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Hydrothermal (NN)-N-15-N-15 abundances constrain the origins of mantle nitrogen 期刊论文
NATURE, 2020, 580 (7803) : 367-+
作者:  Zhao, Steven;  Jang, Cholsoon;  Liu, Joyce;  Uehara, Kahealani;  Gilbert, Michael;  Izzo, Luke;  Zeng, Xianfeng;  Trefely, Sophie;  Fernandez, Sully;  Carrer, Alessandro;  Miller, Katelyn D.;  Schug, Zachary T.;  Snyder, Nathaniel W.;  Gade, Terence P.;  Titchenell, Paul M.;  Rabinowitz, Joshua D.;  Wellen, Kathryn E.
收藏  |  浏览/下载:14/0  |  提交时间:2020/05/13

Nitrogen is the main constituent of the Earth'  s atmosphere, but its provenance in the Earth'  s mantle remains uncertain. The relative contribution of primordial nitrogen inherited during the Earth'  s accretion versus that subducted from the Earth'  s surface is unclear(1-6). Here we show that the mantle may have retained remnants of such primordial nitrogen. We use the rare (NN)-N-15-N-15 isotopologue of N-2 as a new tracer of air contamination in volcanic gas effusions. By constraining air contamination in gases from Iceland, Eifel (Germany) and Yellowstone (USA), we derive estimates of mantle delta N-15 (the fractional difference in N-15/N-14 from air), N-2/Ar-36 and N-2/He-3. Our results show that negative delta N-15 values observed in gases, previously regarded as indicating a mantle origin for nitrogen(7-10), in fact represent dominantly air-derived N-2 that experienced N-15/N-14 fractionation in hydrothermal systems. Using two-component mixing models to correct for this effect, the (NN)-N-15-N-15 data allow extrapolations that characterize mantle endmember delta N-15, N-2/Ar-36 and N-2/He-3 values. We show that the Eifel region has slightly increased delta N-15 and N-2/Ar-36 values relative to estimates for the convective mantle provided by mid-ocean-ridge basalts(11), consistent with subducted nitrogen being added to the mantle source. In contrast, we find that whereas the Yellowstone plume has delta N-15 values substantially greater than that of the convective mantle, resembling surface components(12-15), its N-2/Ar-36 and N-2/He-3 ratios are indistinguishable from those of the convective mantle. This observation raises the possibility that the plume hosts a primordial component. We provide a test of the subduction hypothesis with a two-box model, describing the evolution of mantle and surface nitrogen through geological time. We show that the effect of subduction on the deep nitrogen cycle may be less important than has been suggested by previous investigations. We propose instead that high mid-ocean-ridge basalt and plume delta N-15 values may both be dominantly primordial features.


  
The fate of carbon in a mature forest under carbon dioxide enrichment 期刊论文
NATURE, 2020, 580 (7802) : 227-+
作者:  Sun, P. Z.;  Yang, Q.;  Kuang, W. J.;  Stebunov, Y. V.;  Xiong, W. Q.;  Yu, J.;  Nair, R. R.;  Katsnelson, M. I.;  Yuan, S. J.;  Grigorieva, I. V.;  Lozada-Hidalgo, M.;  Wang, F. C.;  Geim, A. K.
收藏  |  浏览/下载:70/0  |  提交时间:2020/05/13

Carbon dioxide enrichment of a mature forest resulted in the emission of the excess carbon back into the atmosphere via enhanced ecosystem respiration, suggesting that mature forests may be limited in their capacity to mitigate climate change.


Atmospheric carbon dioxide enrichment (eCO(2)) can enhance plant carbon uptake and growth(1-5), thereby providing an important negative feedback to climate change by slowing the rate of increase of the atmospheric CO2 concentration(6). Although evidence gathered from young aggrading forests has generally indicated a strong CO2 fertilization effect on biomass growth(3-5), it is unclear whether mature forests respond to eCO(2) in a similar way. In mature trees and forest stands(7-10), photosynthetic uptake has been found to increase under eCO(2) without any apparent accompanying growth response, leaving the fate of additional carbon fixed under eCO(2) unclear(4,5,7-11). Here using data from the first ecosystem-scale Free-Air CO2 Enrichment (FACE) experiment in a mature forest, we constructed a comprehensive ecosystem carbon budget to track the fate of carbon as the forest responded to four years of eCO(2) exposure. We show that, although the eCO(2) treatment of +150 parts per million (+38 per cent) above ambient levels induced a 12 per cent (+247 grams of carbon per square metre per year) increase in carbon uptake through gross primary production, this additional carbon uptake did not lead to increased carbon sequestration at the ecosystem level. Instead, the majority of the extra carbon was emitted back into the atmosphere via several respiratory fluxes, with increased soil respiration alone accounting for half of the total uptake surplus. Our results call into question the predominant thinking that the capacity of forests to act as carbon sinks will be generally enhanced under eCO(2), and challenge the efficacy of climate mitigation strategies that rely on ubiquitous CO2 fertilization as a driver of increased carbon sinks in global forests.


  
Spin-cooling of the motion of a trapped diamond 期刊论文
NATURE, 2020
作者:  Auer, Thomas O.;  Khallaf, Mohammed A.;  Silbering, Ana F.;  Zappia, Giovanna;  Ellis, Kaitlyn;  Alvarez-Ocana, Raquel;  Arguello, J. Roman;  Hansson, Bill S.;  Jefferis, Gregory S. X. E.;  Caron, Sophie J. C.;  Knaden, Markus;  Benton, Richard
收藏  |  浏览/下载:15/0  |  提交时间:2020/07/03

Coupling the spins of many nitrogen-vacancy centres in a trapped diamond to its orientation produces a spin-dependent torque and spin-cooling of the motion of the diamond.


Observing and controlling macroscopic quantum systems has long been a driving force in quantum physics research. In particular, strong coupling between individual quantum systems and mechanical oscillators is being actively studied(1-3). Whereas both read-out of mechanical motion using coherent control of spin systems(4-9) and single-spin read-out using pristine oscillators have been demonstrated(10,11), temperature control of the motion of a macroscopic object using long-lived electronic spins has not been reported. Here we observe a spin-dependent torque and spin-cooling of the motion of a trapped microdiamond. Using a combination of microwave and laser excitation enables the spins of nitrogen-vacancy centres to act on the diamond orientation and to cool the diamond libration via a dynamical back-action. Furthermore, by driving the system in the nonlinear regime, we demonstrate bistability and self-sustained coherent oscillations stimulated by spin-mechanical coupling, which offers the prospect of spin-driven generation of non-classical states of motion. Such a levitating diamond-held in position by electric field gradients under vacuum-can operate as a '  compass'  with controlled dissipation and has potential use in high-precision torque sensing(12-14), emulation of the spin-boson problem(15) and probing of quantum phase transitions(16). In the single-spin limit(17) and using ultrapure nanoscale diamonds, it could allow quantum non-demolition read-out of the spin of nitrogen-vacancy centres at ambient conditions, deterministic entanglement between distant individual spins(18) and matter-wave interferometry(16,19,20).


  
Late-stage oxidative C(sp(3))-H methylation 期刊论文
NATURE, 2020, 580 (7805) : 621-+
作者:  Fessler, Evelyn;  Eckl, Eva-Maria;  Schmitt, Sabine;  Mancilla, Igor Alves;  Meyer-Bender, Matthias F.;  Hanf, Monika;  Philippou-Massier, Julia;  Krebs, Stefan;  Zischka, Hans;  Jae, Lucas T.
收藏  |  浏览/下载:46/0  |  提交时间:2020/07/03

Frequently referred to as the '  magic methyl effect'  , the installation of methyl groups-especially adjacent (alpha) to heteroatoms-has been shown to dramatically increase the potency of biologically active molecules(1-3). However, existing methylation methods show limited scope and have not been demonstrated in complex settings(1). Here we report a regioselective and chemoselective oxidative C(sp(3))-H methylation method that is compatible with late-stage functionalization of drug scaffolds and natural products. This combines a highly site-selective and chemoselective C-H hydroxylation with a mild, functional-group-tolerant methylation. Using a small-molecule manganese catalyst, Mn(CF3PDP), at low loading (at a substrate/catalyst ratio of 200) affords targeted C-H hydroxylation on heterocyclic cores, while preserving electron-neutral and electron-rich aryls. Fluorine- or Lewis-acid-assisted formation of reactive iminium or oxonium intermediates enables the use of a mildly nucleophilic organoaluminium methylating reagent that preserves other electrophilic functionalities on the substrate. We show this late-stage C(sp(3))-H methylation on 41 substrates housing 16 different medicinally important cores that include electron-rich aryls, heterocycles, carbonyls and amines. Eighteen pharmacologically relevant molecules with competing sites-including drugs (for example, tedizolid) and natural products-are methylated site-selectively at the most electron rich, least sterically hindered position. We demonstrate the syntheses of two magic methyl substrates-an inverse agonist for the nuclear receptor RORc and an antagonist of the sphingosine-1-phosphate receptor-1-via late-stage methylation from the drug or its advanced precursor. We also show a remote methylation of the B-ring carbocycle of an abiraterone analogue. The ability to methylate such complex molecules at late stages will reduce synthetic effort and thereby expedite broader exploration of the magic methyl effect in pursuit of new small-molecule therapeutics and chemical probes.


A manganese-catalysed oxidative C(sp(3))-H methylation method allows a methyl group to be selectively installed into medicinally important heterocycles, providing a way to improve pharmaceuticals and better understand the '  magic methyl effect'  .


  
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.


  
Premature mortality related to United States cross-state air pollution 期刊论文
NATURE, 2020, 578 (7794) : 261-+
作者:  Helmink, Beth A.;  Reddy, Sangeetha M.;  Gao, Jianjun;  Zhang, Shaojun;  Basar, Rafet;  Thakur, Rohit;  Yizhak, Keren;  Sade-Feldman, Moshe;  Blando, Jorge;  Han, Guangchun;  Gopalakrishnan, Vancheswaran;  Xi, Yuanxin;  Zhao, Hao;  Amaria, Rodabe N.;  Tawbi, Hussein A.;  Cogdill, Alex P.;  Liu, Wenbin;  LeBleu, Valerie S.;  Kugeratski, Fernanda G.;  Patel, Sapna;  Davies, Michael A.;  Hwu, Patrick;  Lee, Jeffrey E.;  Gershenwald, Jeffrey E.;  Lucci, Anthony;  Arora, Reetakshi;  Woodman, Scott;  Keung, Emily Z.;  Gaudreau, Pierre-Olivier;  Reuben, Alexandre;  Spencer, Christine N.;  Burton, Elizabeth M.;  Haydu, Lauren E.;  Lazar, Alexander J.;  Zapassodi, Roberta;  Hudgens, Courtney W.;  Ledesma, Deborah A.;  Ong, SuFey;  Bailey, Michael;  Warren, Sarah;  Rao, Disha;  Krijgsman, Oscar;  Rozeman, Elisa A.;  Peeper, Daniel;  Blank, Christian U.;  Schumacher, Ton N.;  Butterfield, Lisa H.;  Zelazowska, Monika A.;  McBride, Kevin M.;  Kalluri, Raghu;  Allison, James;  Petitprez, Florent;  Fridman, Wolf Herman;  Sautes-Fridman, Catherine;  Hacohen, Nir;  Rezvani, Katayoun;  Sharma, Padmanee;  Tetzlaff, Michael T.;  Wang, Linghua;  Wargo, Jennifer A.
收藏  |  浏览/下载:37/0  |  提交时间:2020/05/13

Outdoor air pollution adversely affects human health and is estimated to be responsible for five to ten per cent of the total annual premature mortality in the contiguous United States(1-3). Combustion emissions from a variety of sources, such as power generation or road traffic, make a large contribution to harmful air pollutants such as ozone and fine particulate matter (PM2.5)(4). Efforts to mitigate air pollution have focused mainly on the relationship between local emission sources and local air quality(2). Air quality can also be affected by distant emission sources, however, including emissions from neighbouring federal states(5,6). This cross-state exchange of pollution poses additional regulatory challenges. Here we quantify the exchange of air pollution among the contiguous United States, and assess its impact on premature mortality that is linked to increased human exposure to PM2.5 and ozone from seven emission sectors for 2005 to 2018. On average, we find that 41 to 53 per cent of air-quality-related premature mortality resulting from a state'  s emissions occurs outside that state. We also find variations in the cross-state contributions of different emission sectors and chemical species to premature mortality, and changes in these variations over time. Emissions from electric power generation have the greatest cross-state impacts as a fraction of their total impacts, whereas commercial/residential emissions have the smallest. However, reductions in emissions from electric power generation since 2005 have meant that, by 2018, cross-state premature mortality associated with the commercial/residential sector was twice that associated with power generation. In terms of the chemical species emitted, nitrogen oxides and sulfur dioxide emissions caused the most cross-state premature deaths in 2005, but by 2018 primary PM2.5 emissions led to cross-state premature deaths equal to three times those associated with sulfur dioxide emissions. These reported shifts in emission sectors and emission species that contribute to premature mortality may help to guide improvements to air quality in the contiguous United States.


  
Limits on gas impermeability of graphene 期刊论文
NATURE, 2020, 579 (7798) : 229-+
作者:  Pagano, Justin K.;  Xie, Jing;  Erickson, Karla A.;  Cope, Stephen K.;  Scott, Brian L.;  Wu, Ruilian;  Waterman, Rory;  Morris, David E.;  Yang, Ping;  Gagliardi, Laura;  Kiplinger, Jaqueline L.
收藏  |  浏览/下载:27/0  |  提交时间:2020/07/03

Despite being only one-atom thick, defect-free graphene is considered to be completely impermeable to all gases and liquids(1-10). This conclusion is based on theory(3-8) and supported by experiments(1,9,10) that could not detect gas permeation through micrometre-size membranes within a detection limit of 10(5) to 10(6) atoms per second. Here, using small monocrystalline containers tightly sealed with graphene, we show that defect-free graphene is impermeable with an accuracy of eight to nine orders of magnitude higher than in the previous experiments. We are capable of discerning (but did not observe) permeation of just a few helium atoms per hour, and this detection limit is also valid for all other gases tested (neon, nitrogen, oxygen, argon, krypton and xenon), except for hydrogen. Hydrogen shows noticeable permeation, even though its molecule is larger than helium and should experience a higher energy barrier. This puzzling observation is attributed to a two-stage process that involves dissociation of molecular hydrogen at catalytically active graphene ripples, followed by adsorbed atoms flipping to the other side of the graphene sheet with a relatively low activation energy of about 1.0 electronvolt, a value close to that previously reported for proton transport(11,12). Our work provides a key reference for the impermeability of two-dimensional materials and is important from a fundamental perspective and for their potential applications.


  
CPS1 maintains pyrimidine pools and DNA synthesis in KRAS/LKB1-mutant lung cancer cells 期刊论文
NATURE, 2017, 546 (7656) : 168-+
作者:  Kim, Jiyeon;  Hu, Zeping;  Cai, Ling;  Li, Kailong;  Choi, Eunhee;  Faubert, Brandon;  Bezwada, Divya;  Rodriguez-Canales, Jaime;  Villalobos, Pamela;  Lin, Yu-Fen;  Ni, Min;  Huffman, Kenneth E.;  Girard, Luc;  Byers, Lauren A.;  Unsal-Kacmaz, Keziban;  Pena, Christopher G.;  Heymach, John V.;  Wauters, Els;  Vansteenkiste, Johan;  Castrillon, Diego H.;  Chen, Benjamin P. C.;  Wistuba, Ignacio;  Lambrechts, Diether;  Xu, Jian;  Minna, John D.;  DeBerardinis, Ralph J.
收藏  |  浏览/下载:13/0  |  提交时间:2019/04/09