β-Cyclodextrins grafted with chiral amino acids: A promising supramolecular stabilizer of nanoparticles for asymmetric hydrogenation?

International audienceWater-soluble ruthenium nanoparticles stabilized by randomly methylated β-cyclodextrins (RaMeCDs) grafted with chiral amino-acid moieties like l-alanine (Ala) and l-leucine (Leu) were prepared in aqueous solution by two approaches: (i) a one-step hydrogen reduction of ruthenium trichloride as metal source in the presence of appropriate cyclodextrins (one-pot method) or (ii) a NaBH4 reduction of the metal salts, followed by the stabilization of ruthenium hydrosol by the addition of chirally modified RaMeCDs (cascade method). The influence of the ligand's nature and the synthesis methodologies on the size, dispersion and surface properties of the obtained ruthenium colloids were studied by TEM and NMR analyses. The spherical ruthenium suspensions contain very small particles (0.82-1.00 nm) with narrow size distributions. Their catalytic properties were evaluated in biphasic hydrogenation of various prochiral compounds (olefins, ketones and disubstituted arenes) showing promising results in terms of activity and selectivity. Nevertheless, no significant enantiomeric excesses were observed

Global Carbon Budget 2023

Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere in a changing climate is critical to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe and synthesize data sets and methodology to quantify the five major components of the global carbon budget and their uncertainties. Fossil CO2 emissions (EFOS) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on land-use and land-use change data and bookkeeping models. Atmospheric CO2 concentration is measured directly, and its growth rate (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) is estimated with global ocean biogeochemistry models and observation-based f CO2 products. The terrestrial CO2 sink (SLAND) is estimated with dynamic global vegetation models. Additional lines of evidence on land and ocean sinks are provided by atmospheric inversions, atmospheric oxygen measurements, and Earth system models. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and incomplete understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the year 2022, EFOS increased by 0.9 % relative to 2021, with fossil emissions at 9.9 ± 0.5 Gt C yr−1 (10.2 ± 0.5 Gt C yr−1 when the cement carbonation sink is not included), and ELUC was 1.2 ± 0.7 Gt C yr−1, for a total anthropogenic CO2 emission (including the cement carbonation sink) of 11.1 ± 0.8 Gt C yr−1 (40.7±3.2 Gt CO2 yr−1). Also, for 2022, GATM was 4.6±0.2 Gt C yr−1 (2.18±0.1 ppm yr−1; ppm denotes parts per million), SOCEAN was 2.8 ± 0.4 Gt C yr−1, and SLAND was 3.8 ± 0.8 Gt C yr−1, with a BIM of −0.1 Gt C yr−1 (i.e. total estimated sources marginally too low or sinks marginally too high). The global atmospheric CO2 concentration averaged over 2022 reached 417.1 ± 0.1 ppm. Preliminary data for 2023 suggest an increase in EFOS relative to 2022 of +1.1 % (0.0 % to 2.1 %) globally and atmospheric CO2 concentration reaching 419.3 ppm, 51 % above the pre-industrial level (around 278 ppm in 1750). Overall, the mean of and trend in the components of the global carbon budget are consistently estimated over the period 1959–2022, with a near-zero overall budget imbalance, although discrepancies of up to around 1 Gt C yr−1 persist for the representation of annual to semi-decadal variability in CO2 fluxes. Comparison of estimates from multiple approaches and observations shows the following: (1) a persistent large uncertainty in the estimate of land-use changes emissions, (2) a low agreement between the different methods on the magnitude of the land CO2 flux in the northern extra-tropics, and (3) a discrepancy between the different methods on the strength of the ocean sink over the last decade. This living-data update documents changes in methods and data sets applied to this most recent global carbon budget as well as evolving community understanding of the global carbon cycle. The data presented in this work are available at https://doi.org/10.18160/GCP-2023 (Friedlingstein et al., 2023)

Global Analysis of Surface Ocean CO₂ Fugacity and Air‐Sea Fluxes With Low Latency

International audienceAbstract The Surface Ocean CO 2 Atlas (SOCAT) of CO 2 fugacity ( f CO 2 ) observations is a key resource supporting annual assessments of CO 2 uptake by the ocean and its side effects on the marine ecosystem. SOCAT data are usually released with a lag of up to 1.5 years which hampers timely quantification of recent variations of carbon fluxes between the Earth System components, not only with the ocean. This study uses a statistical ensemble approach to analyze f CO 2 with a latency of one month only based on the previous SOCAT release and a series of predictors. Results indicate a modest degradation in a retrospective prediction test for 2021–2022. The generated f CO 2 and fluxes for January–August 2023 show a progressive reduction in the Equatorial Pacific source following the La Niña retreat. A breaking‐record decrease in the northeastern Atlantic CO 2 sink has been diagnosed on account of the marine heatwave event in June 2023

Global ocean surface carbon product

Quality Information DocumentThis product corresponds to a REP L4 time series of monthly global reconstructed surface ocean pCO2, air-sea fluxes of CO2 and pH and associated uncertainties on a 1° x 1° regular grid. The product is obtained from an ensemble-based forward feed neural network approach mapping situ data for surface ocean fugacity (SOCAT data base, Bakker et al. 2016, https://www.socat.info/) and sea surface salinity, temperature, sea surface height, chlorophyll a, mixed layer depth and atmospheric CO2 mole fraction. Sea-air flux fields are computed from the air-sea gradient of pCO2 and the dependence on wind speed of Wanninkhof (1992). Surface ocean pH on total scale is then computed from surface ocean pCO2 and reconstructed surface ocean alkalinity using the CO2sys speciation software.This document presents approaches and tools used to produce and validate the Global Ocean Surface Carbon Product MULTIOBS_GLO_BIO_CARBON_SURFACE_REP_015_008

CMEMS-LSCE: a global, 0.25 • , monthly reconstruction of the surface ocean carbonate system

International audienceObservation-based data reconstructions of global surface ocean carbonate system variables play an essential role in monitoring the recent status of ocean carbon uptake and ocean acidification, as well as their impacts on marine organisms and ecosystems. So far, ongoing efforts are directed towards exploring new approaches to describe the complete marine carbonate system and to better recover its fine-scale features. In this respect, our research activities within the Copernicus Marine Environment Monitoring Service (CMEMS) aim to develop a sustainable production chain of observation-derived global ocean carbonate system datasets at high space-time resolutions. As the start of the long-term objective, this study introduces a new global 0.25 • monthly reconstruction, namely CMEMS-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) for the period 1985-2021. The CMEMS-LSCE reconstruction derives datasets of six carbonate system variables, including surface ocean partial pressure of CO 2 (pCO 2), total alkalinity (A T), total dissolved inorganic carbon (C T), surface ocean pH, and saturation states with respect to aragonite (ar) and calcite (ca). Reconstructing pCO 2 relies on an ensemble of neural network models mapping gridded observation-based data provided by the Surface Ocean CO 2 ATlas (SOCAT). Surface ocean A T is estimated with a multiple-linear-regression approach, and the remaining carbonate variables are resolved by CO 2 system speciation given the reconstructed pCO 2 and A T ; 1σ uncertainty associated with these estimates is also provided. Here, σ stands for either the ensemble standard deviation of pCO 2 estimates or the total uncertainty for each of the five other variables propagated through the processing chain with input data uncertainty. We demonstrate that the 0.25 • resolution pCO 2 product outperforms a coarser spatial resolution (1 •) thanks to higher data coverage nearshore and a better description of horizontal and temporal variations in pCO 2 across diverse ocean basins, particularly in the coastal-open-ocean continuum. Product qualification with observation-based data confirms reliable reconstructions with root-meansquare deviation from observations of less than 8 %, 4 %, and 1 % relative to the global mean of pCO 2 , A T (C T), and pH. The global average 1σ uncertainty is below 5 % and 8 % for pCO 2 and ar (ca), 2 % for A T and C T , and 0.4 % for pH relative to their global mean values. Both model-observation misfit and model uncertainty indicate that coastal data reproduction still needs further improvement, wherein high temporal and horizontal gradients of carbonate variables and representative uncertainty from data sampling would be taken into account as a priority. This study also presents a potential use case of the CMEMS-LSCE carbonate data product in tracking the recent state of ocean acidification. The data associated with this study are available at https://doi.org/10.14768/a2f0891b-763a-49e9-af1b-78ed78b16982 (Chau et al., 2023)

CMEMS-LSCE: A global 0.25-degree, monthly reconstruction of the surface ocean carbonate system

International audienceAbstract. Observation-based data reconstructions of global surface ocean carbonate system variables play an essential role in monitoring the recent status of ocean carbon uptake and ocean acidification as well as their impacts on marine organisms and ecosystems. So far ongoing efforts are directed towards exploring new approaches to describe the complete marine carbonate system and to better recover its fine-scale features. In this respect, our research activities within the Copernicus Marine Environment Monitoring Service (CMEMS) aim at developing a sustainable production chain of observation-derived global ocean carbonate system datasets at high space-time resolution. As the start of the long-term objective, this study introduces a new global 0.25° monthly reconstruction, namely CMEMS-LSCE, for the period 1985–2021. The CMEMS-LSCE reconstruction derives datasets of six carbonate system variables including surface ocean partial pressure of CO2 (pCO2), total alkalinity (AT), total dissolved inorganic carbon (DIC), surface ocean pH, and saturation states with respect to aragonite (Ωar) and calcite (Ωca). Reconstructing pCO2 relies on an ensemble of neural network models mapping gridded observation-based data provided by the Surface Ocean CO2 ATlas (SOCAT). Surface ocean AT is estimated with a multiple linear regression approach, and the remaining carbonate variables are resolved by CO2 system speciation given the reconstructed pCO2 and AT. 1σ-uncertainty associated with these estimates is also provided. Here, σ stands for either ensemble standard deviation of pCO2 estimates or total uncertainty for each of the five other variables propagated through the processing chain with input data uncertainty. We demonstrate that the 0.25°-resolution pCO2 product outperforms a coarser spatial resolution (1°) thanks to a higher data coverage nearshore and a better description of horizontal and temporal variations in pCO2 across diverse ocean basins, particularly in the coastal-open-ocean continuum. Product qualification with observation-based data confirms reliable reconstructions with root-of-mean–square–deviation from observations less than 8 %, 4 %, and 1 % relative to the global mean of pCO2, AT (DIC), and pH. The global average 1σ-uncertainty is below 5 % and 8 % for pCO2 and Ωar (Ωca), 2 % for AT and DIC, and 0.4 % for pH relative to their global mean values. Both model-observation misfit and model uncertainty indicate that coastal data reproduction still needs further improvement, wherein high temporal and horizontal gradients of carbonate variables and representative uncertainty from data sampling would be taken into account in priority. This study also presents a potential use case of the CMEMS-LSCE carbonate data product in tracking the recent state of ocean acidification

Total clavicle reconstruction with free peroneal graft for the surgical management of chronic nonbacterial osteomyelitis of the clavicle: a case report

Abstract Background Chronic nonbacterial osteomyelitis (CNO) is a rare chronic autoinflammatory syndrome affecting mainly children and young adults. The natural history of the disease is marked by recurrent pain as the mainstay of inflammatory outbreaks. Typical radiographic findings are osteosclerosis and hyperostosis of the medial clavicle, sternum and first rib. Compression of the brachial plexus is exceedingly rare and one of the few surgical indications. Literature on total clavicle reconstruction is scarce. While claviclectomy alone has been associated with fair functional and cosmetic outcomes, several reconstruction techniques with autograft, allograft or even cement (“Oklahoma prosthesis”) have been reported with the aim of achieving better pain control, cosmetic outcome and protecting the brachial plexus and subclavian vessels. We herewith report a unique case of complicated CNO of the clavicle treated with total clavicle reconstruction using a free peroneal graft. Case presentation A 21-year-old female patient presented with CNO of her left clavicle, associated with recurrent, progressive and debilitating pain as well as limited range of motion. In recent years, she started complaining of paresthesia, weakness and pain radiating to her left arm during arm abduction. The clavicle diameter reached 6 cm on computed tomography, with direct compression of the brachial plexus and subclavian vessels. Following surgical biopsy for diagnosis confirmation, she further developed a chronic cutaneous fistula. Therefore, a two-stage total clavicle reconstruction using a vascularized peroneal graft stabilized by ligamentous reconstruction was performed. At two-year follow-up, complete pain relief and improvement of her left shoulder Constant-Murley score were observed, along with satisfactory cosmetic outcome. Conclusions This case illustrates a rarely described complication of CNO with direct compression of the brachial plexus and subclavian vessels, and chronic cutaneous fistula. To our knowledge, there is no consensus regarding the optimal management of this rare condition in this context. Advantages and complications of clavicle reconstruction should be carefully discussed with patients due to limited evidence of superior clinical outcome and potential local and donor-site complications. While in our case the outcomes met the patient’s satisfaction, it remains an isolated case and further reports are awaited to help surgeons and patients in their decision process

Spatial-Controlled Coating of Pro-Angiogenic Proteins on 3D Porous Hydrogels Guides Endothelial Cell Behavior

International audienceIn tissue engineering, the composition and the structural arrangement of molecular components within the extracellular matrix (ECM) determine the physical and biochemical features of a scaffold, which consequently modulate cell behavior and function. The microenvironment of the ECM plays a fundamental role in regulating angiogenesis. Numerous strategies in tissue engineering have attempted to control the spatial cues mimicking in vivo angiogenesis by using simplified systems. The aim of this study was to develop 3D porous crosslinked hydrogels with different spatial presentation of pro-angiogenic molecules to guide endothelial cell (EC) behavior. Hydrogels with pores and preformed microchannels were made with pharmaceutical-grade pullulan and dextran and functionalized with novel pro-angiogenic protein polymers (Caf1-YIGSR and Caf1-VEGF). Hydrogel functionalization was achieved by electrostatic interactions via incorporation of diethylaminoethyl (DEAE)-dextran. Spatial-controlled coating of hydrogels was realized through a combination of freeze-drying and physical absorption with Caf1 molecules. Cells in functionalized scaffolds survived, adhered, and proliferated over seven days. When incorporated alone, Caf1-YIGSR mainly induced cell adhesion and proliferation, whereas Caf1-VEGF promoted cell migration and sprouting. Most importantly, directed cell migration required the presence of both proteins in the microchannel and in the pores, highlighting the need for an adhesive substrate provided by Caf1-YIGSR for Caf1-VEGF to be effective. This study demonstrates the ability to guide EC behavior through spatial control of pro-angiogenic cues for the study of pro-angiogenic signals in 3D and to develop pro-angiogenic implantable materials