Lived experience of work and long COVID in healthcare staff.

BACKGROUND: Healthcare workers (HCWs) had a greater occupational risk of exposure to coronavirus disease 2019 (COVID-19) and reported higher rates of long COVID (LC). This has implications for the provision of health care in already stretched health services. AIMS: This study explored the impact of LC on a range of UK National Health Service (NHS) HCWs, their health and well-being, the effect on work patterns, and occupational support received. METHODS: Mixed-methods study, online survey and qualitative interviews. Participants self-reporting LC symptoms were recruited through social media and NHS channels. Interviews used maximum variation sampling of 50 HCWs including healthcare professionals, ancillary and administration staff. Thematic analysis was conducted using NVivo software. RESULTS: A total of 471 HCWs completed the online survey. Multiple LC symptoms were reported, revealing activity limitations for 90%. Two-thirds had taken sick leave, 18% were off-work and 33% reported changes in work duties. There were few differences in work practices by occupational group. Most participants were working but managing complex and dynamic symptoms, with periods of improvement and exacerbation. They engaged in a range of strategies: rest, pacing, planning and prioritizing, with work prioritized over other aspects of life. Symptom improvements were often linked to occupational medicine, managerial, colleague support and flexible workplace adjustments. CONCLUSIONS: LC has a significant impact on the lives of HCWs suffering prolonged symptoms. Due to the variability and dynamic nature of symptoms, workplace support and flexible policies are needed to help retain staff.

Pediatrician-Authored Opinion/Editorial Articles Published in Newspapers Before and After the Start of the COVID-19 Pandemic.

BACKGROUND: Pediatricians publish opinion/editorials in newspapers as a form of advocacy. No research has characterized these publications to determine the scope of this communication. OBJECTIVE: We examined the characteristics of pediatrician-authored op-eds, comparing articles published in a seasonally matched six-month period before and after the onset of the COVID-19 pandemic. METHODS: We reviewed 249 pediatrician-authored op-eds (109 before COVID-19; 140 during COVID-19 pandemic) over two six-month periods accessed through America's Newspapers database in June 2021. Each article was coded for topics covered, presumed motivations for the publication, and communication techniques used. RESULTS: Total number of articles published by pediatricians was higher after the start of COVID-19 compared with a period before the pandemic. Authors commonly asked for legislative action before and during the COVID-19 pandemic, but within the COVID-19 pandemic authors more often asked for behavioral changes in the readers themselves. Personal stories were a common technique used in both time periods; shaming of government became more common during COVID-19. CONCLUSIONS: These data provide context for additional studies examining the usefulness of op-eds in pediatrician advocacy.

Intracellular Zn(II) induced turn-on fluorescence of an L-phenylalanine-derived pseudopeptide.

A C2 symmetric L-phenylalanine-derived pseudopeptide has been synthesized for selective and sensitive recognition of Zn(II) ions in aqueous-organic media. The pseudopeptidic probes exhibit intracellular Zn(II) ion-sensing capabilities as demonstrated via live-cell fluorescence studies on RAW264.7 cells. Hence, we present a bioinspired pseudopeptide for potential biological applications involving intracellular Zn(II) ion detection.

The key role of pretreatment for the one-step and multi-step conversions of European lignocellulosic materials into furan compounds.

Nowadays, an increased interest from the chemical industry towards the furanic compounds production, renewable molecules alternatives to fossil molecules, which can be transformed into a wide range of chemicals and biopolymers. These molecules are produced following hexose and pentose dehydration. In this context, lignocellulosic biomass, owing to its richness in carbohydrates, notably cellulose and hemicellulose, can be the starting material for monosaccharide supply to be converted into bio-based products. Nevertheless, processing biomass is essential to overcome the recalcitrance of biomass, cellulose crystallinity, and lignin crosslinked structure. The previous reports describe only the furanic compound production from monosaccharides, without considering the starting raw material from which they would be extracted, and without paying attention to raw material pretreatment for the furan production pathway, nor the mass balance of the whole process. Taking account of these shortcomings, this review focuses, firstly, on the conversion potential of different European abundant lignocellulosic matrices into 5-hydroxymethyl furfural and 2-furfural based on their chemical composition. The second line of discussion is focused on the many technological approaches reported so far for the conversion of feedstocks into furan intermediates for polymer technology but highlighting those adopting the minimum possible steps and with the lowest possible environmental impact. The focus of this review is to providing an updated discussion of the important issues relevant to bringing chemically furan derivatives into a market context within a green European context.

The Debye length and anionic transport properties of composite membranes based on supported ionic liquid-like phases (SILLPS).

An analysis of the ionic transport properties of BMIM [NTf2] in supported ionic-liquid-like phase (SILLP)-based membranes has been carried out based on experimental impedance spectroscopy measurements. The direct current (dc)-conductivity was analyzed to determine the temperature and frequency dependence. The fit of the loss tangent curve data with the Cole-Cole approximation of the electrode polarization model provides the conductivity, diffusivity, and density of charge carriers. Among these quantities, a significant increase in conductivity is observed when an ionic liquid is added to the polymeric matrix containing imidazolium fragments. The use of a recent generalization of Eyring's absolute rate theory allowed the elucidation of how the local entropy restrictions, due to the porosity of the polymeric matrix, control the conductive process. The fit of the conductivity data as a function of temperature manifests the behavior of the excess entropy with respect to the temperature. The activation entropy and enthalpy were also determined. Our results correlate the Debye length (LD) with the experimental values of conductivity, electrode polarization relaxation time, and sample relaxation time involved. Our work provides novel insights into the description of ionic transport in membranes as the diffusivity, mobility, and free charge density depend on the LD. Moreover, we discuss the behavior of the polarization relaxation time, the sample relaxation time, and the static permittivity as a function of the temperature.

Pseudopeptidic host adaptation in peptide recognition unveiled by ion mobility mass spectrometry.

Complexation of the glutamic-tyrosine-glutamic tripeptide (EYE) with a series of pseudopeptidic cages has been thoroughly investigated using different analytical techniques. The stoichiometry and affinities of the supramolecular host : guest complexes both in aqueous solution and in the gas-phase were obtained from a suitable combination of fluorescence spectroscopy, NMR, and mass spectrometry (MS) methods. The cages bearing basic groups (lysine, ornitine and histidine) display the tightest EYE binding in aqueous media following the order CyHis > CyLys > CyOrn, thus suggesting that Tyr side chain encapsulation is additionally modulated by the identity of the cage side chains and their ability to be engaged in polar interactions with the EYE peptide. Similarly, binding affinities estimated by MS methods clearly point towards a reduced affinity for the Cy cages with acidic pendant groups and a higher affinity of the CyHis cage over CyLys and CyOrn. Ion mobility spectrometry (IMS)-MS, assisted by molecular modelling, has been used to uncover the structural and conformational characteristics of the pseudopeptidic hosts and their supramolecular adducts with the EYE peptide. The cages display a collisional cross-section increase upon EYE inclusion that is associated with the expansion of the binding pocket of the cage cavity, thus constituting a unique example of conformational pseudopeptidic host adaptation to accommodate the inclusion of the guest.

Basically, nucleophilicity matters little: towards unravelling the supramolecular driving forces in enzyme-like CO2 conversion.

The reaction mechanism for the cycloaddition of CO2 to styrene oxide in the presence of macrocyclic pseudopeptides has been studied using DFT methods. Computational calculations indicate that the unprecedented catalytic behaviour previously observed experimentally, in which the most reactive species was not the most nucleophilic but the most basic one, can be associated to the tight cooperativity between several supramolecular interactions promoted by simple peptidomimetics able to display a synzymatic behaviour. This bizarre catalytic performance afforded remarkable conversions of a sluggish substrate like styrene oxide into the desired cyclic carbonate, even under relatively mild reaction conditions, opening the way for the practical use of CO2 as a raw material in the preparation of valuable chemicals. Furthermore, the remote modification of essential structural features of the macrocycle (synzyme engineering) permitted the driving forces of the synzymatic system to be analyzed, stressing the crucial synergic effect between an elegantly preorganized oxyanion hole and additional aromatic interactions.

Unravelling the Supramolecular Driving Forces in the Formation of CO2-Responsive Pseudopeptidic Low-Molecular-Weight Hydrogelators.

A new family of C2-symmetric pseudopeptides with a high functional density for supramolecular interactions has been synthetized through the attachment of four amino acid subunits to a diamino aliphatic spacer. The resulting open-chain compounds present remarkable properties as low-molecular-weight hydrogelators. The self-assembled 3D networks were characterized by SEM analyses, observing regular nanofibres with 80-100 nm diameters. Spectroscopic and molecular modelling experiments revealed the presence of strong synergic effects between the H-bonding and π-π interactions, with the best results obtained for the homoleptic tetra-pseudopeptide derived from l-Phe. In addition, these bioinspired hydrogels possessed pH- and CO2-responsive sol-gel transitions. The formation of ammonium carbamate derivatives in the presence of carbon dioxide led to a detrimental change in its adequate self-assembly. CO2 desorption temperatures of ca. 70 °C were assigned to the thermodynamically favoured recovery of the supramolecular gel.

Continuous Flow Processes as an Enabling Tool for the Synthesis of Constrained Pseudopeptidic Macrocycles.

Herein we report our efforts to develop a continuous flow methodology for the efficient preparation of pseudopeptidic macrocyclic compounds containing the hexahydropyrrolo-[3,4-f]-isoindolocyclophane scaffold and involving four coupled substitution reactions in the macrocyclization process. Appropriate design of a supported base permitted the continuous production of the macrocycles even at large scales, taking advantage of the positive template effect promoted by the bromide anions. In addition, the use of flow protocols allowed a ca. 20-fold increase in productivity as well as reducing the environmental impact almost 2 orders of magnitude, in comparison with the related batch macrocyclization process.

Cemetery Relocations in Hidroituango: An Interdisciplinary Study.

This study realized the exhumation and transfer of human remains buried in the cemeteries at Orobajo, Barbacoas and La Fortuna (Municipality of Sabanalarga, Peque and Buriticá respectively) within the framework of "Social Management" of the Ituango Hydroelectric Project and the program Integral Restitution of Living Conditions for communities. Methods and techniques from bioanthropology, forensic sciences, archeology and Soil Sciences were used. Cemeteries were characterized by unconventional burials; moreover, documentation of tombs and burial practices were not generalized, nor did they show patterns. In the field assessment, 2,883 pit tests and soil probes using a penetrometer were carried out over a total area of 2,288 square meters. A total of 349 skeletonized human remains were exhumed, almost double of what was expected; of these, 180 were from Orabajo, 151 from Barbacoas, and 18 from La Fortuna. Though the remains showed a great deal of deterioration, age at death was determined for 59% of cases, and sex identified in 49%. Personal artifacts and clothing items were recovered along with the bones in many cases. Remains from Barbacoas and La Fortuna were given over to communities, and final dispositions were made in sites previously agreed upon (cemeteries in Peque, Buriticá and Sabanalarga respectively).

Rational Design of Simple Organocatalysts for the HSiCl3 Enantioselective Reduction of (E)-N-(1-Phenylethylidene)aniline.

Prolinamides are well-known organocatalysts for the HSiCl3 reduction of imines; however, custom design of catalysts is based on trial-and-error experiments. In this work, we have used a combination of computational calculations and experimental work, including kinetic analyses, to properly understand this process and to design optimized catalysts for the benchmark (E)-N-(1-phenylethylidene)aniline. The best results have been obtained with the amide derived from 4-methoxyaniline and the N-pivaloyl protected proline, for which the catalyzed process is almost 600 times faster than the uncatalyzed one. Mechanistic studies reveal that the formation of the component supramolecular complex catalyst-HSiCl3-substrate, involving hydrogen bonding breaking and costly conformational changes in the prolinamide, is an important step in the overall process.

Preparation of Nanofibers Mats Derived from Task-Specific Polymeric Ionic Liquid for Sensing and Catalytic Applications.

Nanofibers mats derived from the task-specific functionalized polymeric ionic liquids based on homocysteine thiolactone are obtained by electrospinning them as blends with polyvinylpyrrolidone. The presence of this functional moiety allowed the post-functionalization of these mats through the aminolysis of the thiolactone ring in the presence of an amine by a thiol-alkene "click" reaction. Under controlled experimental conditions the modification can be performed introducing different functionalization and crosslinking of the electrospun fibers, while maintaining the nanostructure obtained by the electrospinning. Initial studies suggest that the nanofibers based on these functionalized polymeric ionic liquids can be used in both sensing and catalytic applications.

Chiral Imidazolium Prolinate Salts as Efficient Synzymatic Organocatalysts for the Asymmetric Aldol Reaction.

Chiral imidazolium l-prolinate salts, providing a complex network of supramolecular interaction in a chiral environment, have been studied as synzymatic catalytic systems. They are demonstrated to be green and efficient chiral organocatalysts for direct asymmetric aldol reactions at room temperature. The corresponding aldol products were obtained with moderate to good enantioselectivities. The influence of the presence of chirality in both the imidazolium cation and the prolinate anion on the transfer of chirality from the organocatalyst to the aldol product has been studied. Moreover, interesting match/mismatch situations have been observed regarding configuration of chirality of the two components through the analysis of results for organocatalysts derived from both enantiomers of prolinate (R/S) and the trans/cis isomers for the chiral fragment of the cation. This is associated with differences in the corresponding reaction rates but also to the different tendencies for the formation of aggregates, as evidenced by nonlinear effects studies (NLE). Excellent activities, selectivities, and enantioselectivities could be achieved by an appropriate selection of the structural elements at the cation and anion.

Correction: Free ion diffusivity and charge concentration on cross-linked polymeric ionic liquid iongel films based on sulfonated zwitterionic salts and lithium ions.

Correction for 'Free ion diffusivity and charge concentration on cross-linked polymeric ionic liquid iongel films based on sulfonated zwitterionic salts and lithium ions' by David Valverde et al., Phys. Chem. Chem. Phys., 2019, 21, 17923-17932, DOI: 10.1039/C9CP01903K.

Imidazole and Imidazolium Antibacterial Drugs Derived from Amino Acids.

The antibacterial activity of imidazole and imidazolium salts is highly dependent upon their lipophilicity, which can be tuned through the introduction of different hydrophobic substituents on the nitrogen atoms of the imidazole or imidazolium ring of the molecule. Taking this into consideration, we have synthesized and characterized a series of imidazole and imidazolium salts derived from L-valine and L-phenylalanine containing different hydrophobic groups and tested their antibacterial activity against two model bacterial strains, Gram-negative E. coli and Gram-positive B. subtilis. Importantly, the results demonstrate that the minimum bactericidal concentration (MBC) of these derivatives can be tuned to fall close to the cytotoxicity values in eukaryotic cell lines. The MBC value of one of these compounds toward B. subtilis was found to be lower than the IC50 cytotoxicity value for the control cell line, HEK-293. Furthermore, the aggregation behavior of these compounds has been studied in pure water, in cell culture media, and in mixtures thereof, in order to determine if the compounds formed self-assembled aggregates at their bioactive concentrations with the aim of determining whether the monomeric species were in fact responsible for the observed antibacterial activity. Overall, these results indicate that imidazole and imidazolium compounds derived from L-valine and L-phenylalanine-with different alkyl lengths in the amide substitution-can serve as potent antibacterial agents with low cytotoxicity to human cell lines.

Polymeric Ionic Liquids Derived from L-Valine for the Preparation of Highly Selective Silica-Supported Stationary Phases in Gas Chromatography.

A series of silica-supported polymeric ionic liquid (PIL)-based stationary phases derived from a vinylic L-valine ionic liquid monomer and divinylbenzene (DVB) as the crosslinking agent have been prepared and studied as gas chromatographic stationary phases. These coated gas chromatographic columns exhibited good thermal stabilities (230-300 °C) and high efficiencies (1700-2700 plates/m), and were characterized using a linear solvation parameter model in order to understand the effects of the amount of DVB on the features of the resulting composite systems. Their retention behavior and separation efficiencies were demonstrated using the Grob test. By tuning the crosslinking degree for the IL-derived stationary phase, the separation selectivity and resolution of different compounds were improved. The different retention behaviors observed for many analytes indicate that these stationary phases may be applicable as new types of GC stationary phases.

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene-phosphine complexes for the Negishi reaction under flow conditions.

The combination of supported ionic liquids and immobilized NHC-Pd-RuPhos led to active and more stable systems for the Negishi reaction under continuous flow conditions than those solely based on NHC-Pd-RuPhos. The fine tuning of the NHC-Pd catalyst and the SILLPs is a key factor for the optimization of the release and catch mechanism leading to a catalytic system easily recoverable and reusable for a large number of catalytic cycles enhancing the long-term catalytic performance.

Urea-Based Low-Molecular-Weight Pseudopeptidic Organogelators for the Encapsulation and Slow Release of (R)-Limonene.

Low-molecular-weight compounds containing alkylurea fragments attached to the amino end of different miminalistic pseudopeptidic structures have been shown to be excellent organogelators in a variety of organic solvents and liquid organic compounds of different nature. The formation of gels in this work is defined through rheological measurements for those cases where G' > G''. Both the topology and the symmetry of the corresponding urea compounds play a role in defining their organogelator behavior. This can also be tuned by the presence of additional supramolecular guests, as is the case for suberic acid. These compounds also achieve the gelation of relevant active substances such as terpene natural oils and complex mixtures of flavors and fragrances. This provides a simple and mass-efficient supramolecular system for the quantitative encapsulation of active substances, without the need for any additional solvent or complex processes, and their consequent controlled release.

Synthesis of second-generation self-assembling Gemini Amphiphilic Pseudopeptides.

HYPOTHESIS: The structural modularity of Gemini Amphiphilic Pseudopeptides (GAPs) allows the tuning of the self-assembling properties by slight modifications in the chemical structures. We hypothesized that the introduction of a flexible linker containing a central nitrogen atom in bipodal and tripodal GAPs would improve their self-assembly properties in aqueous media. EXPERIMENTS: After preparation of the corresponding GAPs, a combination of SEM, TEM and AFM techniques were used to study the morphology of the self-assembled structures in different media. The solution structures in non-aggregated states were also analyzed by combining NMR, UV and CD studies. The transition from the non-aggregated species to the hierarchical self-assembly was monitored by ATR FT-IR spectroscopy, while the critical aggregation concentration in water was determined by fluorescence spectroscopy. FINDINGS: The formation of different morphologies (vesicles or fibers) highly depends on the polarity and the pH of the medium. A reasonable mechanism for the self-assembly has been established in agreement with the experimental techniques used, where the protonation of the nitrogen in the linker must play a key role. In general, the obtained GAPs showed an improved formation of vesicles in aqueous media (different pH or ionic strength) with potential applications in biomedicine and drug delivery.

Highly Selective Anion Template Effect in the Synthesis of Constrained Pseudopeptidic Macrocyclic Cyclophanes.

Herein, we report the synthesis of a novel family of constrained pseudopeptidic macrocyclic compounds containing the hexahydropyrrolo[3,4-f]isoindolocyclophane scaffold and involving four coupled substitution reactions in the macrocyclization process. Although the increase in the number of steps involved in the macrocyclization could lead to a larger number of possible side products, the optimization of the methodology and the study of the driving forces have made it possible to obtain the desired macrocycles in excellent yields. A thorough computational study has been carried out to understand the macrocyclization process, and the results obtained nicely agree with experimental data. Moreover, the bromide anion had a clear catalytic template effect in the macrocyclization reaction, and surprisingly, the chloride anion had a negative template effect in opposition to the results obtained for analogous macrocycles. The parameters responsible for the specific kinetic template effect observed have been studied in detail.