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.

Sequence analysis of sickness absence and disability pension days in 2012-2018 among privately employed white-collar workers in Sweden: a prospective cohort study.

Objective: The aim of the study is to explore sequences of sickness absence (SA) and disability pension (DP) days from 2012 to 2018 among privately employed white-collar workers.

Design: A 7-year prospective cohort study using microdata from nationwide registers.

Setting: Sweden.

Labour market trajectories after part-time sickness absence: a nationwide cohort study from Finland.

Objectives: The use of part-time sickness absence (pSA) enables return to part-time work from full sickness absence. However, subsequent labour market outcomes of pSA users depend on various individual and work-related characteristics. We investigated labour market paths of private and public sector employees after having a pSA spell.

Disability pension and sociodemographic & work-related risk factors among 2.3 million migrants and natives in Finland (2011-2019): a prospective population study.

Background: Increasing employment and immigration have been proposed as possible solutions to tackle the problem of the labour force shortage in aging societies. Ensuring sufficient health and work ability among migrants is a key factor in increasing and maintaining their employment. Many studies have found higher disability pension (DP) rates among migrants compared to natives but such studies lack in determining the risk of DP by occupational class and industrial sector.

Contribution of compositional changes in the workforce to sickness absence trends in Finland.

In this study, we assessed whether the long-term decrease in sickness absences in Finland is explained by observed and unobserved compositional changes in the workforce. Utilizing register-based panel data on Finnish wage earners aged 30-62, we examined the annual onset of compensated sickness absence (granted after 10 weekdays) in the period 2005-2016. We applied random effects models adjusting for changes in the observed sociodemographic and occupational characteristics of the study population.

Does previous sickness absence affect work participation after vocational labour market training? A difference-in-differences propensity score matching approach.

Background: Reduced work ability is relatively common among job seekers and it can hinder future labour market attachment. A commonly used measure to increase employability is the use of active labour market programmes. While vocational labour market training (LMT) has been shown to be an effective way to increase work participation among job seekers, there is still uncertainty about how LMT works in different population groups, for example, among persons with a work disability history.

Towards All-Non-Vacuum-Processed Photovoltaic Systems: A Water-Based Screen-Printed Cu(In,Ga)Se Photoabsorber with a 6.6% Efficiency.

During the last few decades, major advances have been made in photovoltaic systems based on Cu(In,Ga)Se chalcopyrite. However, the most efficient photovoltaic cells are processed under high-energy-demanding vacuum conditions. To lower the costs and facilitate high-throughput production, printing/coating processes are proving to be effective solutions.

Evaluation of Covalent Organic Frameworks for the low-cost, rapid detection of Shiga Toxin-producing Escherichia coli in ready-to-eat salads.

Background: Ready-to-eat products, such as leafy greens, must be carefully controlled as they are directly consumed without any treatment to reduce the presence of potential pathogens. Food industries, especially those that process products with short shelf-life, demand rapid detection of foodborne pathogens such as Shiga Toxin-producing Escherichia coli (STEC). In this sense, molecular methods can fulfill both requirements of turnaround time and consumer safety.

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.

A carboxyl-functionalized covalent organic polymer for the efficient adsorption of saxitoxin.

Saxitoxin (STX), the most widely distributed neurotoxin in marine waters and emerging cyanotoxin of concern in freshwaters, causes paralytic shellfish poisoning in humans upon consumption of contaminated shellfish. To allow for the efficient monitoring of this biotoxin, it is of high importance to find high-affinity materials for its adsorption. Herein, we report the design and synthesis of a covalent organic polymer for the efficient adsorption of STX.

Threefold reactivity of a COF-embedded rhenium catalyst: reductive etherification, oxidative esterification or transfer hydrogenation.

The reactivity of the novel Re(I) catalyst [Re(Anth-py)(CO)Br] is modulated by its interactions with the covalent organic framework (COF) TFB-BD. The complex catalyzes either reductive etherification, oxidative esterification, or transfer hydrogenation depending on its local environment (embedded in TFB-BD, in homogeneous solution or co-incubated with TFB-BD, respectively). The results highlight that COFs can drastically modulate the reactivity of homogeneous catalysts.

Deep Eutectic Solvent Synthesis of Perovskite Electrocatalysts for Water Oxidation.

Oxide perovskites have attracted great interest as materials for energy conversion due to their stability and structural tunability. La-based perovskites of 3d-transition metals have demonstrated excellent activities as electrocatalysts in water oxidation. Herein, we report the synthesis route to La-based perovskites using an environmentally friendly deep eutectic solvent (DES) consisting of choline chloride and malonic acid.

Covalent organic framework as adsorbent for ultrasound-assisted dispersive (micro)solid phase extraction of polycyclic synthetic fragrances from seawater followed by fluorescent determination.

In this work, a new analytical approach based on ultrasound-assisted dispersive (micro)solid phase extraction (US-D-μSPE) using TpBD-Me covalent organic framework (COF) as adsorbent for simple, rapid and selective fluorescent determination of two polycyclic synthetic fragrances in seawater, i.e., 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-(γ)-2-benzopyran (HHCB), branded galaxolide®, and 7-acetyl-1,1,3,4,4,6-hexamethyltetralin (AHTN), branded tonalide®, is proposed.

Large-scale aqueous synthesis of Cu(In,Ga)Se nanoparticles for photocatalytic degradation of ciprofloxacin.

Environmentally friendly synthesis of Cu(In,Ga)Se (CIGS) nanoparticles (NPs) is pivotal for producing sustainable photocatalytic compounds to be applied in the remediation of contaminants of emerging concern from water. To this end, we herein report an aqueous synthesis of CIGS NPs, followed by annealing, to give access to phase-pure CIGS crystals with chalcopyrite structure and no signs of secondary phases. Morphological and compositional characterization revealed NPs with an average size of 10-35 nm and uniform distribution of Cu, In, Ga, and Se elements.

Study on the efficiency of a covalent organic framework as adsorbent for the screening of pharmaceuticals in estuary waters.

Herein, we demonstrate, for the first time, that covalent organic frameworks (COFs) can be efficient adsorbents for the screening of pharmaceuticals in real water samples, obtaining highly representative data on their occurrence and avoiding the cost of carrying high volume samples and tedious and costly clean-up and preconcentration steps. Of the 23 pharmaceuticals found present in the water samples from the Tagus river estuary using state-of-the-art solid-phase extraction (SPE), 22 were also detected (adsorbed and recovered for analysis) using a COF as the adsorbent material with adsorption efficiency of over 80% for nearly all compounds. In specific cases, acidification of the water samples was identified to lead to a dramatic loss of adsorption efficiency, underlining the effect of sample pre-treatment on the results.

Selection of Covalent Organic Framework Pore Functionalities for Differential Adsorption of Microcystin Toxin Analogues.

Microcystins (MCs), produced by sp, are the most commonly detected cyanotoxins in freshwater, and due to their toxicity, worldwide distribution, and persistence in water, an improvement in the monitoring programs for their early detection and removal from water is necessary. To this end, we investigate the performance of three covalent organic frameworks (COFs), TpBD-(CF), TpBD-(NO), and TpBD-(NH), for the adsorption of the most common and/or toxic MC derivatives, MC-LR, MC-RR, MC-LA, and MC-YR, from water. While MC-LR and MC-YR can be efficiently adsorbed using all three COF derivatives, high adsorption efficiencies were found for the most lipophilic toxin, MC-LA, with TpBD-(NH), and the most hydrophilic one, MC-RR, with TpBD-(NO).

Covalent Organic Framework Composites: Synthesis and Analytical Applications.

In the recent years, composite materials containing covalent organic frameworks (COFs) have raised increasing interest for analytical applications. To date, various synthesis techniques have emerged that allow for the preparation of crystalline and porous COF composites with various materials. Herein, we summarize the most common methods used to gain access to crystalline COF composites with magnetic nanoparticles, other oxide materials, graphene and graphene oxide, and metal nanoparticles.

Extraction of Ibuprofen from Natural Waters Using a Covalent Organic Framework.

Ibuprofen is one of the most widely used pharmaceuticals, and due to its inefficient removal by conventional wastewater treatment, it can be found in natural surface waters at high concentrations. Recently, we demonstrated that the TpBD-(CF) covalent organic framework (COF) can adsorb ibuprofen from ultrapure water with high efficiency. Here, we investigate the performance of the COF for the extraction of ibuprofen from natural water samples from a lake, river, and estuary.

From long-term sickness absence to disability retirement: diagnostic and occupational class differences within the working-age Finnish population.

Background: It is well documented that sickness absence is strongly associated with disability retirement. A long-term sickness absence (LTSA) in particular increases the risk of disability retirement, but little is known about the variation of this risk across diagnostic causes. Further, as occupational classes differ in their diagnostic profiles, it is likely that the role of diagnosis in the pathway from LTSA to disability retirement varies between occupational classes.

Combinations of Job Demands and Job Control and Future Trajectories of Sickness Absence and Disability Pension An 11-year Follow-up of Two Million Employees in Sweden.

Objective: The aim of this study was to examine the association between combinations of job demands/control and future sickness absence (SA) and disability pension (DP) trajectories over 11 years.

Methods: A population-based prospective cohort study of female (n = 1,079,631) and male (n = 1,107,999) employees in 2001. With group-based trajectory analysis, we modeled the trajectories of annual mean SA/DP days in 2002 to 2012.

Recyclable magnetic covalent organic framework for the extraction of marine biotoxins.

A novel procedure for the preparation of magnetic covalent organic frameworks (COFs) is reported. In situ functionalization of Fe3O4 with dopamine rapidly afforded amino-functionalized magnetic nanoparticles, which after decoration with a COF building block and subsequent COF growth gave access to magnetic composite mTpBD-Me2. The optimized synthesis conditions yielded crystalline and superparamagnetic material with no loss in surface area as compared to bulk COF.

Tailoring Covalent Organic Frameworks To Capture Water Contaminants.

Covalent organic frameworks (COFs) are attractive materials receiving increasing interest in the literature due to their crystallinity, large surface area, and pore uniformity. Their properties can be tailored towards specific applications by judicious design of COF building blocks, giving access to tailor-made pore sizes and surfaces. In this Concept article, developments in the field of COFs that have allowed these materials to be explored for contaminant adsorption are discussed.

Adsorption of Pharmaceutical Pollutants from Water Using Covalent Organic Frameworks.

Capture of pharmaceutical pollutants from water was studied using a novel fluorine-bearing covalent organic framework TpBD-(CF ) , which showed ibuprofen adsorption capacity of 119 mg g at neutral pH. This value is further enhanced at pH 2, highlighting the potential of this class of materials to serve as adsorbents even under harsh conditions. The adsorbed pharmaceutical can be recovered from TpBD-(CF ) in high yield, offering the option of recycling both the adsorbent and the pharmaceutical.

Sickness absence as a predictor of disability retirement in different occupational classes: a register-based study of a working-age cohort in Finland in 2007-2014.

Objectives: The objective of the study was to examine diagnosis-specific sickness absences of different lengths as predictors of disability retirement in different occupational classes.

Design: Register-based prospective cohort study up to 8 years of follow-up.

Participants: A 70% random sample of the non-retired Finnish population aged 25-62 at the end of 2006 was included (n=1 727 644) and linked to data on sickness absences in 2005 and data on disability retirement in 2007-2014.

Orthogonal Clickable Iron Oxide Nanoparticle Platform for Targeting, Imaging, and On-Demand Release.

A versatile iron oxide nanoparticle platform is reported that can be orthogonally functionalized to obtain highly derivatized nanomaterials required for a wide variety of applications, such as drug delivery, targeted therapy, or imaging. Facile functionalization of the nanoparticles with two ligands containing isocyanate moieties allows for high coverage of the surface with maleimide and alkyne groups. As a proof-of-principle, the nanoparticles were subsequently functionalized with a fluorophore as a drug model and with biotin as a targeting ligand towards tumor cells through Diels-Alder and azide-alkyne cycloaddition reactions, respectively.