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Single-chain heteropolymers transport protons selectively and rapidly 期刊论文
NATURE, 2020, 577 (7789) : 216-+
作者:  Jiang, Tao;  Hall, Aaron;  Eres, Marco;  Hemmatian, Zahra;  Qiao, Baofu;  Zhou, Yun;  Ruan, Zhiyuan;  Couse, Andrew D.;  Heller, William T.;  Huang, Haiyan;  de la Cruz, Monica Olvera;  Rolandi, Marco;  Xu, Ting
收藏  |  浏览/下载:20/0  |  提交时间:2020/07/03

Precise protein sequencing and folding are believed to generate the structure and chemical diversity of natural channels(1,2), both of which are essential to synthetically achieve proton transport performance comparable to that seen in natural systems. Geometrically defined channels have been fabricated using peptides, DNAs, carbon nanotubes, sequence-defined polymers and organic frameworks(3-13). However, none of these channels rivals the performance observed in their natural counterparts. Here we show that without forming an atomically structured channel, four-monomer-based random heteropolymers (RHPs)(14) can mimic membrane proteins and exhibit selective proton transport across lipid bilayers at a rate similar to those of natural proton channels. Statistical control over the monomer distribution in an RHP leads to segmental heterogeneity in hydrophobicity, which facilitates the insertion of single RHPs into the lipid bilayers. It also results in bilayer-spanning segments containing polar monomers that promote the formation of hydrogen-bonded chains(15,16) for proton transport. Our study demonstrates the importance of the adaptability that is enabled by statistical similarity among RHP chains and of the modularity provided by the chemical diversity of monomers, to achieve uniform behaviour in heterogeneous systems. Our results also validate statistical randomness as an unexplored approach to realize protein-like behaviour at the single-polymer-chain level in a predictable manner.


  
Millennial-scale hydroclimate control of tropical soil carbon storage 期刊论文
NATURE, 2020, 581 (7806) : 63-+
作者:  Lam, Tommy Tsan-Yuk;  Jia, Na;  Zhang, Ya-Wei;  Shum, Marcus Ho-Hin;  Jiang, Jia-Fu;  Zhu, Hua-Chen;  Tong, Yi-Gang;  Shi, Yong-Xia;  Ni, Xue-Bing;  Liao, Yun-Shi;  Li, Wen-Juan;  Jiang, Bao-Gui;  Wei, Wei;  Yuan, Ting-Ting;  Zheng, Kui;  Cui, Xiao-Ming;  Li, Jie;  Pei, Guang-Qian
收藏  |  浏览/下载:62/0  |  提交时间:2020/05/13

Over the past 18,000 years, the residence time and amount of soil carbon stored in the Ganges-Brahmaputra basin have been controlled by the intensity of Indian Summer Monsoon rainfall, with greater carbon destabilization during wetter, warmer conditions.


The storage of organic carbon in the terrestrial biosphere directly affects atmospheric concentrations of carbon dioxide over a wide range of timescales. Within the terrestrial biosphere, the magnitude of carbon storage can vary in response to environmental perturbations such as changing temperature or hydroclimate(1), potentially generating feedback on the atmospheric inventory of carbon dioxide. Although temperature controls the storage of soil organic carbon at mid and high latitudes(2,3), hydroclimate may be the dominant driver of soil carbon persistence in the tropics(4,5)  however, the sensitivity of tropical soil carbon turnover to large-scale hydroclimate variability remains poorly understood. Here we show that changes in Indian Summer Monsoon rainfall have controlled the residence time of soil carbon in the Ganges-Brahmaputra basin over the past 18,000 years. Comparison of radiocarbon ages of bulk organic carbon and terrestrial higher-plant biomarkers with co-located palaeohydrological records(6) reveals a negative relationship between monsoon rainfall and soil organic carbon stocks on a millennial timescale. Across the deglaciation period, a depletion of basin-wide soil carbon stocks was triggered by increasing rainfall and associated enhanced soil respiration rates. Our results suggest that future hydroclimate changes in tropical regions are likely to accelerate soil carbon destabilization, further increasing atmospheric carbon dioxide concentrations.


  
Molecular tuning of CO2-to-ethylene conversion 期刊论文
NATURE, 2020, 577 (7791) : 509-+
作者:  Li, Fengwang;  39;Brien, Colin P.
收藏  |  浏览/下载:27/0  |  提交时间:2020/07/03

The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of energy produced by intermittent renewable sources(1). However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CO2RR) remains a challenge(2). Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity(3-5), and this has recently been explored for the reaction on copper by controlling morphology(6), grain boundaries(7), facets(8), oxidation state(9) and dopants(10). Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 milliamperes per square centimetre in the best catalyst reported so far(9)), resulting in a low energy efficiency. Here we present a molecular tuning strategy-the functionalization of the surface of electrocatalysts with organic molecules-that stabilizes intermediates for more selective CO2RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived by electro-dimerization of arylpyridiniums(11), adsorbed on copper. We find that the adhered molecules improve the stabilization of an '  atop-bound'  CO intermediate (that is, an intermediate bound to a single copper atom), thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO2RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 milliamperes per square centimetre in a liquid-electrolyte flow cell in a neutral medium. We report stable ethylene electrosynthesis for 190 hours in a system based on a membrane-electrode assembly that provides a full-cell energy efficiency of 20 per cent. We anticipate that this may be generalized to enable molecular strategies to complement heterogeneous catalysts by stabilizing intermediates through local molecular tuning.


Electrocatalytic reduction of CO2 over copper can be made highly selective by '  tuning'  the copper surface with adsorbed organic molecules to stabilize intermediates for carbon-based fuels such as ethylene


  
Confinement of atomically defined metal halide sheets in a metal-organic framework 期刊论文
NATURE, 2020, 577 (7788) : 64-+
作者:  Gonzalez, Miguel I.;  Turkiewicz, Ari B.;  Darago, Lucy E.;  Oktawiec, Julia;  Bustillo, Karen;  Grandjean, Fernande;  Long, Gary J.;  Long, Jeffrey R.
收藏  |  浏览/下载:25/0  |  提交时间:2020/07/03

The size-dependent and shape-dependent characteristics that distinguish nanoscale materials from bulk solids arise from constraining the dimensionality of an inorganic structure(1-3). As a consequence, many studies have focused on rationally shaping these materials to influence and enhance their optical, electronic, magnetic and catalytic properties(4-6). Although a select number of stable clusters can typically be synthesized within the nanoscale regime for a specific composition, isolating clusters of a predetermined size and shape remains a challenge, especially for those derived from two-dimensional materials. Here we realize a multidentate coordination environment in a metal-organic framework to stabilize discrete inorganic clusters within a porous crystalline support. We show confined growth of atomically defined nickel(ii) bromide, nickel(ii) chloride, cobalt(ii) chloride and iron(ii) chloride sheets through the peripheral coordination of six chelating bipyridine linkers. Notably, confinement within the framework defines the structure and composition of these sheets and facilitates their precise characterization by crystallography. Each metal(ii) halide sheet represents a fragment excised from a single layer of the bulk solid structure, and structures obtained at different precursor loadings enable observation of successive stages of sheet assembly. Finally, the isolated sheets exhibit magnetic behaviours distinct from those of the bulk metal halides, including the isolation of ferromagnetically coupled large-spin ground states through the elimination of long-range, interlayer magnetic ordering. Overall, these results demonstrate that the pore environment of a metal-organic framework can be designed to afford precise control over the size, structure and spatial arrangement of inorganic clusters.


  
The first dinosaur egg was soft 期刊论文
NATURE, 2020
作者:  Rodstrom, Karin E. J.;  Kiper, Aytug K.;  Zhang, Wei;  Rinne, Susanne;  Pike, Ashley C. W.;  Goldstein, Matthias;  Conrad, Linus J.;  Delbeck, Martina;  Hahn, Michael G.;  Meier, Heinrich;  Platzk, Magdalena;  Quigley, Andrew;  Speedman, David;  Shrestha, Leela;  Mukhopadhyay, Shubhashish M. M.
收藏  |  浏览/下载:70/0  |  提交时间:2020/07/03

Molecular analyses of newly discovered, embryo-bearing ornithischian and sauropod dinosaur eggs suggest that the ancestral dinosaur egg was soft-shelled, and that hard-shelled eggs evolved independently at least three times in the major dinosaur lineages.


Calcified eggshells protect developing embryos against environmental stress and contribute to reproductive success(1). As modern crocodilians and birds lay hard-shelled eggs, this eggshell type has been inferred for non-avian dinosaurs. Known dinosaur eggshells are characterized by an innermost membrane, an overlying protein matrix containing calcite, and an outermost waxy cuticle(2-7). The calcitic eggshell consists of one or more ultrastructural layers that differ markedly among the three major dinosaur clades, as do the configurations of respiratory pores. So far, only hadrosaurid, a few sauropodomorph and tetanuran eggshells have been discovered  the paucity of the fossil record and the lack of intermediate eggshell types challenge efforts to homologize eggshell structures across all dinosaurs(8-18). Here we present mineralogical, organochemical and ultrastructural evidence for an originally non-biomineralized, soft-shelled nature of exceptionally preserved ornithischianProtoceratopsand basal sauropodomorphMussauruseggs. Statistical evaluation of in situ Raman spectra obtained for a representative set of hard- and soft-shelled, fossil and extant diapsid eggshells clusters the originally organic but secondarily phosphatizedProtoceratopsand the organicMussauruseggshells with soft, non-biomineralized eggshells. Histology corroborates the organic composition of these soft-shelled dinosaur eggs, revealing a stratified arrangement resembling turtle soft eggshell. Through an ancestral-state reconstruction of composition and ultrastructure, we compare eggshells fromProtoceratopsandMussauruswith those from other diapsids, revealing that the first dinosaur egg was soft-shelled. The calcified, hard-shelled dinosaur egg evolved independently at least three times throughout the Mesozoic era, explaining the bias towards eggshells of derived dinosaurs in the fossil record.


  
Accurate compound-specific C-14 dating of archaeological pottery vessels 期刊论文
NATURE, 2020, 580 (7804) : 506-+
作者:  Yin, Yafei;  Lu, J. Yuyang;  Zhang, Xuechun;  Shao, Wen;  Xu, Yanhui;  Li, Pan;  Hong, Yantao;  Cui, Li;  Shan, Ge;  Tian, Bin;  Zhang, Qiangfeng Cliff;  Shen, Xiaohua
收藏  |  浏览/下载:35/0  |  提交时间:2020/05/13

Pottery is one of the most commonly recovered artefacts from archaeological sites. Despite more than a century of relative dating based on typology and seriation(1), accurate dating of pottery using the radiocarbon dating method has proven extremely challenging owing to the limited survival of organic temper and unreliability of visible residues(2-4). Here we report a method to directly date archaeological pottery based on accelerator mass spectrometry analysis of C-14 in absorbed food residues using palmitic (C-16:0) and stearic (C-18:0) fatty acids purified by preparative gas chromatography(5-8). We present accurate compound-specific radiocarbon determinations of lipids extracted from pottery vessels, which were rigorously evaluated by comparison with dendrochronological dates(9,10) and inclusion in site and regional chronologies that contained previously determined radiocarbon dates on other materials(11-15). Notably, the compound-specific dates from each of the C-16:0 and C-18:0 fatty acids in pottery vessels provide an internal quality control of the results(6) and are entirely compatible with dates for other commonly dated materials. Accurate radiocarbon dating of pottery vessels can reveal: (1) the period of use of pottery  (2) the antiquity of organic residues, including when specific foodstuffs were exploited  (3) the chronology of sites in the absence of traditionally datable materials  and (4) direct verification of pottery typochronologies. Here we used the method to date the exploitation of dairy and carcass products in Neolithic vessels from Britain, Anatolia, central and western Europe, and Saharan Africa.


Using lipid residues absorbed in potsherds, the ages of pottery from various archaeological sites are determined and validated using sites for which the dates are well known from other methods.


  
Automated synthesis on a hub-and-spoke system 期刊论文
NATURE, 2020, 579 (7799) : 346-348
作者:  Bae-Jump, Victoria L.;  Levine, Douglas A.
收藏  |  浏览/下载:16/0  |  提交时间:2020/07/03

A non-linear platform for flow chemistry.


Organic compounds can be synthesized in a continuous flow of solutions, but the need to balance mass flow across multiple reactors complicates the development of such systems. A new platform for flow chemistry addresses this issue.


  
Two-dimensional halide perovskite lateral epitaxial heterostructures 期刊论文
NATURE, 2020, 580 (7805) : 614-+
作者:  Cabrita, Rita;  Lauss, Martin;  Sanna, Adriana;  Donia, Marco;  Larsen, Mathilde;  Mitra, Shamik;  Johansson, Iva;  Phung, Bengt;  Harbst, Katja;  Vallon-Christersson, Johan;  van Schoiack, Alison;  Lovgren, Kristina;  Warren, Sarah;  Jirstrom, Karin;  Olsson, Hakan;  Pietras, Kristian;  Ingvar, Christian;  Isaksson, Karolin
收藏  |  浏览/下载:47/0  |  提交时间:2020/07/03

Epitaxial heterostructures based on oxide perovskites and III-V, II-VI and transition metal dichalcogenide semiconductors form the foundation of modern electronics and optoelectronics(1-7). Halide perovskites-an emerging family of tunable semiconductors with desirable properties-are attractive for applications such as solution-processed solar cells, light-emitting diodes, detectors and lasers(8-15). Their inherently soft crystal lattice allows greater tolerance to lattice mismatch, making them promising for heterostructure formation and semiconductor integration(16,17). Atomically sharp epitaxial interfaces are necessary to improve performance and for device miniaturization. However, epitaxial growth of atomically sharp heterostructures of halide perovskites has not yet been achieved, owing to their high intrinsic ion mobility, which leads to interdiffusion and large junction widths(18-21), and owing to their poor chemical stability, which leads to decomposition of prior layers during the fabrication of subsequent layers. Therefore, understanding the origins of this instability and identifying effective approaches to suppress ion diffusion are of great importance(22-26). Here we report an effective strategy to substantially inhibit in-plane ion diffusion in two-dimensional halide perovskites by incorporating rigid pi-conjugated organic ligands. We demonstrate highly stable and tunable lateral epitaxial heterostructures, multiheterostructures and superlattices. Near-atomically sharp interfaces and epitaxial growth are revealed by low-dose aberration-corrected high-resolution transmission electron microscopy. Molecular dynamics simulations confirm the reduced heterostructure disorder and larger vacancy formation energies of the two-dimensional perovskites in the presence of conjugated ligands. These findings provide insights into the immobilization and stabilization of halide perovskite semiconductors and demonstrate a materials platform for complex and molecularly thin superlattices, devices and integrated circuits.


An epitaxial growth strategy that improves the stability of two-dimensional halide perovskites by inhibiting ion diffusion in their heterostructures using rigid pi-conjugated ligands is demonstrated, and shows near-atomically sharp interfaces.


  
Recycling and metabolic flexibility dictate life in the lower oceanic crust 期刊论文
NATURE, 2020, 579 (7798) : 250-+
作者:  Zhou, Peng;  Yang, Xing-Lou;  Wang, Xian-Guang;  Hu, Ben;  Zhang, Lei;  Zhang, Wei;  Si, Hao-Rui;  Zhu, Yan;  Li, Bei;  Huang, Chao-Lin;  Chen, Hui-Dong;  Chen, Jing;  Luo, Yun;  Guo, Hua;  Jiang, Ren-Di;  Liu, Mei-Qin;  Chen, Ying;  Shen, Xu-Rui;  Wang, Xi;  Zheng, Xiao-Shuang;  Zhao, Kai;  Chen, Quan-Jiao;  Deng, Fei;  Liu, Lin-Lin;  Yan, Bing;  Zhan, Fa-Xian;  Wang, Yan-Yi;  Xiao, Geng-Fu;  Shi, Zheng-Li
收藏  |  浏览/下载:62/0  |  提交时间:2020/05/13

The lithified lower oceanic crust is one of Earth'  s last biological frontiers as it is difficult to access. It is challenging for microbiota that live in marine subsurface sediments or igneous basement to obtain sufficient carbon resources and energy to support growth(1-3) or to meet basal power requirements(4) during periods of resource scarcity. Here we show how limited and unpredictable sources of carbon and energy dictate survival strategies used by low-biomass microbial communities that live 10-750 m below the seafloor at Atlantis Bank, Indian Ocean, where Earth'  s lower crust is exposed at the seafloor. Assays of enzyme activities, lipid biomarkers, marker genes and microscopy indicate heterogeneously distributed and viable biomass with ultralow cell densities (fewer than 2,000 cells per cm(3)). Expression of genes involved in unexpected heterotrophic processes includes those with a role in the degradation of polyaromatic hydrocarbons, use of polyhydroxyalkanoates as carbon-storage molecules and recycling of amino acids to produce compounds that can participate in redox reactions and energy production. Our study provides insights into how microorganisms in the plutonic crust are able to survive within fractures or porous substrates by coupling sources of energy to organic and inorganic carbon resources that are probably delivered through the circulation of subseafloor fluids or seawater.


  
Layered nanocomposites by shear-flow-induced alignment of nanosheets 期刊论文
NATURE, 2020, 580 (7802) : 210-+
作者:  Rollie, Clare;  Chevallereau, Anne;  Watson, Bridget N. J.;  Chyou, Te-yuan;  Fradet, Olivier;  McLeod, Isobel;  Fineran, Peter C.;  Brown, Chris M.;  Gandon, Sylvain;  Westra, Edze R.
收藏  |  浏览/下载:61/0  |  提交时间:2020/07/03

Layered nanocomposites fabricated using a continuous and scalable process achieve properties exceeding those of natural nacre, the result of stiffened matrix polymer chains confined between highly aligned nanosheets.


Biological materials, such as bones, teeth and mollusc shells, are well known for their excellent strength, modulus and toughness(1-3). Such properties are attributed to the elaborate layered microstructure of inorganic reinforcing nanofillers, especially two-dimensional nanosheets or nanoplatelets, within a ductile organic matrix(4-6). Inspired by these biological structures, several assembly strategies-including layer-by-layer(4,7,8), casting(9,10), vacuum filtration(11-13) and use of magnetic fields(14,15)-have been used to develop layered nanocomposites. However, how to produce ultrastrong layered nanocomposites in a universal, viable and scalable manner remains an open issue. Here we present a strategy to produce nanocomposites with highly ordered layered structures using shear-flow-induced alignment of two-dimensional nanosheets at an immiscible hydrogel/oil interface. For example, nanocomposites based on nanosheets of graphene oxide and clay exhibit a tensile strength of up to 1,215 +/- 80 megapascals and a Young'  s modulus of 198.8 +/- 6.5 gigapascals, which are 9.0 and 2.8 times higher, respectively, than those of natural nacre (mother of pearl). When nanosheets of clay are used, the toughness of the resulting nanocomposite can reach 36.7 +/- 3.0 megajoules per cubic metre, which is 20.4 times higher than that of natural nacre  meanwhile, the tensile strength is 1,195 +/- 60 megapascals. Quantitative analysis indicates that the well aligned nanosheets form a critical interphase, and this results in the observed mechanical properties. We consider that our strategy, which could be readily extended to align a variety of two-dimensional nanofillers, could be applied to a wide range of structural composites and lead to the development of high-performance composites.