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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:12/0  |  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


  
Accelerated discovery of CO2 electrocatalysts using active machine learning 期刊论文
NATURE, 2020, 581 (7807) : 178-+
作者:  Lan, Jun;  Ge, Jiwan;  Yu, Jinfang;  Shan, Sisi;  Zhou, Huan;  Fan, Shilong;  Zhang, Qi;  Shi, Xuanling;  Wang, Qisheng;  Zhang, Linqi;  Wang, Xinquan
收藏  |  浏览/下载:89/0  |  提交时间:2020/07/03

The rapid increase in global energy demand and the need to replace carbon dioxide (CO2)-emitting fossil fuels with renewable sources have driven interest in chemical storage of intermittent solar and wind energy(1,2). Particularly attractive is the electrochemical reduction of CO2 to chemical feedstocks, which uses both CO2 and renewable energy(3-8). Copper has been the predominant electrocatalyst for this reaction when aiming for more valuable multi-carbon products(9-16), and process improvements have been particularly notable when targeting ethylene. However, the energy efficiency and productivity (current density) achieved so far still fall below the values required to produce ethylene at cost-competitive prices. Here we describe Cu-Al electrocatalysts, identified using density functional theory calculations in combination with active machine learning, that efficiently reduce CO2 to ethylene with the highest Faradaic efficiency reported so far. This Faradaic efficiency of over 80 per cent (compared to about 66 per cent for pure Cu) is achieved at a current density of 400 milliamperes per square centimetre (at 1.5 volts versus a reversible hydrogen electrode) and a cathodic-side (half-cell) ethylene power conversion efficiency of 55 +/- 2 per cent at 150 milliamperes per square centimetre. We perform computational studies that suggest that the Cu-Al alloys provide multiple sites and surface orientations with near-optimal CO binding for both efficient and selective CO2 reduction(17). Furthermore, in situ X-ray absorption measurements reveal that Cu and Al enable a favourable Cu coordination environment that enhances C-C dimerization. These findings illustrate the value of computation and machine learning in guiding the experimental exploration of multi-metallic systems that go beyond the limitations of conventional single-metal electrocatalysts.


  
Structure and mechanism of human diacylglycerol O-acyltransferase 1 期刊论文
NATURE, 2020, 581 (7808) : 329-+
作者:  Wu, Fan;  Zhao, Su;  Yu, Bin;  Chen, Yan-Mei;  Wang, Wen;  Song, Zhi-Gang;  Hu, Yi;  Tao, Zhao-Wu;  Tian, Jun-Hua;  Pei, Yuan-Yuan;  Yuan, Ming-Li;  Zhang, Yu-Ling;  Dai, Fa-Hui;  Liu, Yi;  Wang, Qi-Min;  Zheng, Jiao-Jiao;  Xu, Lin;  Holmes, Edward C.;  Zhang, Yong-Zhen
收藏  |  浏览/下载:24/0  |  提交时间:2020/07/03

The structure of human diacylglycerol O-acyltransferase 1, a membrane protein that synthesizes triacylglycerides, is solved with cryo-electron microscopy, providing insight into its function and mechanism of enzymatic activity.


Diacylglycerol O-acyltransferase 1 (DGAT1) synthesizes triacylglycerides and is required for dietary fat absorption and fat storage in humans(1). DGAT1 belongs to the membrane-bound O-acyltransferase (MBOAT) superfamily, members of which are found in all kingdoms of life and are involved in the acylation of lipids and proteins(2,3). How human DGAT1 and other mammalian members of the MBOAT family recognize their substrates and catalyse their reactions is unknown. The absence of three-dimensional structures also hampers rational targeting of DGAT1 for therapeutic purposes. Here we present the cryo-electron microscopy structure of human DGAT1 in complex with an oleoyl-CoA substrate. Each DGAT1 protomer has nine transmembrane helices, eight of which form a conserved structural fold that we name the MBOAT fold. The MBOAT fold in DGAT1 forms a hollow chamber in the membrane that encloses highly conserved catalytic residues. The chamber has separate entrances for each of the two substrates, fatty acyl-CoA and diacylglycerol. DGAT1 can exist as either a homodimer or a homotetramer and the two forms have similar enzymatic activity. The N terminus of DGAT1 interacts with the neighbouring protomer and these interactions are required for enzymatic activity.


  
Quantum entanglement between an atom and a molecule 期刊论文
NATURE, 2020, 581 (7808) : 273-+
作者:  Trisos, Christopher H.;  Merow, Cory;  Pigot, Alex L.
收藏  |  浏览/下载:30/0  |  提交时间:2020/07/03

Conventional information processors convert information between different physical carriers for processing, storage and transmission. It seems plausible that quantum information will also be held by different physical carriers in applications such as tests of fundamental physics, quantum enhanced sensors and quantum information processing. Quantum controlled molecules, in particular, could transduce quantum information across a wide range of quantum bit (qubit) frequencies-from a few kilohertz for transitions within the same rotational manifold(1), a few gigahertz for hyperfine transitions, a few terahertz for rotational transitions, to hundreds of terahertz for fundamental and overtone vibrational and electronic transitions-possibly all within the same molecule. Here we demonstrate entanglement between the rotational states of a (CaH+)-Ca-40 molecular ion and the internal states of a Ca-40(+) atomic ion(2). We extend methods used in quantum logic spectroscopy(1,3) for pure-state initialization, laser manipulation and state readout of the molecular ion. The quantum coherence of the Coulomb coupled motion between the atomic and molecular ions enables subsequent entangling manipulations. The qubit addressed in the molecule has a frequency of either 13.4 kilohertz(1) or 855 gigahertz(3), highlighting the versatility of molecular qubits. Our work demonstrates how molecules can transduce quantum information between qubits with different frequencies to enable hybrid quantum systems. We anticipate that our method of quantum control and measurement of molecules will find applications in quantum information science, quantum sensors, fundamental and applied physics, and controlled quantum chemistry.


Quantum entanglement is realized between rotational levels of a molecular ion with energy differences spanning several orders of magnitude and long-lived internal states of a single atomic ion.


  
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.


  
Control and single-shot readout of an ion embedded in a nanophotonic cavity 期刊论文
NATURE, 2020, 580 (7802) : 201-+
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:22/0  |  提交时间:2020/07/03

Distributing entanglement over long distances using optical networks is an intriguing macroscopic quantum phenomenon with applications in quantum systems for advanced computing and secure communication(1,2). Building quantum networks requires scalable quantum light-matter interfaces(1) based on atoms(3), ions(4) or other optically addressable qubits. Solid-state emitters(5), such as quantum dots and defects in diamond or silicon carbide(6-10), have emerged as promising candidates for such interfaces. So far, it has not been possible to scale up these systems, motivating the development of alternative platforms. A central challenge is identifying emitters that exhibit coherent optical and spin transitions while coupled to photonic cavities that enhance the light-matter interaction and channel emission into optical fibres. Rare-earth ions in crystals are known to have highly coherent 4f-4f optical and spin transitions suited to quantum storage and transduction(11-15), but only recently have single rare-earth ions been isolated(16,17) and coupled to nanocavities(18,19). The crucial next steps towards using single rare-earth ions for quantum networks are realizing long spin coherence and single-shot readout in photonic resonators. Here we demonstrate spin initialization, coherent optical and spin manipulation, and high-fidelity single-shot optical readout of the hyperfine spin state of single Yb-171(3+) ions coupled to a nanophotonic cavity fabricated in an yttrium orthovanadate host crystal. These ions have optical and spin transitions that are first-order insensitive to magnetic field fluctuations, enabling optical linewidths of less than one megahertz and spin coherence times exceeding thirty milliseconds for cavity-coupled ions, even at temperatures greater than one kelvin. The cavity-enhanced optical emission rate facilitates efficient spin initialization and single-shot readout with conditional fidelity greater than 95 per cent. These results showcase a solid-state platform based on single coherent rare-earth ions for the future quantum internet.


Single ytterbium ion qubits in nanophotonic cavities have long coherence times and can be optically read out in a single shot, establishing them as excellent candidates for optical quantum networks.


  
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.


  
In situ NMR metrology reveals reaction mechanisms in redox flow batteries 期刊论文
NATURE, 2020, 579 (7798) : 224-+
作者:  Ma, Jianfei;  You, Xin;  Sun, Shan;  Wang, Xiaoxiao;  Qin, Song;  Sui, Sen-Fang
收藏  |  浏览/下载:12/0  |  提交时间:2020/07/03

Large-scale energy storage is becoming increasingly critical to balancing renewable energy production and consumption(1). Organic redox flow batteries, made from inexpensive and sustainable redox-active materials, are promising storage technologies that are cheaper and less environmentally hazardous than vanadium-based batteries, but they have shorter lifetimes and lower energy density(2,3). Thus, fundamental insight at the molecular level is required to improve performance(4,5). Here we report two in situ nuclear magnetic resonance (NMR) methods of studying redox flow batteries, which are applied to two redox-active electrolytes: 2,6-dihydroxyanthraquinone (DHAQ) and 4,4 '  -((9,10-anthraquinone-2,6-diyl)dioxy) dibutyrate (DBEAQ). In the first method, we monitor the changes in the H-1 NMR shift of the liquid electrolyte as it flows out of the electrochemical cell. In the second method, we observe the changes that occur simultaneously in the positive and negative electrodes in the full electrochemical cell. Using the bulk magnetization changes (observed via the H-1 NMR shift of the water resonance) and the line broadening of the H-1 shifts of the quinone resonances as a function of the state of charge, we measure the potential differences of the two single-electron couples, identify and quantify the rate of electron transfer between the reduced and oxidized species, and determine the extent of electron delocalization of the unpaired spins over the radical anions. These NMR techniques enable electrolyte decomposition and battery self-discharge to be explored in real time, and show that DHAQ is decomposed electrochemically via a reaction that can be minimized by limiting the voltage used on charging. We foresee applications of these NMR methods in understanding a wide range of redox processes in flow and other electrochemical systems.


  
Synthesis of rare sugar isomers through site-selective epimerization 期刊论文
NATURE, 2020: 403-+
作者:  Jackson, Hartland W.;  Fischer, Jana R.;  Zanotelli, Vito R. T.;  Ali, H. Raza;  Mechera, Robert;  Soysal, Savas D.;  Moch, Holger;  Muenst, Simone;  Varga, Zsuzsanna;  Weber, Walter P.;  Bodenmiller, Bernd
收藏  |  浏览/下载:15/0  |  提交时间:2020/07/03

Glycans have diverse physiological functions, ranging from energy storage and structural integrity to cell signalling and the regulation of intracellular processes(1). Although biomass-derived carbohydrates (such as d-glucose, d-xylose and d-galactose) are extracted on commercial scales, and serve as renewable chemical feedstocks and building blocks(2,3), there are hundreds of distinct monosaccharides that typically cannot be isolated from their natural sources and must instead be prepared through multistep chemical or enzymatic syntheses(4,5). These '  rare'  sugars feature prominently in bioactive natural products and pharmaceuticals, including antiviral, antibacterial, anticancer and cardiac drugs(6,7). Here we report the preparation of rare sugar isomers directly from biomass carbohydrates through site-selective epimerization reactions. Mechanistic studies establish that these reactions proceed under kinetic control, through sequential steps of hydrogen-atom abstraction and hydrogen-atom donation mediated by two distinct catalysts. This synthetic strategy provides concise and potentially extensive access to this valuable class of natural compounds.


Various rare sugars that cannot be isolated from natural sources are synthesized using light-driven epimerization, a process which may find application in other synthetic scenarios.