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Materials and pathways of the organic carbon cycle through time 期刊论文
NATURE GEOSCIENCE, 2020
作者:  Galvez, Matthieu E.;  Fischer, Woodward W.;  Jaccard, Samuel L.;  Eglinton, Timothy I.
收藏  |  浏览/下载:15/0  |  提交时间:2020/08/09
Synthesis and properties of free-standing monolayer amorphous carbon 期刊论文
NATURE, 2020, 577 (7789) : 199-+
作者:  Toh, Chee-Tat;  Zhang, Hongji;  Lin, Junhao;  Mayorov, Alexander S.;  Wang, Yun-Peng;  Orofeo, Carlo M.;  Ferry, Darim Badur;  Andersen, Henrik;  Kakenov, Nurbek;  Guo, Zenglong;  Abidi, Irfan Haider;  Sims, Hunter;  Suenaga, Kazu;  Pantelides, Sokrates T.;  Ozyilmaz, Barbaros
收藏  |  浏览/下载:7/0  |  提交时间:2020/07/03

Bulk amorphous materials have been studied extensively and are widely used, yet their atomic arrangement remains an open issue. Although they are generally believed to be Zachariasen continuous random networks(1), recent experimental evidence favours the competing crystallite model in the case of amorphous silicon(2-4). In two-dimensional materials, however, the corresponding questions remain unanswered. Here we report the synthesis, by laser-assisted chemical vapour deposition(5), of centimetre-scale, free-standing, continuous and stable monolayer amorphous carbon, topologically distinct from disordered graphene. Unlike in bulk materials, the structure of monolayer amorphous carbon can be determined by atomic-resolution imaging. Extensive characterization by Raman and X-ray spectroscopy and transmission electron microscopy reveals the complete absence of long-range periodicity and a threefold-coordinated structure with a wide distribution of bond lengths, bond angles, and five-, six-, seven- and eight-member rings. The ring distribution is not a Zachariasen continuous random network, but resembles the competing (nano)crystallite model(6). We construct a corresponding model that enables density-functional-theory calculations of the properties of monolayer amorphous carbon, in accordance with observations. Direct measurements confirm that it is insulating, with resistivity values similar to those of boron nitride grown by chemical vapour deposition. Free-standing monolayer amorphous carbon is surprisingly stable and deforms to a high breaking strength, without crack propagation from the point of fracture. The excellent physical properties of this stable, free-standing monolayer amorphous carbon could prove useful for permeation and diffusion barriers in applications such as magnetic recording devices and flexible electronics.


  
Global reconstruction reduces the uncertainty of oceanic nitrous oxide emissions and reveals a vigorous seasonal cycle 期刊论文
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2020, 117 (22) : 11954-11960
作者:  Yang, Simon;  Chang, Bonnie X.;  Warner, Mark J.;  Weber, Thomas S.;  Bourbonnais, Annie M.;  Santoro, Alyson E.;  Kock, Annette;  Sonnerup, Rolf E.;  Bullister, John L.;  Wilson, Samuel T.;  Bianchi, Daniele
收藏  |  浏览/下载:13/0  |  提交时间:2020/05/20
nitrous oxide  air-sea gas exchange  seasonal variability  nitrogen cycle  greenhouse gases  
Evidence for sodium-rich alkaline water in the Tagish Lake parent body and implications for amino acid synthesis and racemization 期刊论文
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2020, 117 (21) : 11217-11219
作者:  White, Lee F.;  Tait, Kimberly T.;  Langelier, Brian;  Lymer, Elizabeth A.;  Cernok, Ana;  Kizovski, Tanya V.;  Ma, Chi;  Tschauner, Oliver;  Nicklin, Richard I.
收藏  |  浏览/下载:7/0  |  提交时间:2020/05/13
Tagish Lake  framboidal magnetite  atom probe tomography  amino acid  
Large H2O solubility in dense silica and its implications for the interiors of water-rich planets 期刊论文
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2020, 117 (18) : 9747-9754
作者:  Nisr, Carole;  Chen, Huawei;  Leinenweber, Kurt;  Chizmeshya, Andrew;  Prakapenka, Vitali B.;  Prescher, Clemens;  Tkachev, Sergey N.;  Meng, Yue;  Liu, Zhenxian;  Shim, Sang-Heon
收藏  |  浏览/下载:10/0  |  提交时间:2020/05/13
silica  water  sub-Neptunes  waterworlds  exoplanets  
Structure of the human metapneumovirus polymerase phosphoprotein complex 期刊论文
NATURE, 2020, 577 (7789) : 275-+
作者:  Pan, Junhua;  Qian, Xinlei;  Lattmann, Simon;  El Sahili, Abbas;  Yeo, Tiong Han;  Jia, Huan;  Cressey, Tessa;  Ludeke, Barbara;  Noton, Sarah;  Kalocsay, Marian;  Fearns, Rachel;  Lescar, Julien
收藏  |  浏览/下载:14/0  |  提交时间:2020/07/03

Respiratory syncytial virus (RSV) and human metapneumovirus (HMPV) cause severe respiratory diseases in infants and elderly adults(1). No vaccine or effective antiviral therapy currently exists to control RSV or HMPV infections. During viral genome replication and transcription, the tetrameric phosphoprotein P serves as a crucial adaptor between the ribonucleoprotein template and the L protein, which has RNA-dependent RNA polymerase (RdRp), GDP polyribonucleotidyltransferase and cap-specific methyltransferase activities(2,3). How P interacts with L and mediates the association with the free form of N and with the ribonucleoprotein is not clear for HMPV or other major human pathogens, including the viruses that cause measles, Ebola and rabies. Here we report a cryo-electron microscopy reconstruction that shows the ring-shaped structure of the polymerase and capping domains of HMPV-L bound to a tetramer of P. The connector and methyltransferase domains of L are mobile with respect to the core. The putative priming loop that is important for the initiation of RNA synthesis is fully retracted, which leaves space in the active-site cavity for RNA elongation. P interacts extensively with the N-terminal region of L, burying more than 4,016 angstrom(2) of the molecular surface area in the interface. Two of the four helices that form the coiled-coil tetramerization domain of P, and long C-terminal extensions projecting from these two helices, wrap around the L protein in a manner similar to tentacles. The structural versatility of the four P protomers-which are largely disordered in their free state-demonstrates an example of a '  folding-upon-partner-binding'  mechanism for carrying out P adaptor functions. The structure shows that P has the potential to modulate multiple functions of L and these results should accelerate the design of specific antiviral drugs.


  
Lactonization as a general route to beta-C(sp(3))-H functionalization 期刊论文
NATURE, 2020, 577 (7792) : 656-+
作者:  Washington, Harriet A.
收藏  |  浏览/下载:17/0  |  提交时间:2020/07/03

Functionalization of the beta-C-H bonds of aliphatic acids is emerging as a valuable synthetic disconnection that complements a wide range of conjugate addition reactions(1-5). Despite efforts for beta-C-H functionalization in carbon-carbon and carbon-heteroatom bond-forming reactions, these have numerous crucial limitations, especially for industrial-scale applications, including lack of mono-selectivity, use of expensive oxidants and limited scope(6-13). Notably, the majority of these reactions are incompatible with free aliphatic acids without exogenous directing groups. Considering the challenge of developing C-H activation reactions, it is not surprising that achieving different transformations requires independent catalyst design and directing group optimizations in each case. Here we report a Pd-catalysed beta-C(sp(3))-H lactonization of aliphatic acids enabled by a mono-N-protected beta-amino acid ligand. The highly strained and reactive beta-lactone products are versatile linchpins for the mono-selective installation of diverse alkyl, alkenyl, aryl, alkynyl, fluoro, hydroxyl and amino groups at the beta position of the parent acid, thus providing a route to many carboxylic acids. The use of inexpensive tert-butyl hydrogen peroxide as the oxidant to promote the desired selective reductive elimination from the Pd(IV) centre, as well as the ease of product purification without column chromatography, render this reaction amenable to tonne-scale manufacturing.


  
poly(UG)-tailed RNAs in genome protection and epigenetic inheritance 期刊论文
NATURE, 2020, 582 (7811) : 283-+
作者:  Raj, Dipak K.;  Das Mohapatra, Alok;  Jnawali, Anup;  Zuromski, Jenna;  Jha, Ambrish;  Cham-Kpu, Gerald;  Sherman, Brett;  Rudlaff, Rachel M.;  Nixon, Christina E.;  Hilton, Nicholas;  Oleinikov, Andrew V.;  Chesnokov, Olga;  Merritt, Jordan;  Pond-Tor, Sunthorn
收藏  |  浏览/下载:19/0  |  提交时间:2020/07/03

Mobile genetic elements threaten genome integrity in all organisms. RDE-3 (also known as MUT-2) is a ribonucleotidyltransferase that is required for transposon silencing and RNA interference in Caenorhabditis elegans(1-4). When tethered to RNAs in heterologous expression systems, RDE-3 can add long stretches of alternating non-templated uridine (U) and guanosine (G) ribonucleotides to the 3 '  termini of these RNAs (designated poly(UG) or pUG tails)(5). Here we show that, in its natural context in C. elegans, RDE-3 adds pUG tails to targets of RNA interference, as well as to transposon RNAs. RNA fragments attached to pUG tails with more than 16 perfectly alternating 3 '  U and G nucleotides become gene-silencing agents. pUG tails promote gene silencing by recruiting RNA-dependent RNA polymerases, which use pUG-tailed RNAs (pUG RNAs) as templates to synthesize small interfering RNAs (siRNAs). Our results show that cycles of pUG RNA-templated siRNA synthesis and siRNA-directed pUG RNA biogenesis underlie double-stranded-RNA-directed transgenerational epigenetic inheritance in the C. elegans germline. We speculate that this pUG RNA-siRNA silencing loop enables parents to inoculate progeny against the expression of unwanted or parasitic genetic elements.


In Caenorhabditis elegans, the ribonucleotidyltransferase RDE-3 adds alternating uridine and guanosine ribonucleotides to the 3 '  termini of RNAs, a key step in RNA interference and thus epigenetic inheritance in the C. elegans germline.


  
Preparation of cyclohexene isotopologues and stereoisotopomers from benzene 期刊论文
NATURE, 2020, 581 (7808) : 288-+
作者:  Shimazaki, Yuya;  Schwartz, Ido;  Watanabe, Kenji;  Taniguchi, Takashi;  Kroner, Martin;  Imamoglu, Atac
收藏  |  浏览/下载:12/0  |  提交时间:2020/07/03

The hydrogen isotopes deuterium (D) and tritium (T) have become essential tools in chemistry, biology and medicine(1). Beyond their widespread use in spectroscopy, mass spectrometry and mechanistic and pharmacokinetic studies, there has been considerable interest in incorporating deuterium into drug molecules(1). Deutetrabenazine, a deuterated drug that is promising for the treatment of Huntington'  s disease(2), was recently approved by the United States'  Food and Drug Administration. The deuterium kinetic isotope effect, which compares the rate of a chemical reaction for a compound with that for its deuterated counterpart, can be substantial(1,3,4). The strategic replacement of hydrogen with deuterium can affect both the rate of metabolism and the distribution of metabolites for a compound(5), improving the efficacy and safety of a drug. The pharmacokinetics of a deuterated compound depends on the location(s) of deuterium. Although methods are available for deuterium incorporation at both early and late stages of the synthesis of a drug(6,7), these processes are often unselective and the stereoisotopic purity can be difficult to measure(7,8). Here we describe the preparation of stereoselectively deuterated building blocks for pharmaceutical research. As a proof of concept, we demonstrate a four-step conversion of benzene to cyclohexene with varying degrees of deuterium incorporation, via binding to a tungsten complex. Using different combinations of deuterated and proteated acid and hydride reagents, the deuterated positions on the cyclohexene ring can be controlled precisely. In total, 52 unique stereoisotopomers of cyclohexene are available, in the form of ten different isotopologues. This concept can be extended to prepare discrete stereoisotopomers of functionalized cyclohexenes. Such systematic methods for the preparation of pharmacologically active compounds as discrete stereoisotopomers could improve the pharmacological and toxicological properties of drugs and provide mechanistic information related to their distribution and metabolism in the body.


Cyclohexene isotopologues and stereoisotopomers with varying degrees of deuteration are formed by binding a tungsten complex to benzene, which facilitates the selective incorporation of deuterium into any position on the ring.


  
The architecture of the Gram-positive bacterial cell wall 期刊论文
NATURE, 2020, 582 (7811) : 294-+
作者:  Farquharson, Jamie I.;  Amelung, Falk
收藏  |  浏览/下载:25/0  |  提交时间:2020/07/03

The primary structural component of the bacterial cell wall is peptidoglycan, which is essential for viability and the synthesis of which is the target for crucial antibiotics(1,2). Peptidoglycan is a single macromolecule made of glycan chains crosslinked by peptide side branches that surrounds the cell, acting as a constraint to internal turgor(1,3). In Gram-positive bacteria, peptidoglycan is tens of nanometres thick, generally portrayed as a homogeneous structure that provides mechanical strength(4-6). Here we applied atomic force microscopy(7-12) to interrogate the morphologically distinct Staphylococcus aureus and Bacillus subtilis species, using live cells and purified peptidoglycan. The mature surface of live cells is characterized by a landscape of large (up to 60 nm in diameter), deep (up to 23 nm) pores constituting a disordered gel of peptidoglycan. The inner peptidoglycan surface, consisting of more nascent material, is much denser, with glycan strand spacing typically less than 7 nm. The inner surface architecture is location dependent  the cylinder of B. subtilis has dense circumferential orientation, while in S. aureus and division septa for both species, peptidoglycan is dense but randomly oriented. Revealing the molecular architecture of the cell envelope frames our understanding of its mechanical properties and role as the environmental interface(13,14), providing information complementary to traditional structural biology approaches.


Using high-resolution atomic force microscopy of live cells, the authors present an updated view of the cell walls of both Staphylococcus aureus and Bacillus subtilis.