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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:8/0  |  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.


  
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:26/0  |  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: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.


  
The ABC exporter IrtAB imports and reduces mycobacterial siderophores 期刊论文
NATURE, 2020, 580 (7803) : 413-+
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:13/0  |  提交时间:2020/07/03

Intracellular replication of the deadly pathogen Mycobacterium tuberculosis relies on the production of small organic molecules called siderophores that scavenge iron from host proteins(1). M. tuberculosis produces two classes of siderophore, lipid-bound mycobactin and water-soluble carboxymycobactin(2,3). Functional studies have revealed that iron-loaded carboxymycobactin is imported into the cytoplasm by the ATP binding cassette (ABC) transporter IrtAB(4), which features an additional cytoplasmic siderophore interaction domain(5). However, the predicted ABC exporter fold of IrtAB is seemingly contradictory to its import function. Here we show that membrane-reconstituted IrtAB is sufficient to import mycobactins, which are then reduced by the siderophore interaction domain to facilitate iron release. Structure determination by X-ray crystallography and cryo-electron microscopy not only confirms that IrtAB has an ABC exporter fold, but also reveals structural peculiarities at the transmembrane region of IrtAB that result in a partially collapsed inward-facing substrate-binding cavity. The siderophore interaction domain is positioned in close proximity to the inner membrane leaflet, enabling the reduction of membrane-inserted mycobactin. Enzymatic ATPase activity and in vivo growth assays show that IrtAB has a preference for mycobactin over carboxymycobactin as its substrate. Our study provides insights into an unusual ABC exporter that evolved as highly specialized siderophore-import machinery in mycobacteria.


  
Antagonistic cooperativity between crystal growth modifiers 期刊论文
NATURE, 2020, 577 (7791) : 497-+
作者:  Ma, Wenchuan;  Lutsko, James F.;  Rimer, Jeffrey D.;  Vekilov, Peter G.
收藏  |  浏览/下载:8/0  |  提交时间:2020/07/03

Inhibitor pairs that suppress the crystallization of haematin, which is a part of malaria parasites'  physiology, show unexpected antagonism due to attenuation of step pinning by kink blockers.


Ubiquitous processes in nature and the industry exploit crystallization from multicomponent environments(1-5)  however, laboratory efforts have focused on the crystallization of pure solutes(6,7) and the effects of single growth modifiers(8,9). Here we examine the molecular mechanisms employed by pairs of inhibitors in blocking the crystallization of haematin, which is a model organic compound with relevance to the physiology of malaria parasites(10,11). We use a combination of scanning probe microscopy and molecular modelling to demonstrate that inhibitor pairs, whose constituents adopt distinct mechanisms of haematin growth inhibition, kink blocking and step pinning(12,13), exhibit both synergistic and antagonistic cooperativity depending on the inhibitor combination and applied concentrations. Synergism between two crystal growth modifiers is expected, but the antagonistic cooperativity of haematin inhibitors is not reflected in current crystal growth models. We demonstrate that kink blockers reduce the line tension of step edges, which facilitates both the nucleation of crystal layers and step propagation through the gates created by step pinners. The molecular viewpoint on cooperativity between crystallization modifiers provides guidance on the pairing of modifiers in the synthesis of crystalline materials. The proposed mechanisms indicate strategies to understand and control crystallization in both natural and engineered systems, which occurs in complex multicomponent media(1-3,8,9). In a broader context, our results highlight the complexity of crystal-modifier interactions mediated by the structure and dynamics of the crystal interface.


  
How corals made rocks through the ages 期刊论文
GLOBAL CHANGE BIOLOGY, 2020, 26 (1) : 31-53
作者:  Drake, Jeana L.;  Mass, Tali;  Stolarski, Jaroslaw;  Von Euw, Stanislas;  van de Schootbrugge, Bas;  Falkowski, Paul G.
收藏  |  浏览/下载:8/0  |  提交时间:2020/02/17
amorphous calcium carbonate  aragonite  biomineralization  calcite  calicoblastic cells  corals  crystal growth  skeletal organic matrix  
Organic-mineral interfacial chemistry drives heterogeneous nucleation of Sr-rich (Ba-x, Sr1-x)SO4 from undersaturated solution 期刊论文
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2019, 116 (27) : 13221-13226
作者:  Deng, Ning;  Stack, Andrew G.;  Weber, Juliane;  Cao, Bo;  De Yoreo, James J.;  Hu, Yandi
收藏  |  浏览/下载:7/0  |  提交时间:2019/11/27
Sr-rich marine barite  organic-mineral interactions  solid solution  nucleation and growth  paleoenvironments  
Organic–mineral interfacial chemistry drives heterogeneous nucleation of Sr-rich (Bax, Sr1−x)SO4 from undersaturated solution 期刊论文
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2019, 116 (27) : 13221-13226
作者:  Ning Deng;  Andrew G. Stack;  Juliane Weber;  Bo Cao;  James J. De Yoreo;  and Yandi Hu
收藏  |  浏览/下载:6/0  |  提交时间:2019/11/27
Sr-rich marine barite  organic–mineral interactions  solid solution  nucleation and growth  paleoenvironments  
Larger Submicron Particles for Emissions With Residential Burning in Wintertime San Joaquin Valley (Fresno) than for Vehicle Combustion in Summertime South Coast Air Basin (Fontana) 期刊论文
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 2018, 123 (18) : 10526-10545
作者:  Betha, Raghu;  Russell, Lynn M.;  Chen, Chia-Li;  Liu, Jun;  Price, Derek J.;  Sanchez, Kevin J.;  Chen, Sijie;  Lee, Alex K. Y.;  Collier, Sonya C.;  Zhang, Qi;  Zhang, Xiaolu;  Cappa, Christopher D.
收藏  |  浏览/下载:16/0  |  提交时间:2019/04/09
aerosol size distribution  refractory black carbon  aerosol growth mechanisms  size-resolved organic aerosol sources  San Joaquin Valley  Southern California Air Basin  
Partitioning of soil phosphorus among arbuscular and ectomycorrhizal trees in tropical and subtropical forests 期刊论文
ECOLOGY LETTERS, 2018, 21 (5) : 713-723
作者:  Liu, Xubing;  Burslem, David F. R. P.;  Taylor, Joe D.;  Taylor, Andy F. S.;  Khoo, Eyen;  Majalap-Lee, Noreen;  Helgason, Thorunn;  Johnson, David
收藏  |  浏览/下载:8/0  |  提交时间:2019/04/09
Mycorrhizal fungi  phosphate  resource partitioning  seedling growth  soil organic phosphorus  tropical and subtropical forests