31 research outputs found

    An investigation of alternative separation strategies for common chemical mixtures by means of host-guest chemistry protocols with host compounds N,Nâ€Č- bis(5-phenyl-5-dibenzo[a,d]cycloheptenyl)ethylenediamine and N,N’-bis(5-phenyl-10,11- dihydro-5-dibenzo[a,d]cycloheptenyl)ethylenediamine

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    In this work, the selectivity behaviour of two host compounds, namely N,N’-bis(5-phenyl-5- ibenzo[a,d]cycloheptenyl)ethylenediamine (H1) and N,N’-bis(5-phenyl-10,11-dihydro-5- ibenzo[a,d]cycloheptenyl)ethylenediamine (H2), was assessed in mixtures of difficult-toseparate compounds, including the xylenes and ethylbenzene, pyridine and methylpyridines, and anisole and methylanisoles. These host compounds were synthesized using Grignard addition reactions with phenylmagnesium bromide on dibenzo[a,d]cyclohepten-5-one and 10,11- dihydrodibenzo[a,d]cyclohepten-5-one, respectively. The resultant alcohols were treated with perchloric acid to form the corresponding perchlorate salts, which were then reacted with ethylenediamine to afford the required H1 and H2 host compounds. Yields were 95 ad 52% for this final step in each case. An investigation of the conformations, both from experiment (using single crystal X-ray diffractometry (SCXRD) on the apohost compound) and computational calculations was undertaken. Unfortunately, H1 always crystallized out as a powder unless this host compound formed a complex with a guest species, and so could not be subjected to SCXRD analysis as apohost alone. However, a single crystal structure for apohost H2 was successfully obtained and compared with computational data from a previous investigation. It was observed that the conformation of apohost H2 compared favourably with that of the lowest energy conformer from that work. In single solvent recrystallization experiments with o-, m-, p-xylene (o-Xy, m-Xy, p-Xy) and ethylbenzene (EB), both H1 and H2 formed complexes with only one of the four guest species, namely p-Xy and o-Xy, respectively. The host:guest (H:G) ratios were 1:1 for both of these complexes. In the equimolar guest/guest competition experiments, inclusion complexes only formed when p-Xy or o-Xy, respectively, were present in the mixtures; if p-Xy (for experiments with H1) or o-Xy (H2) was absent from these mixtures, only apohost was recovered from the glass vessels. Three selectivity profiles were constructed for each of these host compounds, in which each one was recrystallized from binary mixed guests in various proportions. These demonstrated an overwhelming preference of H1 for p-Xy and H2 for o-Xy, which concurred with the results from the equimolar experiments. Thermal analysis using H1∙p-Xy revealed that this complex was unstable at ambient conditions, while SCXRD explained this observation: this complex may be defined as a true clathrate since no host‧‧‧guest interactions were identified at all, and the guest was retained in the complex by means of steric factors alone. Furthermore, the guest molecules resided in wide open channels that may have facilitated the guest release process. H2∙o-Xy, on the other hand, was stable at room temperature, and the guest release event only commenced at 69.7 °C (Ton). This too was explained by SCXRD analyses in that interactions between host and guest species were observed in this case. Additionally, the guest molecules were housed in discrete cages, which made their escape more challenging compared with p-Xy in H1∙p-Xy. It was concluded that, in this guest series, both of the host compounds would be effective as separatory tools employing host-guest chemistry protocols due to their remarkable selectivities for p-Xy (H1) and o-Xy (H2).Thesis (MSc) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 202

    Purposeful leadership for the future police service

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    Purpose – This paper examines the prevalence of purposeful and ethical leadership in a UK county police force – referred to by the pseudonym PoliceOrg. It also evaluates the extent to which officers feel their values fit with those of the organisation, and the outcomes achieved by purposeful and ethical leaders. Design/methodology/approach – A questionnaire survey, interviews and focus groups were conducted at PoliceOrg. Findings are compared with those from a public sector case study and with a representative sample of the UK working population. Findings – Purposeful leaders at PoliceOrg have a positive impact on important outcomes for their direct reports, and provide a sense of direction and guidance to those who do not feel a strong fit between their values and those of their organisation. Research limitations/implication – The study focuses on a new construct (purposeful leadership) that has not previously been explored in the academic literature. Consequently, our findings cannot be directly compared with those of other studies. The survey focused on the views of police sergeants and constables, and only one police force participated as a case study; hence, the generalisability of the findings is limited. Practical implication – Police organisations should nurture and sustain workplace environments where leaders can translate their personal moral code and ethical values into their role behaviours to address the policing challenges of the future. Originality/value – This study elucidates the concept of purposeful leadership in the context of a police force

    An investigation of alternative separation strategies for common chemical mixtures by means of host-guest chemistry protocols with host compounds N,Nâ€Č- bis(5-phenyl-5-dibenzo[a,d]cycloheptenyl)ethylenediamine and N,N’-bis(5-phenyl-10,11- dihydro-5-dibenzo[a,d]cycloheptenyl)ethylenediamine

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    In this work, the selectivity behaviour of two host compounds, namely N,N’-bis(5-phenyl-5- ibenzo[a,d]cycloheptenyl)ethylenediamine (H1) and N,N’-bis(5-phenyl-10,11-dihydro-5- ibenzo[a,d]cycloheptenyl)ethylenediamine (H2), was assessed in mixtures of difficult-toseparate compounds, including the xylenes and ethylbenzene, pyridine and methylpyridines, and anisole and methylanisoles. These host compounds were synthesized using Grignard addition reactions with phenylmagnesium bromide on dibenzo[a,d]cyclohepten-5-one and 10,11- dihydrodibenzo[a,d]cyclohepten-5-one, respectively. The resultant alcohols were treated with perchloric acid to form the corresponding perchlorate salts, which were then reacted with ethylenediamine to afford the required H1 and H2 host compounds. Yields were 95 ad 52% for this final step in each case. An investigation of the conformations, both from experiment (using single crystal X-ray diffractometry (SCXRD) on the apohost compound) and computational calculations was undertaken. Unfortunately, H1 always crystallized out as a powder unless this host compound formed a complex with a guest species, and so could not be subjected to SCXRD analysis as apohost alone. However, a single crystal structure for apohost H2 was successfully obtained and compared with computational data from a previous investigation. It was observed that the conformation of apohost H2 compared favourably with that of the lowest energy conformer from that work. In single solvent recrystallization experiments with o-, m-, p-xylene (o-Xy, m-Xy, p-Xy) and ethylbenzene (EB), both H1 and H2 formed complexes with only one of the four guest species, namely p-Xy and o-Xy, respectively. The host:guest (H:G) ratios were 1:1 for both of these complexes. In the equimolar guest/guest competition experiments, inclusion complexes only formed when p-Xy or o-Xy, respectively, were present in the mixtures; if p-Xy (for experiments with H1) or o-Xy (H2) was absent from these mixtures, only apohost was recovered from the glass vessels. Three selectivity profiles were constructed for each of these host compounds, in which each one was recrystallized from binary mixed guests in various proportions. These demonstrated an overwhelming preference of H1 for p-Xy and H2 for o-Xy, which concurred with the results from the equimolar experiments. Thermal analysis using H1∙p-Xy revealed that this complex was unstable at ambient conditions, while SCXRD explained this observation: this complex may be defined as a true clathrate since no host‧‧‧guest interactions were identified at all, and the guest was retained in the complex by means of steric factors alone. Furthermore, the guest molecules resided in wide open channels that may have facilitated the guest release process. H2∙o-Xy, on the other hand, was stable at room temperature, and the guest release event only commenced at 69.7 °C (Ton). This too was explained by SCXRD analyses in that interactions between host and guest species were observed in this case. Additionally, the guest molecules were housed in discrete cages, which made their escape more challenging compared with p-Xy in H1∙p-Xy. It was concluded that, in this guest series, both of the host compounds would be effective as separatory tools employing host-guest chemistry protocols due to their remarkable selectivities for p-Xy (H1) and o-Xy (H2).Thesis (MSc) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 202

    The United Kingdom and the Netherlands maternity care responses to COVID-19: A comparative study

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    BackgroundThe national health care response to coronavirus (COVID-19) has varied between countries. The United Kingdom (UK) and the Netherlands (NL) have comparable maternity and neonatal care systems, and experienced similar numbers of COVID-19 infections, but had different organisational responses to the pandemic. Understanding why and how similarities and differences occurred in these two contexts could inform optimal care in normal circumstances, and during future crises.AimTo compare the UK and Dutch COVID-19 maternity and neonatal care responses in three key domains: choice of birthplace, companionship, and families in vulnerable situations.MethodA multi-method study, including documentary analysis of national organisation policy and guidance on COVID-19, and interviews with national and regional stakeholders.FindingsBoth countries had an infection control focus, with less emphasis on the impact of restrictions, especially for families in vulnerable situations. Differences included care providers’ fear of contracting COVID-19; the extent to which community- and personalised care was embedded in the care system before the pandemic; and how far multidisciplinary collaboration and service-user involvement were prioritised.ConclusionWe recommend that countries should 1) make a systematic plan for crisis decision-making before a serious event occurs, and that this must include authentic service-user involvement, multidisciplinary collaboration, and protection of staff wellbeing 2) integrate women’s and families’ values into the maternity and neonatal care system, ensuring equitable inclusion of the most vulnerable and 3) strengthen community provision to ensure system wide resilience to future shocks from pandemics, or other unexpected large-scale events

    LEARNING FROM THE PAST SO THAT THE PEOPLE MAY LIVE: AN ETHNOGRAPHIC STUDY ON FEDERAL POLICIES AND MENTAL HEALTH AMONG NATIVE AMERICANS

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    Eight enrolled members of various Native tribes interviewed person- to-person, and over the phone and audio recorded, with the use of a semi-structured interview that focused on an overarching research question on what federal policies have shaped the mental health among Native members. Before any interviews were conducted, each participant received information about the research study. After individual interviews were completed, each participant recommended changes in procedure, possible research endeavors for the future, and possible individuals to interview. During the interviews, each participant provided responses that include biological, psychological, social, and cultural factors influenced by federal policies implemented on this population. These results support the Biopsychosocial model and the critical indigenous theory. The findings of the study centered around three overarching themes that related to the participants experiences. The findings focused around the themes of trauma testament, trauma response, and resiliency

    Code Switching: Are You Talking Too Black?

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    A short and efficient synthesis of (R,R)-2-methylcyclopropanecarboxylic acid

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    We report herein a short and efficient synthesis of (RR)-2methyleyclopropanecarboxylic acid via a Horner-Wadsworth-Emmons reaction involving commercially available (S)-propylene oxide and triethylphosphonoacetate (TEPA). The TEPA/ base/propylene oxide stoichiometry was found critical to achieve high yields. We therefore studied the TEPA anion formation and stability using in situ IR spectroscopy. The reaction yield is strongly influenced by the counterion and solvent, whereas high diastereoselectivities are always obtained. Under the best experimental conditions (HexLi/MeTHF/150 degrees C), crude (RR)2-methylcyclopropanecarboxylic acid is obtained in 85-90% yield with > 98% trans selectivity
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