Use of 15N NMR spectroscopy to probe covalency in a thorium nitride.

Reaction of the thorium metallacycle, [Th{N(R)(SiMe2)CH2}(NR2)2] (R = SiMe3) with 1 equiv. of NaNH2 in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et2O)][(R2N)3Th(μ-N)(Th(NR2)3] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe2)CH2}(NR2)2] by NaNH2, which results in formation of the thorium bis(metallacycle) complex, [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)], and NH3. NH3 then reacts with unreacted [Th{N(R)(SiMe2)CH2}(NR2)2], forming [Th(NR2)3(NH2)] (2), which protonates [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)] to give [Na][1]. Consistent with hypothesis, addition of excess NH3 to a THF solution of [Th{N(R)(SiMe2)CH2}(NR2)2] results in formation of [Th(NR2)3(NH2)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] with 2, in THF-d 8, results in clean formation of [K][1], according to 1H NMR spectroscopy. The electronic structures of [1]- and 2 were investigated by 15N NMR spectroscopy and DFT calculations. This analysis reveals that the Th-Nnitride bond in [1]- features more covalency and a greater degree of bond multiplicity than the Th-NH2 bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]- vs. comparable thorium imido and oxo complexes

Leadership Styles and Innovative Entrepreneurship: An International Study

This research attempts to empirically examine the relationship between leadership styles and innovative entrepreneurship through regression analysis, using a sample of 43 countries and data from Global Entrepreneurship Monitor and Global Leadership and Organizational Behavior Effectiveness. In light of institutional approaches and specifically based on the normative dimension, the main findings of the study indicate that participative leadership and higher education represent the strongest explanatory factor in the variance of the current rates of innovative entrepreneurship. This study has contributions for both researchers and policymakers on new firm creation (entrepreneurship) and on the generation of innovation within organizations (intrapreneurship).Stefan van Hemmen acknowledges the financial resources from ECO2013-48496-C4-4-R (Spanish Ministry of Economy & Competitiveness) and 2014-SGR-1259 (Economy & Knowledge Department -Catalan Government-). Marta Peris-Ortiz acknowledges support from the Universitat Politecnica de Valencia through the project Paid-06-12 (Sp 20120792). Claudia Alvarez and David Urbano acknowledge the financial support from the Projects ECO2013-44027-P (Spanish Ministry of Economy & Competitiveness) and 2014-SGR-1626)Economy & Knowledge Department -Catalan Government-).Van Hemmen, S.; Alvarez, C.; Peris-Ortiz, M.; Urbano, D. (2015). Leadership Styles and Innovative Entrepreneurship: An International Study. Cybernetics and Systems. 46(3-4):271-286. https://doi.org/10.1080/01969722.2015.1012896S271286463-

The role of measuring exhaled breath biomarkers in sarcoidosis: A systematic review

Introduction: Sarcoidosis is a chronic granulomatous disease of unknown aetiology with a variable clinical course and prognosis. There is a growing need to identify non-invasive biomarkers to differentiate between clinical phenotypes, identify those at risk of disease progression and monitor response to treatment. Objectives: We undertook a systematic review and meta-analysis, to evaluate the utility of breath-based biomarkers in discriminating sarcoidosis from healthy controls, alongside correlation with existing non-breath based biomarkers used in clinical practice, radiological stage, markers of disease activity and response to treatment. Methods: Electronic searches were undertaken during November 2017 using PubMed, Ebsco, Embase and Web of Science to capture relevant studies evaluating breath-based biomarkers in adult patients with sarcoidosis. Results: 353 papers were screened; 21 met the inclusion criteria and assessed 25 different biomarkers alongside VOCs in exhaled breath gas or condensate. Considerable heterogeneity existed amongst the studies in terms of participant characteristics, sampling and analytical methods. Elevated biomarkers in sarcoidosis included 8-isoprostane, carbon monoxide, neopterin, TGF-β1, TNFα, CysLT and several metallic elements including chromium, silicon and nickel. Three studies exploring VOCs were able to distinguish sarcoidosis from controls. Meta-analysis of four studies assessing alveolar nitric oxide showed no significant difference between sarcoidosis and healthy controls (2.22ppb; 95% CI -0.83, 5.27) however, a high degree of heterogeneity was observed with an I2 of 93.4% (p<0.001). Inconsistent or statistically insignificant results were observed for correlations between several biomarkers and radiological stage, markers of disease activity or treatment. Conclusions: The evidence for using breath biomarkers to diagnose and monitor sarcoidosis remains inconclusive with many studies limited by small sample sizes and lack of standardisation. VOCs have shown promising potential but further research is required to evaluate their prognostic role

The presentation, diagnosis and management of non-traumatic wrist pain: an evaluation of current practice in secondary care in the UK NHS

AbstractObjectivesThe study aims were to assess the burden of non-traumatic wrist pain in terms of numbers of referrals to secondary care, and to characterise how patients present, are diagnosed and are managed in secondary care in the United Kingdom National Health Service.MethodsTen consecutive patients presenting with non-traumatic wrist pain were identified retrospectively at each of 16 participating hospitals and data was extracted for twelve months following the initial referral.ResultsThe 160 patients consisted of 100 females and 60 males with a median age of 49, accounting for approximately 13% of all new hand/wrist referrals. The dominant wrist was affected in 60% of cases and the mean symptom duration was 13.3 months. Diagnoses were grouped into: osteoarthritis (OA) (31%), tendinopathy (13%), ganglion (14%), ulnar sided pain (17%) and other (25%). The OA group was significantly older than other groups, while other groups contained a predominance of females.The non-surgical interventions in decreasing frequency of usage were: steroid injections (39%), physiotherapy (32%), splint (31%) and analgesics (12%). Of those who underwent surgery, all patients had previously received non-surgical treatment, however 42% had undergone only one non-surgical intervention.ConclusionNon-traumatic wrist pain represents a significant burden to secondary care both in terms of new patient referrals and in terms of investigation, follow up and treatment. Those presenting with osteoarthritis are more likely to be older and male, while those presenting with other diagnoses are more likely to be younger and female

'Let the Right Ones In!': Widening Participation, Academic Writing and the Standards Debate in Higher Education

This paper challenges the frequently expressed concern, post-1992, that widening participation (WP) has contributed to a general ‘dumbing down’ of higher education in English universities *(Burke, 2005; Leathwood, 2010). In particular, it explores the implications of a long-standing ‘moral panic’ (Cohen, 1972) about the poor quality of students’ academic writing, particularly in the ‘new’ universities, which have been raised in various academic reports and countless media articles. A vampire metaphor is used throughout the paper to highlight ways in which assumptions about these falling standards in undergraduates’ academic writing feed on the foundations of a longstanding, albeit implicit, distrust of the growth in the sector on elitist, ideological grounds. The second half of the paper investigates how academic writing practices, whilst difficult to define, nonetheless wield a ‘disciplinary power’ (Foucault, 1980), over lecturers and students in the academy. This includes a discussion about how a situated, New Literacy Studies (NLS) approach to academic writing development challenges the view that students’ academic writing standards are falling. In contrast, the paper suggests that all universities have a responsibility to acknowledge and develop the different literacies that students, especially widening participation students, bring with them to university. (193

The Lung Screen Uptake Trial (LSUT): protocol for a randomised controlled demonstration lung cancer screening pilot testing a targeted invitation strategy for high risk and ‘hard-to-reach’ patients

Background Participation in low-dose CT (LDCT) lung cancer screening offered in the trial context has been poor, especially among smokers from socioeconomically deprived backgrounds; a group for whom the risk-benefit ratio is improved due to their high risk of lung cancer. Attracting high risk participants is essential to the success and equity of any future screening programme. This study will investigate whether the observed low and biased uptake of screening can be improved using a targeted invitation strategy. Methods/design A randomised controlled trial design will be used to test whether targeted invitation materials are effective at improving engagement with an offer of lung cancer screening for high risk candidates. Two thousand patients aged 60–75 and recorded as a smoker within the last five years by their GP, will be identified from primary care records and individually randomised to receive either intervention invitation materials (which take a targeted, stepped and low burden approach to information provision prior to the appointment) or control invitation materials. The primary outcome is uptake of a nurse-led ‘lung health check’ hospital appointment, during which patients will be offered a spirometry test, an exhaled carbon monoxide (CO) reading, and an LDCT if eligible. Initial data on demographics (i.e. age, sex, ethnicity, deprivation score) and smoking status will be collected in primary care and analysed to explore differences between attenders and non-attenders with respect to invitation group. Those who attend the lung health check will have further data on smoking collected during their appointment (including pack-year history, nicotine dependence and confidence to quit). Secondary outcomes will include willingness to be screened, uptake of LDCT and measures of informed decision-making to ensure the latter is not compromised by either invitation strategy. Discussion If effective at improving informed uptake of screening and reducing bias in participation, this invitation strategy could be adopted by local screening pilots or a national programme. Trial registration This study was registered with the ISRCTN (International Standard Registered Clinical/soCial sTudy Number : ISRCTN21774741) on the 23rd September 2015 and the NIH ClinicalTrials.gov database (NCT0255810) on the 22nd September 2015

Bioavailability of prednisolone tablets

Two fourtreatment crossover studies were performed using 12 adult male volunteers in each with seven different commercially available prednisolone tablets. Plasma samples were assayed for prednisolone by a radioimmunoassay method. Statisacal analyses of the data, by analysis of variance for crossover design (ANOVA), showed no significant differences among the treatment averages at any of the sampling times except at 0.25 and 4 hr in one of the studies. There were also no significant differences among the treatment averages for peak plasma level, time of peak plasma level, area 0–12 hr, area 0–24 hr, and the halflife of elimination of prednisolone. We conclude that the average plasma concentrations of prednisolone are superimposable in a statistical sense and that the tablets tested are bioequivalent. Results of dissolution studies of six tablets of each of the seven lots of prednisolone tablets, using deaerated water in the spin filter apparatus, are presented.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45072/1/10928_2005_Article_BF01065399.pd