Infrared spectroscopic studies of hydrogen bonding in substituted nitrophenols: substituent and solvent effects

A detailed infrared spectroscopic study of the substituted phenols 2-cyano-4,6-dinitrophenol and 4-cyano-2,6-dinitrophenol has been carried out (in several different solvents) in order to investigate the substituent and solvent effects on their intra- and inter-molecular hydrogen bonding properties. In benzene or dichloromethane it is found that both isomers form strong intramolecular hydrogen bonds with the 2-cyano (2CN) isomer having a stronger intramolecular interaction (in accordance with the higher pKa). The 4-cyano (4CN) isomer shows two distinct NO2 groups and exchange between the two possible hydrogen bonding sites is probably slow on the infrared time-scale. In protic solvents such as methanol the intramolecular hydrogen bonds are broken (more easily for the 4CN isomer) by intermolecular hydrogen bonding to the solvent. The differential “reactivity” towards methanol may be associated with steric congestion in the 4CN isomer leading to the forcing of at least one of the NO2 groups out of the aromatic plane. The use of mixed solvents (benzene-methanol) has established that the two hydrogen bonded species are observed together and that a high concentration of methanol is required to drive the equilibrium towards the intermolecular hydrogen bonded species. In dimethyl sulphoxide the behaviour of the two isomers is even more interesting. The 4CN isomer is ionised to produce the corresponding phenolate. However the 2CN isomer remains neutral (but highly solvated). We attribute this difference to the requirement for the 4CN isomer to allow the 2- and 6-NO2 groups to recover planarity with the aromatic ring. The energy compensation involved in this process is clearly sufficient to break a stronger intramolecular hydrogen bond.info:eu-repo/semantics/publishedVersio

The basicity of alkali metal methoxides in methanol. The effects of ion association on methoxide additions to activated anisoles

The formation of adducts with 1 :2 and 1:3 stoichiometry by methoxide addition to nitro-activated anisoles has been examined spectrophotometrically. For these equilibria the ‘basicity’ of sodium methoxide solutions in methanol is appreciably greater than that of corresponding potassium methoxide solutions. This is in contrast with other measures of basicity and is attributed to the association of the multi-charged adducts with cations which is stronger with sodium than with potassium ions.info:eu-repo/semantics/publishedVersio

Building a grounded theory: some reflections

This article focuses on some of our reflections of using processes inherent within classic grounded theory methodology to build knowledge surrounding military personnel who experienced combat-related limb-loss from the Iraq and Afghanistan conflicts. We conclude that instead of adding to the issue of mixing different grounded theory perspectives, researchers should instead follow guidance from one approach to avoid becoming perplexed as each strand produces a different product. This article provides our own philosophy and compatibility with a classic grounded theory approach, and we encourage researchers to capitalise on the wealth of exemplar theories within the Grounded Theory Review journal and to engage with Barney Glaser’s books

Optimising informed consent in school-based adolescent vaccination programmes in England: A multiple methods analysis.

The process of obtaining informed consent for school-based adolescent immunisation provides an opportunity to engage families. However, the fact that parental consent needs to be obtained remotely adds complexity to the process and can have a detrimental effect on vaccine uptake. We conducted a multiple methods analysis to examine the practice of obtaining informed consent in adolescent immunisation programmes. This involved a thematic analysis of consent related data from 39 interviews with immunisation managers and providers collected as part of a 2017 service evaluation of the English adolescent girls' HPV vaccine programme and a descriptive statistical analysis of data from questions related to consent included in a 2017 survey of parents' and adolescents' attitudes to adolescent vaccination. The findings indicated that the non-return of consent forms was a significant logistical challenge for immunisation teams, and some were piloting opt-out consent mechanisms, increasing the proportion of adolescents consenting for their own immunisations, and introducing electronic consent. Communicating vaccine related information to parents and schools and managing uncertainties about obtaining adolescent self-consent for vaccination were the main practical challenges encountered. Survey data showed that parents and adolescents generally agreed on vaccine decisions although only 32% of parents discussed vaccination with their teenager. Parental awareness about the option for adolescents to self-consent for vaccination was limited and adolescents favoured leaving the decision-making to parents. From the interviews and variability of consent forms it was evident that health professionals were not always clear about the best way to manage the consent process. Some were also unfamiliar with self-consent processes and lacked confidence in assessing for 'Gillick competency'. Developing pathways and related interventions to improve the logistics and practice of consent in school-based adolescent immunisation programmes could help improve uptake

Strengthening HPV vaccination delivery: findings from a qualitative service evaluation of the adolescent girls' HPV vaccination programme in England.

BACKGROUND: In 2014, the number of HPV vaccine doses given to adolescent girls as part of the English school-based immunization programme was reduced from three to two. This was based on evidence that a two-dose schedule provides long-lasting protection against HPV infection. In 2015/16 a small decline in HPV vaccination coverage in adolescent girls was noted; from 86.7% for the three-dose schedule in 2013/14 to 85.1% for the two-dose schedule. This evaluation examined whether service-related factors contributed to this decline. METHODS: In May-August 2017, we conducted semi-structured qualitative interviews with 39 participants responsible for commissioning or delivering immunization programmes in six local authorities in the South West, North Central Midlands and South Central Midlands, England. RESULTS: Effective planning and data management were key for successful service provision of HPV vaccination, as well as close collaboration between commissioners, service providers and data system managers, a team skill mix with experienced staff, pro-active engagement with schools and service providers equipped to respond to parental concerns. CONCLUSIONS: To maintain and improve the high HPV adolescent girls' vaccine coverage rates achieved in England, in the context of an expanding school-based immunization programme, it is essential to strengthen the organizational capacity of the delivery system

Organisational factors affecting performance in delivering influenza vaccination to staff in NHS Acute Hospital Trusts in England: A qualitative study.

Health care workers are a priority group for seasonal influenza vaccination, which is recommended by the World Health Organisation. There is a wide variation in uptake between and within countries. England has achieved 69.5% of health care workers vaccinated overall in 2017/18 across NHS acute and community health care settings, but it varies between Trusts from 50% to over 92.3%. While attitudinal factors have been well researched, there is limited evidence on organisational factors associated with high uptake. In England, most NHS Trusts are now implementing a similar range of interventions as part of their flu programme, and it remains unclear why performance remains so variable. This qualitative study is the first to explore reasons for this variation and provide recommendations for lower performing Trusts on how to improve. Fifty-seven interviews of managers and vaccinators were conducted in nine hospitals with flu vaccination uptake ranging from just over 55% to above 90%. Our study found that while Trusts deployed a wide range of both demand generating and supply interventions to increase uptake, there were marked differences in the organisational and delivery models utilised. Our study suggests that organisational culture was possibly the most important ingredient when trying to differentiate between high and low performing Trusts. We found that a positive culture aimed at fostering continuous improvement and favouring non-coercion on balance yielded more adherence from staff. Where influenza vaccination was embedded in the organisation wellbeing strategy, rather than executed as a siloed seasonal programme, this tended to foster good performance. Improving performance of influenza vaccination in health care workers will involve not only deploying the right interventions, and following "best practices". It will require the adaptation of flu progamme delivery strategies to the organisation context, and embedding vaccination into the organisational culture, thus supporting the normalisation of yearly vaccination

Global patient outcomes after elective surgery: prospective cohort study in 27 low-, middle- and high-income countries.

BACKGROUND: As global initiatives increase patient access to surgical treatments, there remains a need to understand the adverse effects of surgery and define appropriate levels of perioperative care. METHODS: We designed a prospective international 7-day cohort study of outcomes following elective adult inpatient surgery in 27 countries. The primary outcome was in-hospital complications. Secondary outcomes were death following a complication (failure to rescue) and death in hospital. Process measures were admission to critical care immediately after surgery or to treat a complication and duration of hospital stay. A single definition of critical care was used for all countries. RESULTS: A total of 474 hospitals in 19 high-, 7 middle- and 1 low-income country were included in the primary analysis. Data included 44 814 patients with a median hospital stay of 4 (range 2-7) days. A total of 7508 patients (16.8%) developed one or more postoperative complication and 207 died (0.5%). The overall mortality among patients who developed complications was 2.8%. Mortality following complications ranged from 2.4% for pulmonary embolism to 43.9% for cardiac arrest. A total of 4360 (9.7%) patients were admitted to a critical care unit as routine immediately after surgery, of whom 2198 (50.4%) developed a complication, with 105 (2.4%) deaths. A total of 1233 patients (16.4%) were admitted to a critical care unit to treat complications, with 119 (9.7%) deaths. Despite lower baseline risk, outcomes were similar in low- and middle-income compared with high-income countries. CONCLUSIONS: Poor patient outcomes are common after inpatient surgery. Global initiatives to increase access to surgical treatments should also address the need for safe perioperative care. STUDY REGISTRATION: ISRCTN5181700

FAR INFRARED INTENSITY STUDIES ON CHARGE TRANSFER COMPLEXES OF IODINE AND IODINE MONOCHLORIDE

Financial support from Public Health Service Research Grant No. GM-10168 from the Division of General Medicine, PHS, is gratefully acknowledged. $^{1}$ W. B. Person, R. E. Humphrey, W. A. Deskin and A. I. Popov, J. Am. Chem, Soc. 80, 2049 (1958). $^{2}$ W. B. Person, R. E. Humphrey and A. I. Popov, J. Am Chem. Soc. 81, 273 (1959). $^{3}$ W. B. Person, R. E. Erickson and R. E. Buckles, J. Am. Chem. Soc. 82, 29 (1960). $^{4}$ H. B. Friedrich and W. B. Person, J. Chem. Phys. 44, 2161 (1966).Author Institution: Department of Chemistry, University of IowaThe infrared intensities of the $\nu(I-CI), \nu(I-I)$ and $\nu (D-A)$ vibrational bands found in charge-transfer complexes of n and $\pi$ electron donors with $I_{2}$ and ICl have been measured in benzene and n-heptane solutions. A Beckman IR-11 spectrometer was used together with a cell constructed of high density polyethylene. Pathlength calibrations have been carried out using bands of known intensity in pure liquid $CHCl_{2} CCl_{4}$ and benzene, and it has been shown that the pathlength variation when using such a cell is sufficiently small to give good Beers Law plots and intensity values with a random error of less than $\pm 12$. The results extend the $earlier^{1-2}$ higher frequency intensity studies on complexes with $Br_{2}, ICl$ and ICN. Quantitative confirmation that the intensity of the $\nu(N-I)$ vibration is significantly lower than that of the $\nu (I-Cl)$ vibration in the pyridine-ICl complex has been obtained, indicating a smaller vibronic $effect^{4}$ in the former vibration

MICROWAVE SPECTRUM OF DIAZOACETONITRILE (N2:CH⋅CN)(N_{2}:CH \cdot CN).

Author Institution: Division of Pure Physics, National Research CouncilThe microwave spectrum of $N_{2}:CH\cdot CN$ has been studied between 12 and 28 kMc/sec at a temperature of between -30 and $-35^{\circ}C$. Preliminary rotational constants for the normal isotopic species in the ground state are $A = 29,102.6$ Mc/sec., $B = 3024.8$ Mc/sec., and $C = 2735.7$ Mc/sec. The value of the inertial defect, $\Delta = +0.291$ amu$\cdot$ {\AA}$^{2}$, indicates that the molecule is planar. Lines in the spectrum due to molecules in the first excited state of a vibration with a frequency of approximately $115 cm^{-1}$ have been observed