Imidazolylidene Cu(II) complexes: synthesis using imidazolium carboxylate precursors and structure rearrangement pathways

Copper(II) complexes of type (NHC)CuX2 (X = OAc, Cl, Br, BF4, NO3) bearing monodentate N-heterocyclic carbenes (NHCs) were prepared by in situ decarboxylation of imidazolium carboxylates as a new synthetic methodology for Cu(II)-NHC complexes. In contrast to the classical deprotonation method, the decarboxylation protocol does not require anaerobic conditions and provides access to complexes with NHCs that are unstable as free carbenes such as N,N’-diisopropyl-imidazolylidene and N,N’-dimethyl-imidazolylidene. Spectroscopic evidence of the formation of the Cu‒CNHC bond is provided by UV-vis and EPR, in particular by the 44 MHz carbene hyperfine coupling constant using a 13C-labelled imidazolylidene ligand. A variation of the nature of the carbene N-substituents and the anions bound to the Cu(II) center is possible with this methodology. These variations strongly influence the stability of the complexes. Structural rearrangement and ligand reorganization was observed during recrystallisation, which are comprised of heterolytic Cu‒CNHC bond dissociation for unstable NHC ligands as well as homolytic Cu‒X bond cleavage and disproportionation reactions depending on the nature of the anion X in the copper complex

Latitude dictates plant diversity effects on instream decomposition

Running waters contribute substantially to global carbon fluxes through decomposition of terrestrial plant litter by aquatic microorganisms and detritivores. Diversity of this litter may influence instream decomposition globally in ways that are not yet understood. We investigated latitudinal differences in decomposition of litter mixtures of low and high functional diversity in 40 streams on 6 continents and spanning 113 degrees of latitude. Despite important variability in our dataset, we found latitudinal differences in the effect of litter functional diversity on decomposition, which we explained as evolutionary adaptations of litter-consuming detritivores to resource availability. Specifically, a balanced diet effect appears to operate at lower latitudes versus a resource concentration effect at higher latitudes. The latitudinal pattern indicates that loss of plant functional diversity will have different consequences on carbon fluxes across the globe, with greater repercussions likely at low latitudes

How to Develop and Implement a Computerized Decision Support System Integrated for Antimicrobial Stewardship? Experiences From Two Swiss Hospital Systems

Background: Computerized decision support systems (CDSS) provide new opportunities for automating antimicrobial stewardship (AMS) interventions and integrating them in routine healthcare. CDSS are recommended as part of AMS programs by international guidelines but few have been implemented so far. In the context of the publicly funded COMPuterized Antibiotic Stewardship Study (COMPASS), we developed and implemented two CDSSs for antimicrobial prescriptions integrated into the in-house electronic health records of two public hospitals in Switzerland. Developing and implementing such systems was a unique opportunity for learning during which we faced several challenges. In this narrative review we describe key lessons learned. Recommendations: (1) During the initial planning and development stage, start by drafting the CDSS as an algorithm and use a standardized format to communicate clearly the desired functionalities of the tool to all stakeholders. (2) Set up a multidisciplinary team bringing together Information Technologies (IT) specialists with development expertise, clinicians familiar with "real-life" processes in the wards and if possible, involve collaborators having knowledge in both areas. (3) When designing the CDSS, make the underlying decision-making process transparent for physicians and start simple and make sure to find the right balance between force and persuasion to ensure adoption by end-users. (4) Correctly assess the clinical and economic impact of your tool, therefore try to use standardized terminologies and limit the use of free text for analysis purpose. (5) At the implementation stage, plan usability testing early, develop an appropriate training plan suitable to end users' skills and time-constraints and think ahead of additional challenges related to the study design that may occur (such as a cluster randomized trial). Stay also tuned to react quickly during the intervention phase. (6) Finally, during the assessment stage plan ahead maintenance, adaptation and related financial challenges and stay connected with institutional partners to leverage potential synergies with other informatics projects

Latitude dictates plant diversity effects on instream decomposition

Abstract Running waters contribute substantially to global carbon fluxes through decomposition of terrestrial plant litter by aquatic microorganisms and detritivores. Diversity of this litter may influence instream decomposition globally in ways that are not yet understood. We investigated latitudinal differences in decomposition of litter mixtures of low and high functional diversity in 40 streams on 6 continents and spanning 113° of latitude. Despite important variability in our dataset, we found latitudinal differences in the effect of litter functional diversity on decomposition, which we explained as evolutionary adaptations of litter-consuming detritivores to resource availability. Specifically, a balanced diet effect appears to operate at lower latitudes versus a resource concentration effect at higher latitudes. The latitudinal pattern indicates that loss of plant functional diversity will have different consequences on carbon fluxes across the globe, with greater repercussions likely at low latitudes

Impacts of detritivore diversity loss on instream decomposition are greatest in the tropics

It is unclear whether stream detritivore diversity enhances decomposition across climates. Here the authors manipulate litter diversity and examine detritivore assemblages in a globally distributed stream litterbag experiment, finding a positive diversity-decomposition relationship stronger in tropical streams, where detritivore diversity is lower

Impacts of detritivore diversity loss on instream decomposition are greatest in the tropics

The relationship between detritivore diversity and decomposition can provide information on how biogeochemical cycles are affected by ongoing rates of extinction, but such evidence has come mostly from local studies and microcosm experiments. We conducted a globally distributed experiment (38 streams across 23 countries in 6 continents) using standardised methods to test the hypothesis that detritivore diversity enhances litter decomposition in streams, to establish the role of other characteristics of detritivore assemblages (abundance, biomass and body size), and to determine how patterns vary across realms, biomes and climates. We observed a positive relationship between diversity and decomposition, strongest in tropical areas, and a key role of abundance and biomass at higher latitudes. Our results suggest that litter decomposition might be altered by detritivore extinctions, particularly in tropical areas, where detritivore diversity is already relatively low and some environmental stressors particularly prevalent

Outcome after failure of allogeneic hematopoietic stem cell transplantation in children with acute leukemia: a study by the société Francophone de greffe de moelle et de thérapie cellulaire (SFGM-TC)

International audienc

A highly virulent variant of HIV-1 circulating in the Netherlands

We discovered a highly virulent variant of subtype-B HIV-1 in the Netherlands. One hundred nine individuals with this variant had a 0.54 to 0.74 log10 increase (i.e., a ~3.5-fold to 5.5-fold increase) in viral load compared with, and exhibited CD4 cell decline twice as fast as, 6604 individuals with other subtype-B strains. Without treatment, advanced HIV-CD4 cell counts below 350 cells per cubic millimeter, with long-term clinical consequences-is expected to be reached, on average, 9 months after diagnosis for individuals in their thirties with this variant. Age, sex, suspected mode of transmission, and place of birth for the aforementioned 109 individuals were typical for HIV-positive people in the Netherlands, which suggests that the increased virulence is attributable to the viral strain. Genetic sequence analysis suggests that this variant arose in the 1990s from de novo mutation, not recombination, with increased transmissibility and an unfamiliar molecular mechanism of virulence

Factors associated with COVID-19-related death in people with rheumatic diseases: results from the COVID-19 Global Rheumatology Alliance physician-reported registry

Objectives: To determine factors associated with COVID-19-related death in people with rheumatic diseases. Methods: Physician-reported registry of adults with rheumatic disease and confirmed or presumptive COVID-19 (from 24 March to 1 July 2020). The primary outcome was COVID-19-related death. Age, sex, smoking status, comorbidities, rheumatic disease diagnosis, disease activity and medications were included as covariates in multivariable logistic regression models. Analyses were further stratified according to rheumatic disease category. Results: Of 3729 patients (mean age 57 years, 68% female), 390 (10.5%) died. Independent factors associated with COVID-19-related death were age (66-75 years: OR 3.00, 95% CI 2.13 to 4.22; >75 years: 6.18, 4.47 to 8.53; both vs ≤65 years), male sex (1.46, 1.11 to 1.91), hypertension combined with cardiovascular disease (1.89, 1.31 to 2.73), chronic lung disease (1.68, 1.26 to 2.25) and prednisolone-equivalent dosage >10 mg/day (1.69, 1.18 to 2.41; vs no glucocorticoid intake). Moderate/high disease activity (vs remission/low disease activity) was associated with higher odds of death (1.87, 1.27 to 2.77). Rituximab (4.04, 2.32 to 7.03), sulfasalazine (3.60, 1.66 to 7.78), immunosuppressants (azathioprine, cyclophosphamide, ciclosporin, mycophenolate or tacrolimus: 2.22, 1.43 to 3.46) and not receiving any disease-modifying anti-rheumatic drug (DMARD) (2.11, 1.48 to 3.01) were associated with higher odds of death, compared with methotrexate monotherapy. Other synthetic/biological DMARDs were not associated with COVID-19-related death. Conclusion: Among people with rheumatic disease, COVID-19-related death was associated with known general factors (older age, male sex and specific comorbidities) and disease-specific factors (disease activity and specific medications). The association with moderate/high disease activity highlights the importance of adequate disease control with DMARDs, preferably without increasing glucocorticoid dosages. Caution may be required with rituximab, sulfasalazine and some immunosuppressants