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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:9/0  |  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:25/0  |  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:13/0  |  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


  
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:37/0  |  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.


  
Automated radial synthesis of organic molecules 期刊论文
NATURE, 2020, 579 (7799) : 379-+
作者:  van den Brink, Susanne C.;  Alemany, Anna;  van Batenburg, Vincent;  Moris, Naomi;  Blotenburg, Marloes;  Vivie, Judith;  Baillie-Johnson, Peter;  Nichols, Jennifer;  Sonnen, Katharina F.;  Martinez Arias, Alfonso;  van Oudenaarden, Alexander
收藏  |  浏览/下载:16/0  |  提交时间:2020/07/03

An automated synthesis instrument comprising a series of continuous flow modules that are radially arranged around a central switching station can achieve both linear and convergent syntheses.


Automated synthesis platforms accelerate and simplify the preparation of molecules by removing the physical barriers to organic synthesis. This provides unrestricted access to biopolymers and small molecules via reproducible and directly comparable chemical processes. Current automated multistep syntheses rely on either iterative(1-4) or linear processes(5-9), and require compromises in terms of versatility and the use of equipment. Here we report an approach towards the automated synthesis of small molecules, based on a series of continuous flow modules that are radially arranged around a central switching station. Using this approach, concise volumes can be exposed to any reaction conditions required for a desired transformation. Sequential, non-simultaneous reactions can be combined to perform multistep processes, enabling the use of variable flow rates, reuse of reactors under different conditions, and the storage of intermediates. This fully automated instrument is capable of both linear and convergent syntheses and does not require manual reconfiguration between different processes. The capabilities of this approach are demonstrated by performing optimizations and multistep syntheses of targets, varying concentrations via inline dilutions, exploring several strategies for the multistep synthesis of the anticonvulsant drug rufinamide(10), synthesizing eighteen compounds of two derivative libraries that are prepared using different reaction pathways and chemistries, and using the same reagents to perform metallaphotoredox carbon-nitrogen cross-couplings(11) in a photochemical module-all without instrument reconfiguration.


  
Actinide 2-metallabiphenylenes that satisfy Huckel's rule 期刊论文
NATURE, 2020, 578 (7796) : 563-+
作者:  Achar, Yathish Jagadheesh;  Adhil, Mohamood;  Choudhary, Ramveer;  Gilbert, Nick;  Foiani, Marco
收藏  |  浏览/下载:8/0  |  提交时间:2020/07/03

Aromaticity and antiaromaticity, as defined by Huckel'  s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene(1-3)-a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) pi-electron system have so far been associated only with organic compounds(4,5). In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead(6). Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn-Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f(2) electrons with the carbon-containing ligand.


The synthesis of uranium- and thorium-containing metallabiphenylenes demonstrates the ability of the actinides to stabilize aromatic/antiaromatic structures where transition metals have failed.


  
Gram-scale bottom-up flash graphene synthesis 期刊论文
NATURE, 2020, 577 (7792) : 647-651
作者:  Long, Haizhen;  Zhang, Liwei;  Lv, Mengjie;  Wen, Zengqi;  Zhang, Wenhao;  Chen, Xiulan;  Zhang, Peitao;  Li, Tongqing;  Chang, Luyuan;  Jin, Caiwei;  Wu, Guozhao;  Wang, Xi;  Yang, Fuquan;  Pei, Jianfeng;  Chen, Ping;  Margueron, Raphael;  Deng, Haiteng;  Zhu, Mingzhao;  Li, Guohong
收藏  |  浏览/下载:14/0  |  提交时间:2020/07/03

Most bulk-scale graphene is produced by a top-down approach, exfoliating graphite, which often requires large amounts of solvent with high-energy mixing, shearing, sonication or electrochemical treatment(1-3). Although chemical oxidation of graphite to graphene oxide promotes exfoliation, it requires harsh oxidants and leaves the graphene with a defective perforated structure after the subsequent reduction step(3,4). Bottom-up synthesis of high-quality graphene is often restricted to ultrasmall amounts if performed by chemical vapour deposition or advanced synthetic organic methods, or it provides a defect-ridden structure if carried out in bulk solution(4-6). Here we show that flash Joule heating of inexpensive carbon sources-such as coal, petroleum coke, biochar, carbon black, discarded food, rubber tyres and mixed plastic waste-can afford gram-scale quantities of graphene in less than one second. The product, named flash graphene (FG) after the process used to produce it, shows turbostratic arrangement (that is, little order) between the stacked graphene layers. FG synthesis uses no furnace and no solvents or reactive gases. Yields depend on the carbon content of the source  when using a high-carbon source, such as carbon black, anthracitic coal or calcined coke, yields can range from 80 to 90 per cent with carbon purity greater than 99 per cent. No purification steps are necessary. Raman spectroscopy analysis shows a low-intensity or absent D band for FG, indicating that FG has among the lowest defect concentrations reported so far for graphene, and confirms the turbostratic stacking of FG, which is clearly distinguished from turbostratic graphite. The disordered orientation of FG layers facilitates its rapid exfoliation upon mixing during composite formation. The electric energy cost for FG synthesis is only about 7.2 kilojoules per gram, which could render FG suitable for use in bulk composites of plastic, metals, plywood, concrete and other building materials.


Flash Joule heating of inexpensive carbon sources is used to produce gram-scale quantities of high-quality graphene in under a second, without the need for a furnace, solvents or reactive gases.


  
Redox-switchable carboranes for uranium capture and release 期刊论文
NATURE, 2020, 577 (7792) : 652-+
作者:  Marques, Joao C.;  Li, Meng;  Schaak, Diane;  Robson, Drew N.;  Li, Jennifer M.
收藏  |  浏览/下载:31/0  |  提交时间:2020/07/03

The uranyl ion (UO22+  U(vi) oxidation state) is the most common form of uranium found in terrestrial and aquatic environments and is a central component in nuclear fuel processing and waste remediation efforts. Uranyl capture from either seawater or nuclear waste has been well studied and typically relies on extremely strong chelating/binding affinities to UO22+ using chelating polymers(1,2), porous inorganic(3-5) or carbon-based(6,7) materials, as well as homogeneous(8) compounds. By contrast, the controlled release of uranyl after capture is less established and can be difficult, expensive or destructive to the initial material(2,9). Here we show how harnessing the redox-switchable chelating and donating properties of an ortho-substituted closo-carborane (1,2-(Ph2PO)(2)-1,2-C2B10H10) cluster molecule can lead to the controlled chemical or electrochemical capture and release of UO22+ in monophasic (organic) or biphasic (organic/aqueous) model solvent systems. This is achieved by taking advantage of the increase in the ligand bite angle when the closo-carborane is reduced to the nido-carborane, resulting in C-C bond rupture and cage opening. The use of electrochemical methods for uranyl capture and release may complement existing sorbent and processing systems.


Redox-switchable chelation is demonstrated for a carborane cluster molecule, leading to controlled chemical or electrochemical capture and release of uranyl in monophasic or biphasic model solvent systems.


  
An orbital water-ice cycle on comet 67P from colour changes 期刊论文
NATURE, 2020, 578 (7793) : 49-+
作者:  Oh, Myoung Hwan;  Cho, Min Gee;  Chung, Dong Young;  Park, Inchul;  Kwon, Youngwook Paul;  Ophus, Colin;  Kim, Dokyoon;  Kim, Min Gyu;  Jeong, Beomgyun;  Gu, X. Wendy;  Jo, Jinwoung;  Yoo, Ji Mun;  Hong, Jaeyoung;  McMains, Sara;  Kang, Kisuk;  Sung, Yung-Eun;  Alivisatos, A. Paul;  Hyeon, Taeghwan
收藏  |  浏览/下载:52/0  |  提交时间:2020/07/03

Solar heating of a cometary surface provides the energy necessary to sustain gaseous activity, through which dust is removed(1,2). In this dynamical environment, both the coma(3,4) and the nucleus(5,6) evolve during the orbit, changing their physical and compositional properties. The environment around an active nucleus is populated by dust grains with complex and variegated shapes(7), lifted and diffused by gases freed from the sublimation of surface ices(8,9). The visible colour of dust particles is highly variable: carbonaceous organic material-rich grains(10) appear red while magnesium silicate-rich(11,12) and water-ice-rich(13,14) grains appear blue, with some dependence on grain size distribution, viewing geometry, activity level and comet family type. We know that local colour changes are associated with grain size variations, such as in the bluer jets made of submicrometre grains on comet Hale-Bopp(15) or in the fragmented grains in the coma(16) of C/1999 S4 (LINEAR). Apart from grain size, composition also influences the coma'  s colour response, because transparent volatiles can introduce a substantial blueing in scattered light, as observed in the dust particles ejected after the collision of the Deep Impact probe with comet 9P/Tempel 1(17). Here we report observations of two opposite seasonal colour cycles in the coma and on the surface of comet 67P/Churyumov-Gerasimenko through its perihelion passage(18). Spectral analysis indicates an enrichment of submicrometre grains made of organic material and amorphous carbon in the coma, causing reddening during the passage. At the same time, the progressive removal of dust from the nucleus causes the exposure of more pristine and bluish icy layers on the surface. Far from the Sun, we find that the abundance of water ice on the nucleus is reduced owing to redeposition of dust and dehydration of the surface layer while the coma becomes less red.