Low temperature solvent-free allylic oxidation of cyclohexene using graphitic oxide catalysts

A range of graphitic oxides have been utilised as metal free carbocatalysts for the low temperature oxidation of cyclohexene. The activity of the catalysts was correlated with the amount of surface oxygen on the graphitic oxide. In the case of cyclohexene oxidation, major selectivity is observed to allylic oxidation products. This is in contrast to the epoxide being the major product in linear alkene oxidation. This selectivity was maintained over long reaction times and at a conversion of above 50 %. Only small amounts of epoxide were observed, which eventually decreases at higher conversion due to hydrolysis to cyclohexane diol. The similarity between the non-catalysed and the catalysed product distribution suggests that these catalysts act as a solid initiator, and the role of the graphitic oxide is to decrease the lengthy induction period observed in the blank non-catalysed reaction

A narrative review of the surgical management of Paget-Schroetter syndrome: case series and long-term follow-up

BACKGROUND AND OBJECTIVE: Paget-Schroetter syndrome (PSS) is an uncommon disorder which causes thrombosis of the subclavian vein (SV). This is due to compression of the SV by the surrounding anatomical structures. The optimal management of PSS remains subject to debate, with endovascular intervention and open surgical decompression being favoured current options. This review article evaluates both approaches to the management of PSS, while also presenting a case series with long-term follow-up of patients that underwent open surgical intervention for PSS. METHODS: The clinical outcomes of PSS patients undergoing different 4 surgical approaches to perform surgical decompression are included. A literature review, across publications from PubMed, Embase, and Web of Science, was conducted with specific criteria to facilitate evaluation of both open surgical and endovascular approaches to the management of PSS. KEY CONTENT AND FINDINGS: Evaluation of data from the included case series and available literature suggests that endovascular thrombolytic devices offer better clinical results, however, SV decompression is still required for successful resolution. CONCLUSIONS: An approach to PSS encompassing endovascular intervention followed by surgical anatomical decompression may provide optimal outcomes as both intrinsic lesions and extrinsic compression of the SV is treated. However, further prospective investigation into this field is warranted

Exploración vocacional en adolescentes: evaluación de una intervención en clase

Analisa-se o impacto de uma intervenção psicológica na exploração e tomada de decisão vocacional em adolescentes portugueses. Em contexto curricular e de classe, desenvolveram-se actividades de exploração do meio e do Eu com 39 alunos e 43 alunas do 9o ano, entre 13 e 17 anos (M=14,4, DP=0,95). Em um design pré/pós-teste, aplicaram-se o Career Exploration Survey (CES) e o Career Decision Difficulties Questionnaire (CDDQ). Os resultados do teste do sinal evidenciaram ganhos significativos (p<0,01) nas dimensões de exploração e diminuição significativa da falta de informação profissional (p<0,01) e do total das dificuldades de decisão (p<0,05). Observou-se um padrão de correlações negativas (ró de Spearman) entre as duas medidas vocacionais, evidenciando uma relação entre a informação explorada na intervenção e a diminuição das dificuldades de decisão por falta de motivação. Em geral, os resultados suportam a importância do papel da exploração da carreira na diminuição das dificuldades de tomada de decisão.This study analyses the impact of a psychological intervention to promote vocational exploration and decisionmaking in Portuguese adolescents. Activities to foster exploration of self and environment were developed in a classroom program with 39 boys and 43 girls, all 9th grade students, between 13 and 17 years of age (M=14,4, SD=0.95). Following a pre/post-test design, the Career Exploration Survey (CES), and the Career Decision Difficulties Questionnaire (CDDQ) were administered. Results of sign-test showed significant increments (p<0.01) in all of the exploration dimensions, significant reduction of lack of occupational information (p<0.01) and of the total of career decision-making difficulties (p<0.05). Negative correlations (Spearman’s rho) between the two career measures was observed, evidencing a relationship between information explored during intervention and decreased difficulty with decision-making due to lack of motivation. In general, results support the importance of career exploration on diminishing decision-making difficulties.Evalúa-se el impacto de una intervención psicológica que fomenta la exploración y la decisión vocacional en adolescentes portugueses. Fueran efectuadas actividades de exploración del medio ambiente y del yo en contexto curricular de clase con 39 alumnos y 43 alumnas del curso 3º ESO, 13 hasta 17 años (M=14,4, DP=0,95). Utilizó-se un diseño pre/posteste, con aplicación del Career Exploration Survey (CES) y Career Decision Difficulties Questionnaire (CDDQ). Resultados del test del señal evidencian beneficios significativos (p<0,01) en las dimensiones de la exploración, reducción significativa de ausencia de información ocupacional (p<0,01) y total de dificultades de decisión (p<0,05). Ha sido observado un patrón de correlaciones negativas (ró de Spearman) entre las dos medidas vocacionales, mostrando relación entre la información explorada e la disminución de las dificultades de decisión por falta de motivación. En general, resultados sostienen la importancia de la exploración de carrera en la disminución de las dificultades de decisió

Erratum to: ‘Integrated analysis of the local and systemic changes preceding the development of post-partum cytological endometritis’

ErratumErratum to: ‘Integrated analysis of the local and systemic changes preceding the development of post-partum cytological endometritis’ -http://hdl.handle.net/11019/90

Bounds on the diameter of Cayley graphs of the symmetric group

In this paper we are concerned with the conjecture that, for any set of generators S of the symmetric group of degree n, the word length in terms of S of every permutation is bounded above by a polynomial of n. We prove this conjecture for sets of generators containing a permutation fixing at least 37% of the points.Comment: 17 pages, 6 table

Retroperitoneal Compared to Transperitoneal Approach for Open Abdominal Aortic Aneurysm Repair Is Associated with Reduced Systemic Inflammation and Postoperative Morbidity

Background  In the United Kingdom, the most common surgical approach for repair of open abdominal aortic aneurysms (AAAs) is transperitoneal (TP). However, retroperitoneal (RP) approach is favored in those with more complex vascular anatomy often requiring a cross-clamp on the aorta superior to the renal arteries. This study compared these approaches in patients matched on all major demographic, comorbid, anatomic, and physiological variables. Methods  Fifty-seven patients (TP: n  = 24; RP: n  = 33) unsuitable for endovascular aneurysm repair underwent preoperative cardiopulmonary exercise testing prior to open AAA repair. The surgical approach undertaken was dictated by individual surgeon preference. Postoperative mortality, complications, and length of hospital stay (LoS) were recorded. Patients were further stratified according to infrarenal (IR) or suprarenal/supraceliac (SR/SC) surgical clamping. Systemic inflammation (C-reactive protein) and renal function (serum creatinine and estimated glomerular filtration rate) were recorded. Results  Twenty-three (96%) of TP patients only required an IR clamp compared with 12 (36%) in the RP group. Postoperative systemic inflammation was lower in RP patients ( p  = 0.002 vs. TP) and fewer reported pulmonary/gastrointestinal complications whereas renal impairment was more marked in those receiving SR/SC clamps ( p  < 0.001 vs. IR clamp). RP patients were defined by lower LoS ( p  = 0.001), while mid-/long-term mortality was low/comparable with TP, resulting in considerable cost savings. Conclusion  Despite the demands of more complicated vascular anatomy, the clinical and economic benefits highlighted by these findings justify the more routine adoption of the RP approach for complex AAA repair

First principles investigation of manganese catalyst structure and coordination in the p -xylene oxidation process

The oxidation of p-xylene to terephtalic acid has global importance, with the product used as a precursor for polyethylene terephthalate (PET). The oxidation of p-xylene proceeds via a redox cascade that involves cobalt, manganese, and bromide, with a synergy allowing for high selectivity and reactivity; however, the equilibrium coordination environment of the catalyst species remains uncertain due to the hostile industrial operating conditions. To build knowledge of the catalyst speciation and develop understanding of the reaction process, a density functional theory approach is applied herein to determine the static and dynamic properties of the divalent (reduced) and trivalent (oxidized) manganese catalysts in the redox cascade. The Gibbs free energy has been calculated for manganese as a function of ligands in the inner coordination sphere, with the octahedrally-coordinated Mn(OAc)2(HOAc)2 and Mn(OAc)3(H2O)1 identified as the most thermodynamically stable coordination environments for Mn(ii) and Mn(iii), respectively. Dynamic properties of these catalysts in the presence of an explicit solvent environment have been determined using first principles molecular dynamics simulations. The simulations indicate 0–2 coordinating water ligands are present in the inner coordination sphere under standard industrial temperatures and pressures. The dynamical simulations have been extended to include HBr, which couples with Mn in the redox cascade, and the bromide species does not enter in the inner-coordination sphere of the oxidized Mn(iii) catalyst, providing evidence that the electron transfer between bromide and Mn(iii) proceeds via an outer sphere mechanism. Our results suggest that oxidation of Mn(ii) has the potential for facilitating L-type ligand exchange in the inner-sphere coordination environment. The results are a platform for developing a more complete knowledge of the reaction mechanism at the atomistic scale

Laboratory practice is central to earlier myeloma diagnosis:Utilizing a primary care diagnostic tool and laboratory guidelines integrated into haematology services

Treatment advances have greatly improved survival, but myeloma is among the worst of all cancers for delayed diagnosis, causing serious morbidities and early deaths. This delay is largely because the symptom profile of myeloma has very low specificity, and in primary care, myeloma is rare. However, initiating the journey to diagnosis simply requires considering myeloma and sending blood to test for monoclonal immunoglobulin. Laboratory tests reliably detect monoclonal immunoglobulin, which is present in 99% of myeloma cases, so why do health care systems have such a problem with delayed diagnosis? The Myeloma UK early diagnosis programme has brought together diverse expertise to investigate this problem, and this article was prepared by the programme's working group for laboratory best practice. It reviews evidence for test requesting, analysis and reporting, for which there is large variation in practice across the United Kingdom. It presents a ‘GP Myeloma diagnostic tool’ and how it can be integrated into laboratory practice alongside a laboratory best practice tool. It proposes improved requesting and integration with haematology services for reporting and interpretation. Here the laboratory has a central role in creating efficient and cost-effective pathways for appropriate and timely bone marrow examination for myeloma diagnosis.<br/

Profiling post-COVID-19 condition across different variants of SARS-CoV-2: a prospective longitudinal study in unvaccinated wild-type, unvaccinated alpha-variant, and vaccinated delta-variant populations

BACKGROUND: Self-reported symptom studies rapidly increased understanding of SARS-CoV-2 during the COVID-19 pandemic and enabled monitoring of long-term effects of COVID-19 outside hospital settings. Post-COVID-19 condition presents as heterogeneous profiles, which need characterisation to enable personalised patient care. We aimed to describe post-COVID-19 condition profiles by viral variant and vaccination status. METHODS: In this prospective longitudinal cohort study, we analysed data from UK-based adults (aged 18–100 years) who regularly provided health reports via the Covid Symptom Study smartphone app between March 24, 2020, and Dec 8, 2021. We included participants who reported feeling physically normal for at least 30 days before testing positive for SARS-CoV-2 who subsequently developed long COVID (ie, symptoms lasting longer than 28 days from the date of the initial positive test). We separately defined post-COVID-19 condition as symptoms that persisted for at least 84 days after the initial positive test. We did unsupervised clustering analysis of time-series data to identify distinct symptom profiles for vaccinated and unvaccinated people with post-COVID-19 condition after infection with the wild-type, alpha (B.1.1.7), or delta (B.1.617.2 and AY.x) variants of SARS-CoV-2. Clusters were then characterised on the basis of symptom prevalence, duration, demography, and previous comorbidities. We also used an additional testing sample with additional data from the Covid Symptom Study Biobank (collected between October, 2020, and April, 2021) to investigate the effects of the identified symptom clusters of post-COVID-19 condition on the lives of affected people. FINDINGS: We included 9804 people from the COVID Symptom Study with long COVID, 1513 (15%) of whom developed post-COVID-19 condition. Sample sizes were sufficient only for analyses of the unvaccinated wild-type, unvaccinated alpha variant, and vaccinated delta variant groups. We identified distinct profiles of symptoms for post-COVID-19 condition within and across variants: four endotypes were identified for infections due to the wild-type variant (in unvaccinated people), seven for the alpha variant (in unvaccinated people), and five for the delta variant (in vaccinated people). Across all variants, we identified a cardiorespiratory cluster of symptoms, a central neurological cluster, and a multi-organ systemic inflammatory cluster. These three main clusers were confirmed in a testing sample. Gastrointestinal symptoms clustered in no more than two specific phenotypes per viral variant. INTERPRETATION: Our unsupervised analysis identified different profiles of post-COVID-19 condition, characterised by differing symptom combinations, durations, and functional outcomes. Our classification could be useful for understanding the distinct mechanisms of post-COVID-19 condition, as well as for identification of subgroups of individuals who might be at risk of prolonged debilitation. FUNDING: UK Government Department of Health and Social Care, Chronic Disease Research Foundation, The Wellcome Trust, UK Engineering and Physical Sciences Research Council, UK Research and Innovation London Medical Imaging & Artificial Intelligence Centre for Value-Based Healthcare, UK National Institute for Health Research, UK Medical Research Council, British Heart Foundation, UK Alzheimer's Society, and ZOE