17 research outputs found

    N-Heterocyclic Carbenes Supported on Vinylic Addition Polynorbornene: A Recyclable and Recoverable Organocatalyst

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    ProducciĂłn CientĂ­ficaA bromoalkyl functionalized vinylic addition polynorbornene has been used as an inert new scaffold to support imidazolium salts by straightforward nucleophilic substitution using different imidazoles ImR (R=Me, mesityl, 2,6-iPr2C6H3). These polymers, VA-PNB-(CH2)4ImRBr, are precursors of N-heterocyclic carbenes which are useful as heterogeneous organocatalysts. The polymeric carbenes have been tested in two model reactions: The synthesis of saturated esters from α,ÎČ-unsaturated aldehydes and the conjugate umpolung reaction of α,ÎČ-unsaturated aldehydes for the synthesis of Îł-butyrolactones. The supported catalyst (R=mesityl) is fully recyclable and can be recovered as an imidazolium salt and stored for further use.Ministerio de EconomĂ­a, Industria y Competitividad (CTQ2013-48406-P)Ministerio de EconomĂ­a, Industria y Competitividad (CTQ2010-18901/BQU)Junta de Castilla y LeĂłn (programa de apoyo a proyectos de investigaciĂłn – Ref. VA302U13

    Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts

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    Polynorbornenes prepared by vinyl addition poly- merization and bearing pendant alkenyl groups serve as skeletons to support trispyrazolylborate ligands (Tpx) built at those alkenyl sites. Reaction with CuI in acetonitrile led to VA-PNB–TpxCu(NCMe) (VA-PBN = vinyl addition polynorbor- nene) with a 0.8–1.4 mmol incorporation of Cu per gram of polymer. The presence of tetracoordinated copper(I) ions was been assessed by FTIR studies on the corresponding VA-PNB-TpxCu(CO) adducts, in agreement with those on discrete TpxCu(CO). The new materials were employed as heteroge- neous catalysts in several carbene- and nitrene-transfer reac- tions, showing a behavior similar to that of the homogene- ous counterparts but also being recycled several times main- taining a high degree of activity and selectivity. This is the first example of supported Tpx ligands onto polymeric sup- ports with catalytic applications.MINECO (CTQ2017-82893-C2-1-R, CTQ2016-80913-P and Red Intecat CTQ2016-81923-REDC)Junta de Castilla y León (VA051P17, VA062G18)European Union (CHAOS COST ACTION CA-15106)

    La subnormalidad a debate: discursos y prĂĄcticas sobre la discapacidad intelectual en el segundo franquismo

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    Treatment with tocilizumab or corticosteroids for COVID-19 patients with hyperinflammatory state: a multicentre cohort study (SAM-COVID-19)

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    Objectives: The objective of this study was to estimate the association between tocilizumab or corticosteroids and the risk of intubation or death in patients with coronavirus disease 19 (COVID-19) with a hyperinflammatory state according to clinical and laboratory parameters. Methods: A cohort study was performed in 60 Spanish hospitals including 778 patients with COVID-19 and clinical and laboratory data indicative of a hyperinflammatory state. Treatment was mainly with tocilizumab, an intermediate-high dose of corticosteroids (IHDC), a pulse dose of corticosteroids (PDC), combination therapy, or no treatment. Primary outcome was intubation or death; follow-up was 21 days. Propensity score-adjusted estimations using Cox regression (logistic regression if needed) were calculated. Propensity scores were used as confounders, matching variables and for the inverse probability of treatment weights (IPTWs). Results: In all, 88, 117, 78 and 151 patients treated with tocilizumab, IHDC, PDC, and combination therapy, respectively, were compared with 344 untreated patients. The primary endpoint occurred in 10 (11.4%), 27 (23.1%), 12 (15.4%), 40 (25.6%) and 69 (21.1%), respectively. The IPTW-based hazard ratios (odds ratio for combination therapy) for the primary endpoint were 0.32 (95%CI 0.22-0.47; p < 0.001) for tocilizumab, 0.82 (0.71-1.30; p 0.82) for IHDC, 0.61 (0.43-0.86; p 0.006) for PDC, and 1.17 (0.86-1.58; p 0.30) for combination therapy. Other applications of the propensity score provided similar results, but were not significant for PDC. Tocilizumab was also associated with lower hazard of death alone in IPTW analysis (0.07; 0.02-0.17; p < 0.001). Conclusions: Tocilizumab might be useful in COVID-19 patients with a hyperinflammatory state and should be prioritized for randomized trials in this situatio

    PhDAY 2020 -FOO (Facultad de Óptica y Optometría)

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    Por cuarto año consecutivo los doctorandos de la Facultad de Óptica y OptometrĂ­a de la Universidad Complutense de Madrid cuentan con un congreso propio organizado por y para ellos, el 4Âș PhDAY- FOO. Se trata de un congreso gratuito abierto en la que estos jĂłvenes cientĂ­ficos podrĂĄn presentar sus investigaciones al resto de sus compañeros predoctorales y a toda la comunidad universitaria que quiera disfrutar de este evento. Apunta en tu agenda: el 15 de octubre de 2020. En esta ocasiĂłn serĂĄ un Congreso On-line para evitar que la incertidumbre asociada a la pandemia Covid-19 pudiera condicionar su celebraciĂłn

    Spatiotemporal Characteristics of the Largest HIV-1 CRF02_AG Outbreak in Spain: Evidence for Onward Transmissions

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    Background and Aim: The circulating recombinant form 02_AG (CRF02_AG) is the predominant clade among the human immunodeficiency virus type-1 (HIV-1) non-Bs with a prevalence of 5.97% (95% Confidence Interval-CI: 5.41–6.57%) across Spain. Our aim was to estimate the levels of regional clustering for CRF02_AG and the spatiotemporal characteristics of the largest CRF02_AG subepidemic in Spain.Methods: We studied 396 CRF02_AG sequences obtained from HIV-1 diagnosed patients during 2000–2014 from 10 autonomous communities of Spain. Phylogenetic analysis was performed on the 391 CRF02_AG sequences along with all globally sampled CRF02_AG sequences (N = 3,302) as references. Phylodynamic and phylogeographic analysis was performed to the largest CRF02_AG monophyletic cluster by a Bayesian method in BEAST v1.8.0 and by reconstructing ancestral states using the criterion of parsimony in Mesquite v3.4, respectively.Results: The HIV-1 CRF02_AG prevalence differed across Spanish autonomous communities we sampled from (p &lt; 0.001). Phylogenetic analysis revealed that 52.7% of the CRF02_AG sequences formed 56 monophyletic clusters, with a range of 2–79 sequences. The CRF02_AG regional dispersal differed across Spain (p = 0.003), as suggested by monophyletic clustering. For the largest monophyletic cluster (subepidemic) (N = 79), 49.4% of the clustered sequences originated from Madrid, while most sequences (51.9%) had been obtained from men having sex with men (MSM). Molecular clock analysis suggested that the origin (tMRCA) of the CRF02_AG subepidemic was in 2002 (median estimate; 95% Highest Posterior Density-HPD interval: 1999–2004). Additionally, we found significant clustering within the CRF02_AG subepidemic according to the ethnic origin.Conclusion: CRF02_AG has been introduced as a result of multiple introductions in Spain, following regional dispersal in several cases. We showed that CRF02_AG transmissions were mostly due to regional dispersal in Spain. The hot-spot for the largest CRF02_AG regional subepidemic in Spain was in Madrid associated with MSM transmission risk group. The existence of subepidemics suggest that several spillovers occurred from Madrid to other areas. CRF02_AG sequences from Hispanics were clustered in a separate subclade suggesting no linkage between the local and Hispanic subepidemics

    Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

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    Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

    Vinylic Addition Polynorbornene as a Support for N-Heterocyclic Carbene Palladium Complexes: Catalytic Activity in C–C Cross– Coupling Reactions

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    ProducciĂłn CientĂ­ficaA vinylic addition polynorbornene (VA-PNB) functionalized with imidazolium groups can be used to synthesize a well-defined supported palladium carbene complex. This complex is a suitable precatalyst for Suzuki and Negishi cross coupling reactions, and it can be reused. A close look to how the catalysis work reveals that palladium aggregates form on the polymer surface after the first catalytic reaction. However, they are not easily washed out and serve as a source of a small amount of homogeneous palladium active species (about 0.1‰ mol) that are responsible for the catalysis. The recovered polymer can be reused several times although increased induction and reaction times are observed in consecutive uses from one run to the next. The reaction was followed up by in situ IR spectroscopy using the Îœ(C-Br) absorption of the electrophile, so there is no need of an additional functional group to apply this technique.2017-12-15Ministerio de EconomĂ­a, Industria y Competitividad (CTQ2013-48406-P)Junta de Castilla y LeĂłn (programa de apoyo a proyectos de investigaciĂłn – Ref. VA302U13

    Intermittent Hypoxia Is Associated With High Hypoxia Inducible Factor-1α but Not High Vascular Endothelial Growth Factor Cell Expression in Tumors of Cutaneous Melanoma Patients

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    Epidemiological associations linking between obstructive sleep apnea and poorer solid malignant tumor outcomes have recently emerged. Putative pathways proposed to explain that these associations have included enhanced hypoxia inducible factor (HIF)-1α and vascular endothelial growth factor (VEGF) cell expression in the tumor and altered immune functions via intermittent hypoxia (IH). Here, we examined relationships between HIF-1α and VEGF expression and nocturnal IH in cutaneous melanoma (CM) tumor samples. Prospectively recruited patients with CM tumor samples were included and underwent overnight polygraphy. General clinical features, apnea–hypopnea index (AHI), desaturation index (DI4%), and CM characteristics were recorded. Histochemical assessments of VEGF and HIF-1α were performed, and the percentage of positive cells (0, &lt;25, 25–50, 51–75, &gt;75%) was blindly tabulated for VEGF expression, and as 0, 0–5.9, 6.0–10.0, &gt;10.0% for HIF-1α expression, respectively. Cases with HIF-1α expression &gt;6% (high expression) were compared with those &lt;6%, and VEGF expression &gt;75% of cells was compared with those with &lt;75%. 376 patients were included. High expression of VEGF and HIF-1α were seen in 88.8 and 4.2% of samples, respectively. High expression of VEGF was only associated with increasing age. However, high expression of HIF-1α was significantly associated with age, Breslow index, AHI, and DI4%. Logistic regression showed that DI4% [OR 1.03 (95% CI: 1.01–1.06)] and Breslow index [OR 1.28 (95% CI: 1.18–1.46)], but not AHI, remained independently associated with the presence of high HIF-1α expression. Thus, IH emerges as an independent risk factor for higher HIF-1α expression in CM tumors and is inferentially linked to worse clinical CM prognostic indicators

    How do women living with HIV experience menopause? Menopausal symptoms, anxiety and depression according to reproductive age in a multicenter cohort

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    CatedresBackground: To estimate the prevalence and severity of menopausal symptoms and anxiety/depression and to assess the differences according to menopausal status among women living with HIV aged 45-60 years from the cohort of Spanish HIV/AIDS Research Network (CoRIS). Methods: Women were interviewed by phone between September 2017 and December 2018 to determine whether they had experienced menopausal symptoms and anxiety/depression. The Menopause Rating Scale was used to evaluate the prevalence and severity of symptoms related to menopause in three subscales: somatic, psychologic and urogenital; and the 4-item Patient Health Questionnaire was used for anxiety/depression. Logistic regression models were used to estimate odds ratios (ORs) of association between menopausal status, and other potential risk factors, the presence and severity of somatic, psychological and urogenital symptoms and of anxiety/depression. Results: Of 251 women included, 137 (54.6%) were post-, 70 (27.9%) peri- and 44 (17.5%) pre-menopausal, respectively. Median age of onset menopause was 48 years (IQR 45-50). The proportions of pre-, peri- and post-menopausal women who had experienced any menopausal symptoms were 45.5%, 60.0% and 66.4%, respectively. Both peri- and post-menopause were associated with a higher likelihood of having somatic symptoms (aOR 3.01; 95% CI 1.38-6.55 and 2.63; 1.44-4.81, respectively), while post-menopause increased the likelihood of having psychological (2.16; 1.13-4.14) and urogenital symptoms (2.54; 1.42-4.85). By other hand, post-menopausal women had a statistically significant five-fold increase in the likelihood of presenting severe urogenital symptoms than pre-menopausal women (4.90; 1.74-13.84). No significant differences by menopausal status were found for anxiety/depression. Joint/muscle problems, exhaustion and sleeping disorders were the most commonly reported symptoms among all women. Differences in the prevalences of vaginal dryness (p = 0.002), joint/muscle complaints (p = 0.032), and sweating/flush (p = 0.032) were found among the three groups. Conclusions: Women living with HIV experienced a wide variety of menopausal symptoms, some of them initiated before women had any menstrual irregularity. We found a higher likelihood of somatic symptoms in peri- and post-menopausal women, while a higher likelihood of psychological and urogenital symptoms was found in post-menopausal women. Most somatic symptoms were of low or moderate severity, probably due to the good clinical and immunological situation of these women
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