201 results on '"Clément, P."'
Search Results
2. The 2025 Motile Active Matter Roadmap.
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Gompper, Gerhard, Stone, Howard, Kurzthaler, Christina, Saintillan, David, Peruani, Fernado, Fedosov, Dmitry, Auth, Thorsten, Cottin-Bizonne, Cecile, Ybert, Christophe, Clément, Eric, Darnige, Thierry, Lindner, Anke, Goldstein, Raymond, Liebchen, Benno, Binysh, Jack, Souslov, Anton, Isa, Lucio, di Leonardo, Roberto, Frangipane, Giacomo, Gu, Hongri, Nelson, Bradley, Brauns, Fridtjof, Marchetti, Cristina, Cichos, Frank, Heuthe, Veit-Lorenz, Bechinger, Clemens, Korman, Amos, Feinerman, Ofer, Cavagna, Andrea, Giardina, Irene, Jeckel, Hannah, and Drescher, Knut
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Active Matter ,Intelligent Matter ,Microbots ,Microswimmers ,Non-equilibrium Systems ,Non-reciprocal Interactions ,Swarming - Abstract
Activity and autonomous motion are fundamental aspects of many living and engineering systems. Here, the scale of biological agents covers a wide range, from nanomotors, cytoskeleton, and cells, to insects, fish, birds, and people. Inspired by biological active systems, various types of autonomous synthetic nano- and micromachines have been designed, which provide the basis for multifunctional, highly responsive, intelligent active materials. A major challenge for understanding and designing active matter is their inherent non-equilibrium nature due to persistent energy consumption, which invalidates equilibrium concepts such as free energy, detailed balance, and time-reversal symmetry. Furthermore, interactions in ensembles of active agents are often non-additive and non-reciprocal. An important aspect of biological agents is their ability to sense the environment, process this information, and adjust their motion accordingly. It is an important goal for the engineering of micro-robotic systems to achieve similar functionality.With many fundamental properties of motile active matter now reasonably well understood and under control, the ground is prepared for the study of physical aspects and mechanisms of motion in complex environments, of the behavior of systems with new physical features like chirality, of the development of novel micromachines and microbots, of the emergent collective behavior and swarming of intelligent self-propelled particles, and of particular features of microbial systems.The vast complexity of phenomena and mechanisms involved in the self-organization and dynamics of motile active matter poses major challenges, which can only be addressed by a truly interdisciplinary effort involving scientists from biology, chemistry, ecology, engineering, mathematics, and physics. The 2024 motile active matter roadmap of Journal of Physics: Condensed Matter reviews the current state of the art of the field and provides guidance for further progress in this fascinating research area.
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- 2025
3. Surface molecular engineering to enable processing of sulfide solid electrolytes in humid ambient air
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Liu, Mengchen, Hong, Jessica J, Sebti, Elias, Zhou, Ke, Wang, Shen, Feng, Shijie, Pennebaker, Tyler, Hui, Zeyu, Miao, Qiushi, Lu, Ershuang, Harpak, Nimrod, Yu, Sicen, Zhou, Jianbin, Oh, Jeong Woo, Song, Min-Sang, Luo, Jian, Clément, Raphaële J, and Liu, Ping
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Engineering ,Chemical Sciences ,Physical Chemistry - Abstract
Sulfide solid-state electrolytes (SSEs) are promising candidates to realize all solid-state batteries (ASSBs) due to their superior ionic conductivity and excellent ductility. However, their hypersensitivity to moisture requires processing environments that are not compatible with today's lithium-ion battery manufacturing infrastructure. Herein, we present a reversible surface modification strategy that enables the processability of sulfide SSEs (e. g., Li6PS5Cl) under humid ambient air. We demonstrate that a long chain alkyl thiol, 1-undecanethiol, is chemically compatible with the electrolyte with negligible impact on its ion conductivity. Importantly, the thiol modification extends the amount of time that the sulfide SSE can be exposed to air with 33% relative humidity (33% RH) with limited degradation of its structure while retaining a conductivity of above 1 mS cm-1 for up to 2 days, a more than 100-fold improvement in protection time over competing approaches. Experimental and computational results reveal that the thiol group anchors to the SSE surface, while the hydrophobic hydrocarbon tail provides protection by repelling water. The modified Li6PS5Cl SSE maintains its function after exposure to ambient humidity when implemented in a Li0.5In | |LiNi0.8Co0.1Mn0.1O2 ASSB. The proposed protection strategy based on surface molecular interactions represents a major step forward towards cost-competitive and energy-efficient sulfide SSE manufacturing for ASSB applications.
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- 2025
4. Soil Moisture‐Cloud‐Precipitation Feedback in the Lower Atmosphere From Functional Decomposition of Satellite Observations
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Gao, Yifu, Guilloteau, Clément, Foufoula‐Georgiou, Efi, Xu, Chonggang, Sun, Xiaoming, and Vrugt, Jasper A
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Earth Sciences ,Geomatic Engineering ,Atmospheric Sciences ,Engineering ,Climate Action ,United States ,hydroclimatology ,land‐atmosphere interaction ,precipitation ,soil moisture ,Meteorology & Atmospheric Sciences - Abstract
The feedback of topsoil moisture (SM) content on convective clouds and precipitation is not well understood and represented in the current generation of weather and climate models. Here, we use functional decomposition of satellite-derived SM and cloud vertical profiles (CVP) to quantify the relationship between SM and the vertical distribution of cloud water in the central US. High-dimensional model representation is used to disentangle the contributions of SM and other land-surface and atmospheric variables to the CVP. Results show that the sign and strength of the SM-cloud-precipitation feedback varies with cloud height and time lag and displays a large spatial variability. Positive anomalies in antecedent 7-hr SM and land-surface temperature enhance cloud reflectivity up to 4 dBZ in the lower atmosphere about 1-3 km above the surface. Our approach presents new insights into the SM-cloud-precipitation feedback and aids in the diagnosis of land-atmosphere interactions simulated by weather and climate models.
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- 2024
5. Flux Synthesis of A-site Disordered Perovskite La0.5M0.5TiO3 (M═Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes.
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Wang, Tao, Ock, Jiyoung, Chen, X, Wang, Fan, Li, Meijia, Chambers, Matthew, Veith, Gabriel, Shepard, Lauren, Sinnott, Susan, Borisevich, Albina, Chi, Miaofang, Bhattacharya, Amit, Clément, Raphaële, Sokolov, Alexei, and Dai, Sheng
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disordered structure ,flux synthesis ,molten salts ,nanomaterials ,solid composite electrolyte - Abstract
Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li+ conductivity on the order of 10-3 S cm-1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li+ diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La0.5M0.5TiO3 (LMTO, M═Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li+-conducting LMTO nanorods as fillers and poly[vinylene carbonate-co-lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm-1 at 303 K).
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- 2024
6. Hematopoietic Stem Cell Transplantation for C1q Deficiency: A Study on Behalf of the EBMT Inborn Errors Working Party.
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Buso, Helena, Adam, Etai, Arkwright, Peter, Bhattad, Sagar, Hamidieh, Amir, Behfar, Maryam, Belot, Alexandre, Benezech, Sarah, Chan, Alice, Crow, Yanick, Dvorak, Christopher, Flinn, Aisling, Kapoor, Urvi, Lankester, Arjan, Kobayashi, Masao, Matsumura, Risa, Mottaghipisheh, Hadi, Okada, Satoshi, Ouachee, Marie, Parvaneh, Nima, Ramprakash, Stalin, Satwani, Prakash, Sharafian, Samin, Triaille, Clément, Wynn, Robert, Movahedi, Nasim, Ziaee, Vahid, Williams, Eleri, Slatter, Mary, and Gennery, Andrew
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Allogeneic HSCT ,C1q deficiency ,SLE ,Humans ,Hematopoietic Stem Cell Transplantation ,Female ,Male ,Child ,Child ,Preschool ,Adolescent ,Complement C1q ,Infant ,Retrospective Studies ,Young Adult ,Treatment Outcome ,Graft vs Host Disease ,Adult - Abstract
C1q deficiency is a rare inborn error of immunity characterized by increased susceptibility to infections and autoimmune manifestations mimicking SLE, with an associated morbidity and mortality. Because C1q is synthesized by monocytes, to date, four patients treated with allogeneic HSCT have been reported, with a positive outcome in three. We conducted an international retrospective study to assess the outcome of HSCT in C1q deficiency. Eighteen patients, fourteen previously unreported, from eleven referral centres, were included. Two patients had two HSCTs, thus 20 HSCTs were performed in total, at a median age of 10 years (range 0.9-19). Indications for HSCT were autoimmune manifestations not controlled by ongoing treatment in seventeen, and early development of MALT lymphoma in one patient. Overall survival (OS) was 71% and event-free survival was 59% at two years (considering an event as acute GvHD ≥ grade III, disease recurrence and death). In eleven patients HSCT led to resolution of autoimmune features and discontinuation of immunosuppressive treatments (follow-up time range 3-84 months). Five patients died due to transplant-related complications. Patients with a severe autoimmune phenotype, defined as neurological and/or renal involvement, had the worst OS (40% vs 84%; p = 0.034). Reviewing data of 69 genetically confirmed C1q deficient patients, we found that anti-Ro antibodies are associated with neurologic involvement, and anti-RNP and anti-DNA antibodies with renal involvement. In conclusion, HSCT may be a valid curative option for C1q deficiency, but careful selection of patients, with an accurate assessment of risk and benefit, is mandatory.
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- 2024
7. MVP: a modular viromics pipeline to identify, filter, cluster, annotate, and bin viruses from metagenomes
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Coclet, Clément, Camargo, Antonio Pedro, and Roux, Simon
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Biological Sciences ,Bioinformatics and Computational Biology ,Genetics ,Bioengineering ,Networking and Information Technology R&D (NITRD) ,Biotechnology ,Generic health relevance ,Metagenome ,Genome ,Viral ,Metagenomics ,Viruses ,Software ,Virome ,Computational Biology ,Molecular Sequence Annotation ,viromics pipeline ,sequencing data ,phages ,viruses ,ecological studies - Abstract
While numerous computational frameworks and workflows are available for recovering prokaryote and eukaryote genomes from metagenome data, only a limited number of pipelines are designed specifically for viromics analysis. With many viromics tools developed in the last few years alone, it can be challenging for scientists with limited bioinformatics experience to easily recover, evaluate quality, annotate genes, dereplicate, assign taxonomy, and calculate relative abundance and coverage of viral genomes using state-of-the-art methods and standards. Here, we describe Modular Viromics Pipeline (MVP) v.1.0, a user-friendly pipeline written in Python and providing a simple framework to perform standard viromics analyses. MVP combines multiple tools to enable viral genome identification, characterization of genome quality, filtering, clustering, taxonomic and functional annotation, genome binning, and comprehensive summaries of results that can be used for downstream ecological analyses. Overall, MVP provides a standardized and reproducible pipeline for both extensive and robust characterization of viruses from large-scale sequencing data including metagenomes, metatranscriptomes, viromes, and isolate genomes. As a typical use case, we show how the entire MVP pipeline can be applied to a set of 20 metagenomes from wetland sediments using only 10 modules executed via command lines, leading to the identification of 11,656 viral contigs and 8,145 viral operational taxonomic units (vOTUs) displaying a clear beta-diversity pattern. Further, acting as a dynamic wrapper, MVP is designed to continuously incorporate updates and integrate new tools, ensuring its ongoing relevance in the rapidly evolving field of viromics. MVP is available at https://gitlab.com/ccoclet/mvp and as versioned packages in PyPi and Conda.IMPORTANCEThe significance of our work lies in the development of Modular Viromics Pipeline (MVP), an integrated and user-friendly pipeline tailored exclusively for viromics analyses. MVP stands out due to its modular design, which ensures easy installation, execution, and integration of new tools and databases. By combining state-of-the-art tools such as geNomad and CheckV, MVP provides high-quality viral genome recovery and taxonomy and host assignment, and functional annotation, addressing the limitations of existing pipelines. MVP's ability to handle diverse sample types, including environmental, human microbiome, and plant-associated samples, makes it a versatile tool for the broader microbiome research community. By standardizing the analysis process and providing easily interpretable results, MVP enables researchers to perform comprehensive studies of viral communities, significantly advancing our understanding of viral ecology and its impact on various ecosystems.
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- 2024
8. A Candidate High-Velocity Exoplanet System in the Galactic Bulge
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Terry, Sean K, Beaulieu, Jean-Philippe, Bennett, David P, Bhattacharya, Aparna, Hulberg, Jon, Huston, Macy J, Koshimoto, Naoki, Blackman, Joshua W, Bond, Ian A, Cole, Andrew A, Lu, Jessica R, Ranc, Clément, Rektsini, Natalia E, and Vandorou, Aikaterini
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astro-ph.EP ,astro-ph.GA ,astro-ph.SR - Abstract
We present an analysis of adaptive optics (AO) images from the Keck-Itelescope of the microlensing event MOA-2011-BLG-262. The original discoverypaper by Bennett et al. 2014 reports two distinct possibilities for the lenssystem; a nearby gas giant lens with an exomoon companion or a very low massstar with a planetary companion in the galactic bulge. The $\sim$10 yearbaseline between the microlensing event and the Keck follow-up observationsallows us to detect the faint candidate lens host (star) at $K = 22.3$ mag andconfirm the distant lens system interpretation. The combination of the hoststar brightness and light curve parameters yields host star and planet massesof $M_{\rm host} = 0.19 \pm 0.03M_{\odot}$ and $m_p = 28.92 \pm 4.75M_{\oplus}$at a distance of $D_L = 7.49 \pm 0.91\,$kpc. We perform a multi-epoch crossreference to \textit{Gaia} DR3 and measure a transverse velocity for thecandidate lens system of $v_L = 541.31 \pm 65.75$ km s$^{-1}$. We conclude thisevent consists of the highest velocity exoplanet system detected to date, andalso the lowest mass microlensing host star with a confirmed mass measurement.The high-velocity nature of the lens system can be definitively confirmed withan additional epoch of high-resolution imaging at any time now. The methodsoutlined in this work demonstrate that the \textit{Roman} Galactic ExoplanetSurvey (RGES) will be able to securely measure low-mass host stars in thebulge.
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- 2024
9. Resolving Structures of Paramagnetic Systems in Chemistry and Materials Science by Solid-State NMR: The Revolving Power of Ultra-Fast MAS.
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Koppe, Jonas, Sanders, Kevin, Robinson, Thomas, Lejeune, Arthur, Proriol, David, Wegner, Sebastian, Purea, Armin, Engelke, Frank, Clément, Raphaële, Grey, Clare, Pell, Andrew, and Pintacuda, Guido
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electronic structures ,high-resolution ,paramagnetic materials ,solid-state NMR ,ultrafast MAS - Abstract
Ultra-fast magic-angle spinning (100+kHz) has revolutionized solid-state NMR of biomolecular systems but has so far failed to gain ground for the analysis of paramagnetic organic and inorganic powders, despite the potential rewards from substantially improved spectral resolution. The principal blockages are that the smaller fast-spinning rotors present significant barriers for sample preparation, particularly for air/moisture-sensitive systems, and are associated with low sensitivity from the reduced sample volumes. Here, we demonstrate that the sensitivity penalty is less severe than expected for highly paramagnetic solids and is more than offset by the associated improved resolution. While previous approaches employing slower MAS are often unsuccessful in providing sufficient resolution, we show that ultra-fast 100+kHz MAS allows site-specific assignments of all resonances from complex paramagnetic solids. Combined with more reliable rotor materials and handling methods, this opens the way to the routine characterization of geometry and electronic structures of functional paramagnetic systems in chemistry, including catalysts and battery materials. We benchmark this approach on a hygroscopic luminescent Tb3+ complex, an air-sensitive homogeneous high-spin Fe2+ catalyst, and a series of mixed Fe2+/Mn2+/Mg2+ olivine-type cathode materials.
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- 2024
10. Strong Magnetic Exchange Interactions and Delocalized Mn-O States Enable High-Voltage Capacity in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2.
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Bassey, Euan, Nguyen, Howie, Insinna, Teresa, Lee, Jeongjae, Barra, Anne-Laure, Cibin, Giannantonio, Bencok, Peter, Clément, Raphaële, and Grey, Clare
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The increased capacity offered by oxygen-redox active cathode materials for rechargeable lithium- and sodium-ion batteries (LIBs and NIBs, respectively) offers a pathway to the next generation of high-gravimetric-capacity cathodes for use in devices, transportation and on the grid. Many of these materials, however, are plagued with voltage fade, voltage hysteresis and O2 loss, the origins of which can be traced back to changes in their electronic and chemical structures on cycling. Developing a detailed understanding of these changes is critical to mitigating these cathodes poor performance. In this work, we present an analysis of the redox mechanism of P2-Na0.67[Mg0.28Mn0.72]O2, a layered NIB cathode whose high capacity has previously been attributed to trapped O2 molecules. We examine a variety of charge compensation scenarios, calculate their corresponding densities of states and spectroscopic properties, and systematically compare the results to experimental data: 25Mg and 17O nuclear magnetic resonance (NMR) spectroscopy, operando X-band and ex situ high-frequency electron paramagnetic resonance (EPR), ex situ magnetometry, and O and Mn K-edge X-ray Absorption Spectroscopy (XAS) and X-ray Absorption Near Edge Spectroscopy (XANES). Via a process of elimination, we suggest that the mechanism for O redox in this material is dominated by a process that involves the formation of strongly antiferromagnetic, delocalized Mn-O states which form after Mg2+ migration at high voltages. Our results primarily rely on noninvasive techniques that are vital to understanding the electronic structure of metastable cycled cathode samples.
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- 2024
11. Revealing the Chemical and Structural Complexity of Electrochemical Ion Exchange in Layered Oxide Materials.
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Mu, Linqin, Hou, Dong, Foley, Emily, Dai, Minyi, Zhang, Jin, Jiang, Zhisen, Rahman, Muhammad, Fu, Yanbao, Ma, Lu, Hu, Enyuan, Sainio, Sami, Nordlund, Dennis, Liu, Jue, Hu, Jia-Mian, Liu, Yijin, Clément, Raphaële, and Lin, Feng
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Soft chemistry techniques, such as ion exchange, hold great potential for the development of battery electrode materials that cannot be stabilized via conventional equilibrium synthesis methods. Nevertheless, the intricate mechanisms governing ion exchange remain elusive. Herein, we investigate the evolution of the long-range and local structure, as well as the ion (de)intercalation mechanism during electrochemical Li-to-Na ion exchange initiated from an O3-type lithium-layered oxide cathode. The in situ-formed mixed-cation electrolyte leads to competitive intercalation of Li and Na ions. While Li ion intercalation predominates at the beginning of initial discharge, Na ion cointercalation into a different layer results in ion redistribution and phase separation, with the emergence of a P3-Na phase alongside an O3-Li phase. Further, this study spatially resolves the heterogeneous nature of electrochemical ion exchange reactions within individual particles and provides insights into the correlations between local Ni redox processes and phase separation. Overall, electrochemical ion exchange leads to a mixed-phase cathode and alters its reaction kinetics. Those findings have important implications for the development of new metastable materials for renewable energy devices and ion separation applications.
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- 2024
12. Structural Evolution in Disordered Rock Salt Cathodes.
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Li, Tianyu, Geraci, Tullio, Koirala, Krishna, Zohar, Arava, Bassey, Euan, Chater, Philip, Wang, Chongmin, Navrotsky, Alexandra, and Clément, Raphaële
- Abstract
Li-excess Mn-based disordered rock salt oxides (DRX) are promising Li-ion cathode materials owing to their cost-effectiveness and high theoretical capacities. It has recently been shown that Mn-rich DRX Li1+xMnyM1-x-yO2 (y ≥ 0.5, M are hypervalent ions such as Ti4+ and Nb5+) exhibit a gradual capacity increase during the first few charge-discharge cycles, which coincides with the emergence of spinel-like domains within the long-range DRX structure coined as δ phase. Here, we systematically study the structural evolution upon heating of Mn-based DRX at different levels of delithiation to gain insight into the structural rearrangements occurring during battery cycling and the mechanism behind δ phase formation. We find in all cases that the original DRX structure relaxes to a δ phase, which in turn leads to capacity enhancement. Synchrotron X-ray and neutron diffraction were employed to examine the structure of the δ phase, revealing that selective migration of Li and Mn/Ti cations to different crystallographic sites within the DRX structure leads to the observed structural rearrangements. Additionally, we show that both Mn-rich (y ≥ 0.5) and Mn-poor (y < 0.5) DRX can thermally relax into a δ phase after delithiation, but the relaxation processes in these distinct compositions lead to different domain structures. Thermochemical studies and in situ heating XRD experiments further indicate that the structural relaxation has a larger thermodynamic driving force and a lower activation energy for Mn-rich DRX, as compared to Mn-poor systems, which underpins why this structural evolution is only observed for Mn-rich systems during battery cycling.
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- 2024
13. CO 2 cleavage by tantalum/M (M = iridium, osmium) heterobimetallic complexes
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Lachguar, Abdelhak, Ye, Christopher Z, Kelly, Sheridon N, Jeanneau, Erwann, Del Rosal, Iker, Maron, Laurent, Veyre, Laurent, Thieuleux, Chloé, Arnold, John, and Camp, Clément
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Inorganic Chemistry ,Chemical Sciences ,Organic Chemistry ,Chemical sciences ,Engineering - Abstract
A novel Ta/Os heterobimetallic complex, [Ta(CH2tBu)3(μ-H)3OsCp*], 2, is prepared by protonolysis of Ta(CHtBu)(CH2tBu)3 with Cp*OsH5. Treatment of 2 and its iridium analogue [Ta(CH2tBu)3(μ-H)2IrCp*], 1, with CO2 under mild conditions reveal the efficient cleavage of CO2, driven by the formation of a tantalum oxo species in conjunction with CO transfer to the osmium or iridium fragments, to form Cp*Ir(CO)H2 and Cp*Os(CO)H3, respectively. This bimetallic reactivity diverges from more classical CO2 insertion into metal-X (X = metal, hydride, alkyl) bonds.
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- 2024
14. Substrate complexity buffers negative interactions in a synthetic community of leaf litter degraders.
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Abdoli, Parmis, Vulin, Clément, Lepiz, Miriam, Chase, Alexander, Weihe, Claudia, and Rodríguez-Verdugo, Alejandra
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Curtobacterium ,biopolymer degradation ,bottom-up approach ,extracellular enzymes ,interspecific interactions ,leaf litter microbiome ,Plant Leaves ,Bacteria ,Ecosystem ,Species Specificity ,Xylans ,Xylose ,Models ,Theoretical ,Actinobacteria ,Bacteroidetes ,Proteobacteria ,Microbial Interactions ,Poaceae - Abstract
Leaf litter microbes collectively degrade plant polysaccharides, influencing land-atmosphere carbon exchange. An open question is how substrate complexity-defined as the structure of the saccharide and the amount of external processing by extracellular enzymes-influences species interactions. We tested the hypothesis that monosaccharides (i.e. xylose) promote negative interactions through resource competition, and polysaccharides (i.e. xylan) promote neutral or positive interactions through resource partitioning or synergism among extracellular enzymes. We assembled a three-species community of leaf litter-degrading bacteria isolated from a grassland site in Southern California. In the polysaccharide xylan, pairs of species stably coexisted and grew equally in coculture and in monoculture. Conversely, in the monosaccharide xylose, competitive exclusion and negative interactions prevailed. These pairwise dynamics remained consistent in a three-species community: all three species coexisted in xylan, while only two species coexisted in xylose, with one species capable of using peptone. A mathematical model showed that in xylose these dynamics could be explained by resource competition. Instead, the model could not predict the coexistence patterns in xylan, suggesting other interactions exist during biopolymer degradation. Overall, our study shows that substrate complexity influences species interactions and patterns of coexistence in a synthetic microbial community of leaf litter degraders.
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- 2024
15. Enhanced Electrochemical Performance of Disordered Rocksalt Cathodes in a Localized High‐Concentration Electrolyte
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Ahmed, Ridwan A, Koirala, Krishna P, Lee, Gi‐Hyeok, Li, Tianyu, Zhao, Qian, Fu, Yanbao, Zhong, Lirong, Daddona, Joseph D, Zuba, Mateusz, Siu, Carrie, Kahvecioglu, Ozgenur, Battaglia, Vincent S, Clément, Raphaële J, Yang, Wanli, Wang, Chongmin, and Xu, Wu
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Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,cathode-electrolyte interphase ,disordered rock salt cathode ,electrolyte ,lithium metal ,structural integrity ,Macromolecular and Materials Chemistry ,Interdisciplinary Engineering ,Macromolecular and materials chemistry ,Materials engineering - Abstract
Lithium (Li)-rich transition metal oxide cathodes with a cation disordered rock salt structure (DRX) are increasingly gaining popularity for advanced Li batteries as they offer high capacity and cost benefits over the commonly used layered Li transition metal oxide cathodes. However, the performance of DRX cathodes and their applications are limited by severe side reactions between the cathode and the state-of-the-art carbonate-based electrolytes at high voltage of 4.8 V, transition metal dissolution, and structural instability of the cathode particles. In this work, an advanced localized high-concentration electrolyte (LHCE) is developed to form a stable cathode-electrolyte interphase and mitigate structural instability of the Li1.13Mn0.66Ti0.21O2 (LMTO) DRX during electrochemical cycling. Li||LMTO half cells with the LHCE demonstrate increased capacity, cycling stability, and superior rate capability compared with cells containing a conventional carbonate electrolyte. For instance, the Li||LMTO cells cycled in LHCE show a higher initial capacity of 205.2 mAh g−1 and a better capacity retention of 72.5% after 200 cycles at a current density of 20 mA g−1 than those with the conventional electrolyte (initial capacity of 187.7 mAh g−1 and capacity retention of 19.9%). This work paves the way to the development of practical DRX cathode-based high-energy Li batteries.
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- 2024
16. Photolysis-driven bond activation by thorium and uranium tetraosmate polyhydride complexes
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Ye, Christopher Z, Del Rosal, Iker, Kelly, Sheridon N, Brackbill, I Joseph, Maron, Laurent, Camp, Clément, and Arnold, John
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Inorganic Chemistry ,Chemical Sciences ,Chemical sciences - Abstract
Transition metal multimetallic complexes have seen intense study due to their unique bonding and potential for cooperative reactivity, but actinide-transition metal (An-TM) species are far less understood. We have synthesized uranium- and thorium-osmium heterometallic polyhydride complexes in order to study An-Os bonding and investigate the reactivity of An-Os interactions. Computational studies suggest the presence of a significant bonding interaction between the actinide center and the four coordinated osmium centers supported by bridging hydrides. Upon photolysis, these complexes undergo intramolecular C-H activation with the formation of an Os-Os bond, while the thorium complex may activate an additional C-H bond of the benzene solvent, resulting in a μ-η1,η1 phenyl ligand across one Th-Os interaction.
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- 2024
17. The Limited Incorporation and Role of Fluorine in Mn-rich Disordered Rocksalt Cathodes
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Wu, Vincent C, Zhong, Peichen, Ong, Julia, Yoshida, Eric, Kwon, Andrew, Ceder, Gerbrand, and Clément, Raphaële J
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Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,Chemical sciences - Abstract
Disordered rocksalt oxide (DRX) cathodes are promising candidates for next-generation Co- and Ni-free Li-ion batteries. While fluorine substitution for oxygen has been explored as an avenue to enhance their performance, the amount of fluorine incorporated into the DRX structure is particularly challenging to quantify and impedes our ability to relate fluorination to electrochemical performance. Herein, an experimental-computational method combining 7Li and 19F solid-state nuclear magnetic resonance, and ab initio cluster expansion Monte Carlo simulations, is developed to determine the composition of DRX oxyfluorides. Using this method, the synthesis of Mn- and Ti-containing DRX via standard high temperature sintering and microwave heating is optimized. Further, the upper fluorination limit attainable using each of these two synthesis routes is established for various Mn-rich DRX compounds. A comparison of their electrochemical performance reveals that the capacity and capacity retention mostly depend on the Mn content, while fluorination plays a secondary role.
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- 2024
18. Giant Modulation of Refractive Index from Picoscale Atomic Displacements
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Zhao, Boyang, Ren, Guodong, Mei, Hongyan, Wu, Vincent C, Singh, Shantanu, Jung, Gwan Yeong, Chen, Huandong, Giovine, Raynald, Niu, Shanyuan, Thind, Arashdeep S, Salman, Jad, Settineri, Nick S, Chakoumakos, Bryan C, Manley, Michael E, Hermann, Raphael P, Lupini, Andrew R, Chi, Miaofang, Hachtel, Jordan A, Simonov, Arkadiy, Teat, Simon J, Clément, Raphaële J, Kats, Mikhail A, Ravichandran, Jayakanth, and Mishra, Rohan
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Quantum Physics ,Physical Sciences ,anisotropy ,structural disorder ,STEM ,DFT ,NMR ,refractive index ,synchrotron diffraction ,Chemical Sciences ,Engineering ,Nanoscience & Nanotechnology ,Chemical sciences ,Physical sciences - Abstract
It is shown that structural disorder-in the form of anisotropic, picoscale atomic displacements-modulates the refractive index tensor and results in the giant optical anisotropy observed in BaTiS3, a quasi-1D hexagonal chalcogenide. Single-crystal X-ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS6 chains along the c-axis, and threefold degenerate Ti displacements in the a-b plane. 47/49Ti solid-state NMR provides additional evidence for those Ti displacements in the form of a three-horned NMR lineshape resulting from a low symmetry local environment around Ti atoms. Scanning transmission electron microscopy is used to directly observe the globally disordered Ti a-b plane displacements and find them to be ordered locally over a few unit cells. First-principles calculations show that the Ti a-b plane displacements selectively reduce the refractive index along the ab-plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between structural disorder with picoscale displacements and the optical response in BaTiS3, this study opens a pathway for designing optical materials with high refractive index and functionalities such as large optical anisotropy and nonlinearity.
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- 2024
19. Investigating Fire–Atmosphere Interaction in a Forest Canopy Using Wavelets
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Desai, Ajinkya, Guilloteau, Clément, Heilman, Warren E, Charney, Joseph J, Skowronski, Nicholas S, Clark, Kenneth L, Gallagher, Michael R, Foufoula-Georgiou, Efi, and Banerjee, Tirtha
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Earth Sciences ,Atmospheric Sciences ,Heading surface fire ,Time-frequency plane ,Ramp-cliff structures ,Cross-wavelet coherence ,Heat/momentum fluxes ,Ramp–cliff structures ,Time–frequency plane ,Meteorology & Atmospheric Sciences ,Atmospheric sciences - Abstract
Wildland fire-atmosphere interaction generates complex turbulence patterns, organized across multiple scales, which inform fire-spread behaviour, firebrand transport, and smoke dispersion. Here, we utilize wavelet-based techniques to explore the characteristic temporal scales associated with coherent patterns in the measured temperature and the turbulent fluxes during a prescribed wind-driven (heading) surface fire beneath a forest canopy. We use temperature and velocity measurements from tower-mounted sonic anemometers at multiple heights. Patterns in the wavelet-based energy density of the measured temperature plotted on a time-frequency plane indicate the presence of fire-modulated ramp-cliff structures in the low-to-mid-frequency band (0.01-0.33 Hz), with mean ramp durations approximately 20% shorter and ramp slopes that are an order of magnitude higher compared to no-fire conditions. We then investigate heat- and momentum-flux events near the canopy top through a cross-wavelet coherence analysis. Briefly before the fire-front arrives at the tower base, momentum-flux events are relatively suppressed and turbulent fluxes are chiefly thermally-driven near the canopy top, owing to the tilting of the flame in the direction of the wind. Fire-induced heat-flux events comprising warm updrafts and cool downdrafts are coherent down to periods of a second, whereas ambient heat-flux events operate mainly at higher periods (above 17 s). Later, when the strongest temperature fluctuations are recorded near the surface, fire-induced heat-flux events occur intermittently at shorter scales and cool sweeps start being seen for periods ranging from 8 to 35 s near the canopy top, suggesting a diminishing influence of the flame and increasing background atmospheric variability thereat. The improved understanding of the characteristic time scales associated with fire-induced turbulence features, as the fire-front evolves, will help develop more reliable fire behaviour and scalar transport models.
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- 2024
20. An Experimental Approach to Assess Fluorine Incorporation into Disordered Rock Salt Oxide Cathodes.
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Yoshida, Eric, Wu, Vincent, Ji, Yuefan, Crafton, Matthew, Clément, Raphaële, Mccloskey, Bryan, and Giovine, Raynald
- Abstract
Disordered rock salt oxides (DRX) have shown great promise as high-energy-density and sustainable Li-ion cathodes. While partial substitution of oxygen for fluorine in the rock salt framework has been related to increased capacity, lower charge-discharge hysteresis, and longer cycle life, fluorination is poorly characterized and controlled. This work presents a multistep method aimed at assessing fluorine incorporation into DRX cathodes, a challenging task due to the difficulty in distinguishing oxygen from fluorine using X-ray and neutron-based techniques and the presence of partially amorphous impurities in all DRX samples. This method is applied to Li1.25Mn0.25Ti0.5O1.75F0.25 prepared by solid-state synthesis and reveals that the presence of LiF impurities in the sample and F content in the DRX phase is well below the target. Those results are used for compositional optimization, and a synthesis product with drastically reduced LiF content and a DRX stoichiometry close to the new target composition (Li1.25Mn0.225Ti0.525O1.85F0.15) is obtained, demonstrating the effectiveness of the strategy. The analytical method is also applied to Li1.33Mn0.33Ti0.33O1.33F0.66 obtained via mechanochemical synthesis, and the results confirm that much higher fluorination levels can be achieved via ball-milling. Finally, a simple and rapid water washing procedure is developed to reduce the impurity content in as-prepared DRX samples: this procedure results in a ca. 10% increase in initial discharge capacity and a ca. 11% increase in capacity retention after 25 cycles for Li1.25Mn0.25Ti0.50O1.75F0.25. Overall, this work establishes new analytical and material processing methods that enable the development of more robust design rules for high-energy-density DRX cathodes.
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- 2024
21. Overcoming low initial coulombic efficiencies of Si anodes through prelithiation in all-solid-state batteries.
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Ham, So-Yeon, Sebti, Elias, Cronk, Ashley, Pennebaker, Tyler, Deysher, Grayson, Chen, Yu-Ting, Oh, Jin, Lee, Jeong, Song, Min, Ridley, Phillip, Tan, Darren, Clément, Raphaële, Jang, Jihyun, and Meng, Ying
- Abstract
All-solid-state batteries using Si as the anode have shown promising performance without continual solid-electrolyte interface (SEI) growth. However, the first cycle irreversible capacity loss yields low initial Coulombic efficiency (ICE) of Si, limiting the energy density. To address this, we adopt a prelithiation strategy to increase ICE and conductivity of all-solid-state Si cells. A significant increase in ICE is observed for Li1Si anode paired with a lithium cobalt oxide (LCO) cathode. Additionally, a comparison with lithium nickel manganese cobalt oxide (NCM) reveals that performance improvements with Si prelithiation is only applicable for full cells dominated by high anode irreversibility. With this prelithiation strategy, 15% improvement in capacity retention is achieved after 1000 cycles compared to a pure Si. With Li1Si, a high areal capacity of up to 10 mAh cm-2 is attained using a dry-processed LCO cathode film, suggesting that the prelithiation method may be suitable for high-loading next-generation all-solid-state batteries.
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- 2024
22. Neutralizing IFN-γ autoantibodies are rare and pathogenic in HLA-DRB1*15:02 or 16:02 individuals.
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Peel, Jessica, Yang, Rui, Le Voyer, Tom, Gervais, Adrian, Rosain, Jérémie, Bastard, Paul, Behere, Anish, Cederholm, Axel, Bodansky, Aaron, Seeleuthner, Yoann, Conil, Clément, Ding, Jing-Ya, Lei, Wei-Te, Bizien, Lucy, Soudee, Camille, Migaud, Mélanie, Ogishi, Masato, Yatim, Ahmad, Lee, Danyel, Bohlen, Jonathan, Perpoint, Thomas, Perez, Laura, Messina, Fernando, Genet, Roxana, Karkowski, Ludovic, Blot, Mathieu, Lafont, Emmanuel, Toullec, Laurie, Goulvestre, Claire, Mehlal-Sedkaoui, Souad, Sallette, Jérôme, Martin, Fernando, Puel, Anne, Jouanguy, Emmanuelle, Anderson, Mark, Landegren, Nils, Tiberghien, Pierre, Abel, Laurent, Boisson-Dupuis, Stéphanie, Bustamante, Jacinta, Ku, Cheng-Lung, and Casanova, Jean-Laurent
- Subjects
Autoimmune diseases ,Cytokines ,Genetics ,Immunology ,Adult ,Humans ,Autoantibodies ,Autoimmune Diseases ,Genetic Predisposition to Disease ,Genotype ,HLA-DRB1 Chains ,Mycobacterium Infections ,Nontuberculous - Abstract
BACKGROUNDWeakly virulent environmental mycobacteria (EM) can cause severe disease in HLA-DRB1*15:02 or 16:02 adults harboring neutralizing anti-IFN-γ autoantibodies (nAIGAs). The overall prevalence of nAIGAs in the general population is unknown, as are the penetrance of nAIGAs in HLA-DRB1*15:02 or 16:02 individuals and the proportion of patients with unexplained, adult-onset EM infections carrying nAIGAs.METHODSThis study analyzed the detection and neutralization of anti-IFN-γ autoantibodies (auto-Abs) from 8,430 healthy individuals of the general population, 257 HLA-DRB1*15:02 or 16:02 carriers, 1,063 patients with autoimmune disease, and 497 patients with unexplained severe disease due to EM.RESULTSWe found that anti-IFN-γ auto-Abs detected in 4,148 of 8,430 healthy individuals (49.2%) from the general population of an unknown HLA-DRB1 genotype were not neutralizing. Moreover, we did not find nAIGAs in 257 individuals carrying HLA-DRB1* 15:02 or 16:02. Additionally, nAIGAs were absent in 1,063 patients with an autoimmune disease. Finally, 7 of 497 patients (1.4%) with unexplained severe disease due to EM harbored nAIGAs.CONCLUSIONThese findings suggest that nAIGAs are isolated and that their penetrance in HLA-DRB1*15:02 or 16:02 individuals is low, implying that they may be triggered by rare germline or somatic variants. In contrast, the risk of mycobacterial disease in patients with nAIGAs is high, confirming that these nAIGAs are the cause of EM disease.FUNDINGThe Laboratory of Human Genetics of Infectious Diseases is supported by the Howard Hughes Medical Institute, the Rockefeller University, the St. Giles Foundation, the National Institutes of Health (NIH) (R01AI095983 and U19AIN1625568), the National Center for Advancing Translational Sciences (NCATS), the NIH Clinical and Translational Science Award (CTSA) program (UL1 TR001866), the French National Research Agency (ANR) under the Investments for the Future program (ANR-10-IAHU-01), the Integrative Biology of Emerging Infectious Diseases Laboratory of Excellence (ANR-10-LABX-62-IBEID), ANR-GENMSMD (ANR-16-CE17-0005-01), ANR-MAFMACRO (ANR-22-CE92-0008), ANRSECTZ170784, the French Foundation for Medical Research (FRM) (EQU201903007798), the ANRS-COV05, ANR GENVIR (ANR-20-CE93-003), and ANR AI2D (ANR-22-CE15-0046) projects, the ANR-RHU program (ANR-21-RHUS-08-COVIFERON), the European Unions Horizon 2020 research and innovation program under grant agreement no. 824110 (EASI-genomics), the Square Foundation, Grandir - Fonds de solidarité pour lenfance, the Fondation du Souffle, the SCOR Corporate Foundation for Science, the Battersea & Bowery Advisory Group, William E. Ford, General Atlantics Chairman and Chief Executive Officer, Gabriel Caillaux, General Atlantics Co-President, Managing Director, and Head of business in EMEA, and the General Atlantic Foundation, Institut National de la Santé et de la Recherche Médicale (INSERM) and of Paris Cité University. JR was supported by the INSERM PhD program for doctors of pharmacy (poste daccueil INSERM). JR and TLV were supported by the Bettencourt-Schueller Foundation and the MD-PhD program of the Imagine Institute. MO was supported by the David Rockefeller Graduate Program, the Funai Foundation for Information Technology (FFIT), the Honjo International Scholarship Foundation (HISF), and the New York Hideyo Noguchi Memorial Society (HNMS).
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- 2024
23. Recommendations for accelerating open preprint peer review to improve the culture of science.
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Avissar-Whiting, Michele, Belliard, Frédérique, Bertozzi, Stefano, Brand, Amy, Brown, Katherine, Clément-Stoneham, Géraldine, Dawson, Stephanie, Dey, Gautam, Ecer, Daniel, Edmunds, Scott, Farley, Ashley, Fischer, Tara, Franko, Maryrose, Fraser, James, Funk, Kathryn, Ganier, Clarisse, Harrison, Melissa, Hatch, Anna, Hazlett, Haley, Hindle, Samantha, Hook, Daniel, Hurst, Phil, Kamoun, Sophien, Kiley, Robert, Lacy, Michael, LaFlamme, Marcel, Lawrence, Rebecca, Lemberger, Thomas, Leptin, Maria, Lumb, Elliott, MacCallum, Catriona, Marcum, Christopher, Marinello, Gabriele, Mendonça, Alex, Monaco, Sara, Neves, Kleber, Pattinson, Damian, Polka, Jessica, Puebla, Iratxe, Rittman, Martyn, Royle, Stephen, Saderi, Daniela, Sever, Richard, Shearer, Kathleen, Spiro, John, Stern, Bodo, Taraborelli, Dario, Vale, Ron, Vasquez, Claudia, Waltman, Ludo, Watt, Fiona, Weinberg, Zara, and Williams, Mark
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Humans ,Motion ,Peer Review ,Research Personnel - Abstract
Peer review is an important part of the scientific process, but traditional peer review at journals is coming under increased scrutiny for its inefficiency and lack of transparency. As preprints become more widely used and accepted, they raise the possibility of rethinking the peer-review process. Preprints are enabling new forms of peer review that have the potential to be more thorough, inclusive, and collegial than traditional journal peer review, and to thus fundamentally shift the culture of peer review toward constructive collaboration. In this Consensus View, we make a call to action to stakeholders in the community to accelerate the growing momentum of preprint sharing and provide recommendations to empower researchers to provide open and constructive peer review for preprints.
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- 2024
24. Impact of Mg Substitution on the Structure, Stability, and Properties of the Na2Fe2F7 Weberite Cathode
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Porter, Hanna Z, Foley, Emily E, Jin, Wen, Chen, Eric, Lawrence, Erick A, Bassey, Euan N, and Clément, Raphaële J
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Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,sodium-ion battery ,structure stabilization ,materials design ,transition metal fluorides ,weberite - Published
- 2024
25. On linear intervals in the alt \(\nu\)-Tamari lattices
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Ceballos, Cesar and Chenevière, Clément
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Lattices ,intervals ,Tamari - Abstract
Given a lattice path \(\nu\), the \(\nu\)-Tamari lattice and the \(\nu\)-Dyck lattice are two natural examples of partial order structures on the set of lattice paths that lie weakly above \(\nu\). In this paper, we introduce a more general family of lattices, called alt \(\nu\)-Tamari lattices, which contains these two examples as particular cases. Unexpectedly, we show that all these lattices have the same number of linear intervals.Mathematics Subject Classifications: 06A07, 06B05, 05A19Keywords: Lattices, intervals, Tamari
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- 2024
26. In-situ experiment reveals CO2 enriched fluid migration in faulted caprock.
- Author
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Weber, Ulrich, Rinaldi, Antonio, Roques, Clément, Wenning, Quinn, Bernasconi, Stefano, Brennwald, Matthias, Jaggi, Madalina, Nussbaum, Christophe, Schefer, Senecio, Mazzotti, Marco, Wiemer, Stefan, Giardini, Domenico, Zappone, Alba, and Kipfer, Rolf
- Abstract
The sealing characteristics of the geological formation located above a CO2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO2 were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid-rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO2-enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO2 migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO2-enriched fluid and resident formation water and to describe the temporal evolution of water-rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO2 in fault zones.
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- 2023
27. Rapid and Reversible Lithium Insertion in the Wadsley-Roth-Derived Phase NaNb13O33
- Author
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Patterson, Ashlea R, Elizalde-Segovia, Rodrigo, Wyckoff, Kira E, Zohar, Arava, Ding, Patrick P, Turner, Wiley M, Poeppelmeier, Kenneth R, Narayan, Sri R, Clément, Raphaéle J, Seshadri, Ram, and Griffith, Kent J
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- 2023
28. Remediation of Thirdhand Tobacco Smoke with Ozone: Probing Deep Reservoirs in Carpets
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Tang, Xiaochen, Gambier, Clément, López-Gálvez, Nicolás, Padilla, Samuel, Rapp, Vi H, Russell, Marion L, Klivansky, Liana M, Mayorga, Raphael, Perrino, Charles, Gundel, Lara A, Hoh, Eunha, Dodder, Nathan G, Hammond, S Katharine, Zhang, Haofei, Matt, George E, Quintana, Penelope JE, and Destaillats, Hugo
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Environmental Sciences ,Pollution and Contamination ,Tobacco Smoke and Health ,Tobacco ,Good Health and Well Being ,Nicotine ,Tobacco Smoke Pollution ,Floors and Floorcoverings ,Ozone ,fast mobility particle sizer ,ultrafine particles ,PAHs ,VOCs ,GC ,MS ,GC/MS - Abstract
We assessed the efficacy of ozonation as an indoor remediation strategy by evaluating how a carpet serves as a sink and long-term source of thirdhand tobacco smoke (THS) while protecting contaminants absorbed in deep reservoirs by scavenging ozone. Specimens from unused carpet that was exposed to smoke in the lab ("fresh THS") and contaminated carpets retrieved from smokers' homes ("aged THS") were treated with 1000 ppb ozone in bench-scale tests. Nicotine was partially removed from fresh THS specimens by volatilization and oxidation, but it was not significantly eliminated from aged THS samples. By contrast, most of the 24 polycyclic aromatic hydrocarbons detected in both samples were partially removed by ozone. One of the home-aged carpets was installed in an 18 m3 room-sized chamber, where its nicotine emission rate was 950 ng day-1 m-2. In a typical home, such daily emissions could amount to a non-negligible fraction of the nicotine released by smoking one cigarette. The operation of a commercial ozone generator for a total duration of 156 min, reaching concentrations up to 10,000 ppb, did not significantly reduce the carpet nicotine loading (26-122 mg m-2). Ozone reacted primarily with carpet fibers, rather than with THS, leading to short-term emissions of aldehydes and aerosol particles. Hence, by being absorbed deeply into carpet fibers, THS constituents can be partially shielded from ozonation.
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- 2023
29. Adaptive duplication and genetic diversification of protein kinase R contribute to the specificity of bat-virus interactions
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Jacquet, Stéphanie, Culbertson, Michelle, Zhang, Chi, El Filali, Adil, De La Myre Mory, Clément, Pons, Jean-Baptiste, Filippi-Codaccioni, Ondine, Lauterbur, M Elise, Ngoubangoye, Barthélémy, Duhayer, Jeanne, Verez, Clément, Park, Chorong, Dahoui, Clara, Carey, Clayton M, Brennan, Greg, Enard, David, Cimarelli, Andrea, Rothenburg, Stefan, Elde, Nels C, Pontier, Dominique, and Etienne, Lucie
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Medical Microbiology ,Biomedical and Clinical Sciences ,Genetics ,Biological Sciences ,Emerging Infectious Diseases ,Infectious Diseases ,Rare Diseases ,Biodefense ,Small Pox ,Infection - Abstract
Several bat species act as asymptomatic reservoirs for many viruses that are highly pathogenic in other mammals. Here, we have characterized the functional diversification of the protein kinase R (PKR), a major antiviral innate defense system. Our data indicate that PKR has evolved under positive selection and has undergone repeated genomic duplications in bats in contrast to all studied mammals that have a single copy of the gene. Functional testing of the relationship between PKR and poxvirus antagonists revealed how an evolutionary conflict with ancient pathogenic poxviruses has shaped a specific bat host-virus interface. We determined that duplicated PKRs of the Myotis species have undergone genetic diversification, allowing them to collectively escape from and enhance the control of DNA and RNA viruses. These findings suggest that viral-driven adaptations in PKR contribute to modern virus-bat interactions and may account for bat-specific immunity.
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- 2022
30. Probing Water and Ion Diffusion in Functional Hydrogel Membranes by PFG-NMR
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Nordness, Oscar, Moon, Joshua D, Marioni, Nico, Zofchak, Everett S, Richardson, Peter M, Landsman, Matthew R, Katz, Lynn E, Hawker, Craig J, Ganesan, Venkat, Segalman, Rachel A, and Clément, Raphaële J
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Macromolecular and Materials Chemistry ,Chemical Sciences ,Physical Chemistry ,Engineering ,Materials Engineering ,Polymers ,Chemical sciences - Published
- 2023
31. Ultrahigh‐Capacity Rocksalt Cathodes Enabled by Cycling‐Activated Structural Changes
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Ahn, Juhyeon, Giovine, Raynald, Wu, Vincent C, Koirala, Krishna Prasad, Wang, Chongmin, Clément, Raphaële J, and Chen, Guoying
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Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,capacity rise with cycling ,disordered rocksalts ,lithium-ion batteries ,Mn-rich cathode materials ,structural transformation ,Macromolecular and Materials Chemistry ,Interdisciplinary Engineering ,Macromolecular and materials chemistry ,Materials engineering - Abstract
Mn-redox-based oxides and oxyfluorides are considered the most promising earth-abundant high-energy cathode materials for next-generation lithium-ion batteries. While high capacities are obtained in high-Mn content cathodes such as Li- and Mn-rich layered and spinel-type materials, local structure changes and structural distortions (often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn-rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation-disordered rocksalt (DRX) cathode (Li1.1Mn0.8Ti0.1O1.9F0.1, an ultrahigh capacity of ≈320 mAh g−1 (energy density of ≈900 Wh kg−1) can be obtained through dynamic structural rearrangements upon cycling, along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn4+ and Li+ vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn4+ reduction, along with Li+ insertion transform the structure to a partially ordered DRX phase with a β′-LiFeO2-type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high-Mn DRXbut also provide guidance for the future development of Mn-based, high-energy density oxide, and oxyfluoride cathode materials.
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- 2023
32. Polymorphism in Weberite Na2Fe2F7 and its Effects on Electrochemical Properties as a Na-Ion Cathode
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Foley, Emily E, Wu, Vincent C, Jin, Wen, Cui, Wei, Yoshida, Eric, Manche, Alexis, and Clément, Raphaële J
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Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,Materials ,Chemical sciences - Abstract
Weberite-type sodium transition metal fluorides (Na2M2+M'3+F7) have emerged as potential high-performance sodium intercalation cathodes, with predicted energy densities in the 600-800 W h/kg range and fast Na-ion transport. One of the few weberites that have been electrochemically tested is Na2Fe2F7, yet inconsistencies in its reported structure and electrochemical properties have hampered the establishment of clear structure-property relationships. In this study, we reconcile structural characteristics and electrochemical behavior using a combined experimental-computational approach. First-principles calculations reveal the inherent metastability of weberite-type phases, the close energetics of several Na2Fe2F7 weberite polymorphs, and their predicted (de)intercalation behavior. We find that the as-prepared Na2Fe2F7 samples inevitably contain a mixture of polymorphs, with local probes such as solid-state nuclear magnetic resonance (NMR) and Mössbauer spectroscopy providing unique insights into the distribution of Na and Fe local environments. Polymorphic Na2Fe2F7 exhibits a respectable initial capacity yet steady capacity fade, a consequence of the transformation of the Na2Fe2F7 weberite phases to the more stable perovskite-type NaFeF3 phase upon cycling, as revealed by ex situ synchrotron X-ray diffraction and solid-state NMR. Overall, these findings highlight the need for greater control over weberite polymorphism and phase stability through compositional tuning and synthesis optimization.
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- 2023
33. Viruses interact with hosts that span distantly related microbial domains in dense hydrothermal mats
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Hwang, Yunha, Roux, Simon, Coclet, Clément, Krause, Sebastian JE, and Girguis, Peter R
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Microbiology ,Biological Sciences ,Infectious Diseases ,2.2 Factors relating to the physical environment ,Infection ,Bacteria ,Ecosystem ,Viruses ,DNA ,Microbial Interactions ,Medical Microbiology - Abstract
Many microbes in nature reside in dense, metabolically interdependent communities. We investigated the nature and extent of microbe-virus interactions in relation to microbial density and syntrophy by examining microbe-virus interactions in a biomass dense, deep-sea hydrothermal mat. Using metagenomic sequencing, we find numerous instances where phylogenetically distant (up to domain level) microbes encode CRISPR-based immunity against the same viruses in the mat. Evidence of viral interactions with hosts cross-cutting microbial domains is particularly striking between known syntrophic partners, for example those engaged in anaerobic methanotrophy. These patterns are corroborated by proximity-ligation-based (Hi-C) inference. Surveys of public datasets reveal additional viruses interacting with hosts across domains in diverse ecosystems known to harbour syntrophic biofilms. We propose that the entry of viral particles and/or DNA to non-primary host cells may be a common phenomenon in densely populated ecosystems, with eco-evolutionary implications for syntrophic microbes and CRISPR-mediated inter-population augmentation of resilience against viruses.
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- 2023
34. Tuning Bulk Redox and Altering Interfacial Reactivity in Highly Fluorinated Cation-Disordered Rocksalt Cathodes
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Crafton, Matthew J, Huang, Tzu-Yang, Yue, Yuan, Giovine, Raynald, Wu, Vincent C, Dun, Chaochao, Urban, Jeffrey J, Clément, Raphaële J, Tong, Wei, and McCloskey, Bryan D
- Subjects
Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,cation-disordered rocksalt ,differential electrochemical mass spectrometry ,titration mass spectrometry ,cathode-electrolyte interface ,electrolyte degradation ,oxygen redox ,high voltage ,fluoride-scavenging ,cathode−electrolyte interface ,Nanoscience & Nanotechnology ,Chemical sciences ,Physical sciences - Abstract
Lithium-excess, cation-disordered rocksalt (DRX) materials have been subject to intense scrutiny and development in recent years as potential cathode materials for Li-ion batteries. Despite their compositional flexibility and high initial capacity, they suffer from poorly understood parasitic degradation reactions at the cathode-electrolyte interface. These interfacial degradation reactions deteriorate both the DRX material and electrolyte, ultimately leading to capacity fade and voltage hysteresis during cycling. In this work, differential electrochemical mass spectrometry (DEMS) and titration mass spectrometry are combined to quantify the extent of bulk redox and surface degradation reactions for a set of Mn2+/4+-based DRX oxyfluorides during initial cycling with a high-voltage charging cutoff (4.8 V vs Li/Li+). Increasing the fluorine content from 7.5 to 33.75% is shown to diminish oxygen redox and suppresses high-voltage O2 evolution from the DRX surface. Additionally, electrolyte degradation processes resulting in the formation of both gaseous species and electrolyte-soluble protic species are observed. Subsequently, DEMS is paired with a fluoride-scavenging additive to demonstrate that increasing fluorine content leads to increased dissolution of fluorine from the DRX material into the electrolyte. Finally, a suite of ex situ spectroscopy techniques (X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, and solid-state nuclear magnetic resonance spectroscopy) are employed to study the change in DRX composition during charging, revealing the dissolution of manganese and fluorine from the DRX material at high voltages. This work provides insight into the degradation processes occurring at the DRX-electrolyte interface and points toward potential routes of interfacial stabilization.
- Published
- 2023
35. CBDC Field Research Insights: Challenging Common Assumptions about Access to Financial Services: Re
- Author
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Crucifix, Clément
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rural Mexico ,El Progreso ,Sierra of Puebla ,intermediaries - Abstract
CBDC Field Research Insights for the 2023 Report, “CBDC: Expanding Financial Inclusion or Deepening the Divide? Exploring Design Choices that Could Make a Difference”When we think about financial inclusion, we often imagine people going by themselves to financial institutions or directly using payment apps on their phones. We think of access as individual, direct, and unmediated.For people in the village of El Progreso*, in the northern Sierra of Puebla (Mexico), access to financial services is never that simple. Despite cash predominating in this relatively remote rural area, most people also use financial services, whether for saving money, receiving remittances, or accessing credit. However, this access is rarely direct. All sorts of human intermediaries intervene in the process: friends, relatives, people with good credit, or personnel at financial institutions.By analyzing the role played by those actors, I highlight some problems faced by people when they try to access financial services, as well as how they try to resolve these problems. I do not pretend to be exhaustive but rather demonstrate how important it is to look at those spaces of intermediation to understand better people’s monetary practices. This will allow me to challenge some common assumptions about access to financial services in rural areas.
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- 2023
36. Rapid and Energy‐Efficient Synthesis of Disordered Rocksalt Cathodes
- Author
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Wu, Vincent C, Evans, Hayden A, Giovine, Raynald, Preefer, Molleigh B, Ong, Julia, Yoshida, Eric, Cabelguen, Pierre‐Etienne, and Clément, Raphaële J
- Subjects
Engineering ,Materials Engineering ,Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,cations ,disordered rocksalts ,lithium-ion batteries ,microwave synthesis ,Macromolecular and Materials Chemistry ,Interdisciplinary Engineering ,Macromolecular and materials chemistry ,Materials engineering - Abstract
Abstract: Lithium‐rich transition metal oxides with a cation‐disordered rocksalt structure (disordered rocksalt oxides or DRX) are promising candidates for sustainable, next‐generation Li‐ion cathodes due to their high energy densities and compositional flexibility, enabling Co‐ and Ni‐free battery chemistries. However, current methods to synthesize DRX compounds require either high temperature (≈1000 °C) sintering for several hours, or high energy ball milling for several days in an inert atmosphere. Both methods are time‐ and energy‐intensive, limiting the scale up of DRX production. The present study reports the rapid synthesis of various DRX compositions in ambient air via a microwave‐assisted solid‐state technique resulting in reaction times as short as 5 min, which are more than two orders of magnitude faster than current synthesis methods. The DRX compounds synthesized via microwave are phase‐pure and have a similar short‐ and long‐range structure as compared to DRX materials synthesized via a standard solid‐state route, resulting in nearly identical electrochemical performance. In some cases, microwave heating allows for better particle size and morphology control. Overall, the rapid and energy‐efficient microwave technique provides a more sustainable route to produce DRX materials, further incentivizes the development of next‐generation DRX cathodes, and is key to accelerating their optimization via high‐throughput studies.
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- 2023
37. N-Phenylpyridine-3-Carboxamide and 6-Acetyl-1H-Indazole Inhibit the RNA Replication Step of the Dengue Virus Life Cycle.
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Sow, Aïssatou Aïcha, Pahmeier, Felix, Ayotte, Yann, Anton, Anaïs, Mazeaud, Clément, Charpentier, Tania, Angelo, Léna, Woo, Simon, Cerikan, Berati, Falzarano, Darryl, Abrahamyan, Levon, Lamarre, Alain, Labonté, Patrick, Cortese, Mirko, Bartenschlager, Ralf, LaPlante, Steven R, and Chatel-Chaix, Laurent
- Subjects
Animals ,Humans ,Flavivirus ,Dengue Virus ,Dengue ,RNA ,Viral ,Antiviral Agents ,Virus Replication ,Life Cycle Stages ,Zika Virus ,Zika Virus Infection ,RNA Replication ,SARS-CoV-2 ,West Nile virus ,Zika virus ,antivirals ,dengue virus ,Vaccine Related ,Infectious Diseases ,Rare Diseases ,Genetics ,Prevention ,West Nile Virus ,Vector-Borne Diseases ,Biodefense ,Emerging Infectious Diseases ,5.1 Pharmaceuticals ,Development of treatments and therapeutic interventions ,Infection ,Good Health and Well Being ,Microbiology ,Medical Microbiology ,Pharmacology and Pharmaceutical Sciences - Abstract
Dengue virus (DENV) is a Flavivirus that causes the most prevalent arthropod-borne viral disease. Clinical manifestation of DENV infection ranges from asymptomatic to severe symptoms that can lead to death. Unfortunately, no antiviral treatments against DENV are currently available. In order to identify novel DENV inhibitors, we screened a library of 1,604 chemically diversified fragment-based compounds using DENV reporter viruses that allowed quantification of viral replication in infected cells. Following a validation screening, the two best inhibitor candidates were N-phenylpyridine-3-carboxamide (NPP3C) and 6-acetyl-1H-indazole (6A1HI). The half maximal effective concentration of NPP3C and 6A1H1 against DENV were 7.1 μM and 6.5 μM, respectively. 6A1H1 decreased infectious DENV particle production up to 1,000-fold without any cytotoxicity at the used concentrations. While 6A1HI was DENV-specific, NPP3C also inhibited the replication of other flaviviruses such as West Nile virus and Zika virus. Structure-activity relationship (SAR) studies with 151 analogues revealed key structural elements of NPP3C and 6A1HI required for their antiviral activity. Time-of-drug-addition experiments identified a postentry step as a target of these compounds. Consistently, using a DENV subgenomic replicon, we demonstrated that these compounds specifically impede the viral RNA replication step and exhibit a high genetic barrier-to-resistance. In contrast, viral RNA translation and the de novo biogenesis of DENV replication organelles were not affected. Overall, our data unveil NPP3C and 6A1H1 as novel DENV inhibitors. The information revealed by our SAR studies will help chemically optimize NPP3C and 6A1H1 in order to improve their anti-flaviviral potency and to challenge them in in vivo models.
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- 2023
38. A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics
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Ye, Christopher Z, Del Rosal, Iker, Boreen, Michael A, Ouellette, Erik T, Russo, Dominic R, Maron, Laurent, Arnold, John, and Camp, Clément
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Inorganic Chemistry ,Chemical Sciences ,Chemical sciences - Abstract
Reaction of the potassium pentamethylcyclopentadienyl iridate tris-hydride K[IrCp*H3] with UCl4 and ThCl4(DME)2 led to the complete replacement of the halide ligands to generate multimetallic complexes U{(μ-H)3IrCp*}4 (1) and Th{[(μ-H2)(H)IrCp*]2[(μ-H)3IrCp*]2} (2), respectively. These analogues feature a significant discrepancy in hydride bonding modes; 1 contains twelve bridging hydrides while 2 contains ten bridging hydrides and two terminal, Ir-bound hydrides. Use of a U(iii) starting material, UI3(1,4-dioxane)1.5, resulted in the octanuclear complex {U[(μ2-H3)IrCp*]2[(μ3-H2)IrCp*]}2 (3). Computational studies indicate significant bonding character between U/Th and Ir in 1 and 2, with f-orbital involvement in the singly-occupied molecular orbitals of the uranium species 1. In addition, these studies attribute the variation in hydride bonding between 1 and 2 to differences in dispersion effects.
- Published
- 2023
39. Sub-frontal niches of plankton communities driven by transport and trophic interactions at ocean fronts
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Mangolte, Inès, Lévy, Marina, Haëck, Clément, and Ohman, Mark D
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Oceanography ,Biological Sciences ,Ecology ,Microbiology ,Earth Sciences ,Environmental Sciences ,Meteorology & Atmospheric Sciences ,Physical geography and environmental geoscience ,Environmental management - Abstract
Abstract. Observations and theory have suggested that ocean fronts are ecological hotspots, associated with higher diversity and biomass across many trophic levels. The hypothesis that these hotspots are driven by frontal nutrient injections is seemingly supported by the frequent observation of opportunistic diatoms at fronts, but the behavior of the rest of the plankton community is largely unknown.Here we investigate the organization of planktonic communities across fronts by analyzing eight high-resolution transects in the California Current Ecosystem containing extensive data for 24 groups of bacteria, phytoplankton, and zooplankton.We find that a distinct frontal plankton community characterized by enhanced biomass of not only diatoms and copepods but many other groups of plankton such as chaetognaths, rhizarians, and appendicularians emerges over most fronts. Importantly, we find spatial variability at a finer scale (typically 1–5 km) than the width of the front itself (typically 10–30 km) with peaks of different plankton taxa at different locations across the width of a front. Our results suggest that multiple processes, including horizontal stirring and biotic interactions, are responsible for creating this fine-scale patchiness.
- Published
- 2023
40. Inferring genetic structure when there is little: population genetics versus genomics of the threatened bat Miniopterus schreibersii across Europe
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Dufresnes, Christophe, Dutoit, Ludovic, Brelsford, Alan, Goldstein-Witsenburg, Fardo, Clément, Laura, López-Baucells, Adria, Palmeirim, Jorge, Pavlinić, Igor, Scaravelli, Dino, Ševčík, Martin, Christe, Philippe, and Goudet, Jérôme
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Biological Sciences ,Ecology ,Genetics ,Human Genome ,Biotechnology ,Animals ,Chiroptera ,Genetics ,Population ,Europe ,Genomics ,Genetic Structures ,Genetic Variation ,Microsatellite Repeats - Abstract
Despite their paramount importance in molecular ecology and conservation, genetic diversity and structure remain challenging to quantify with traditional genotyping methods. Next-generation sequencing holds great promises, but this has not been properly tested in highly mobile species. In this article, we compared microsatellite and RAD-sequencing (RAD-seq) analyses to investigate population structure in the declining bent-winged bat (Miniopterus schreibersii) across Europe. Both markers retrieved general patterns of weak range-wide differentiation, little sex-biased dispersal, and strong isolation by distance that associated with significant genetic structure between the three Mediterranean Peninsulas, which could have acted as glacial refugia. Microsatellites proved uninformative in individual-based analyses, but the resolution offered by genomic SNPs illuminated on regional substructures within several countries, with colonies sharing migrators of distinct ancestry without admixture. This finding is consistent with a marked philopatry and spatial partitioning between mating and rearing grounds in the species, which was suspected from marked-recaptured data. Our study advocates that genomic data are necessary to properly unveil the genetic footprints left by biogeographic processes and social organization in long-distant flyers, which are otherwise rapidly blurred by their high levels of gene flow.
- Published
- 2023
41. Climate-driven changes in the predictability of seasonal precipitation
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Le, Phong VV, Randerson, James T, Willett, Rebecca, Wright, Stephen, Smyth, Padhraic, Guilloteau, Clément, Mamalakis, Antonios, and Foufoula-Georgiou, Efi
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Earth Sciences ,Oceanography ,Climate Action - Abstract
Climate-driven changes in precipitation amounts and their seasonal variability are expected in many continental-scale regions during the remainder of the 21st century. However, much less is known about future changes in the predictability of seasonal precipitation, an important earth system property relevant for climate adaptation. Here, on the basis of CMIP6 models that capture the present-day teleconnections between seasonal precipitation and previous-season sea surface temperature (SST), we show that climate change is expected to alter the SST-precipitation relationships and thus our ability to predict seasonal precipitation by 2100. Specifically, in the tropics, seasonal precipitation predictability from SSTs is projected to increase throughout the year, except the northern Amazonia during boreal winter. Concurrently, in the extra-tropics predictability is likely to increase in central Asia during boreal spring and winter. The altered predictability, together with enhanced interannual variability of seasonal precipitation, poses new opportunities and challenges for regional water management.
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- 2023
42. Cognitive Flexibility Or Flexibilities? New Insights From A Classroom Study
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Baudier, Laure, Gros, Hippolyte, and Clément, Evelyne
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Education ,Psychology ,Cognitive development ,Skill acquisition and learning ,Classroom studies - Abstract
The definition of cognitive flexibility remains debated in the literature. Some refer to flexibility as a general shifting ability. Others argue that it is a context-dependent skill. For others, flexibility is a dimensional construct including reactive flexibility and spontaneous flexibility. To help decide between these views, we analyzed the performances of first-graders across four flexibility tasks. Two tasks focused on reactive flexibility (rule-shifting and verbally-cued-shifting), and two targeted spontaneous flexibility (role-shifting and divergent thinking). Three additional executive tasks investigated the contribution of inhibition, working memory, and processing speed. Significant — though moderate — positive correlations emerged between all but one of the pairs of flexibility tasks. Besides, executive functions were not found to systematically correlate with any measure of flexibility. Furthermore, confirmatory factorial analyses failed to identify a unique or bi-dimensional structure of flexibility. Taken together, these results did not provide evidence for a domain-general ability. Implications and future directions are discussed.
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- 2023
43. Strain‐Release Pentafluorosulfanylation and Tetrafluoro(aryl)sulfanylation of [1.1.1]Propellane: Reactivity and Structural Insight**
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Kraemer, Yannick, Ghiazza, Clément, Ragan, Abbey N, Ni, Shengyang, Lutz, Sigrid, Neumann, Elizabeth K, Fettinger, James C, Nöthling, Nils, Goddard, Richard, Cornella, Josep, and Pitts, Cody Ross
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Inorganic Chemistry ,Chemical Sciences ,Main Group Chemistry ,Pentafluorosulfanyl ,Propellane ,Strained Molecules ,X-Ray Diffraction ,Organic Chemistry ,Chemical sciences - Abstract
We leveraged the recent increase in synthetic accessibility of SF5 Cl and Ar-SF4 Cl compounds to combine chemistry of the SF5 and SF4 Ar groups with strain-release functionalization. By effectively adding SF5 and SF4 Ar radicals across [1.1.1]propellane, we accessed structurally unique bicyclopentanes, bearing two distinct elements of bioisosterism. Upon evaluating these "hybrid isostere" motifs in the solid state, we measured exceptionally short transannular distances; in one case, the distance rivals the shortest nonbonding C⋅⋅⋅C contact reported to date. This prompted SC-XRD and DFT analyses that support the notion that a donor-acceptor interaction involving the "wing" C-C bonds is playing an important role in stabilization. Thus, these heretofore unknown structures expand the palette for highly coveted three-dimensional fluorinated building blocks and provide insight to a more general effect observed in bicyclopentanes.
- Published
- 2022
44. Synthetic control of structure and conduction properties in Na–Y–Zr–Cl solid electrolytes
- Author
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Sebti, Elias, Qi, Ji, Richardson, Peter M, Ridley, Phillip, Wu, Erik A, Banerjee, Swastika, Giovine, Raynald, Cronk, Ashley, Ham, So-Yeon, Meng, Ying Shirley, Ong, Shyue Ping, and Clément, Raphaële J
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Inorganic Chemistry ,Chemical Sciences ,Physical Chemistry ,Engineering ,Materials Engineering ,Macromolecular and Materials Chemistry ,Interdisciplinary Engineering ,Macromolecular and materials chemistry ,Chemical engineering ,Materials engineering - Abstract
In the development of low cost, sustainable, and energy-dense batteries, chloride-based compounds are promising catholyte materials for solid-state batteries owing to their high Na-ion conductivities and oxidative stabilities. The ability to further improve Na-ion conduction, however, requires an understanding of the impact of long-range and local structural features on transport in these systems. In this study, we leverage different synthesis methods to control polymorphism and cation disorder in Na-Y-Zr-Cl solid electrolytes and interrogate the impact on Na-ion conduction. We demonstrate the existence of a more conductive P21/n polymorph of Na2ZrCl6 formed upon ball milling. In Na3YCl6, the R3̄ polymorph is shown to be more conductive than its P21/n counterpart owing to the presence of intrinsic vacancies and disorder on the Y sublattice. Transition metal ordering in the Na2.25Y0.25Zr0.75Cl6 composition strongly impacts Na-ion transport, where a greater mixing of Y3+ and Zr4+ on the transition metal sublattice facilitates ion migration through partial activation of Cl rotations at relevant temperatures. Overall, Na-ion transport sensitively depends on the phases and transition metal distributions stabilized during synthesis. These results are likely generalizable to other halide compositions and indicate that achieving control over the synthetic protocol and resultant structure is key in the pursuit of improved catholytes for high voltage solid-state sodium-ion batteries.
- Published
- 2022
45. Understanding the Fluorination of Disordered Rocksalt Cathodes through Rational Exploration of Synthesis Pathways
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Szymanski, Nathan J, Zeng, Yan, Bennett, Tyler, Patil, Shripad, Keum, Jong K, Self, Ethan C, Bai, Jianming, Cai, Zijian, Giovine, Raynald, Ouyang, Bin, Wang, Feng, Bartel, Christopher J, Clément, Raphaële J, Tong, Wei, Nanda, Jagjit, and Ceder, Gerbrand
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Chemical Sciences ,Physical Chemistry ,Affordable and Clean Energy ,Engineering ,Materials ,Chemical sciences - Abstract
We have designed and tested several synthesis routes targeting a highly fluorinated disordered rocksalt (DRX) cathode, Li1.2Mn0.4Ti0.4O1.6F0.4, with each route rationalized by thermochemical analysis. Precursor combinations were screened to raise the F chemical potential and avoid the formation of LiF, which inhibits fluorination of the targeted DRX phase. MnF2 was used as a reactive source of F, and Li6MnO4, LiMnO2, and Li2Mn0.33Ti0.66O3 were tested as alternative Li sources. Each synthesis procedure was monitored using a multi-modal suite of characterization techniques including X-ray diffraction, nuclear magnetic resonance, thermogravimetric analysis, and differential scanning calorimetry. From the resulting data, we advance the understanding of oxyfluoride synthesis by outlining the key factors limiting F solubility. At low temperatures, MnF2 consistently reacts with the Li source to form LiF as an intermediate phase, thereby trapping F in strong Li-F bonds. LiF can react with Li2TiO3 to form a highly lithiated and fluorinated DRX (Li3TiO3F); however, MnO is not easily incorporated into this DRX phase. Although higher temperatures typically increase solubility, the volatility of LiF above its melting point (848 °C) inhibits fluorination of the DRX phase. Based on these findings, metastable synthesis techniques are suggested for future work on DRX fluorination.
- Published
- 2022
46. Good scientific practice in EEG and MEG research: Progress and perspectives
- Author
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Niso, Guiomar, Krol, Laurens R, Combrisson, Etienne, Dubarry, A Sophie, Elliott, Madison A, François, Clément, Héjja-Brichard, Yseult, Herbst, Sophie K, Jerbi, Karim, Kovic, Vanja, Lehongre, Katia, Luck, Steven J, Mercier, Manuel, Mosher, John C, Pavlov, Yuri G, Puce, Aina, Schettino, Antonio, Schön, Daniele, Sinnott-Armstrong, Walter, Somon, Bertille, Šoškić, Anđela, Styles, Suzy J, Tibon, Roni, Vilas, Martina G, van Vliet, Marijn, and Chaumon, Maximilien
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Biomedical and Clinical Sciences ,Health Sciences ,Neurosciences ,8.3 Policy ,ethics ,and research governance ,Generic health relevance ,Electroencephalography ,Humans ,Magnetoencephalography ,Good scientific practice ,Medical and Health Sciences ,Psychology and Cognitive Sciences ,Neurology & Neurosurgery ,Biomedical and clinical sciences ,Health sciences - Abstract
Good scientific practice (GSP) refers to both explicit and implicit rules, recommendations, and guidelines that help scientists to produce work that is of the highest quality at any given time, and to efficiently share that work with the community for further scrutiny or utilization. For experimental research using magneto- and electroencephalography (MEEG), GSP includes specific standards and guidelines for technical competence, which are periodically updated and adapted to new findings. However, GSP also needs to be regularly revisited in a broader light. At the LiveMEEG 2020 conference, a reflection on GSP was fostered that included explicitly documented guidelines and technical advances, but also emphasized intangible GSP: a general awareness of personal, organizational, and societal realities and how they can influence MEEG research. This article provides an extensive report on most of the LiveMEEG contributions and new literature, with the additional aim to synthesize ongoing cultural changes in GSP. It first covers GSP with respect to cognitive biases and logical fallacies, pre-registration as a tool to avoid those and other early pitfalls, and a number of resources to enable collaborative and reproducible research as a general approach to minimize misconceptions. Second, it covers GSP with respect to data acquisition, analysis, reporting, and sharing, including new tools and frameworks to support collaborative work. Finally, GSP is considered in light of ethical implications of MEEG research and the resulting responsibility that scientists have to engage with societal challenges. Considering among other things the benefits of peer review and open access at all stages, the need to coordinate larger international projects, the complexity of MEEG subject matter, and today's prioritization of fairness, privacy, and the environment, we find that current GSP tends to favor collective and cooperative work, for both scientific and for societal reasons.
- Published
- 2022
47. Systemic considerations for the surgical treatment of spinal metastatic disease: a scoping literature review.
- Author
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MacLean, Mark A, Touchette, Charles J, Georgiopoulos, Miltiadis, Brunette-Clément, Tristan, Abduljabbar, Fahad H, Ames, Christopher P, Bettegowda, Chetan, Charest-Morin, Raphaele, Dea, Nicolas, Fehlings, Michael G, Gokaslan, Ziya L, Goodwin, C Rory, Laufer, Ilya, Netzer, Cordula, Rhines, Laurence D, Sahgal, Arjun, Shin, John H, Sciubba, Daniel M, Stephens, Byron F, Fourney, Daryl R, Weber, Michael H, and AO Spine Knowledge Forum Tumor
- Subjects
AO Spine Knowledge Forum Tumor ,Humans ,Spinal Cord Neoplasms ,Neoplasm Metastasis ,Female ,Male ,Cardiovascular ,Patient Safety ,Clinical Research ,7.3 Management and decision making ,Management of diseases and conditions ,Good Health and Well Being ,Oncology and Carcinogenesis ,Oncology & Carcinogenesis - Abstract
Systemic assessment is a pillar in the neurological, oncological, mechanical, and systemic (NOMS) decision-making framework for the treatment of patients with spinal metastatic disease. Despite this importance, emerging evidence relating systemic considerations to clinical outcomes following surgery for spinal metastatic disease has not been comprehensively summarised. We aimed to conduct a scoping literature review of this broad topic. We searched MEDLINE, Embase, Scopus, Cochrane Central Register of Controlled Trials, Web of Science, and CINAHL databases from Jan 1, 2000, to July 31, 2021. 61 articles were included, accounting for a total of 22 335 patients. Preoperative systemic variables negatively associated with postoperative clinical outcomes included demographics (eg, older age [>60 years], Black race, male sex, low or elevated body-mass index, and smoking status), medical comorbidities (eg, cardiac, pulmonary, hepatic, renal, endocrine, vascular, and rheumatological), biochemical abnormalities (eg, hypoalbuminaemia, atypical blood cell counts, and elevated C-reactive protein concentration), low muscle mass, generalised motor weakness (American Spinal Cord Injury Association Impairment Scale grade and Frankel grade) and poor ambulation, reduced performance status, and systemic disease burden. This is the first comprehensive scoping review to broadly summarise emerging evidence relevant to the systemic assessment component of the widely used NOMS framework for spinal metastatic disease decision making. Medical, surgical, and radiation oncologists can consider these findings when prognosticating spinal metastatic disease-related surgical outcomes on the basis of patients' systemic condition. These factors might inform a shared decision-making approach with patients and their families.
- Published
- 2022
48. Risk assessment with gut microbiome and metabolite markers in NAFLD development
- Author
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Leung, Howell, Long, Xiaoxue, Ni, Yueqiong, Qian, Lingling, Nychas, Emmanouil, Siliceo, Sara Leal, Pohl, Dennis, Hanhineva, Kati, Liu, Yan, Xu, Aimin, Nielsen, Henrik B, Belda, Eugeni, Clément, Karine, Loomba, Rohit, Li, Huating, Jia, Weiping, and Panagiotou, Gianni
- Subjects
Medical Biochemistry and Metabolomics ,Biomedical and Clinical Sciences ,Microbiome ,Nutrition ,Prevention ,Clinical Research ,Obesity ,Digestive Diseases ,Chronic Liver Disease and Cirrhosis ,Liver Disease ,4.1 Discovery and preclinical testing of markers and technologies ,4.2 Evaluation of markers and technologies ,2.1 Biological and endogenous factors ,Oral and gastrointestinal ,Biomarkers ,Gastrointestinal Microbiome ,Humans ,Non-alcoholic Fatty Liver Disease ,Prospective Studies ,Risk Assessment ,Biological Sciences ,Medical and Health Sciences ,Medical biotechnology ,Biomedical engineering - Abstract
A growing body of evidence suggests interplay between the gut microbiota and the pathogenesis of nonalcoholic fatty liver disease (NAFLD). However, the role of the gut microbiome in early detection of NAFLD is unclear. Prospective studies are necessary for identifying reliable, microbiome markers for early NAFLD. We evaluated 2487 individuals in a community-based cohort who were followed up 4.6 years after initial clinical examination and biospecimen sampling. Metagenomic and metabolomic characterizations using stool and serum samples taken at baseline were performed for 90 participants who progressed to NAFLD and 90 controls who remained NAFLD free at the follow-up visit. Cases and controls were matched for gender, age, body mass index (BMI) at baseline and follow-up, and 4-year BMI change. Machine learning models integrating baseline microbial signatures (14 features) correctly classified participants (auROCs of 0.72 to 0.80) based on their NAFLD status and liver fat accumulation at the 4-year follow up, outperforming other prognostic clinical models (auROCs of 0.58 to 0.60). We confirmed the biological relevance of the microbiome features by testing their diagnostic ability in four external NAFLD case-control cohorts examined by biopsy or magnetic resonance spectroscopy, from Asia, Europe, and the United States. Our findings raise the possibility of using gut microbiota for early clinical warning of NAFLD development.
- Published
- 2022
49. Neutron-proton pairing in the N=Z radioactive fp-shell nuclei 56Ni and 52Fe probed by pair transfer
- Author
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Le Crom, B, Assié, M, Blumenfeld, Y, Guillot, J, Sagawa, H, Suzuki, T, Honma, M, Achouri, NL, Bastin, B, Borcea, R, Catford, WN, Clément, E, Cáceres, L, Caamaño, M, Corsi, A, De France, G, Delaunay, F, De Séréville, N, Fernandez-Dominguez, B, Fisichella, M, Franchoo, S, Georgiadou, A, Gibelin, J, Gillibert, A, Hammache, F, Kamalou, O, Knapton, A, Lapoux, V, Leblond, S, Macchiavelli, AO, Marqués, FM, Matta, A, Ménager, L, Morfouace, P, Orr, NA, Pancin, J, Pereira-Lopez, X, Perrot, L, Piot, J, Pollacco, E, Ramos, D, Roger, T, Rotaru, F, Sánchez-Benítez, AM, Sénoville, M, Sorlin, O, Stanoiu, M, Stefan, I, Stodel, C, Suzuki, D, Thomas, J-C, and Vandebrouck, M
- Subjects
Nuclear and Plasma Physics ,Synchrotrons and Accelerators ,Physical Sciences ,Mathematical Physics ,Astronomical and Space Sciences ,Atomic ,Molecular ,Nuclear ,Particle and Plasma Physics ,Nuclear & Particles Physics ,Mathematical sciences ,Physical sciences - Abstract
The isovector and isoscalar components of neutron-proton pairing are investigated in the N=Z unstable nuclei of the fp-shell through the two-nucleon transfer reaction (p,3He) in inverse kinematics. The combination of particle and gamma-ray detection with radioactive beams of 56Ni and 52Fe, produced by fragmentation at the GANIL/LISE facility, made it possible to carry out this study for the first time in a closed and an open-shell nucleus in the fp-shell. The transfer cross-sections for ground-state to ground-state (J=0+, T=1) and to the first (J=1+, T=0) state were extracted for both cases together with the transfer cross-section ratios σ(0+,T=1)/σ(1+,T=0). They are compared with second-order distorted-wave born approximation (DWBA) calculations. The enhancement of the ground-state to ground-state pair transfer cross-section close to mid-shell, in 52Fe, points towards a superfluid phase in the isovector channel. For the “deuteron-like” transfer, very low cross-sections to the first (J=1+, T=0) state were observed both for 56Ni(p,3He) and 52Fe(p,3He) and are related to a strong hindrance of this channel due to spin-orbit effect. No evidence for an isoscalar deuteron-like condensate is observed.
- Published
- 2022
50. Unlocking New Redox Activity in Alluaudite Cathodes through Compositional Design
- Author
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Wu, Vincent C, Giovine, Raynald, Foley, Emily E, Finzel, Jordan, Balasubramanian, Mahalingam, Sebti, Elias, Mozur, Eve M, Kwon, Andrew H, and Clément, Raphaële J
- Subjects
Affordable and Clean Energy ,Chemical Sciences ,Engineering ,Materials - Published
- 2022
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