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1.
Nature ; 583(7814): 66-71, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32612224

RESUMO

Dental enamel is a principal component of teeth1, and has evolved to bear large chewing forces, resist mechanical fatigue and withstand wear over decades2. Functional impairment and loss of dental enamel, caused by developmental defects or tooth decay (caries), affect health and quality of life, with associated costs to society3. Although the past decade has seen progress in our understanding of enamel formation (amelogenesis) and the functional properties of mature enamel, attempts to repair lesions in this material or to synthesize it in vitro have had limited success4-6. This is partly due to the highly hierarchical structure of enamel and additional complexities arising from chemical gradients7-9. Here we show, using atomic-scale quantitative imaging and correlative spectroscopies, that the nanoscale crystallites of hydroxylapatite (Ca5(PO4)3(OH)), which are the fundamental building blocks of enamel, comprise two nanometric layers enriched in magnesium flanking a core rich in sodium, fluoride and carbonate ions; this sandwich core is surrounded by a shell with lower concentration of substitutional defects. A mechanical model based on density functional theory calculations and X-ray diffraction data predicts that residual stresses arise because of the chemical gradients, in agreement with preferential dissolution of the crystallite core in acidic media. Furthermore, stresses may affect the mechanical resilience of enamel. The two additional layers of hierarchy suggest a possible new model for biological control over crystal growth during amelogenesis, and hint at implications for the preservation of biomarkers during tooth development.


Assuntos
Amelogênese , Esmalte Dentário/química , Ácidos/química , Cálcio/química , Carbonatos/química , Cristalização , Teoria da Densidade Funcional , Esmalte Dentário/ultraestrutura , Durapatita/química , Fluoretos/química , Humanos , Magnésio/química , Microscopia Eletrônica de Transmissão e Varredura , Sódio/química , Tomografia , Difração de Raios X
2.
Nature ; 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32690940

RESUMO

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

3.
Nano Lett ; 2020 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-32574061

RESUMO

A variety of nickel oxide compounds have long been studied for their manifestation of various correlated electron phenomena. Recently, superconductivity was observed in nanoscale infinite layer nickelate thin films of Nd0.8Sr0.2NiO2, epitaxially stabilized on SrTiO3 substrates via topotactic reduction from the perovskite precursor phase. Here, we present the synthesis and properties of PrNiO2 thin films on SrTiO3. Upon doping in Pr0.8Sr0.2NiO2, we observe superconductivity with a transition temperature of 7-12 K and robust critical current density at 2 K of 334 kA/cm2. These findings indicate that superconductivity in the infinite layer nickelates is relatively insensitive to the details of the rare earth 4f configuration. Furthermore, they motivate the exploration of a broader family of compounds based on two-dimensional NiO2 planes, which will enable systematic investigation of the superconducting and normal state properties and their underlying mechanisms.

4.
Microsc Microanal ; : 1-8, 2020 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-32501193

RESUMO

Atomic-resolution cryogenic scanning transmission electron microscopy (cryo-STEM) has provided a path to probing the microscopic nature of select low-temperature phases in quantum materials. Expanding cryo-STEM techniques to broadly tunable temperatures will give access to the rich temperature-dependent phase diagrams of these materials. With existing cryo-holders, however, variations in sample temperature significantly disrupt the thermal equilibrium of the system, resulting in large-scale sample drift. The ability to tune the temperature without negative impact on the overall instrument stability is crucial, particularly for high-resolution experiments. Here, we test a new side-entry continuously variable temperature dual-tilt cryo-holder which integrates liquid nitrogen cooling with a 6-pin micro-electromechanical system (MEMS) sample heater to overcome some of these experimental challenges. We measure consistently low drift rates of 0.3-0.4 Å/s and demonstrate atomic-resolution cryo-STEM imaging across a continuously variable temperature range from ~100 K to well above room temperature. We conduct additional drift stability measurements across several commercial sample stages and discuss implications for further developments of ultra-stable, flexible cryo-stages.

5.
Nano Lett ; 2020 Jun 09.
Artigo em Inglês | MEDLINE | ID: mdl-32484679

RESUMO

Understanding the mechanism and ultimately directing nanocrystal (NC) superlattice assembly and attachment have important implications on future advances in this emerging field. Here, we use 4D-STEM to investigate a monolayer of PbS NCs at various stages of the transformation from a hexatic assembly to a nonconnected square-like superlattice over large fields of view. Maps of nanobeam electron diffraction patterns acquired with an electron microscope pixel array detector (EMPAD) offer unprecedented detail into the 3D crystallographic alignment of the polyhedral NCs. Our analysis reveals that superlattice transformation is dominated by translation of prealigned NCs strongly coupled along the <11n>AL direction and occurs stochastically and gradually throughout single grains. We validate the generality of the proposed mechanism by examining the structure of analogous PbSe NC assemblies using conventional transmission electron microscopy and selected area electron diffraction. The experimental results presented here provide new mechanistic insights into NC self-assembly and oriented attachment.

6.
J Struct Biol ; 210(1): 107474, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-32032755

RESUMO

As interest in the role of extracellular vesicles in cell-to-cell communication has increased, so has the use of microscopy and analytical techniques to assess their formation, release, and morphology. In this study, we evaluate scanning electron microscopy (SEM) and cryo-SEM for characterizing the formation and shedding of vesicles from human breast cell lines, parental and hyaluronan synthase 3-(HAS3)-overexpressing MCF10A cells, grown directly on transmission electron microscopy (TEM) grids. While cells imaged with conventional and cryo-SEM exhibit distinct morphologies due to the sample preparation process for each technique, tubular structures protruding from the cell surfaces were observed with both approaches. For HAS3-MCF10A cells, vesicles were present along the length of membrane protrusions. Once completely shed from the cells, extracellular vesicles were characterized using nanoparticle tracking analysis (NTA) and cryo-TEM. The size distributions obtained by each technique were different not only in the range of vesicles analyzed, but also in the relative proportion of smaller-to-larger vesicles. These differences are attributed to the presence of biological debris in the media, which is difficult to differentiate from vesicles in NTA. Furthermore, we demonstrate that cryo-TEM can be used to distinguish between vesicles based on their respective surface structures, thereby providing a path to differentiating vesicle subpopulations and identifying their size distributions. Our study emphasizes the necessity of pairing several techniques to characterize extracellular vesicles.

7.
Sci Rep ; 9(1): 18537, 2019 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-31811199

RESUMO

Manipulating mosquito reproduction is a promising approach to reducing mosquito populations and the burden of diseases they carry. A thorough understanding of reproductive processes is necessary to develop such strategies, but little is known about how sperm are processed and prepared for fertilization within female mosquitoes. By employing cryo-electron microscopy for the first time to study sperm of the mosquito Aedes aegypti, we reveal that sperm shed their entire outer coat, the glycocalyx, within 24 hours of being stored in the female. Motility assays demonstrate that as their glycocalyx is shed in the female's sperm storage organs, sperm transition from a period of dormancy to rapid motility-a critical prerequisite for sperm to reach the egg. We also show that females gradually become fertile as sperm become motile, and that oviposition behavior increases sharply after females reach peak fertility. Together, these experiments demonstrate a striking coincidence of the timelines of several reproductive events in Ae. aegypti, suggesting a direct relationship between sperm modification and female reproductive capacity.

8.
ACS Nano ; 13(10): 11460-11468, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31502825

RESUMO

Periodic arrays of strongly coupled colloidal quantum dots (QDs) may enable unprecedented control of electronic band structure through manipulation of QD size, shape, composition, spacing, and assembly geometry. This includes the possibilities of precisely engineered bandgaps and charge carrier mobilities, as well as remarkable behaviors such as metal-insulator transitions, massless carriers, and topological states. However, experimental realization of these theoretically predicted electronic structures is presently limited by structural disorder. Here, we use aberration-corrected scanning transmission electron microscopy to precisely quantify the orientational disorder of epitaxially connected QD films. In spite of coherent atomic connectivity between nearest neighbor QDs, we find misalignment persists with a standard deviation of 1.9°, resulting in significant bending strain localized to the adjoining necks. We observe and quantify a range of out-of-plane particle orientations over thousands of QDs and correlate the in-plane and out-of-plane misalignments, finding QDs misoriented out-of-plane display a statistically greater misalignment with respect to their in-plane neighbors as well. Using the bond orientational order metric ψ4, we characterize the 4-fold symmetry and introduce a quantification of the local superlattice (SL) orientation. This enables direct comparison between local orientational order in the SL and atomic lattice (AL). We find significantly larger variations in the SL orientation and a statistically robust but locally highly variable correlation between the orientations of the two differently scaled lattices. Distinct AL and SL behaviors are observed about a grain boundary, with a sharp boundary in the AL orientations, but a more smooth transition in the SL, facilitated by lattice deformation between the neighboring grains. Coupling between the AL and SL is a fundamental driver of film growth, and these results suggest nontrivial underlying mechanics, implying that simplified models of epitaxial attachment may be insufficient to understand QD growth and disorder when oriented attachment and superlattice growth occur in concert.

9.
ACS Nano ; 13(8): 9457-9463, 2019 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-31310516

RESUMO

Incorporating magnetism into two-dimensional (2D) van der Waals (vdW) heterostructures is crucial for the development of functional electronic and magnetic devices. Here, we show that Nb3X8 (X = Cl, Br) is a family of 2D layered trimerized kagomé magnets that are paramagnetic at high temperatures and undergo a first-order phase transition on cooling to a singlet magnetic state. X-ray diffraction shows that a rearrangement of the vdW stacking accompanies the magnetic transition, with high- and low-temperature phases consistent with scanning transmission electron microscopy images of the end members α-Nb3Cl8 and ß-Nb3Br8. The temperature of this transition is systematically varied across the solid solution Nb3Cl8-xBrx (x = 0-8), with x = 6 having transitions near room temperature. The solid solution also varies the optical properties, which are further modulated by the phase transition. As such, they provide a platform on which to understand and exploit the interplay between dimensionality, magnetism, and optoelectronic behavior in vdW materials.

10.
Nat Commun ; 10(1): 3091, 2019 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-31300653

RESUMO

Electrochemical cells that utilize lithium and sodium anodes are under active study for their potential to enable high-energy batteries. Liquid and solid polymer electrolytes based on ether chemistry are among the most promising choices for rechargeable lithium and sodium batteries. However, uncontrolled anionic polymerization of these electrolytes at low anode potentials and oxidative degradation at working potentials of the most interesting cathode chemistries have led to a quite concession in the field that solid-state or flexible batteries based on polymer electrolytes can only be achieved in cells based on low- or moderate-voltage cathodes. Here, we show that cationic chain transfer agents can prevent degradation of ether electrolytes by arresting uncontrolled polymer growth at the anode. We also report that cathode electrolyte interphases composed of preformed anionic polymers and supramolecules provide a fundamental strategy for extending the high voltage stability of ether-based electrolytes to potentials well above conventionally accepted limits.

11.
Nano Lett ; 19(7): 4797-4803, 2019 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-31199150

RESUMO

Aliovalent doping of CdSe nanocrystals (NCs) via cation exchange processes has resulted in interesting and novel observations for the optical and electronic properties of the NCs. However, despite over a decade of study, these observations have largely gone unexplained, partially due to an inability to precisely characterize the physical properties of the doped NCs. Here, electrostatic force microscopy was used to determine the static charge on individual, cation-doped CdSe NCs in order to investigate their net charge as a function of added cations. While the NC charge was relatively insensitive to the relative amount of doped cation per NC, there was a remarkable and unexpected correlation between the average NC charge and PL intensity, for all dopant cations introduced. We conclude that the changes in PL intensity, as tracked also by changes in NC charge, are likely a consequence of changes in the NC radiative rate caused by symmetry breaking of the electronic states of the nominally spherical NC due to the Coulombic potential introduced by ionized cations.

12.
Cell ; 177(7): 1757-1770.e21, 2019 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-31056282

RESUMO

Cells bend their plasma membranes into highly curved forms to interact with the local environment, but how shape generation is regulated is not fully resolved. Here, we report a synergy between shape-generating processes in the cell interior and the external organization and composition of the cell-surface glycocalyx. Mucin biopolymers and long-chain polysaccharides within the glycocalyx can generate entropic forces that favor or disfavor the projection of spherical and finger-like extensions from the cell surface. A polymer brush model of the glycocalyx successfully predicts the effects of polymer size and cell-surface density on membrane morphologies. Specific glycocalyx compositions can also induce plasma membrane instabilities to generate more exotic undulating and pearled membrane structures and drive secretion of extracellular vesicles. Together, our results suggest a fundamental role for the glycocalyx in regulating curved membrane features that serve in communication between cells and with the extracellular matrix.


Assuntos
Forma Celular , Matriz Extracelular/metabolismo , Glicocálix/metabolismo , Glicoproteínas de Membrana/metabolismo , Mucinas/metabolismo , Animais , Linhagem Celular , Matriz Extracelular/genética , Glicocálix/genética , Cavalos , Humanos , Glicoproteínas de Membrana/genética , Mucinas/genética
13.
ACS Nano ; 13(2): 2599-2605, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30615411

RESUMO

We report measurements of current-induced torques in heterostructures of Permalloy (Py) with TaTe2, a transition-metal dichalcogenide (TMD) material possessing low crystal symmetry, and observe a torque component with Dresselhaus symmetry. We suggest that the dominant mechanism for this Dresselhaus component is not a spin-orbit torque but rather the Oersted field arising from a component of current that flows perpendicular to the applied voltage due to resistance anisotropy within the TaTe2. This type of transverse current is not present in wires made from a single uniform layer of a material with resistance anisotropy but will result whenever a material with resistance anisotropy is integrated into a heterostructure with materials having different resistivities, thereby producing a spatially nonuniform pattern of current flow. This effect will therefore influence measurements in a wide variety of heterostructures incorporating 2D TMD materials and other materials with low crystal symmetries.

14.
Sci Adv ; 4(11): eaau8131, 2018 11.
Artigo em Inglês | MEDLINE | ID: mdl-30515458

RESUMO

Electrochemical cells based on aluminum (Al) are of long-standing interest because Al is earth abundant, low cost, and chemically inert. The trivalent Al3+ ions also offer among the highest volume-specific charge storage capacities (8040 mAh cm-3), approximately four times larger than achievable for Li metal anodes. Rapid and irreversible formation of a high-electrical bandgap passivating Al2O3 oxide film on Al have, to date, frustrated all efforts to create aqueous Al-based electrochemical cells with high reversibility. Here, we investigate the interphases formed on metallic Al in contact with ionic liquid (IL)-eutectic electrolytes and find that artificial solid electrolyte interphases (ASEIs) formed spontaneously on the metal permanently transform its interfacial chemistry. The resultant IL-ASEIs are further shown to enable aqueous Al electrochemical cells with unprecedented reversibility. As an illustration of the potential benefits of these interphases, we create simple Al||MnO2 aqueous cells and report that they provide high specific energy (approximately 500 Wh/kg, based on MnO2 mass in the cathode) and intrinsic safety features required for applications.

15.
J Am Chem Soc ; 140(50): 17343-17348, 2018 12 19.
Artigo em Inglês | MEDLINE | ID: mdl-30457849

RESUMO

By combining a surfactant, an organic pore expander, a silane, and poly(ethylene glycol) (PEG), we have observed the formation of a previously unknown set of ultrasmall silica structures in aqueous solutions. At appropriate concentrations of reagents, ∼2 nm primary silica clusters arrange around surfactant micelles to form ultrasmall silica rings, which can further evolve into cage-like structures. With increasing concentration, these rings line up into segmented worm-like one-dimensional (1D) structures, an effect that can be dramatically enhanced by PEG addition. PEG adsorbed 1D striped cylinders further arrange into higher order assemblies in the form of two-dimensional (2D) sheets or three-dimensional (3D) helical structures. Results provide insights into synergies between deformable noncovalent organic molecule assemblies and covalent inorganic network formation as well as early transformation pathways from spherical soft materials into 1D, 2D, and 3D silica solution structures, hallmarks of mesoporous silica materials formation. The ultrasmall silica ring and cage structures may prove useful in nanomedicine and other nanotechnology based applications.


Assuntos
Micelas , Nanoestruturas/química , Dióxido de Silício/química , Derivados de Benzeno/química , Cetrimônio/química , Microscopia Crioeletrônica , Microscopia Eletrônica de Transmissão , Modelos Químicos , Compostos de Organossilício/química , Tamanho da Partícula , Polietilenoglicóis/química , Silanos/química , Tensoativos/química , Água/química
16.
Microsc Microanal ; 24(4): 387-395, 2018 08.
Artigo em Inglês | MEDLINE | ID: mdl-30175707

RESUMO

Layered transition metal dichalcogenides (TMDs) have attracted interest due to their promise for future electronic and optoelectronic technologies. As one approaches the two-dimensional (2D) limit, thickness and local topology can greatly influence the macroscopic properties of a material. To understand the unique behavior of TMDs it is therefore important to identify the number of atomic layers and their stacking in a sample. The goal of this work is to extract the thickness and stacking sequence of TMDs directly by matching experimentally recorded high-angle annular dark-field scanning transmission electron microscope images and convergent-beam electron diffraction (CBED) patterns to quantum mechanical, multislice scattering simulations. Advantageously, CBED approaches do not require a resolved lattice in real space and are capable of neglecting the thickness contribution of amorphous surface layers. Here we demonstrate the crystal thickness can be determined from CBED in exfoliated 1T-TaS2 and 2H-MoS2 to within a single layer for ultrathin ≲9 layers and ±1 atomic layer (or better) in thicker specimens while also revealing information about stacking order-even when the crystal structure is unresolved in real space.

17.
Nature ; 560(7718): 345-349, 2018 08.
Artigo em Inglês | MEDLINE | ID: mdl-30111789

RESUMO

Solid-liquid interfaces are important in a range of chemical, physical and biological processes1-4, but are often not fully understood owing to the lack of high-resolution characterization methods that are compatible with both solid and liquid components5. For example, the related processes of dendritic deposition of lithium metal and the formation of solid-electrolyte interphase layers6,7 are known to be key determinants of battery safety and performance in high-energy-density lithium-metal batteries. But exactly what is involved in these two processes, which occur at a solid-liquid interface, has long been debated8-11 because of the challenges of observing such interfaces directly. Here we adapt a technique that has enabled cryo-transmission electron microscopy (cryo-TEM) of hydrated specimens in biology-immobilization of liquids by rapid freezing, that is, vitrification12. By vitrifying the liquid electrolyte we preserve it and the structures at solid-liquid interfaces in lithium-metal batteries in their native state, and thus enable structural and chemical mapping of these interfaces by cryo-scanning transmission electron microscopy (cryo-STEM). We identify two dendrite types coexisting on the lithium anode, each with distinct structure and composition. One family of dendrites has an extended solid-electrolyte interphase layer, whereas the other unexpectedly consists of lithium hydride instead of lithium metal and may contribute disproportionately to loss of battery capacity. The insights into the formation of lithium dendrites that our work provides demonstrate the potential of cryogenic electron microscopy for probing nanoscale processes at intact solid-liquid interfaces in functional devices such as rechargeable batteries.

18.
Mol Microbiol ; 109(6): 812-825, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-29995992

RESUMO

The size of whole Rhodobacter sphaeroides prevents 3D visualization of centermost chromatophores in their native environment. This study combines cryo-focused ion beam milling with cryo-electron tomography to probe vesicle architecture both in situ and in 3D. Developing chromatophores are membrane-bound buds that remain in topological continuity with the cytoplasmic membrane and detach into vesicles when mature. Mature chromatophores closest to the cell wall are typically isolated vesicles, whereas centermost chromatophores are either linked to neighboring chromatophores or contain smaller, budding structures. Isolated chromatophores comprised a minority of centermost chromatophores. Connections between vesicles in growing bacteria are through ~10 nm-long, ~5 nm-wide linkers, and are thus physical rather than functional in terms of converting photons to ATP. In cells in the stationary phase, chromatophores fuse with neighboring vesicles, lose their spherical structure, and greatly increase in volume. The fusion and morphological changes seen in older bacteria are likely a consequence of the aging process, and are not representative of connectivity in healthy R. sphaeroides. Our results suggest that chromatophores can adopt either isolated or connected morphologies within a single bacterium. Revealing the organization of chromatophore vesicles throughout the cell is an important step in understanding the photosynthetic mechanisms in R. sphaeroides.


Assuntos
Cromatóforos Bacterianos/ultraestrutura , Rhodobacter sphaeroides/ultraestrutura , Membrana Celular/metabolismo , Microscopia Crioeletrônica , Tomografia com Microscopia Eletrônica , Fotossíntese/fisiologia
19.
Adv Mater ; 30(35): e1802598, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-30015987

RESUMO

Solid-state heterostructures are the cornerstone of modern electronics. To enhance the functionality and performance of integrated circuits, the spectrum of materials used in the heterostructures is being expanded by an increasing number of compounds and elements of the periodic table. While the integration of liquids and solid-liquid interfaces into such systems would allow unique and advanced functional properties and would enable integrated nanoionic circuits, solid-state heterostructures that incorporate liquids have not been considered thus far. Here solid-state heterostructures with integrated liquids are proposed, realized, and characterized, thereby opening a vast, new phase space of materials and interfaces for integrated circuits. Devices containing tens of microscopic capacitors and field-effect transistors are fabricated by using integrated patterned NaCl aqueous solutions. This work paves the way to integrated electronic circuits that include highly integrated liquids, thus yielding a wide array of novel research and application opportunities based on microscopic solid/liquid systems.

20.
Ultramicroscopy ; 191: 56-65, 2018 08.
Artigo em Inglês | MEDLINE | ID: mdl-29843097

RESUMO

Combining multiple fast image acquisitions to mitigate scan noise and drift artifacts has proven essential for picometer precision, quantitative analysis of atomic resolution scanning transmission electron microscopy (STEM) data. For very low signal-to-noise ratio (SNR) image stacks - frequently required for undistorted imaging at liquid nitrogen temperatures - image registration is particularly delicate, and standard approaches may either fail, or produce subtly specious reconstructed lattice images. We present an approach which effectively registers and averages image stacks which are challenging due to their low-SNR and propensity for unit cell misalignments. Registering all possible image pairs in a multi-image stack leads to significant information surplus. In combination with a simple physical picture of stage drift, this enables identification of incorrect image registrations, and determination of the optimal image shifts from the complete set of relative shifts. We demonstrate the effectiveness of our approach on experimental, cryogenic STEM datasets, highlighting subtle artifacts endemic to low-SNR lattice images and how they can be avoided. High-SNR average images with information transfer out to 0.72 Å are achieved at 300 kV and with the sample cooled to near liquid nitrogen temperature.

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