Diastereoselective Synthesis of Pyranoquinolines on Zirconium-Containing UiO-66 Metal-Organic Frameworks

[EN] The Zr terephthalate MOFs UiO-66 and UiO-66-NH2 have been found to be highly diastereoselective catalysts for the synthesis of a pyrano[3,2-c]quinoline through an inverse electron -demand aza-Diels-Alder [4+2] cycloaddition of an aryl Qmine (formed in situ from aniline and benzaldehyde) and 3,4-dihydro-2H-pyran in one pot, affording the corresponding trans isomer in diastereomeric excesses of 90-95 %. The solids are stable under the reaction conditions and can be reused at least three times without significant loss of activity or diastereoselectivity.Financial support from the Generalitat Valenciana (projects Consolider-Ingenio MULTICAT and AICO/2015/065), the Spanish Ministry of Economy and Competitiveness (MINECO) (program Severn Ochoa SEV20120267), and the Spanish Ministry of Science and Innovation (MICINN) (project MAT2014-52085-C2-1-P) is gratefully acknowledged. V. L. R. thanks the Fundacion "La Caixa" for a "La Caixa-Severo Ochoa" Ph. D. Scholarship. This project received funding from the European Union's Horizon 2020 Tesearch and Innovation Programme under the Marie Skolodowska Curie grant agreement number 641887.López-Rechac, V.; García Cirujano, F.; Corma Canós, A.; Llabrés I Xamena, FX. (2016). Diastereoselective Synthesis of Pyranoquinolines on Zirconium-Containing UiO-66 Metal-Organic Frameworks. European Journal of Inorganic Chemistry. 27:4512-4516. https://doi.org/10.1002/ejic.201600372S4512451627Li, B., Wang, H., & Chen, B. (2014). Microporous Metal-Organic Frameworks for Gas Separation. Chemistry - An Asian Journal, 9(6), 1474-1498. doi:10.1002/asia.201400031Li, J.-R., Sculley, J., & Zhou, H.-C. (2011). Metal–Organic Frameworks for Separations. Chemical Reviews, 112(2), 869-932. doi:10.1021/cr200190sRodenas, T., Luz, I., Prieto, G., Seoane, B., Miro, H., Corma, A., … Gascon, J. (2014). Metal–organic framework nanosheets in polymer composite materials for gas separation. 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Clinical and neuroimaging correlates of antiphospholipid antibodies in multiple sclerosis: a preliminary study

<p>Abstract</p> <p>Background</p> <p>The presence of antiphospholipid antibodies (APLA) in multiple sclerosis (MS) patients has been reported frequently but no clear relationship between APLA and the clinical and neuroimaging features of MS have heretofore been shown. We assessed the clinical and neuroimaging features of MS patients with plasma APLA.</p> <p>Methods</p> <p>A consecutive cohort of 24 subjects with relapsing-remitting (RR) MS were studied of whom 7 were in remission (Rem) and 17 in exacerbation (Exc). All subjects were examined and underwent MRI of brain. Patients' plasma was tested by standard ELISA for the presence of both IgM and IgG antibodies using a panel of 6 targets: cardiolipin (CL), β2 glycoprotein I (β2GPI), Factor VII/VIIa (FVIIa), phosphatidylcholine (PC), phosphatidylserine (PS) and phosphatidylethanolamine (PE).</p> <p>Results</p> <p>In exacerbation up to 80% of MS subjects had elevated titers of IgM antibodies directed against the above antigens. However, in remission, less than half of MS patients had elevated titers of IgM antibodies against one or more of the above antigens. This difference was significant, p < 0.01, for all 6 target antigens. Interestingly, none of the MS patients had elevated plasma titers of IgG against any of the target antigens tested. Correlation analysis between MRI enhancing lesions and plasma levels of APLA revealed high correlation for aPC, aPS and aFVIIa (p ≤ 0.0065), a trend for aPE and aCL (p = 0.056), and no correlation for aβ2GP1. The strongest correlation was for aFVIIa, p = 0.0002.</p> <p>Conclusion</p> <p>The findings of this preliminary study show that increased APLA IgM is associated with exacerbations of MS. Currently, the significance of this association in pathogenesis of MS remains unknown. However, systematic longitudinal studies to measure APLA in larger cohorts of patients with relapsing-remitting MS, particularly before and after treatment with immunomodulatory agents, are needed to confirm these preliminary findings.</p

Food consumption frequency and perceived stress and depressive symptoms among students in three European countries

Mikolajczyk RT, El Ansari W, Maxwell AE. Food consumption frequency and perceived stress and depressive symptoms among students in three European countries. Nutrition Journal. 2009;8(1):31.Background: Certain foods might be more frequently eaten under stress or when higher levels of depressive symptoms are experienced. We examined whether poor nutritional habits are associated with stress and depressive symptoms and whether the relationships differ by country and gender in a sample from three European countries collected as part of a Cross National Student Health Survey. Methods: A cross-sectional survey was conducted among first-year students in Germany (N = 696), Poland (N = 489) and Bulgaria (N = 654). Self-administered questionnaires included a 12-item food frequency questionnaire, Cohen's Perceived Stress Scale, and a modified Beck Depression Index. Linear regression analyses were conducted for two outcomes, perceived stress and depressive symptoms. Results: Food consumption frequencies differed by country and gender, as did depressive symptoms and perceived stress. For male students, none of the food consumption groups were associated with perceived stress or depressive symptoms. In females, perceived stress was associated with more frequent consumption of sweets/fast foods and less frequent consumption of fruits/vegetables. Additionally, depressive symptoms were associated with less frequent consumption of fruits/vegetables and meat. Conclusion: Our data show consistent associations between unhealthy food consumption and depressive symptoms and perceived stress among female students from three European countries, but not among male students. This suggests that efforts to reduce depressive symptoms and stress among female students may also lead to the consumption of healthier foods and/or vice-versa

Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest

Zr-containing metal organic frameworks (MOFs) formed by terephthalate (UiO-66) and 2-aminoterephthalate ligands (UiO-66-NH2) are active and stable catalysts for the acid catalyzed esterification of various saturated and unsaturated fatty acids with MeOH and EtOH, with activities comparable (in some cases superior) to other solid acid catalysts previously reported in literature. Besides the formation of the corresponding fatty acid alkyl esters as biodiesel compounds (FAMEs and FAEEs), esterification of biomass-derived fatty acids with other alcohols catalyzed by the Zr-MOFs allows preparing other compounds of interest, such as oleyl oleate or isopropyl palmitate, with good yields under mild conditions.Financial support from the Consolider-Ingenio 2010 (project MULTICAT), the Severo Ochoa program, and the Spanish Ministry of Science and Innovation (project MAT2011-29020-C02-01) is gratefully acknowledged.García Cirujano, F.; Corma Canós, A.; Llabrés I Xamena, FX. (2015). Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest. Catalysis Today. 257:213-220. https://doi.org/10.1016/j.cattod.2014.08.015S21322025

Prognostic model to predict postoperative acute kidney injury in patients undergoing major gastrointestinal surgery based on a national prospective observational cohort study.

Background: Acute illness, existing co-morbidities and surgical stress response can all contribute to postoperative acute kidney injury (AKI) in patients undergoing major gastrointestinal surgery. The aim of this study was prospectively to develop a pragmatic prognostic model to stratify patients according to risk of developing AKI after major gastrointestinal surgery. Methods: This prospective multicentre cohort study included consecutive adults undergoing elective or emergency gastrointestinal resection, liver resection or stoma reversal in 2-week blocks over a continuous 3-month period. The primary outcome was the rate of AKI within 7 days of surgery. Bootstrap stability was used to select clinically plausible risk factors into the model. Internal model validation was carried out by bootstrap validation. Results: A total of 4544 patients were included across 173 centres in the UK and Ireland. The overall rate of AKI was 14·2 per cent (646 of 4544) and the 30-day mortality rate was 1·8 per cent (84 of 4544). Stage 1 AKI was significantly associated with 30-day mortality (unadjusted odds ratio 7·61, 95 per cent c.i. 4·49 to 12·90; P < 0·001), with increasing odds of death with each AKI stage. Six variables were selected for inclusion in the prognostic model: age, sex, ASA grade, preoperative estimated glomerular filtration rate, planned open surgery and preoperative use of either an angiotensin-converting enzyme inhibitor or an angiotensin receptor blocker. Internal validation demonstrated good model discrimination (c-statistic 0·65). Discussion: Following major gastrointestinal surgery, AKI occurred in one in seven patients. This preoperative prognostic model identified patients at high risk of postoperative AKI. Validation in an independent data set is required to ensure generalizability

Perception of educational value in clinical rotations by medical students

David A Kandiah School of Psychiatry and Clinical Neurosciences, Faculty of Medicine, Dentistry and Health Sciences, University of Western Australia, Perth, WA, Australia Aim: Clinical teaching in Australian medical schools has changed to meet the needs of substantially increased medical student cohorts. As such, formal feedback from these student cohorts is needed about the value they place on the educational input from each clinical rotation. This study aims to determine which aspects of clinical placements are most educationally useful to medical students.Methods: In this study, final year medical students from the University of Western Australia (UWA) were surveyed via an anonymous online questionnaire, identifying which clinical placements were found to be the most and the least useful to their learning and the positive aspects of these placements. Two focus groups were conducted prior to the design of the questionnaire to determine the key areas of focus important to medical students. Ethics approval for this study was obtained from the UWA Human Research Ethics Committee.Results: Our focus groups were consistent in finding that students enjoyed placements where they were included as a part of the medical team and played a role in patient care. This was consistent with the concept that inclusiveness and participation in the clinical setting are important in developing competence in tasks and skills. The ratio of students to doctors was crucial, with a low ratio given a higher rating as seen in the rural clinical school.Conclusion: The results of this project could benefit both the local and national medical curricula in identifying the most effective clinical attachments for learning and preparation for prevocational training. This is relevant especially due to the limited number of clinical placements and growing cohort of medical students. The results of this study can also be extrapolated to international medical education. Keywords: educational value, clinical rotations, medical students, satisfactio

Clinical reasoning and knowledge management in final year medical students: the role of Student-led Grand Rounds

David Arumaisingam Kandiah Division of Psychiatry, Medical School, Faculty of Health and Medical Sciences, The University of Western Australia, Perth, WA, Australia Objectives: The development of clinical reasoning and decision-making skills is often limited in medical school curricula. In reality, medical graduates acquire these skills during their first few years of residency. For many, this can be stressful as they may be working under limited supervision as a part of their rotations.Methods: Student-led Grand Rounds was developed to transfer both explicit and tacit knowledge to final year medical students. This pilot project was to apply the principles of knowledge management to allow students to be exposed to the reasoning and decision making of common clinical&nbsp;presentations. Student feedback through questionnaires was collated at the end of the program.Results: Based on feedback and focus groups, modifications were made to produce a stable program in subsequent clinical rotations. Formal feedback was collated from all the 76 students who participated in the first year. This represented 100% of the cohort for this clinical school for that year. There was a 100% response rate as the feedback forms were given and collected at the end of the last session per block. The student responses were both in ratings defined in a feedback forms and in written comments. A total of 74 of the 76 students rated the program highly. They enjoyed the nonthreatening interactions. The remaining two students preferred more didactic teaching.Conclusion: This initiative allows an efficient transfer and utilization of knowledge. This could maximize the acquisition of practical knowledge by medical students as they finish their course in the transition to graduate medical practice. Keywords: Student-led Grand Rounds, clinical reasoning, knowledge management, final year medicine, curriculum developmen

Atypical scleromyxedema presenting with cutaneous and cardiovascular manifestations

Sue-Ann Teh,1 David A Kandiah2 1Department of Health Western Australia, Bunbury Hospital, Bunbury, 2School of Psychiatry and Clinical Neurosciences, Faculty of Medicine, Dentistry and Health Sciences, University of Western Australia, Crawley, WA, Australia Abstract: Scleromyxedema is part of a group of cutaneous mucinoses, characterized by a generalized papular eruption, dermal mucin deposition, and an increase in dermal collagen. This condition can be localized as discrete papular lichen myxedematous skin or as a systemic condition usually associated with paraproteinaemia. To date, there is no unifying treatment and is limited by rarity, small number of case reports, and the lack of randomized controlled trials. We describe the case of a 56-year-old gentleman with features of scleromyxedema who had cutaneous and cardiac involvement, and significant mediastinal lymphadenopathy without monoclonal gammopathy. Keywords: scleromyxedema, heart failure, dermal muci