Synthetic strategies to extended aromatic covalent organic frameworks

π‐Conjugated materials are highly attractive owing to their unique optical and electronic properties. Covalent organic frameworks (COFs) offer a great opportunity for precise arrangement of building units in a π‐conjugated crystalline matrix and tuning of the properties through choice of functionalities or post‐synthetic modification. With this review, we aim at summarizing both the most representative as well as emerging strategies for the synthesis of π‐conjugated COFs. We give examples of direct synthesis using large, π‐extended building blocks. COFs featuring fully conjugated linkages such as vinylene, pyrazine, and azole are discussed. Then, post‐synthetic modification methods that result in the extension of the COF π‐system are reviewed. Throughout, mechanistic insights are presented when available. In the context of their utilization as film devices, we conduct a concise survey of the prominent COF layer deposition techniques reported and their aptness for the deposition of fused aromatic systems.Agencia Estatal de Investigación | Ref. PID2022-137591NA-I00Agencia Estatal de Investigación | Ref. RYC2020-030414-IFundação para a Ciência e a Tecnologia | Ref. 2021.05983.BDDeutsche Forschungsgemeinschaft | Ref. SPP 1928 ME 4515/1-2Universidade de Vigo/CISU

Building blocks and COFs formed in concert —Three‐component synthesis of pyrene‐fused Azaacene covalent organic framework in the bulk and as films

A three‐component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation‐inducing COF precursor and the diamines o‐phenylenediamine (Ph), 2,3‐diaminonaphthalene (Naph), or (1R,2R)‐(+)‐1,2‐diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11‐hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene‐fused azaacene, i.e., Aza‐COF series with full conversion of the dione moiety, long‐range order, and high surface area. In addition, the novel three‐component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza‐COFs with nanostructured surfaces on various substrates. The Aza‐COFs exhibit light absorption maxima in the blue spectral region, and each Aza‐COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza‐Ph‐ and Aza‐Naph‐COFs suggest ultrafast relaxation dynamics of excited‐states within these COFs.Deutsche Forschungsgemeinschaft | Ref. ME 4515/1-2Fundação para a Ciência e a Tecnologia | Ref. SFRH/BD/141865/2018Fundação para a Ciência e a Tecnologia | Ref. PTDC/QUI-OUT/2095/2021Fundação para a Ciência e a Tecnologia | Ref. UIDB/50011/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/50011/2020Fundação para a Ciência e a Tecnologia | Ref. LA/P/0006/2020National Science Foundation (EE.UU.) | Ref. DMR-1848067Engineering and Physical Sciences Research Council (Reino Unido) | Ref. EP/V055127/1Agencia Estatal de Investigación | Ref. RYC2020-030414-IUniversidade de Vigo/CISU

From benzodithiophene to diethoxy-benzodithiophene covalent organic frameworks – structural investigations

The incorporation of side groups into a covalent organic framework (COF) backbone can be of significant importance for developing new frameworks with enhanced properties. Here we present a novel π-stacked thiophene-based COF containing a benzodithiophene building unit modified with ethoxy side chains. The resulting BDT-OEt COF is a crystalline mesoporous material featuring high surface area and accessible hexagonal pores. We further synthesized a series of COFs containing both BDT and BDT-OEt building units at different ratios. The impact of the gradual incorporation of the BDT-OEt building units into the COF backbone on the crystallinity and porosity was investigated. Furthermore, molecular dynamic simulations shed light on the possible processes governing the COF assembly from molecular building blocks

A post-synthetic modification strategy for the synthesis of pyrene-fused azaacene covalent organic frameworks

Post-synthetic modification strategy is presented to extend the π-system of covalent organic framework (COF) backbone giving access to boronic ester based pyrene-fused azaacene COFs. Optimized catalyst-free reaction conditions yield COFs post-synthetically modified with up to 33% conversion and corresponding intriguing optical properties. The presented chemistry is expected to find application in post-synthetic tailoring of the optical properties of COFs.S.P.S.F. acknowledges the FCT − Fundação para a Ciência e Tecnologia for the Ph.D. scholarship SFRH/BD/131791/2017. This work received funding from the COFforH2 project (UTA-EXPL/NPN/0055/2019) through the Portuguese Foundation for Science and Technology funds under UT Austin Portugal, Charm project (PTDC/QUI-OUT/2095/2021) through the Portuguese Foundation for Science and Technology funds, The Excellence Clusters ‘Nanosystems Initiative Munich (NIM)’, and from the Free State of Bavaria through the Research Network ‘Solar Technologies go Hybrid’.Peer reviewe

Antimicrobial resistance among migrants in Europe: a systematic review and meta-analysis

BACKGROUND: Rates of antimicrobial resistance (AMR) are rising globally and there is concern that increased migration is contributing to the burden of antibiotic resistance in Europe. However, the effect of migration on the burden of AMR in Europe has not yet been comprehensively examined. Therefore, we did a systematic review and meta-analysis to identify and synthesise data for AMR carriage or infection in migrants to Europe to examine differences in patterns of AMR across migrant groups and in different settings. METHODS: For this systematic review and meta-analysis, we searched MEDLINE, Embase, PubMed, and Scopus with no language restrictions from Jan 1, 2000, to Jan 18, 2017, for primary data from observational studies reporting antibacterial resistance in common bacterial pathogens among migrants to 21 European Union-15 and European Economic Area countries. To be eligible for inclusion, studies had to report data on carriage or infection with laboratory-confirmed antibiotic-resistant organisms in migrant populations. We extracted data from eligible studies and assessed quality using piloted, standardised forms. We did not examine drug resistance in tuberculosis and excluded articles solely reporting on this parameter. We also excluded articles in which migrant status was determined by ethnicity, country of birth of participants' parents, or was not defined, and articles in which data were not disaggregated by migrant status. Outcomes were carriage of or infection with antibiotic-resistant organisms. We used random-effects models to calculate the pooled prevalence of each outcome. The study protocol is registered with PROSPERO, number CRD42016043681. FINDINGS: We identified 2274 articles, of which 23 observational studies reporting on antibiotic resistance in 2319 migrants were included. The pooled prevalence of any AMR carriage or AMR infection in migrants was 25·4% (95% CI 19·1-31·8; I2 =98%), including meticillin-resistant Staphylococcus aureus (7·8%, 4·8-10·7; I2 =92%) and antibiotic-resistant Gram-negative bacteria (27·2%, 17·6-36·8; I2 =94%). The pooled prevalence of any AMR carriage or infection was higher in refugees and asylum seekers (33·0%, 18·3-47·6; I2 =98%) than in other migrant groups (6·6%, 1·8-11·3; I2 =92%). The pooled prevalence of antibiotic-resistant organisms was slightly higher in high-migrant community settings (33·1%, 11·1-55·1; I2 =96%) than in migrants in hospitals (24·3%, 16·1-32·6; I2 =98%). We did not find evidence of high rates of transmission of AMR from migrant to host populations. INTERPRETATION: Migrants are exposed to conditions favouring the emergence of drug resistance during transit and in host countries in Europe. Increased antibiotic resistance among refugees and asylum seekers and in high-migrant community settings (such as refugee camps and detention facilities) highlights the need for improved living conditions, access to health care, and initiatives to facilitate detection of and appropriate high-quality treatment for antibiotic-resistant infections during transit and in host countries. Protocols for the prevention and control of infection and for antibiotic surveillance need to be integrated in all aspects of health care, which should be accessible for all migrant groups, and should target determinants of AMR before, during, and after migration. FUNDING: UK National Institute for Health Research Imperial Biomedical Research Centre, Imperial College Healthcare Charity, the Wellcome Trust, and UK National Institute for Health Research Health Protection Research Unit in Healthcare-associated Infections and Antimictobial Resistance at Imperial College London

WGS-based telomere length analysis in Dutch family trios implicates stronger maternal inheritance and a role for RRM1 gene

Telomere length (TL) regulation is an important factor in ageing, reproduction and cancer development. Genetic, hereditary and environmental factors regulating TL are currently widely investigated, however, their relative contribution to TL variability is still understudied. We have used whole genome sequencing data of 250 family trios from the Genome of the Netherlands project to perform computational measurement of TL and a series of regression and genome-wide association analyses to reveal TL inheritance patterns and associated genetic factors. Our results confirm that TL is a largely heritable trait, primarily with mother’s, and, to a lesser extent, with father’s TL having the strongest influence on the offspring. In this cohort, mother’s, but not father’s age at conception was positively linked to offspring TL. Age-related TL attrition of 40 bp/year had relatively small influence on TL variability. Finally, we have identified TL-associated variations in ribonuclease reductase catalytic subunit M1 (RRM1 gene), which is known to regulate telomere maintenance in yeast. We also highlight the importance of multivariate approach and the limitations of existing tools for the analysis of TL as a polygenic heritable quantitative trait

Allergic Rhinitis and its Impact on Asthma (ARIA) Phase 4 (2018) : Change management in allergic rhinitis and asthma multimorbidity using mobile technology

Allergic Rhinitis and its Impact on Asthma (ARIA) has evolved from a guideline by using the best approach to integrated care pathways using mobile technology in patients with allergic rhinitis (AR) and asthma multimorbidity. The proposed next phase of ARIA is change management, with the aim of providing an active and healthy life to patients with rhinitis and to those with asthma multimorbidity across the lifecycle irrespective of their sex or socioeconomic status to reduce health and social inequities incurred by the disease. ARIA has followed the 8-step model of Kotter to assess and implement the effect of rhinitis on asthma multimorbidity and to propose multimorbid guidelines. A second change management strategy is proposed by ARIA Phase 4 to increase self-medication and shared decision making in rhinitis and asthma multimorbidity. An innovation of ARIA has been the development and validation of information technology evidence-based tools (Mobile Airways Sentinel Network [MASK]) that can inform patient decisions on the basis of a self-care plan proposed by the health care professional.Peer reviewe