixe

Get screened: a pragmatic randomized controlled trial to increase mammography and colorectal cancer screening in a large, safety net practice

Abstract Background Most randomized controlled trials of interventions designed to promote cancer screening, particularly those targeting poor and minority patients, enroll selected patients. Relatively little is known about the benefits of these interventions among unselected patients. Methods/Design "Get Screened" is an American Cancer Society-sponsored randomized controlled trial designed to promote mammography and colorectal cancer screening in a primary care practice serving low-income patients. Eligible patients who are past due for mammography or colorectal cancer screening are entered into a tracking registry and randomly assigned to early or delayed intervention. This 6-month intervention is multimodal, involving patient prompts, clinician prompts, and outreach. At the time of the patient visit, eligible patients receive a low-literacy patient education tool. At the same time, clinicians receive a prompt to remind them to order the test and, when appropriate, a tool designed to simplify colorectal cancer screening decision-making. Patient outreach consists of personalized letters, automated telephone reminders, assistance with scheduling, and linkage of uninsured patients to the local National Breast and Cervical Cancer Early Detection program. Interventions are repeated for patients who fail to respond to early interventions. We will compare rates of screening between randomized groups, as well as planned secondary analyses of minority patients and uninsured patients. Data from the pilot phase show that this multimodal intervention triples rates of cancer screening (adjusted odds ratio 3.63; 95% CI 2.35 - 5.61). Discussion This study protocol is designed to assess a multimodal approach to promotion of breast and colorectal cancer screening among underserved patients. We hypothesize that a multimodal approach will significantly improve cancer screening rates. The trial was registered at Clinical Trials.gov NCT00818857http://deepblue.lib.umich.edu/bitstream/2027.42/78264/1/1472-6963-10-280.xmlhttp://deepblue.lib.umich.edu/bitstream/2027.42/78264/2/1472-6963-10-280.pdfPeer Reviewe

Whistle communication in mammal-eating killer whales (Orcinus orca): further evidence for acoustic divergence between ecotypes

Public signaling plays an important role in territorial and sexual displays in animals; however, in certain situations, it is advantageous to keep signaling private to prevent eavesdropping by unintended receivers. In the northeastern Pacific, two populations of killer whales (Orcinus orca), fish-eating “resident” killer whales and mammal-eating “transient” killer whales, share the same habitat. Previous studies have shown that residents use whistles as private signals during close-range communication, where they probably serve to coordinate behavioral interactions. Here, we investigated the whistling behavior of mammal-eating killer whales, and, based on divergent social structures and social behaviors between residents and transients, we predicted to find differences in both whistle usage and whistle parameters. Our results show that, like resident killer whales, transients produce both variable and stereotyped whistles. However, clear differences in whistle parameters between ecotypes show that the whistle repertoire of mammal-eating killer whales is clearly distinct from and less complex than that of fish-eating killer whales. Furthermore, mammal-eating killer whales only produce whistles during “milling after kill” and “surface-active” behaviors, but are almost completely silent during all other activities. Nonetheless, whistles of transient killer whales may still serve a role similar to that of resident killer whales. Mammal-eating killer whales seem to be under strong selection to keep their communication private from potential prey (whose hearing ranges overlap with that of killer whales), and they appear to accomplish this mainly by restricting vocal activity rather than by changes in whistle parameters