Showing papers by "Michigan State University published in 2022"

Global Carbon Budget 2021

Abstract: Abstract. Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere in a changing climate is critical to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe and synthesize datasets and methodology to quantify the five major components of the global carbon budget and their uncertainties. Fossil CO2 emissions (EFOS) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on land use and land-use change data and bookkeeping models. Atmospheric CO2 concentration is measured directly, and its growth rate (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) is estimated with global ocean biogeochemistry models and observation-based data products. The terrestrial CO2 sink (SLAND) is estimated with dynamic global vegetation models. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the first time, an approach is shown to reconcile the difference in our ELUC estimate with the one from national greenhouse gas inventories, supporting the assessment of collective countries' climate progress. For the year 2020, EFOS declined by 5.4 % relative to 2019, with fossil emissions at 9.5 ± 0.5 GtC yr−1 (9.3 ± 0.5 GtC yr−1 when the cement carbonation sink is included), and ELUC was 0.9 ± 0.7 GtC yr−1, for a total anthropogenic CO2 emission of 10.2 ± 0.8 GtC yr−1 (37.4 ± 2.9 GtCO2). Also, for 2020, GATM was 5.0 ± 0.2 GtC yr−1 (2.4 ± 0.1 ppm yr−1), SOCEAN was 3.0 ± 0.4 GtC yr−1, and SLAND was 2.9 ± 1 GtC yr−1, with a BIM of −0.8 GtC yr−1. The global atmospheric CO2 concentration averaged over 2020 reached 412.45 ± 0.1 ppm. Preliminary data for 2021 suggest a rebound in EFOS relative to 2020 of +4.8 % (4.2 % to 5.4 %) globally. Overall, the mean and trend in the components of the global carbon budget are consistently estimated over the period 1959–2020, but discrepancies of up to 1 GtC yr−1 persist for the representation of annual to semi-decadal variability in CO2 fluxes. Comparison of estimates from multiple approaches and observations shows (1) a persistent large uncertainty in the estimate of land-use changes emissions, (2) a low agreement between the different methods on the magnitude of the land CO2 flux in the northern extra-tropics, and (3) a discrepancy between the different methods on the strength of the ocean sink over the last decade. This living data update documents changes in the methods and datasets used in this new global carbon budget and the progress in understanding of the global carbon cycle compared with previous publications of this dataset (Friedlingstein et al., 2020, 2019; Le Quéré et al., 2018b, a, 2016, 2015b, a, 2014, 2013). The data presented in this work are available at https://doi.org/10.18160/gcp-2021 (Friedlingstein et al., 2021).

Global Carbon Budget 2022

Abstract: Abstract. Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere in a changing climate is critical to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe and synthesize data sets and methodologies to quantify the five major components of the global carbon budget and their uncertainties. Fossil CO2 emissions (EFOS) are based on energy statistics and cement production data, while emissions from land-use change (ELUC), mainly deforestation, are based on land use and land-use change data and bookkeeping models. Atmospheric CO2 concentration is measured directly, and its growth rate (GATM) is computed from the annual changes in concentration. The ocean CO2 sink (SOCEAN) is estimated with global ocean biogeochemistry models and observation-based data products. The terrestrial CO2 sink (SLAND) is estimated with dynamic global vegetation models. The resulting carbon budget imbalance (BIM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as ±1σ. For the year 2021, EFOS increased by 5.1 % relative to 2020, with fossil emissions at 10.1 ± 0.5 GtC yr−1 (9.9 ± 0.5 GtC yr−1 when the cement carbonation sink is included), and ELUC was 1.1 ± 0.7 GtC yr−1, for a total anthropogenic CO2 emission (including the cement carbonation sink) of 10.9 ± 0.8 GtC yr−1 (40.0 ± 2.9 GtCO2). Also, for 2021, GATM was 5.2 ± 0.2 GtC yr−1 (2.5 ± 0.1 ppm yr−1), SOCEAN was 2.9 ± 0.4 GtC yr−1, and SLAND was 3.5 ± 0.9 GtC yr−1, with a BIM of −0.6 GtC yr−1 (i.e. the total estimated sources were too low or sinks were too high). The global atmospheric CO2 concentration averaged over 2021 reached 414.71 ± 0.1 ppm. Preliminary data for 2022 suggest an increase in EFOS relative to 2021 of +1.0 % (0.1 % to 1.9 %) globally and atmospheric CO2 concentration reaching 417.2 ppm, more than 50 % above pre-industrial levels (around 278 ppm). Overall, the mean and trend in the components of the global carbon budget are consistently estimated over the period 1959–2021, but discrepancies of up to 1 GtC yr−1 persist for the representation of annual to semi-decadal variability in CO2 fluxes. Comparison of estimates from multiple approaches and observations shows (1) a persistent large uncertainty in the estimate of land-use change emissions, (2) a low agreement between the different methods on the magnitude of the land CO2 flux in the northern extratropics, and (3) a discrepancy between the different methods on the strength of the ocean sink over the last decade. This living data update documents changes in the methods and data sets used in this new global carbon budget and the progress in understanding of the global carbon cycle compared with previous publications of this data set. The data presented in this work are available at https://doi.org/10.18160/GCP-2022 (Friedlingstein et al., 2022b).

Omicron BA.2 (B.1.1.529.2): High Potential for Becoming the Next Dominant Variant

Abstract: The Omicron variant has three subvariants: BA.1 (B.1.1.529.1), BA.2 (B.1.1.529.2), and BA.3 (B.1.1.529.3). BA.2 is found to be able to alarmingly reinfect patients originally infected by Omicron BA.1. An important question is whether BA.2 or BA.3 will become a new dominating "variant of concern". Currently, no experimental data has been reported about BA.2 and BA.3. We construct a novel algebraic topology-based deep learning model to systematically evaluate BA.2's and BA.3's infectivity, vaccine breakthrough capability, and antibody resistance. Our comparative analysis of all main variants, namely, Alpha, Beta, Gamma, Delta, Lambda, Mu, BA.1, BA.2, and BA.3, unveils that BA.2 is about 1.5 and 4.2 times as contagious as BA.1 and Delta, respectively. It is also 30% and 17-fold more capable than BA.1 and Delta, respectively, to escape current vaccines. Therefore, we project that Omicron BA.2 is on a path to becoming the next dominant variant. We forecast that like Omicron BA.1, BA.2 will also seriously compromise most existing monoclonal antibodies. All key predictions have been nearly perfectly confirmed before the official publication of this work.

Multi‐state modeling of G‐protein coupled receptors at experimental accuracy

Abstract: The family of G-protein coupled receptors (GPCRs) is one of the largest protein families in the human genome. GPCRs transduct chemical signals from extracellular to intracellular regions via a conformational switch between active and inactive states upon ligand binding. While experimental structures of GPCRs remain limited, high-accuracy computational predictions are now possible with AlphaFold2. However, AlphaFold2 only predicts one state and is biased toward either the active or inactive conformation depending on the GPCR class. Here, a multi-state prediction protocol is introduced that extends AlphaFold2 to predict either active or inactive states at very high accuracy using state-annotated templated GPCR databases. The predicted models accurately capture the main structural changes upon activation of the GPCR at the atomic level. For most of the benchmarked GPCRs (10 out of 15), models in the active and inactive states were closer to their corresponding activation state structures. Median RMSDs of the transmembrane regions were 1.12 Å and 1.41 Å for the active and inactive state models, respectively. The models were more suitable for protein-ligand docking than the original AlphaFold2 models and template-based models. Finally, our prediction protocol predicted accurate GPCR structures and GPCR-peptide complex structures in GPCR Dock 2021, a blind GPCR-ligand complex modeling competition. We expect that high accuracy GPCR models in both activation states will promote understanding in GPCR activation mechanisms and drug discovery for GPCRs. At the time, the new protocol paves the way towards capturing the dynamics of proteins at high-accuracy via machine-learning methods.

Comparing national greenhouse gas budgets reported in UNFCCC inventories against atmospheric inversions

Abstract: Abstract. In support of the global stocktake of the Paris Agreement on climate change, this study presents a comprehensive framework to process the results of an ensemble of atmospheric inversions in order to make their net ecosystem exchange (NEE) carbon dioxide (CO2) flux suitable for evaluating national greenhouse gas inventories (NGHGIs) submitted by countries to the United Nations Framework Convention on Climate Change (UNFCCC). From inversions we also deduced anthropogenic methane (CH4) emissions regrouped into fossil and agriculture and waste emissions, as well as anthropogenic nitrous oxide (N2O) emissions. To compare inversion results with national reports, we compiled a new global harmonized database of emissions and removals from periodical UNFCCC inventories by Annex I countries, and from sporadic and less detailed emissions reports by non-Annex I countries, given by national communications and biennial update reports. No gap filling was applied. The method to reconcile inversions with inventories is applied to selected large countries covering ∼90 % of the global land carbon uptake for CO2 and top emitters of CH4 and N2O. Our method uses results from an ensemble of global inversions produced by the Global Carbon Project for the three greenhouse gases, with ancillary data. We examine the role of CO2 fluxes caused by lateral transfer processes from rivers and from trade in crop and wood products and the role of carbon uptake in unmanaged lands, both not accounted for by NGHGIs. Here we show that, despite a large spread across the inversions, the median of available inversion models points to a larger terrestrial carbon sink than inventories over temperate countries or groups of countries of the Northern Hemisphere like Russia, Canada and the European Union. For CH4, we find good consistency between the inversions assimilating only data from the global in situ network and those using satellite CH4 retrievals and a tendency for inversions to diagnose higher CH4 emission estimates than reported by NGHGIs. In particular, oil- and gas-extracting countries in central Asia and the Persian Gulf region tend to systematically report lower emissions compared to those estimated by inversions. For N2O, inversions tend to produce higher anthropogenic emissions than inventories for tropical countries, even when attempting to consider only managed land emissions. In the inventories of many non-Annex I countries, this can be tentatively attributed to a lack of reporting indirect N2O emissions from atmospheric deposition and from leaching to rivers, to the existence of natural sources intertwined with managed lands, or to an underestimation of N2O emission factors for direct agricultural soil emissions. Inversions provide insights into seasonal and interannual greenhouse gas fluxes anomalies, e.g., during extreme events such as drought or abnormal fire episodes, whereas inventory methods are established to estimate trends and multi-annual changes. As a much denser sampling of atmospheric CO2 and CH4 concentrations by different satellites coordinated into a global constellation is expected in the coming years, the methodology proposed here to compare inversion results with inventory reports (e.g., NGHGIs) could be applied regularly for monitoring the effectiveness of mitigation policy and progress by countries to meet the objective of their pledges. The dataset constructed by this study is publicly available at https://doi.org/10.5281/zenodo.5089799 (Deng et al., 2021).

Assessment of cracking performance indices of asphalt mixtures at intermediate temperatures

Abstract: In recent years, two types of test methods have emerged to evaluate the susceptibility of asphalt mixtures to cracking at intermediate temperatures as part of performance-related mix design specifi...

Organometallic lanthanide bismuth cluster single-molecule magnets

Abstract: •Isolation of organometallic f-element bismuth cluster complexes•Heterometallocubane [Ln2Bi6] featuring two lanthanides bridged through a Bi66− unit•Single-molecule magnets containing bismuth donors•Magnetic hysteresis in superexchange-coupled lanthanide complexes Single-molecule magnets are molecules that act as nanoscopic analogs to classical magnets and have garnered substantial interest due to their potential applications in high-density information storage, magnetic refrigeration, spin-based electronics, and quantum computation. To realize such applications, memory loss needs to be prevented, which requires judicious design of coordination complexes. Herein, we developed a strategy to unprecedented organometallic SMMs comprising lanthanide and bismuth ions that exhibit magnetic memory. The core heterometallocubane includes bismuth and lanthanides and was hitherto unknown. Despite the contracted nature of the lanthanide 4f-orbitals, the bismuth cluster allows significant magnetic superexchange, thus defining a new platform for SMM design. This peerless class of compounds leads also to new prospects in physics and synthetic chemistry. Single-molecule magnets (SMMs) are molecules that can retain magnetic polarization in the absence of an external magnetic field and embody the ultimate size limit for spin-based information storage and processing. Multimetallic lanthanide complexes lacking magnetic exchange coupling enable fast relaxation pathways that attenuate the full potential of these species. Employment of diamagnetic heavy main group elements with diffuse orbitals may lead to unprecedented strong coupling. Herein, two bismuth-cluster-bridged lanthanide complexes, [K(THF)4]2[Cp∗2Ln2Bi6] (Cp∗ = pentamethylcyclopentadienyl; 1-Ln, Ln = Tb, Dy), were synthesized via a solution organometallic approach. The neutral [Ln2Bi6] heterometallocubane core features lanthanide centers that are bridged by a rare Bi66− Zintl ion, which supports strong ferromagnetic interactions between lanthanides. This affords the rare observation of magnetic blocking and open hysteresis loops for superexchange-coupled SMMs comprising solely lanthanide ions. Both compounds constitute the first SMMs containing bismuth donors paving the way for promising synthetic targets for quantum computation. Single-molecule magnets (SMMs) are molecules that can retain magnetic polarization in the absence of an external magnetic field and embody the ultimate size limit for spin-based information storage and processing. Multimetallic lanthanide complexes lacking magnetic exchange coupling enable fast relaxation pathways that attenuate the full potential of these species. Employment of diamagnetic heavy main group elements with diffuse orbitals may lead to unprecedented strong coupling. Herein, two bismuth-cluster-bridged lanthanide complexes, [K(THF)4]2[Cp∗2Ln2Bi6] (Cp∗ = pentamethylcyclopentadienyl; 1-Ln, Ln = Tb, Dy), were synthesized via a solution organometallic approach. The neutral [Ln2Bi6] heterometallocubane core features lanthanide centers that are bridged by a rare Bi66− Zintl ion, which supports strong ferromagnetic interactions between lanthanides. This affords the rare observation of magnetic blocking and open hysteresis loops for superexchange-coupled SMMs comprising solely lanthanide ions. Both compounds constitute the first SMMs containing bismuth donors paving the way for promising synthetic targets for quantum computation. Molecular magnetism is a textbook example of synergetic effects arising from the interplay of chemistry and physics that composes a vibrant, multidisciplinary, and established research field.1Gatteschi D. Sessoli R. Vallain J. Molecular Nanomagnets. Oxford University Press, 2006Google Scholar The development of the field relies on the design and synthesis of new molecules, followed by thorough magnetic, spectroscopic, and theoretical investigations.2Moreno Pineda E. Chilton N.F. Marx R. Dörfel M. Sells D.O. Neugebauer P. Jiang S.-D. Collison D. van Slageren J. McInnes E.J.L. Winpenny R.E.P. Direct measurement of dysprosium(III)˙˙˙dysprosium(III) interactions in a single-molecule magnet.Nat. Commun. 2014; 5: 5243Google Scholar In particular, synthetic inorganic chemistry enables access to a wide range of organic, coordination, and organometallic compounds bearing signatures of interesting single-molecule magnet (SMM) behavior.3Woodruff D.N. Winpenny R.E.P. Layfield R.A. Lanthanide single-molecule magnets.Chem. Rev. 2013; 113: 5110-5148Google Scholar Lanthanides (Ln) are especially well suited for the design of SMMs due to their large magnetic anisotropy originating from near-unquenched orbital angular momentum and strong spin-orbit coupling.4Rinehart J.D. Long J.R. Exploiting single-ion anisotropy in the design of f-element single-molecule magnets.Chem. Sci. 2011; 2: 2078-2085Google Scholar Recently, the judicious optimization of crystal field resulted in magnetic bistability persisting up to liquid nitrogen temperature in a mononuclear Dy-based metallocene complex, representing the current performance record for a SMM.5Guo F.-S. Day B.M. Chen Y.-C. Tong M.-L. Mansikkamäki A. Layfield R.A. Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet.Science. 2018; 362: 1400-1403Google Scholar A parallel strategy exploits the synthesis of multimetallic systems, where in addition to tailored crystal fields, the magnetic communication between highly anisotropic lanthanide centers is of utmost importance. However, multimetallic lanthanide complexes with requisite large spin ground states pose a synthetic challenge since the contracted 4f-orbitals of the metal centers only engender weak magnetic exchange.6Rinehart J.D. Fang M. Evans W.J. Long J.R. Strong exchange and magnetic blocking in N23−-radical-bridged lanthanide complexes.Nat. Chem. 2011; 3: 538-542Google Scholar Here, several viable strategies have resulted in significant breakthroughs in the design of high-performance SMMs via enhancing magnetic coupling to lanthanide ions, which includes, but is not limited to, the coupling through nd metal ions, radical ligands, and single-electron Ln–Ln bonds stabilized as endohedral metallofullerenes (EMFs).7Mondal K.C. Sundt A. Lan Y. Kostakis G.E. Waldmann O. Ungur L. et al.Coexistence of distinct single-ion and exchange-based mechanisms for blocking of magnetization in a Co(II)2Dy(III)2 single-molecule magnet.Angew. Chem. Int. Ed. Engl. 2012; 51: 7550-7554Google Scholar, 8Langley S.K. Wielechowski D.P. Vieru V. Chilton N.F. Moubaraki B. Abrahams B.F. et al.A {Cr(III)2Dy(III)2} single-molecule magnet: enhancing the blocking temperature through 3d magnetic exchange.Angew. Chem. Int. Ed. Engl. 2013; 52: 12014-12019Google Scholar, 9Wang J. Li Q.-W. Wu S.-G. Chen Y.-C. Wan R.-C. Huang G.-Z. Liu Y. Liu J.-L. Reta D. Giansiracusa M.J. et al.Opening magnetic hysteresis by axial ferromagnetic coupling: from mono-decker to double-decker metallacrown.Angew. Chem. Int. Ed. Engl. 2021; 60: 5299-5306Google Scholar, 10Demir S. Jeon I.-R. Long J.R. Harris T.D. Radical ligand-containing single-molecule magnets.Coord. Chem. Rev. 2015; 289: 149-176Google Scholar, 11Liu F. Spree L. Krylov D.S. Velkos G. Avdoshenko S.M. Popov A.A. Single-electron lanthanide-lanthanide bonds inside fullerenes toward robust redox-active molecular magnets.Acc. Chem. Res. 2019; 52: 2981-2993Google Scholar, 12Liu F. Velkos G. Krylov D.S. Spree L. Zalibera M. Ray R. Samoylova N.A. Chen C.-H. Rosenkranz M. Schiemenz S. et al.Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal–metal bond.Nat. Commun. 2019; 10: 571Google Scholar Albeit synthetically challenging, the implementation of radical-bridging ligands has proven to be a particularly successful approach, which is attributed to the diffuse radical spin orbitals that are able to penetrate the core electron density of the 4f-orbitals resulting in enhanced magnetic exchange coupling to lanthanide centers. The successful stabilization, isolation, and purification of lanthanide radical SMMs occurred with bridging radicals, which gave rise to open magnetic hysteresis loops comprising a giant coercive field of approximately 8 T for a SMM.10Demir S. Jeon I.-R. Long J.R. Harris T.D. Radical ligand-containing single-molecule magnets.Coord. Chem. Rev. 2015; 289: 149-176Google Scholar,13Demir S. Gonzalez M.I. Darago L.E. Evans W.J. Long J.R. Giant coercivity and high magnetic blocking temperatures for N23− radical-bridged dilanthanide complexes upon ligand dissociation.Nat. Commun. 2017; 8: 2144Google Scholar,14Gould C.A. Mu E. Vieru V. Darago L.E. Chakarawet K. Gonzalez M.I. Demir S. Long J.R. Substituent effects on exchange coupling and magnetic relaxation in 2,2′-bipyrimidine radical-bridged dilanthanide complexes.J. Am. Chem. Soc. 2020; 142: 21197-21209Google Scholar Although a desirable approach, the generation of radical-bridges necessitates redox-active ligands, which dramatically limits the number of target molecules and adds an additional layer of sensitivity and reactivity of the compounds due to the open-shell ligands employed. A promising route to SMMs that show magnetic memory at high temperatures is to enhance magnetic exchange between the lanthanide centers using diamagnetic heavy p-block donor atoms, since their diffuse valence orbitals may facilitate better penetration of the core electron density of the lanthanide ions and better energy matching, compared with the more commonly employed diamagnetic ligands with lighter C/N/O/Cl donor atoms.15Guo F.S. Bar A.K. Layfield R.A. Main group chemistry at the interface with molecular magnetism.Chem. Rev. 2019; 119: 8479-8505Google Scholar This theory is supported by observations, such as the doubled magnetic exchange interaction in the sulfur-bridged dinuclear dysprosium SMM, [(C5H4Me)2Dy(μ-SSiPh3)]2, compared with the similar chloride-bridged complex, [Cp2Dy(thf)(μ-Cl)]2, which consequently results in more efficient mitigation of quantum tunneling relaxation processes at low temperatures.16Tuna F. Smith C.A. Bodensteiner M. Ungur L. Chibotaru L.F. McInnes E.J.L. Winpenny R.E.P. Collison D. Layfield R.A. A high anisotropy barrier in a sulfur-bridged organodysprosium single-molecule magnet.Angew. Chem. Int. Ed. Engl. 2012; 51: 6976-6980Google Scholar The exploration of ligands containing heavier main group elements for the construction of SMMs is scarce.15Guo F.S. Bar A.K. Layfield R.A. Main group chemistry at the interface with molecular magnetism.Chem. Rev. 2019; 119: 8479-8505Google Scholar Noteworthy is a series of Dy-based SMMs containing DyIII–P, DyIII–As, and DyIII–Sb bonds, which demonstrated the critical role in moderating the magnitude of barriers to spin relaxation (Ueff) among the different pnictogen donors, showing decreasing coordination ability from P, As to Sb.17Pugh T. Tuna F. Ungur L. Collison D. McInnes E.J.L. Chibotaru L.F. Layfield R.A. Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands.Nat. Commun. 2015; 6: 7492Google Scholar, 18Pugh T. Vieru V. Chibotaru L.F. Layfield R.A. Magneto-structural correlations in arsenic- and selenium-ligated dysprosium single-molecule magnets.Chem. Sci. 2016; 7: 2128-2137Google Scholar, 19Pugh T. Chilton N.F. Layfield R.A. Antimony-ligated dysprosium single-molecule magnets as catalysts for stibine dehydrocoupling.Chem. Sci. 2017; 8: 2073-2080Google Scholar Similarly, the impact of covalent bonding on magnetic relaxation dynamics was also illustrated in Dy-based SMMs bearing DyIII–GeII and DyIII–SnII bonds, respectively, where the former features stronger DyIII–GeII bonding in the equatorial position leading to a lower effective spin-reversal barrier and faster quantum tunneling of the magnetization.20Chen S.-M. Xiong J. Zhang Y.-Q. Ma F. Sun H.-L. Wang B.-W. et al.Dysprosium complexes bearing unsupported DyIII–GeII/SnII metal-metal bonds as single-ion magnets.Chem. Commun. (Camb). 2019; 55: 8250-8253Google Scholar Notably, magnetic blocking derived from coupled states has been observed in multinuclear systems, such as 3d-4f clusters,7Mondal K.C. Sundt A. Lan Y. Kostakis G.E. Waldmann O. Ungur L. et al.Coexistence of distinct single-ion and exchange-based mechanisms for blocking of magnetization in a Co(II)2Dy(III)2 single-molecule magnet.Angew. Chem. Int. Ed. Engl. 2012; 51: 7550-7554Google Scholar radical-bridged lanthanide complexes,13Demir S. Gonzalez M.I. Darago L.E. Evans W.J. Long J.R. Giant coercivity and high magnetic blocking temperatures for N23− radical-bridged dilanthanide complexes upon ligand dissociation.Nat. Commun. 2017; 8: 2144Google Scholar and EMFs,21Chen C.-H. Krylov D.S. Avdoshenko S.M. Liu F. Spree L. Yadav R. et al.Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism.Chem. Sci. 2017; 8: 6451-6465Google Scholar where each coupled system operates as a single magnetic unit for the reversal of magnetic moment akin to transition metal cluster complexes. In contrast, such magnetic blocking remains rare for purely lanthanide-based polynuclear SMMs containing diamagnetic bridges between lanthanide centers. In those systems, the observed slow magnetic relaxation is ascribed to the single-ion effect.7Mondal K.C. Sundt A. Lan Y. Kostakis G.E. Waldmann O. Ungur L. et al.Coexistence of distinct single-ion and exchange-based mechanisms for blocking of magnetization in a Co(II)2Dy(III)2 single-molecule magnet.Angew. Chem. Int. Ed. Engl. 2012; 51: 7550-7554Google Scholar,8Langley S.K. Wielechowski D.P. Vieru V. Chilton N.F. Moubaraki B. Abrahams B.F. et al.A {Cr(III)2Dy(III)2} single-molecule magnet: enhancing the blocking temperature through 3d magnetic exchange.Angew. Chem. Int. Ed. Engl. 2013; 52: 12014-12019Google Scholar,22Sessoli R. Gatteschi D. Caneschi A. Novak M.A. Magnetic bistability in a metal-ion cluster.Nature. 1993; 365: 141-143Google Scholar Thus, we pursued the design of cluster complexes consisting of late lanthanide ions and heavy main group element bridges. The latter will engender strong magnetic exchange coupling between lanthanide centers to potentially afford sufficient energy separation between exchange-coupled levels for blocking the reversal of magnetization. Bismuth was long thought to be the heaviest non-radioactive element of the periodic table.23de Marcillac P. Coron N. Dambier G. Leblanc J. Moalic J.-P. Experimental detection of α-particles from the radioactive decay of natural bismuth.Nature. 2003; 422: 876-878Google Scholar It possesses high principle quantum number valence orbitals (6s), and features effects arising from strong spin-orbit coupling. These characteristics create different effects on crystal field and magnetic exchange interactions with metal centers, when compared with the properties arising for its lighter group V homologs.24Lichtenberg C. Well-defined, mononuclear BiI and BiII compounds: towards transition-metal-like behavior.Angew. Chem. Int. Ed. Engl. 2016; 55: 484-486Google Scholar To the best of our knowledge, no SMM with a coordinating bismuth ion to one or more anisotropic metal centers have been reported. Moreover, complexes that contain both transition metal and bismuth ions are exceedingly rare, and magnetic studies on these are even scarcer. In a remarkable MnII–BiIII heterobimetallic complex exhibiting the shortest known Mn−Bi distance, the transfer of spin-orbit coupling effects in diamagnetic BiIII ion to the spin-bearing isotropic MnII ion was elucidated by examining the axial zero-field splitting parameter of the MnII center, which resembles the heavy atom effect observed in heavy halide species.25Pearson T.J. Fataftah M.S. Freedman D.E. Enhancement of magnetic anisotropy in a Mn–Bi heterobimetallic complex.Chem. Commun. (Camb). 2016; 52: 11394-11397Google Scholar Bismuth is a poor coordinating donor ligand owing to unsupported hard-soft linkages and is thus challenging to employ for f-element chemistry.26Rookes T.M. Wildman E.P. Balázs G. Gardner B.M. Wooles A.J. Gregson M. Tuna F. Scheer M. Liddle S.T. Actinide–pnictide (An−Pn) bonds spanning non-metal, metalloid, and metal combinations (An=U, Th; Pn=P, As, Sb, Bi).Angew. Chem. Int. Ed. Engl. 2018; 57: 1332-1336Google Scholar,27Eulenstein A.R. Franzke Y.J. Lichtenberger N. Wilson R.J. Deubner H.L. Kraus F. et al.Substantial π-aromaticity in the anionic heavy-metal cluster [[email protected]12]4−.Nat. Chem. 2021; 13: 149-155Google Scholar Only one dinuclear complex containing SmIII and Bi ions is known,28Evans W.J. Gonzales S.L. Ziller J.W. Organosamarium-mediated synthesis of bismuth-bismuth bonds: X-ray crystal structure of the first dibismuth complex containing a planar M2(μ-η2:η2-Bi2) unit.J. Am. Chem. Soc. 1991; 113: 9880-9882Google Scholar along with a handful of intermetalloid cluster complexes featuring Zintl ions.29Lips F. Clérac R. Dehnen S. [[email protected]6Bi8]4−: a mini-fullerane-type zintl anion containing a lanthanide ion.Angew. Chem. Int. Ed. 2011; 50: 960-964Google Scholar, 30Weinert B. Müller F. Harms K. Clérac R. Dehnen S. Origin and location of electrons and protons during the formation of intermetalloid clusters [[email protected]3−xH3−2xBi10+x]3− (x=0, 1).Angew. Chem. Int. Ed. Engl. 2014; 53: 11979-11983Google Scholar, 31Weinert B. Weigend F. Dehnen S. Subtle impact of atomic ratio, charge and Lewis basicity on structure selection and stability: the zintl anion [([email protected]2Bi11)(μ-Bi)2([email protected]2Bi11)]6–.Chemistry. 2012; 18: 13589-13595Google Scholar, 32Lips F. Hołyńska M. Clérac R. Linne U. Schellenberg I. Pöttgen R. et al.Doped semimetal clusters: ternary, intermetalloid anions [[email protected]7Bi7]4– and [[email protected]4Bi9]4– (Ln = La, Ce) with adjustable magnetic properties.J. Am. Chem. Soc. 2012; 134: 1181-1191Google Scholar The unique electronic and physical properties associated with lanthanide and bismuth ions, respectively, sparked our interest to develop magnetic molecules containing both highly magnetically anisotropic lanthanides and bismuth ions. If the major synthetic challenges of their preparation can be overcome, Ln–Bi species will enrich 4f and main group chemistry, paving the way to discoveries of new structure types and magnetic phenomena. Here, we report the isolation of the first bismuth-cluster-bridged dilanthanide complexes, [K(THF)4]2[Cp∗2Ln2Bi6] (Cp∗ = pentamethylcyclopentadienyl; 1-Ln, Ln = Tb, Dy), where the two lanthanide centers are connected through an exceptional Bi66− unit, forming a unique Ln2Bi6 heterometallocubane. Notably, neither a metallocubane core of formula M2Bi6, nor a Bi66− moiety in any organometallic compound, have yet been reported. Significantly, ferromagnetic interactions between the two lanthanide centers mediated through the Bi66− bridge led to the observation of open magnetic hysteresis at low temperatures in superexchange-coupled Ln-SMMs. Among the few reported, primarily solid-state compounds that contain Ln–Bi fragments, intermetalloid clusters involving Zintl ions are most relevant to this study. These clusters exhibit stronger coordinating ability to metal centers via p-orbital bonding electrons than do single-site bismuthine ligands (BiR3 or BiR2−).29Lips F. Clérac R. Dehnen S. [[email protected]6Bi8]4−: a mini-fullerane-type zintl anion containing a lanthanide ion.Angew. Chem. Int. Ed. 2011; 50: 960-964Google Scholar, 30Weinert B. Müller F. Harms K. Clérac R. Dehnen S. Origin and location of electrons and protons during the formation of intermetalloid clusters [[email protected]3−xH3−2xBi10+x]3− (x=0, 1).Angew. Chem. Int. Ed. Engl. 2014; 53: 11979-11983Google Scholar, 31Weinert B. Weigend F. Dehnen S. Subtle impact of atomic ratio, charge and Lewis basicity on structure selection and stability: the zintl anion [([email protected]2Bi11)(μ-Bi)2([email protected]2Bi11)]6–.Chemistry. 2012; 18: 13589-13595Google Scholar, 32Lips F. Hołyńska M. Clérac R. Linne U. Schellenberg I. Pöttgen R. et al.Doped semimetal clusters: ternary, intermetalloid anions [[email protected]7Bi7]4– and [[email protected]4Bi9]4– (Ln = La, Ce) with adjustable magnetic properties.J. Am. Chem. Soc. 2012; 134: 1181-1191Google Scholar The general synthetic route for intermetalloid clusters comprising heavy main group and d- or f-elements starts with an intermetallic Zintl complex, which is prepared via a solid-state reaction involving alkali metals and heavy main group elements.33Goicoechea J.M. Hull M.W. Sevov S.C. Heteroatomic deltahedral clusters: synthesis and structures of closo-[Bi3Ni4(CO)6]3−, closo-[Bi4Ni4(CO)6]2−, the open cluster [Bi3Ni6(CO)9]3−, and the intermetalloid closo-[Nix@{Bi6Ni6(CO)8}]4–.J. Am. Chem. Soc. 2007; 129: 7885-7893Google Scholar,34Min X. Popov I.A. Pan F.-X. Li L.-J. Matito E. Sun Z.-M. et al.All-metal antiaromaticity in Sb4-type lanthanocene anions.Angew. Chem. Int. Ed. Engl. 2016; 55: 5531-5535Google Scholar The synthetic protocol then requires highly polar solvents, such as ethylenediamine, in order to dissolve the starting materials and products. Drawbacks of these synthetic routes include low yields of the desired products and unavoidable byproducts, which precludes scalable syntheses of pure intermetalloid cluster compounds and, as a result, prevents studies of their chemical and physical properties.35Wilson R.J. Lichtenberger N. Weinert B. Dehnen S. Intermetalloid and heterometallic clusters combining p-block (semi)metals with d- or f-block metals.Chem. Rev. 2019; 119: 8506-8554Google Scholar Modification of Zintl ions or intermetalloid clusters through the coordination of organic or organometallic ligands shows great promise for improving the solubility, stability, reactivity, and purification of these products.36Schenk C. Schnepf A. [AuGe18{Si(SiMe3)3}6]−: a soluble Au–Ge cluster on the way to a molecular cable?.Angew. Chem. Int. Ed. Engl. 2007; 46: 5314-5316Google Scholar Therefore, the development of a facile solution synthetic route to cluster complexes, which readily allows product isolation and purification is highly desirable and demands judicious selection of suitable bismuth and lanthanide starting materials. Decamethylsamarocene, containing highly reducing SmII, produced in solution the only known lanthanide bismuth molecule.28Evans W.J. Gonzales S.L. Ziller J.W. Organosamarium-mediated synthesis of bismuth-bismuth bonds: X-ray crystal structure of the first dibismuth complex containing a planar M2(μ-η2:η2-Bi2) unit.J. Am. Chem. Soc. 1991; 113: 9880-9882Google Scholar Its formation hints at redoxchemistry being generally crucial for the generation of lanthanide bismuth complexes. Importantly, due to their unfavorable reduction potentials, an analogous soluble divalent precursor reagent is not available for the highly anisotropic metals Tb and Dy, which are prevalent in molecular magnetism owing to their large magnetic anisotropy.37Woen D.H. Evans W.J. Chapter 293. Expanding the +2 oxidation state of the rare-earth metals, uranium, and thorium in molecular complexes.in: Bünzli J.-C.G. Pecharsky V.K. Handbook on the Physics and Chemistry of Rare Earths. Elsevier, 2016: 337-394Google Scholar In addition, the construction of Bi–Bi bonded compounds containing single or multiple bonds via direct reductive coupling of organobismuth compounds (BiR3, BiR2X, BiRX2, and BiCl3) is possible in solution.38Balázs L. Breunig H.J. Organometallic compounds with Sb–Sb or Bi–Bi bonds.Coord. Chem. Rev. 2004; 248: 603-621Google Scholar The complexes [K(THF)4]2[Cp∗2Ln2Bi6], 1-Ln, were synthesized by mixing Cp∗2Ln(BPh4) (Ln = Tb, Dy)39Demir S. Zadrozny J.M. Nippe M. Long J.R. Exchange coupling and magnetic blocking in bipyrimidyl radical-bridged dilanthanide complexes.J. Am. Chem. Soc. 2012; 134: 18546-18549Google Scholar and triphenylbismuth in THF and subsequent reduction with potassium graphite at 45°C (Figure 1; Tables S1 and S2). The addition of KC8 generates highly reducing species that reduce BiIII to Bi−I, enabling the formation of the cluster complexes 1-Ln. The byproducts are hexane-soluble Cp∗2LnPh(THF), 2-Ln (Figure S1; Tables S3 and S4) and poorly soluble KBPh4, which precipitates along with graphite. Diffusion of diethyl ether into THF solutions of the products at −35°C afforded crystals of 1-Tb and 1-Dy suitable for X-ray analysis (Figure 1; Tables S1 and S2). The formation and stabilization of an unexpected cyclo-Bi66− unit is supported by observations made in organobismuth chemistry. Organobismuth compounds with non-bulky substituents can rearrange to give flexible Bi homocycles, with equilibria between rings of different size or polymers in solution.38Balázs L. Breunig H.J. Organometallic compounds with Sb–Sb or Bi–Bi bonds.Coord. Chem. Rev. 2004; 248: 603-621Google Scholar,40Breunig H.J. Rösler R. Lork E. The first organobismuth rings: (RBi)3 and (RBi)4, R=(Me3Si)2CH.Angew. Chem. Int. Ed. Engl. 1998; 37: 3175-3177Google Scholar These compounds are the first examples of a cyclic Bi hexamer in an organometallic complex with any metal. The closest structural moiety that contains six bismuth ions is an icosahedral intermetalloid cluster containing nickel ions.33Goicoechea J.M. Hull M.W. Sevov S.C. Heteroatomic deltahedral clusters: synthesis and structures of closo-[Bi3Ni4(CO)6]3−, closo-[Bi4Ni4(CO)6]2−, the open cluster [Bi3Ni6(CO)9]3−, and the intermetalloid closo-[Nix@{Bi6Ni6(CO)8}]4–.J. Am. Chem. Soc. 2007; 129: 7885-7893Google Scholar Complexes 1-Tb and 1-Dy are isostructural and crystallize in the monoclinic space group P21/n. As is shown in Figure 1, the two LnIII centers are bridged by a Bi66− Zintl unit with the chair confirmation observed for cyclohexane, with the metal centers forming a distorted cube. Each LnIII center is coordinated by one Cp∗ ligand, with a Ln–Cp∗ ring centroid distance of 2.338(1) and 2.365(1) Å for 1-Tb and 1-Dy, respectively, and has three close Bi neighbors (see Figure 1). The edges of the Ln2Bi6 cube exhibit similar lengths. The Bi–Bi distances of 3.029(1)–3.042(1) Å and 3.027(1)–3.036(1) Å for 1-Tb and 1-Dy, respectively, are significantly longer than multiple Bi–Bi bonds (2.82–2.87 Å), and are comparable with Bi–Bi single bonds (>2.99 Å).41Jones J.S. Pan B. Gabbaï F.P. Group 15 metal-metal bonds.Molecular Metal-Metal Bonds. 2015; : 519-558https://doi.org/10.1002/9783527673353.ch15Google Scholar This observation suggests that the linkages between the Bi centers in 1-Ln may be described as single bonds, as would be expected stereochemically given the chair conformation of the Bi66− unit. The Ln–Bi distances are 3.055(1)–3.070(1) and 3.042(1)–3.060(1) Å for 1-Tb and 1-Dy, respectively, approximately 0.2 Å shorter than the 3.287 Å Sm–Bi bonds.28Evans W.J. Gonzales S.L. Ziller J.W. Organosamarium-mediated synthesis of bismuth-bismuth bonds: X-ray crystal structure of the first dibismuth complex containing a planar M2(μ-η2:η2-Bi2) unit.J. Am. Chem. Soc. 1991; 113: 9880-9882Google Scholar This difference may be explained by three factors. First, the shorter Ln–Bi bonds are a direct result of the smaller radii of the TbIII and DyIII ions as compared with SmIII owing to the lanthanide contraction.42Cordero B. Gómez V. Platero-Prats A.E. Revés M. Echeverría J. Cremades E. Barragán F. Alvarez S. Covalent radii revisited.Dalton Trans. 2008; : 2832-2838Google Scholar Second, the Bi unit in the Sm complex has a higher bond order, and the greater electron density localized in multiply bonded Bi units leads to relatively weaker donating ability to Ln centers, in contrast with the situation in 1-Ln. Third, the TbIII and DyIII ions in 1-Ln are hexacoordinate, allowing the lanthanides closer to the bismuth core than may be possible in the dinuclear Sm complex, which features an eight-coordinate SmIII ion. The Ln–Bi distances are shorter than the sum of the covalent radii of Ln and Bi, 3.42 and 3.40 Å for Tb and Dy, respectively.42Cordero B. Gómez V. Platero-Prats A.E. Revés M. Echeverría J. Cremades E. Barragán F. Alvarez S. Covalent radii revisited.Dalton Trans. 2008; : 2832-2838Google Scholar This shortness indicates significant bonding interactions between Ln and Bi ions and possibly signals strong covalency (although unlikely involving the 4f-orbitals). Indeed, a few organometallic and intermetalloid endohedral lanthanide compounds are inferred to involve increased covalency of the lanthanide centers when supported with donor ligands that consist of heavy main group elements.20Chen S.-M. Xiong J. Zhang Y.-Q. Ma F. Sun H.-L. Wang B.-W. et al.Dysprosium complexes bearing unsupported DyIII–GeII/SnII metal-metal bonds as single-ion magnets.Chem. Commun. (Camb). 2019; 55: 8250-8253Google Scholar,32Lips F. Hołyńska M. Clérac R. Linne U. Schellenberg I. Pöttgen R. et al.Doped semimetal clusters: ternary, intermetalloid anions [[email protected]7Bi7]4– and [[email protected]4Bi9]4– (Ln = La, Ce) with adjustable magnetic properties.J. Am. Chem. Soc. 2012; 134: 1181-1191Google Scholar For example, calculations on [[email protected]4Bi9]4− (Ln = La, Ce) indicated a delocalization of the free electron pair on one Bi site to the empty dz2-orbital of the Ln center.32Lips F. Hołyńska M. Clérac R. Linne U. Schellenberg I. Pöttgen R. et al.Doped semimetal clusters: ternary, intermetalloid anions [[email protected]7Bi7]4– and [[email protected]4Bi9]4– (Ln = La, Ce) with adjustable magnetic properties.J. Am. Chem. Soc. 2012; 134: 1181-1191Google Scholar The Ln2Bi6 core is compressed along the body diagonal between the two Ln centers, with distances of 4.043(1) and 4.034(1) Å between Tb and Dy centers, respectively, compared with an average distance of 5.632(1) and 5.617(1) Å between the corresponding diagonally opposite Bi centers. The Bi–Ln–Bi angles range from 101.02(2)°–102.19(2)° and 101.06(2)°–102.45(2)° for 1-Tb and 1-Dy, respectively, larger than the 90° angle for an ideal cube. The Ln2Bi6

HWOA: A hybrid whale optimization algorithm with a novel local minima avoidance method for multi-level thresholding color image segmentation

Abstract: Traditional methods to address color image segmentation work efficiently for bi-level thresholding. However, for multi-level thresholding, traditional methods suffer from time complexity that increases exponentially with the increasing number of threshold levels. To overcome this problem, in this paper, a new approach is proposed to tackle multi-threshold color image segmentation by employing the Otsu method as an objective function. This approach is based on a hybrid of the whale optimization algorithm (WOA) with a novel method called the local minima avoidance method (LMAM), abbreviated as HWOA. LMAM avoids local minima by updating the whale either within the search space of the problem or between two whales selected randomly from the population-based on a certain probability. HWOA is validated on ten color images taken from the Berkeley University Dataset by measuring the objective values, peak signal-to-noise ratio (PSNR), structural similarity index (SSIM), features similarity index (FSIM), and CPU time, and compared with a number of the well-known robust meta-heuristic algorithms: the sine–cosine algorithm (SCA), WOA, modified salp swarm algorithm (MSSA), improved marine predators algorithm (IMPA), modified Cuckoo Search (CS) using McCulloch’s algorithm (CSMC), and equilibrium optimizer (EO). The experimental results show that HWOA is superior to all the other algorithms in terms of PSNR, FSIM, and objective values, and is competitive in terms of SSIM.

Highlights on Advancing Frontiers in Tissue Engineering

Abstract: The field of tissue engineering continues to advance, sometimes in exponential leaps forward, but also sometimes at a rate that does not fulfill the promise that the field imagined a few decades ago. This review is in part a catalog of success in an effort to inform the process of innovation. Tissue engineering has recruited new technologies and developed new methods for engineering tissue constructs that can be used to mitigate or model disease states for study. Key to this antecedent statement is that the scientific effort must be anchored in the needs of a disease state and be working toward a functional product in regenerative medicine. It is this focus on the wildly important ideas coupled with partnered research efforts within both academia and industry that have shown most translational potential. The field continues to thrive and among the most important recent developments are the use of three-dimensional bioprinting, organ-on-a-chip, and induced pluripotent stem cell technologies that warrant special attention. Developments in the aforementioned areas as well as future directions are highlighted in this article. Although several early efforts have not come to fruition, there are good examples of commercial profitability that merit continued investment in tissue engineering. Impact statement Tissue engineering led to the development of new methods for regenerative medicine and disease models. Among the most important recent developments in tissue engineering are the use of three-dimensional bioprinting, organ-on-a-chip, and induced pluripotent stem cell technologies. These technologies and an understanding of them will have impact on the success of tissue engineering and its translation to regenerative medicine. Continued investment in tissue engineering will yield products and therapeutics, with both commercial importance and simultaneous disease mitigation.

Definitions and methods to estimate regional land carbon fluxes for the second phase of the REgional Carbon Cycle Assessment and Processes Project (RECCAP-2)

Abstract: Abstract. Regional land carbon budgets provide insights into the spatial distribution of the land uptake of atmospheric carbon dioxide and can be used to evaluate carbon cycle models and to define baselines for land-based additional mitigation efforts. The scientific community has been involved in providing observation-based estimates of regional carbon budgets either by downscaling atmospheric CO2 observations into surface fluxes with atmospheric inversions, by using inventories of carbon stock changes in terrestrial ecosystems, by upscaling local field observations such as flux towers with gridded climate and remote sensing fields, or by integrating data-driven or process-oriented terrestrial carbon cycle models. The first coordinated attempt to collect regional carbon budgets for nine regions covering the entire globe in the RECCAP-1 project has delivered estimates for the decade 2000–2009, but these budgets were not comparable between regions due to different definitions and component fluxes being reported or omitted. The recent recognition of lateral fluxes of carbon by human activities and rivers that connect CO2 uptake in one area with its release in another also requires better definitions and protocols to reach harmonized regional budgets that can be summed up to a globe scale and compared with the atmospheric CO2 growth rate and inversion results. In this study, using the international initiative RECCAP-2 coordinated by the Global Carbon Project, which aims to be an update to regional carbon budgets over the last 2 decades based on observations for 10 regions covering the globe with a better harmonization than the precursor project, we provide recommendations for using atmospheric inversion results to match bottom-up carbon accounting and models, and we define the different component fluxes of the net land atmosphere carbon exchange that should be reported by each research group in charge of each region. Special attention is given to lateral fluxes, inland water fluxes, and land use fluxes.

A National Study to Assess Validity and Psychometrics of the Short Kessler Psychological Distress Scale (K6)

Abstract: This study aimed to test the validity and reliability of the Kessler Psychological Distress Scale-6 (K6) with a nationally representative clinical sample with various mental health disorders. The c...

Microstructure and durability performance of sustainable cementitious composites containing high-volume regenerative biosilica

Abstract: To promote diatom-based biofuel productions in clean energy, this paper explores the potential of using biosilica as a renewable and regenerative byproduct from diatom-based biofuel production in cementitious materials. High-purity diatomite (DE), a biosilica model compound, is selected to investigate the microstructure and durability performance of diatom-based cementitious composites. The replacement of portland cement with 30 wt.% DE significantly enhances the resistance to leaching, reduces the rapid chloride permeability, but increases the drying shrinkage at early ages. The microstructure of DE-containing matrix is refined due to the lime-silica reaction, and the interfacial transition zone of DE-containing concrete is densified. Overall, the DE-induced microstructural changes enhance the durability performance of DE-containing cementitious composites, which in turn demonstrates the feasibility of using biosilica as a sustainable cement substitute. The use of biosilica from diatom-based biofuel production can potentially reduce the CO2 emissions of carbon-intensive concrete production and promote the development of clean energy.

Material consumption and environmental impact of wind turbines in the USA and globally

Abstract: Wind power is one of the fastest-growing energy in the world. Its contribution to global electricity generation should increase from 5 to 30% in 2050. With the increasing number of wind farms, we need to ensure that we will have enough material to meet the expected global capacity growth without creating new environmental issues. In this work, we estimated the material demand for wind turbines in the USA and the rest of the world and compared those values with the expected production until 2050. Based on the annual capacity installation, we quantified the carbon footprint and cumulative energy demand associated with the material production. Cement demand in 2032-2036 could be twice as much as the current amount used for wind turbines and pipeline construction in the USA. Compared to 2018, the USA steel demand in 2033 will increase by 511% (from 853 to 5215 kt). Rare earth elements (REEs) demand in the USA will increase by 254%-815% in 2033 (from 0.33 to 1.16-3 kt) compared to 2018. In the rest of the world, REEs demand will be 38% of the Chinese production in 2050. In 2050, the carbon footprint for materials required for wind turbines globally will be 9.3 times lower than the CO2 emitted currently from coal power plants in the USA. It is important to evaluate the potential impact of large-scale deployment of wind energy to avoid as much as possible creating new issues related to material scarcity, which could increase the carbon footprint of future electricity production.

Aqueous zinc ion batteries based on sodium vanadate electrode materials with long lifespan and high energy density

Abstract: We have prepared Na 7 V 7.6 O 20 ·4H 2 O (NVO) nanobelts by a facile hydrothermal route. The assembled NVO/Zn batteries deliver a capacity of 309.4 mA h g −1 at 0.3 A g −1 and maintain excellent cycling stability after 10 000 cycles at 10 A g −1 .

Gentrifying Neighborhoods, Gentrifying Schools? An Emerging Typology of School Changes in a Gentrifying Urban School District:

Abstract: An increasing number of central cities across the U.S. are experiencing a growth in white middle-class population, which is associated with gentrification in historically disinvested and racially s...