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Robust neural information transfer relies on a delicate molecular nano-architecture of chemical synapses. Neurotransmitter release is controlled by a specific arrangement of proteins within presynaptic active zones. How the specific presynaptic molecular architecture relates to postsynaptic organization and how synaptic nano-architecture is transsynaptically regulated to enable stable synaptic transmission remain enigmatic. Using time-gated stimulated emission-depletion microscopy at the Drosophila neuromuscular junction, we found that presynaptic nanorings formed by the active-zone scaffold Bruchpilot (Brp) align with postsynaptic glutamate receptor (GluR) rings. Individual rings harbor approximately four transsynaptically aligned Brp-GluR nanocolumns. Similar nanocolumn rings are formed by the presynaptic protein Unc13A and GluRs. Intriguingly, acute GluR impairment triggers transsynaptic nanocolumn formation on the minute timescale during homeostatic plasticity. We reveal distinct phases of structural transsynaptic homeostatic plasticity, with postsynaptic GluR reorganization preceding presynaptic Brp modulation. Finally, homeostatic control of transsynaptic nano-architecture and neurotransmitter release requires the auxiliary GluR subunit Neto. Thus, transsynaptic nanocolumn rings provide a substrate for rapid homeostatic stabilization of synaptic efficacy.
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Proteínas de Drosophila , Junção Neuromuscular , Animais , Junção Neuromuscular/metabolismo , Drosophila/metabolismo , Transmissão Sináptica , Sinapses/metabolismo , Receptores de Glutamato/metabolismo , Proteínas de Drosophila/metabolismo , Neurotransmissores/metabolismo , Proteínas de Membrana/metabolismoRESUMO
The pursuit of harnessing superior mechanical properties achieved through the size effect on a macroscopic scale has been a prominent focus in engineering, as size-induced strengthening is enabled only in the nanoscale regime. This study presents a metal/ceramic/metal (MCM) nanocomposite reinforced by ceramic nanoarchitectures. Through proximity-field nanopatterning, the inch-scale production of nanoarchitecture films is enabled in a single fabrication step. The developed three-dimensional (3D) Ni/Al2O3/Ni nanocomposite film exhibits significantly high compressive strength, corresponding to an increase of approximately 30% compared with that calculated using the upper limits of the conventional rule of mixtures. The exceptional strength of the 3D MCM nanocomposite can be attributed to the extrinsic size effect of the ceramic nanoarchitectures. By combining size-induced strengthening of ceramics with the strengthening law for composites, a new type of strengthening model is derived and experimentally validated using the 3D MCM nanocomposite.
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The volume collapse and slow kinetics reaction of anode materials are two key issues for sodium ion batteries (SIBs). Herein, an "embryo" strategy is proposed for synthesis of nanorod-embedded MoO2/MoS2/C network nanoarchitecture as anode for SIBs with high-rate performance. Interestingly, L-cysteine which plays triple roles including sulfur source, reductant, and carbon source can be utilized to produce the sulfur vacancy-enriched heterostructure. Specifically, L-cysteine can combine with metastable monoclinic MoO3 nanorods at room temperature to encapsulate the "nutrient" of MoOx analogues (MoO2.5(OH)0.5 and MoO3·0.5H2O) and hydrogen-deficient L-cysteine in the "embryo" precursor affording for subsequent in situ multistep heating treatment. The resultant MoO2/MoS2/C presents a high-rate capability of 875 and 420 mAh g-1 at 0.5 and 10 A g-1, respectively, which are much better than the MoS2-based anode materials reported by far. Finite element simulation and analysis results verify that the volume expansion can be reduced to 42.8% from 88.8% when building nanorod-embedded porous network structure. Theoretical calculations reveal that the sulfur vacancies and heterointerface engineering can promote the adsorption and migration of Na+ leading to highly enhanced thermodynamic and kinetic reaction. The work provides an efficient approach to develop advanced electrode materials for energy storage.
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Structural engineering and hybridization of heterogeneous 2D materials can be effective for advanced supercapacitor. Furthermore, architectural design of electrodes particularly with vertical construction of structurally anisotropic graphene nanosheets, can significantly enhance the electrochemical performance. Herein, MXene-derived TiO2 nanocomposites hybridized with vertical graphene is synthesized via CO2 laser irradiation on MXene/graphene oxide nanocomposite film. Instantaneous photon energy by laser irradiation enables the formation of vertical graphene structures on nanocomposite films, presenting the controlled anisotropy in free-standing film. This vertical structure enables improved supercapacitor performance by forming an open structure, increasing the electrolyte-electrode interface, and creating efficient electron transport path. In addition, the effective oxidation of MXene nanosheets by instantaneous photon energy leads to the formation of rutile TiO2 . TiO2 nanoparticles directly generated on graphene enables the effective current path, which compensates for the low conductivity of TiO2 and enables the functioning of an effective supercapacitor by utilizing its pseudocapacitive properties. The resulting film exhibits excellent specific areal capacitance of 662.9 mF cm-2 at a current density of 5 mA cm-2 . The film also shows superb cyclic stability during 40 000 repeating cycles, maintaining high capacitance. Also, the pseudocapacitive redox reaction kinetics is evaluated, showing fast redox kinetics with potential for high-performance supercapacitor applications.
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Plasmon-mediated catalysis utilizing hybrid photocatalytic ensembles promises effective light-to-chemical transformation, but current approaches suffer from weak electromagnetic field enhancements from polycrystalline and isotropic plasmonic nanoparticles as well as poor utilization of precious co-catalyst. Here, efficient plasmon-mediated catalysis is achieved by introducing a unique catalyst-on-hotspot nanoarchitecture obtained through the strategic positioning of co-photocatalyst onto plasmonic hotspots to concentrate light energy directly at the point-of-reaction. Using environmental remediation as a proof-of-concept application, the catalyst-on-hotspot design (edge-AgOcta@Cu2O) enhances photocatalytic advanced oxidation processes to achieve superior organic-pollutant degradation at ≈81% albeit having lesser Cu2O co-photocatalyst than the fully deposited design (full-AgOcta@Cu2O). Mass-normalized rate constants of edge-AgOcta@Cu2O reveal up to 20-fold and 3-fold more efficient utilization of Cu2O and Ag nanoparticles, respectively, compared to full-AgOcta@Cu2O and standalone catalysts. Moreover, this design also exhibits catalytic performance >4-fold better than emerging hybrid photocatalytic platforms. Mechanistic studies unveil that the light-concentrating effect facilitated by the dense electromagnetic hotspots is crucial to promote the generation and utilization of energetic photocarriers for enhanced catalysis. By enabling the plasmonic focusing of light onto co-photocatalyst at the single-particle level, the unprecedented design offers valuable insights in enhancing light-driven chemical reactions and realizing efficient energy/catalyst utilizations for diverse chemical, environmental, and energy applications.
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Triboelectric Nanogenerator (TENG) has proven highly effective in converting mechanical energy into electrical energy. Previous research on manipulating microstructure for performance enhancement primarily focused on the surface of TENGs. In this study, an innovative bottom-up strategic design to control the internal nano-architecture for the enhanced output of TENG is proposed. This multiscale structural design strategy consists of defect chemistry (angstrom-scale), surface modification (nano-scale), and spatial regulation of nanoparticles (meso-scale), which helps explore the optimal utilization of TENG's internal structure. After fine-tuning the nano-architecture, the output voltage is significantly increased. This optimized TENG serves as a robust platform for developing self-powered systems, including self-powered electrochemical chlorination systems for sterilization. Additionally, through the utilization of multiscale simulations (density functional theory, all-atom molecular dynamics, and dissipative particle dynamics), the underlying mechanisms governing how the optimized nanoparticle-polymer interface and spatial arrangement of nanoparticles influence the storage and transfer of charges are comprehensively elucidated. This study not only demonstrates the effectiveness of manipulating internal nano-architecture to enhance TENG performance for practical applications but also provides invaluable insights into structural engineering for TENG advancement.
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Light-driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air-promoted strategy is explored for efficient and durable light-driven hydrogen production from ethanol over a core/shell Cr2O3@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the Cr2O3@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H2 evolution by photogenerated electrons. Afterward, O2 can be evolved into active oxygen species and promote the deprotonation and C-C cleavage of the key C2 intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9â mole H2 per gram Cr2O3@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000â mole H2 per mole Cr2O3 over a long-term operation of 180â hours. Notably, an unprecedented light-to-hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising.
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With revolutionary advances in next-generation sequencing, the human transcriptome has been comprehensively interrogated. These discoveries have highlighted the emerging functional and regulatory roles of a large fraction of RNAs suggesting the potential they might hold as stable and minimally invasive disease biomarkers. Although a plethora of molecular-biology- and biosensor-based RNA-detection strategies have been developed, clinical application of most of these is yet to be realized. Multifunctional nanomaterials coupled with sensitive and robust electrochemical readouts may prove useful in these applications. Here, we summarize the major contributions of engineered nanomaterials-based electrochemical biosensing strategies for the analysis of miRNAs. With special emphasis on nanostructure-based detection, this review also chronicles the needs and challenges of miRNA detection and provides a future perspective on the presented strategies.
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Técnicas Biossensoriais , Técnicas Eletroquímicas , MicroRNAs/análise , Nanoestruturas/química , HumanosRESUMO
The enhanced properties of nanomaterials make them attractive for advanced high-performance materials, but their role in promoting toughness has been unclear. Fabrication challenges often prevent the proper organization of nanomaterial constituents, and inadequate testing methods have led to a poor knowledge of toughness at small scales. In this work, the individual roles of nanomaterials and nanoarchitecture on toughness are quantified by creating lightweight materials made from helicoidal polymeric nanofibers (nano-Bouligand). Unidirectional ( θ $\theta $ = 0°) and nano-Bouligand beams ( θ $\theta $ = 2°-90°) are fabricated using two-photon lithography and are designed in a micro-single edge notch bend (µ-SENB) configuration with relative densities ρ ¯ $\overline \rho $ between 48% and 81%. Experiments demonstrate two unique toughening mechanisms. First, size-enhanced ductility of nanoconfined polymer fibers increases specific fracture energy by 70% in the 0° unidirectional beams. Second, nanoscale stiffness heterogeneity created via inter-layer fiber twisting impedes crack growth and improves absolute fracture energy dissipation by 48% in high-density nano-Bouligand materials. This demonstration of size-enhanced ductility and nanoscale heterogeneity as coexisting toughening mechanisms reveals the capacity for nanoengineered materials to greatly improve mechanical resilience in a new generation of advanced materials.
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To realize a high-energy lithium metal battery (LMB) using a high-capacity Li-free cathode, in this work, nanoplate-stacked V2 O5 with dominantly exposed (010) facets and a relatively short [010] length is proposed to be used as a cathode. The V2 O5 nanostructure can be fabricated via a modified hydrothermal method, including a Li+ crystallization inhibitor, followed by heat treatment. In particular, the enlargement of the favorable Li+ diffusion pathway in the [010] direction and the formation of a robust hierarchical nanoplate-stacked structure in the modified V2 O5 improves the electrochemical kinetics and stability; as a result, the nanoplate-stacked V2 O5 electrode exhibits a higher capacity and rate performance (258 mAh g-1 at 50 mA g-1 [0.17 C], 140 mAh g-1 at 1 A g-1 [3.4 C]) and cycling capability (79% capacity retention after 100 cycles at 0.5 C) compared to the previously reported V2 O5 nanobelt electrode. Notably, the LMB composed of Li//nanoplate-stacked V2 O5 full-cells shows high specific energy densities of 594.1 and 296.2 Wh kg-1 at 0.1 and 1.0 C, respectively, and a high Coulombic efficiency of 99.6% during 50 cycles.
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Rapid, accessible, and highly accurate biosensors for the detection of addictive and abused drugs are needed to reduce the adverse personal and societal impacts of addiction. Modern sensors that utilize next-generation technologies, e.g., nanobiotechnology and nanoarchitectonics, have triggered revolutionary progress in the field as they allow accurate detection and tracking of trace levels of major classes of drugs. This paper reviews advances in the field of biosensors for the detection of commonly abused drugs, both prescribed such as codeine and morphine, and illegal narcotics like cocaine.
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Técnicas Biossensoriais , Cocaína , Drogas Ilícitas , MorfinaRESUMO
MOFs-derived metal/carbon materials have been considered as promising candidates for the electrochemical detection of micropollutants. However, the aggregation of metal nanoparticles and structure collapse of precursor MOFs during pyrolysis significantly hamper the improvement on detecting performance. Herein, a dicyandiamide-assisted strategy is utilized to synthesize well-dispersed Cu/N-doped porous carbon nanoarchitecture (CuNC) for the electrochemical detection of acetaminophen (AP). The constructed CuNC sensor exhibits excellent electro-analytical performance for monitoring AP with linear range from 0.01 µM to 921.2 µM, and the low detection limit of 2.46 nM (S/N = 3). The improved performance of CuNC sensor is ascribed to the introduction of dicyandiamide, which can prevent HKUST-1 framework breakage and reduce the aggregation tendency of Cu, leading to the evenly distributed small Cu nanoparticles, abundant N species, hierarchical channel structure, and high conductivity carbon framework. These advantages endow predominant repeatability, stability, and selectivity of CuNC sensor. This strategy provided a novel approach to preparing MOFs-derived carbon nanoarchitectures with excellent electroanalysis performance to monitor micropollutants.
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Acetaminofen , Carbono , Técnicas Eletroquímicas , Guanidinas , Estruturas Metalorgânicas , PorosidadeRESUMO
Although sodium (Na) is one of the most promising alternatives to lithium as an anode material for next-generation batteries, uncontrollable Na dendrite growth still remains the main challenge for Na metal batteries. Herein, a novel 1D/2D Na3Ti5O12-MXene hybrid nanoarchitecture consisting of Na3Ti5O12 nanowires grown between the MXene nanosheets is synthesized by a facile approach using cetyltrimethylammonium bromide (CTAB)-pretreated Ti3C2 MXene. Used as a matrix for the Na metal anode, the Na3Ti5O12 nanowires, formed benefiting from the CTAB stabilization, have chemical interaction with Na and thus provide abundant Na nucleation sites. These 1D nanostructures, together with the unique confinement effect from the 2D nanosheets, effectively guide and control the Na deposition within the interconnected nanochannels, preventing the "hot spot" formation for dendrite growth. A stable cycling performance can be achieved at a high current density up to 10 mA cm-2 along with an ultrahigh capacity up to 20 mAh cm-2.
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In cancer therapy, the application of (fractionated) harsh radiation treatment is state of the art for many types of tumors. However, ionizing radiation is a "double-edged sword"-it can kill the tumor but can also promote the selection of radioresistant tumor cell clones or even initiate carcinogenesis in the normal irradiated tissue. Individualized radiotherapy would reduce these risks and boost the treatment, but its development requires a deep understanding of DNA damage and repair processes and the corresponding control mechanisms. DNA double strand breaks (DSBs) and their repair play a critical role in the cellular response to radiation. In previous years, it has become apparent that, beyond genetic and epigenetic determinants, the structural aspects of damaged chromatin (i.e., not only of DSBs themselves but also of the whole damage-surrounding chromatin domains) form another layer of complex DSB regulation. In the present article, we summarize the application of super-resolution single molecule localization microscopy (SMLM) for investigations of these structural aspects with emphasis on the relationship between the nano-architecture of radiation-induced repair foci (IRIFs), represented here by γH2AX foci, and their chromatin environment. Using irradiated HeLa cell cultures as an example, we show repair-dependent rearrangements of damaged chromatin and analyze the architecture of γH2AX repair clusters according to topological similarities. Although HeLa cells are known to have highly aberrant genomes, the topological similarity of γH2AX was high, indicating a functional, presumptively genome type-independent relevance of structural aspects in DSB repair. Remarkably, nano-scaled chromatin rearrangements during repair depended both on the chromatin domain type and the treatment. Based on these results, we demonstrate how the nano-architecture and topology of IRIFs and chromatin can be determined, point to the methodological relevance of SMLM, and discuss the consequences of the observed phenomena for the DSB repair network regulation or, for instance, radiation treatment outcomes.
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Cromatina/genética , Dano ao DNA/genética , Neoplasias/genética , Linhagem Celular Tumoral , Cromatina/ultraestrutura , Quebras de DNA de Cadeia Dupla/efeitos da radiação , Dano ao DNA/efeitos da radiação , Reparo do DNA/genética , Reparo do DNA/efeitos da radiação , Células HeLa , Humanos , Microscopia/métodos , Radiação Ionizante , Imagem Individual de Molécula/métodosRESUMO
The covalent and noncovalent association of self-assembling peptides and tetrapyrroles was explored as a way to generate systems that mimic Nature's functional supramolecular structures. Different types of peptides spontaneously assemble with porphyrins, phthalocyanines, or corroles to give long-range ordered architectures, whose structure is determined by the features of both components. The regular morphology and ordered molecular arrangement of these systems enhance the photochemical properties of embedded chromophores, allowing applications as photo-catalysts, antennas for dye-sensitized solar cells, biosensors, and agents for light-triggered therapies. Chemical modifications of peptide and tetrapyrrole structures and control over the assembly process can steer the organization and influence the properties of the resulting system. Here we provide a review of the field, focusing on the assemblies obtained from different classes of self-assembling peptides with tetrapyrroles, their morphologies and their applications as innovative functional materials.
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Peptídeos/química , Tetrapirróis/química , Indóis/química , Isoindóis , Fotoquímica/métodos , Porfirinas/químicaRESUMO
Gold nanoparticles (AuNPs) decorated bimetallic CuNi-based hollow nanoarchitecture (CNHN) are reported for the first time as a nonenzymatic sensor for the quantification of nitrite in neutral solution . The CNHN was prepared via a convenient calcining routine using the bimetallic CuNi-MOFs as a coprecursor. The unique chemical structure of hollow CNHN with high specific surface area and abundant terminal amino groups effectively avoid the aggregation of AuNPs and facilitate the subsequent adsorption of nitrite. The Au/CNHN exhibited high electrocatalytic activity towards nitrite oxidation due to the synergetic catalytic effect of AuNPs and CNHN. Chronoamperometric detection of nitrite at the Au/CNHN/GCE achieved a lower linear calibration range of 0.05 to 1.15 mM, with an LOD of 0.017 µM compared with previous reports. The proposed method obtained satisfactory recoveries for nitrite determination in practical applications, which was verified by UV-Vis spectrophotometry. The prepared sensor based on Au/CNHN featured favorable selectivity and stability, which provides a promising approach for real sample analysis. Graphical abstract.
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Biological photonic nanoarchitectures are capable of rapidly and chemically selectively sensing volatile organic compounds due to changing color when exposed to such vapors. Here, stability and the vapor sensing properties of butterfly and moth wings were investigated by optical spectroscopy in the presence of water vapor. It was shown that repeated 30 s vapor exposures over 50 min did not change the resulting optical response signal in a time-dependent manner, and after 5-min exposures the sensor preserved its initial properties. Time-dependent response signals were shown to be species-specific, and by using five test substances they were also shown to be substance-specific. The latter was also evaluated using principal component analysis, which showed that the time-dependent optical responses can be used for real-time analysis of the vapors. It was demonstrated that the capability to detect volatile organic compounds was preserved in the presence of water vapor: high-intensity color change signals with short response times were measured in 25% relative humidity, similar to the one-component case; therefore, our results can contribute to the development of biological photonic nanoarchitecture-based vapor detectors for real-world applications, like living and working environments.
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Borboletas , Gases , Umidade , Mariposas , Asas de Animais/fisiologia , Animais , Óptica e FotônicaRESUMO
Additive manufacturing is a key technology required to realize the production of a personalized bone substitute that exactly meets a patient's need and fills a patient-specific bone defect. Additive manufacturing can optimize the inner architecture of the scaffold for osteoconduction, allowing fast and reliable defect bridging by promoting rapid growth of new bone tissue into the scaffold. The role of scaffold microporosity/nanoarchitecture in osteoconduction remains elusive. To elucidate this relationship, we produced lithography-based osteoconductive scaffolds from tricalcium phosphate (TCP) with identical macro- and microarchitecture, but varied their nanoarchitecture/microporosity by ranging maximum sintering temperatures from 1000 °C to 1200 °C. After characterization of the different scaffolds' microporosity, compression strength, and nanoarchitecture, we performed in vivo studies that showed that ingrowth of bone as an indicator of osteoconduction significantly decreased with decreasing microporosity. Moreover, at the 1200 °C peak sinter temperature and lowest microporosity, osteoclastic degradation of the material was inhibited. Thus, even for wide-open porous TCP-based scaffolds, a high degree of microporosity appears to be essential for optimal osteoconduction and creeping substitution, which can prevent non-unions, the major complication during bone regeneration procedures.
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Reabsorção Óssea , Substitutos Ósseos/química , Fosfatos de Cálcio/química , Osteoclastos/metabolismo , Impressão Tridimensional , Engenharia Tecidual , Alicerces Teciduais/química , Força Compressiva , Teste de Materiais , Osteoclastos/citologia , Porosidade , Próteses e Implantes , Engenharia Tecidual/métodosRESUMO
We conducted in situ three-point bending experiments on beams with roughly square cross-sections, which we fabricated from the frustule of Coscinodiscus sp. We observe failure by brittle fracture at an average stress of 1.1 GPa. Analysis of crack propagation and shell morphology reveals a differentiation in the function of the frustule layers with the basal layer pores, which deflect crack propagation. We calculated the relative density of the frustule to be â¼30% and show that at this density the frustule has the highest strength-to-density ratio of 1,702 kNâ m/kg, a significant departure from all reported biologic materials. We also performed nanoindentation on both the single basal layer of the frustule as well as the girdle band and show that these components display similar mechanical properties that also agree well with bending tests. Transmission electron microscopy analysis reveals that the frustule is made almost entirely of amorphous silica with a nanocrystalline proximal layer. No flaws are observed within the frustule material down to 2 nm. Finite element simulations of the three-point bending experiments show that the basal layer carries most of the applied load whereas stresses within the cribrum and areolae layer are an order of magnitude lower. These results demonstrate the natural development of architecture in live organisms to simultaneously achieve light weight, strength, and exceptional structural integrity and may provide insight into evolutionary design.
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Evolução Biológica , Diatomáceas , Dióxido de Silício/metabolismo , Diatomáceas/metabolismo , Diatomáceas/ultraestruturaRESUMO
Transparent/translucent glass ceramics (GCs) have broad applications in biomedicine, armor, energy, and constructions. However, GCs with improved optical properties typically suffer from impaired mechanical properties, compared to traditional sintered full-ceramics. We present a method of obtaining high-strength, translucent GCs by preparing ZrO2-SiO2 nanocrystalline glass ceramics (NCGCs) with a microstructure of monocrystalline ZrO2 nanoparticles (NPs), embedded in an amorphous SiO2 matrix. The ZrO2-SiO2 NCGC with a composition of 65%ZrO/35%SiO2 (molar ratio, 65Zr) achieved an average flexural strength of 1 GPa. This is one of the highest flexural strength values ever reported for GCs. ZrO2 NPs bond strongly with SiO2 matrix due to the formation of a thin (2-3 nm) amorphous Zr/Si interfacial layer between the ZrO2 NPs and SiO2 matrix. The diffusion of Si atoms into the ZrO2 NPs forms a Zr-O-Si superlattice. Electron tomography results show that some of the ZrO2 NPs are connected in one direction, forming in situ ZrO2 nanofibers (with length of â¼500 nm), and that the ZrO2 nanofibers are stacked in an ordered way in all three dimensions. The nanoarchitecture of the ZrO2 nanofibers mimics the architecture of mineralized collagen fibril in cortical bone. Strong interface bonding enables efficient load transfer from the SiO2 matrix to the 3D nanoarchitecture built by ZrO2 nanofibers and NPs, and the 3D nanoarchitecture carries the majority of the external load. These two factors synergistically contribute to the high strength of the 65Zr NCGC. This study deepens our fundamental understanding of the microstructure-mechanical strength relationship, which could guide the design and manufacture of other high-strength, translucent GCs.