Simulation models represent soil organic carbon (SOC) dynamics in global carbon (C) cycle scenarios to support climate-change studies. It is imperative to increase confidence in long-term predictions of SOC dynamics by reducing the uncertainty in model estimates. We evaluated SOC simulated from an ensemble of 26 process-based C models by comparing simulations to experimental data from seven long-term bare-fallow (vegetation-free) plots at six sites: Denmark (two sites), France, Russia, Sweden and the United Kingdom. The decay of SOC in these plots has been monitored for decades since the last inputs of plant material, providing the opportunity to test decomposition without the continuous input of new organic material. The models were run independently over multi-year simulation periods (from 28 to 80 years) in a blind test with no calibration (Bln) and with the following three calibration scenarios, each providing different levels of information and/or allowing different levels of model fitting: (a) calibrating decomposition parameters separately at each experimental site (Spe); (b) using a generic, knowledge-based, parameterization applicable in the Central European region (Gen); and (c) using a combination of both (a) and (b) strategies (Mix). We addressed uncertainties from different modelling approaches with or without spin-up initialization of SOC. Changes in the multi-model median (MMM) of SOC were used as descriptors of the ensemble performance. On average across sites, Gen proved adequate in describing changes in SOC, with MMM equal to average SOC (and standard deviation) of 39.2 (±15.5) Mg C/ha compared to the observed mean of 36.0 (±19.7) Mg C/ha (last observed year), indicating sufficiently reliable SOC estimates. Moving to Mix (37.5 ± 16.7 Mg C/ha) and Spe (36.8 ± 19.8 Mg C/ha) provided only marginal gains in accuracy, but modellers would need to apply more knowledge and a greater calibration effort than in Gen, thereby limiting the wider applicability of models.
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J Am Chem Soc
January 2025
Department of Chemistry, BioInspired Institute, Syracuse University, Syracuse, New York 13244, United States.
Understanding structure-mechanical activity relationships (SMARs) in polymer mechanochemistry is essential for the rational design of mechanophores with desired properties, yet SMARs in noncovalent mechanical transformations remain relatively underexplored. In this study, we designed a subset of diarylethene mechanophores based on a lever-arm hypothesis and systematically investigated their mechanical activity toward a noncovalent-yet-chemical conversion of atropisomer stereochemistry. Results from Density functional theory (DFT) calculations, single-molecule force spectroscopy (SMFS) measurements, and ultrasonication experiments collectively support the lever-arm hypothesis and confirm the exceptional sensitivity of chemo-mechanical coupling in these atropisomers.
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January 2025
Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States.
Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C-H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp)-H bond functionalization.
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January 2025
Stanford University Medical Center, Stanford, California, United States.
Allogeneic hematopoietic cell transplantation (HCT) is a curative therapy limited by graft-versus-host disease (GVHD). In preclinical studies and early-phase clinical studies enrichment of donor regulatory T cells (Tregs) appears to prevent GVHD and promote healthy immunity.We enrolled 44 patients on an open-label, single-center, phase 2 efficacy study investigating if a precision selected and highly purified Treg cell therapy manufactured from donor mobilized peripheral blood improves one-year GVHD-free relapse free survival (GRFS) after myeloablative conditioning (trial NCT01660607).
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
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View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
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