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Single-phase perovskite oxides that contain nonprecious metals have long been pursued as candidates for catalyzing the oxygen evolution reaction, but their catalytic activity cannot meet the requirements for practical electrochemical energy conversion technologies. Here a cation deficiency-promoted phase separation strategy to design perovskite-based composites with significantly enhanced water oxidation kinetics compared to single-phase counterparts is reported. These composites, self-assembled from perovskite precursors, comprise strongly interacting perovskite and related phases, whose structure, composition, and concentration can be accurately controlled by tailoring the stoichiometry of the precursors. The composite catalyst with optimized phase composition and concentration outperforms known perovskite oxide systems and state-of-the-art catalysts by 1-3 orders of magnitude. It is further demonstrated that the strong interfacial interaction of the composite catalysts plays a key role in promoting oxygen ionic transport to boost the lattice-oxygen participated water oxidation. These results suggest a simple and viable approach to developing high-performance, perovskite-based composite catalysts for electrochemical energy conversion.
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Metal-organic frameworks (MOFs) are very promising host materials for nanoscale guest materials. However, some MOFs such as MIL-53 are known to undergo phase transitions which can complicate the guest particle size control. In this study, Pd nanoparticles embedded in Al-MIL-53 were synthesised via (a) electrodeposition and (b) gas-phase reduction. A thorough structural investigation revealed that each synthesis method most likely favoured a different phase of Al-MIL-53, presenting the possibility of MOF phase selection as a technique for size control of embedded nanoparticles. For the first time, we hereby report the use of pair distribution function analysis to successfully investigate the structure and morphology of guest particles embedded in a MOF host.
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Understanding the molecular and cellular mechanisms that mediate magnetosensation in vertebrates is a formidable scientific problem. One hypothesis is that magnetic information is transduced into neuronal impulses by using a magnetite-based magnetoreceptor. Previous studies claim to have identified a magnetic sense system in the pigeon, common to avian species, which consists of magnetite-containing trigeminal afferents located at six specific loci in the rostral subepidermis of the beak. These studies have been widely accepted in the field and heavily relied upon by both behavioural biologists and physicists. Here we show that clusters of iron-rich cells in the rostro-medial upper beak of the pigeon Columbia livia are macrophages, not magnetosensitive neurons. Our systematic characterization of the pigeon upper beak identified iron-rich cells in the stratum laxum of the subepidermis, the basal region of the respiratory epithelium and the apex of feather follicles. Using a three-dimensional blueprint of the pigeon beak created by magnetic resonance imaging and computed tomography, we mapped the location of iron-rich cells, revealing unexpected variation in their distribution and number--an observation that is inconsistent with a role in magnetic sensation. Ultrastructure analysis of these cells, which are not unique to the beak, showed that their subcellular architecture includes ferritin-like granules, siderosomes, haemosiderin and filopodia, characteristics of iron-rich macrophages. Our conclusion that these cells are macrophages and not magnetosensitive neurons is supported by immunohistological studies showing co-localization with the antigen-presenting molecule major histocompatibility complex class II. Our work necessitates a renewed search for the true magnetite-dependent magnetoreceptor in birds.
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Bico/citologia , Columbidae/anatomia & histologia , Ferro/metabolismo , Macrófagos/metabolismo , Campos Magnéticos , Sensação , Migração Animal , Animais , Bico/anatomia & histologia , Columbidae/fisiologia , Plumas/citologia , Plumas/ultraestrutura , Ferrocianetos/análise , Imuno-Histoquímica , Ferro/análise , Macrófagos/ultraestrutura , Imageamento por Ressonância Magnética , Neurônios/metabolismo , Orientação , Mucosa Respiratória/citologia , Mucosa Respiratória/ultraestrutura , Tomografia Computadorizada de Emissão de Fóton ÚnicoRESUMO
New analytical approaches and discoveries are demanding fresh thinking about the early fossil record. The 1.88-Ga Gunflint chert provides an important benchmark for the analysis of early fossil preservation. High-resolution analysis of Gunflintia shows that microtaphonomy can help to resolve long-standing paleobiological questions. Novel 3D nanoscale reconstructions of the most ancient complex fossil Eosphaera reveal features hitherto unmatched in any crown-group microbe. While Eosphaera may preserve a symbiotic consortium, a stronger conclusion is that multicellular morphospace was differently occupied in the Paleoproterozoic. The 3.46-Ga Apex chert provides a test bed for claims of biogenicity of cell-like structures. Mapping plus focused ion beam milling combined with transmission electron microscopy data demonstrate that microfossil-like taxa, including species of Archaeoscillatoriopsis and Primaevifilum, are pseudofossils formed from vermiform phyllosilicate grains during hydrothermal alteration events. The 3.43-Ga Strelley Pool Formation shows that plausible early fossil candidates are turning up in unexpected environmental settings. Our data reveal how cellular clusters of unexpectedly large coccoids and tubular sheath-like envelopes were trapped between sand grains and entombed within coatings of dripstone beach-rock silica cement. These fossils come from Earth's earliest known intertidal to supratidal shoreline deposit, accumulated under aerated but oxygen poor conditions.
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Planeta Terra , Fósseis , Paleontologia/métodos , Meio Ambiente , Sedimentos Geológicos/química , Ontário , Fatores de Tempo , Austrália OcidentalRESUMO
The cellular basis of the magnetic sense remains an unsolved scientific mystery. One theory that aims to explain how animals detect the magnetic field is the magnetite hypothesis. It argues that intracellular crystals of the iron oxide magnetite (Fe3O4) are coupled to mechanosensitive channels that elicit neuronal activity in specialized sensory cells. Attempts to find these primary sensors have largely relied on the Prussian Blue stain that labels cells rich in ferric iron. This method has proved problematic as it has led investigators to conflate iron-rich macrophages with magnetoreceptors. An alternative approach developed by Eder et al. [Eder SH, et al. (2012) Proc Natl Acad Sci USA 109(30):12022-12027] is to identify candidate magnetoreceptive cells based on their magnetic moment. Here, we explore the utility of this method by undertaking a screen for magnetic cells in the pigeon. We report the identification of a small number of cells (1 in 476,000) with large magnetic moments (8-106 fAm(2)) from various tissues. The development of single-cell correlative light and electron microscopy (CLEM) coupled with electron energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFTEM) permitted subcellular analysis of magnetic cells. This revealed the presence of extracellular structures composed of iron, titanium, and chromium accounting for the magnetic properties of these cells. Application of single-cell CLEM to magnetic cells from the trout failed to identify any intracellular structures consistent with biogenically derived magnetite. Our work illustrates the need for new methods to test the magnetite hypothesis of magnetosensation.
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Óxido Ferroso-Férrico/metabolismo , Espaço Intracelular/metabolismo , Receptores de Superfície Celular/metabolismo , Vertebrados/metabolismo , Animais , Forma Celular , Cóclea/citologia , Cóclea/ultraestrutura , Columbidae , Fenômenos Magnéticos , Frações Subcelulares/metabolismo , TrutaRESUMO
The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO42- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO42-. Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.
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Equilibrium deuterium isotope effects for exchange of hydroxyl deuterons and protons among tert-butanol, phenol, ethanethiol, diethylamine, and ethanol were measured by using NMR and also calculated theoretically. Deuterated ethanol could be used as a probe for measuring equilibrium isotope effects (EIE) for hydroxyl exchange; tert-butanol, phenol, ethanethiol, diethylamine, and pyrrole were used as five representive examples. A procedure called the "one-atom isotope effect" was used to save time in the calculations.
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The mechanism(s) of interactions of phenol with oxygenated functional groups (OH, COO and COOH) in nanopores of activated carbon (AC) is a contentious issue among researchers. This mechanism is of particular interest because a better understanding of the role of such groups in nanopores would essentially translate to advances in AC production and use, especially in regard to the treatment of organic-based wastewaters. We therefore attempt to shed more light on the subject by employing density functional theory (DFT) calculations in which fullerene-like models integrating convex or concave structure, which simulate the eclectic porous structures on AC surface, are adopted. TEM analysis, EDS mapping and Boehm titration are also conducted on actual phenol-adsorbed AC. Our results suggest the widely-reported phenomenon of decreased phenol uptake on AC due to increased concentration of oxygenated functional groups is possibly attributed to the increased presence of the latter on the convex side of the curved carbon sheets. Such a system effectively inhibits phenol from getting direct contact with the carbon sheet, thus constraining any available π-π interaction, while the effect of groups acting on the concave part of the curved sheet does not impart the same detriment.
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Despite the success of genomics in identifying new essential bacterial genes, there is a lack of sustainable leads in antibacterial drug discovery to address increasing multidrug resistance. Type IIA topoisomerases cleave and religate DNA to regulate DNA topology and are a major class of antibacterial and anticancer drug targets, yet there is no well developed structural basis for understanding drug action. Here we report the 2.1 A crystal structure of a potent, new class, broad-spectrum antibacterial agent in complex with Staphylococcus aureus DNA gyrase and DNA, showing a new mode of inhibition that circumvents fluoroquinolone resistance in this clinically important drug target. The inhibitor 'bridges' the DNA and a transient non-catalytic pocket on the two-fold axis at the GyrA dimer interface, and is close to the active sites and fluoroquinolone binding sites. In the inhibitor complex the active site seems poised to cleave the DNA, with a single metal ion observed between the TOPRIM (topoisomerase/primase) domain and the scissile phosphate. This work provides new insights into the mechanism of topoisomerase action and a platform for structure-based drug design of a new class of antibacterial agents against a clinically proven, but conformationally flexible, enzyme class.
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Antibacterianos/química , Antibacterianos/farmacologia , DNA Girase/química , Quinolinas/química , Quinolinas/farmacologia , Staphylococcus aureus/enzimologia , Inibidores da Topoisomerase II , Antibacterianos/metabolismo , Apoenzimas/química , Apoenzimas/metabolismo , Arginina/metabolismo , Ácido Aspártico/metabolismo , Sítios de Ligação , Domínio Catalítico , Ciprofloxacina/química , Ciprofloxacina/metabolismo , Cristalografia por Raios X , DNA/química , DNA/metabolismo , Clivagem do DNA , DNA Girase/metabolismo , DNA Super-Helicoidal/química , DNA Super-Helicoidal/metabolismo , Desenho de Fármacos , Resistência a Medicamentos , Escherichia coli/enzimologia , Manganês/metabolismo , Modelos Moleculares , Conformação Proteica , Quinolinas/metabolismo , Quinolonas/química , Quinolonas/metabolismo , Relação Estrutura-AtividadeRESUMO
The 1.88-Ga Gunflint biota is one of the most famous Precambrian microfossil lagerstätten and provides a key record of the biosphere at a time of changing oceanic redox structure and chemistry. Here, we report on pyritized replicas of the iconic autotrophic Gunflintia-Huroniospora microfossil assemblage from the Schreiber Locality, Canada, that help capture a view through multiple trophic levels in a Paleoproterozoic ecosystem. Nanoscale analysis of pyritic Gunflintia (sheaths) and Huroniospora (cysts) reveals differing relic carbon and nitrogen distributions caused by contrasting spectra of decay and pyritization between taxa, reflecting in part their primary organic compositions. In situ sulfur isotope measurements from individual microfossils (δ(34)S(V-CDT) +6.7 to +21.5) show that pyritization was mediated by sulfate-reducing microbes within sediment pore waters whose sulfate ion concentrations rapidly became depleted, owing to occlusion of pore space by coeval silicification. Three-dimensional nanotomography reveals additional pyritized biomaterial, including hollow, cellular epibionts and extracellular polymeric substances, showing a preference for attachment to Gunflintia over Huroniospora and interpreted as components of a saprophytic heterotrophic, decomposing community. This work also extends the record of remarkable biological preservation in pyrite back to the Paleoproterozoic and provides criteria to assess the authenticity of even older pyritized microstructures that may represent some of the earliest evidence for life on our planet.
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Fósseis , Geologia/métodos , Paleontologia/métodos , Carbono/química , Ecossistema , Sedimentos Geológicos/análise , Sedimentos Geológicos/química , Processos Heterotróficos , Microscopia Eletrônica de Transmissão , Software , Análise Espectral Raman , Isótopos de Enxofre/análiseRESUMO
Despite decades of concerted experimental studies dedicated to providing fundamental insights into the adsorption of aurocyanide ion, Au(CN)2(-), on activated carbon (AC) surface, such a mechanism is still poorly understood and remains a contentious issue. This adsorption process is an essential unit operation for extracting gold from ores using carbon-in-pulp (CIP) technology. We hereby attempt to shed more light on the subject by employing a range of transmission electron microscopy (TEM) associated techniques. Gold-based clusters on the AC surface are observed by Z-contrast scanning TEM imaging and energy-filtered TEM element mapping and are supported by X-ray microanalysis. Density functional theory (DFT) calculations are applied to investigate this adsorption process for the first time. Fullerene-like models incorporating convex, concave, or planar structure which mimic the eclectic porous structures on the AC surface are adopted. Pentagonal, hexagonal, and heptagonal arrangements of carbon rings are duly considered in the DFT study. By determining the favored adsorption sites in water environment, a general adsorption trend of Au(CN)2(-) adsorbed on AC surface is revealed whereby concave > convex ≈ planar. The results suggest a tendency for Au(CN)2(-) ion to adsorb on the carbon sheet defects or edges rather than on the basal plane. In addition, we show that the adsorption energy of Au(CN)2(-) is approximately 5 times higher than that of OH(-) in the alkaline environment (in negative ion form), compared to only about 2 times in acidic environment (in protonated form), indicating the Au extraction process is much favored in basic condition. The overall simulation results resolve certain ambiguities about the adsorption process for earlier studies. Our findings afford crucial information which could assist in enhancing our fundamental understanding of the CIP adsorption process.
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Background: Remineralization of dental enamel is an important intervention strategy for the treatment of demineralized lesions. Existing approaches have limitations such as failure to adequately reproduce both the ideal structural and mechanical properties of the native tooth. The ability of ultrasound to control and accelerate the crystallization processes has been widely reported. Therefore, a new approach was explored for in-vitro enamel remineralization involving the synergistic effect of high-intensity focused ultrasound (HIFU) coupled with calcium phosphate ion clusters (CPICs). Methods: The demineralized enamel was treated with CPICs, with or without subsequent HIFU exposure for different periods (2.5, 5, and 10 min). The specimens were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and Raman spectroscopy. The surface hardness and crystallographic properties of the treated specimens were evaluated using Vickers microhardness testing and X-ray diffraction (XRD), respectively. Results: SEM revealed distinct, organized, and well-defined prismatic structures, showing clear evidence of remineralization in the combined CPIC/HIFU treatment groups. AFM further revealed a decrease in the surface roughness values with increasing HIFU exposure time up to 5 min, reflecting the obliteration of interprismatic spaces created during demineralization. The characteristic Raman band at 960 cm-1 associated with the inorganic phase of enamel dominated well in the HIFU-treated specimens. Importantly, microhardness testing further demonstrated that new mineral growth also recovered the mechanical properties of the enamel in the HIFU-exposed groups. Critical to our aspirations for developing this into a clinical process, these results were achieved in only 5 min. Conclusion: HIFU exposure can synergise and significantly accelerate in-vitro enamel remineralization process via calcium phosphate ion clusters. Therefore, this synergistic approach has the potential for use in future clinical interventions.
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Fosfatos de Cálcio , Esmalte Dentário , Microscopia de Força Atômica , Remineralização Dentária , Fosfatos de Cálcio/química , Fosfatos de Cálcio/farmacologia , Esmalte Dentário/efeitos dos fármacos , Esmalte Dentário/química , Remineralização Dentária/métodos , Análise Espectral Raman , Microscopia Eletrônica de Varredura , Dureza , Propriedades de Superfície , Humanos , Desmineralização do Dente/terapia , Difração de Raios X , Animais , BovinosRESUMO
We present results from high-pressure, high-temperature experiments that generate incipient carbonate melts at mantle conditions (~90 kilometers depth and temperatures between 750° and 1050°C). We show that these primitive carbonate melts can sequester sulfur in its oxidized form of sulfate, as well as base and precious metals from mantle lithologies of peridotite and pyroxenite. It is proposed that these carbonate sulfur-rich melts may be more widespread than previously thought and that they may play a first-order role in the metallogenic enhancement of localized lithospheric domains. They act as effective agents to dissolve, redistribute, and concentrate metals within discrete domains of the mantle and into shallower regions within Earth, where dynamic physicochemical processes can lead to ore genesis at various crustal depths.
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Herein, we firstly utilized H2@C60 to monitor the supramolecular interaction between a pH-driven resorcin[4]arene molecular tweezer and C60 with a notable 1H NMR chemical shift change (ca. 0.34 ppm). This work provides a new strategy for detecting weak or complex supramolecular interactions.
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One of the most important aspects in the research on reef-building corals is the process by which corals accrete biogenic calcium carbonate. This process leads to the formation of a mineral/organic composite and it is believed that the development of the nano- and microstructure of the mineral phase is highly sensitive to the growth conditions. Transmission electron microscopy (TEM) analysis of large-scale (10×30µm) focused ion beam (FIB) prepared lamellae was performed on adult and juvenile scleractinian coral skeleton specimens. This allowed for the investigation of the nano and microstructure and the crystallographic orientation of the aragonite mineral. We found the following microstructural evolution in the adult Porites lobata specimens: randomly oriented nanocrystals with high porosity, partly aligned nanocrystals with high porosity and areas of dense acicular crystals of several micrometers extension, the latter two areas are aligned close to the [001] direction (Pmcn space group). To the best of our knowledge, for the first time the observed microstructure could be directly correlated with the dark/bright bands characteristic of the diurnal growth cycle. We hypothesize that this mineral structure sequence and alignment in the adult specimen is linked to the photosynthetic diurnal cycle of the zooxanthellea regulating the oxygen levels and organic molecule transport to the calcifying medium. These observations reveal a strong control of crystal morphology by the organism and the correlation of the accretion process. No indication for a self-assembly of nanocrystalline units, i.e., a mesocrystal structure, on the micrometer scale could be found.
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Antozoários/ultraestrutura , Animais , Antozoários/química , Cristalografia , Evolução Molecular , Microscopia Eletrônica de Transmissão , Nanopartículas/química , Nanopartículas/ultraestrutura , NanotecnologiaRESUMO
Despite its broad applicability NMR has always been limited by its inherently low sensitivity. Hyperpolarization methods have the potential to overcome this limitation and, in the case of ex situ dynamic nuclear polarization (DNP), large enhancement factors have been achieved. Although many other polarization methods have been described in the past, including chemically and parahydrogen-induced polarization and optical pumping, DNP has recently been the most popular. Here we present an additional polarization mechanism arising from quantum rotor effects in methyl groups, which generates polarizations at temperatures < 1.5 K and interferes with DNP at such temperatures. The polarization generated by this mechanism is efficiently transferred via carbon bound protons. Although quantum rotor polarizations have been studied for a small range of molecules in great detail, we observe such effects for a much broader range of substances with very different polarization rates at temperatures < 1.5 K. Moreover, we report transfer of quantum rotor polarization across a chain of protons. The observed effect not only influences the polarization in low-temperature DNP experiments but also opens a new independent avenue to generate enhanced sensitivity for NMR.
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Membrane separation and sulfate radicals-based advanced oxidation processes (SR-AOPs) can be combined as an efficient technique for the elimination of organic pollutants. The immobilization of metal oxide catalysts on ceramic membranes can enrich the membrane separation technology with catalytic oxidation avoiding recovering suspended catalysts. Herein, nanostructured Co3O4 ceramic catalytic membranes with different Co loadings were fabricated via a simple ball-milling and calcination process. Uniform distribution of Co3O4 nanoparticles in the membrane provided sufficient active sites for catalytic oxidation of 4-hydroxybenzoic acid (HBA). Mechanistic studies were conducted to determine the reactive radicals and showed that both SO4â¢- and â¢OH were present in the catalytic process while SO4â¢- plays the dominant role. The anti-fouling performance of the composite Co@Al2O3 membranes was also evaluated, showing that a great flux recovery was achieved with the addition of PMS for the fouling caused by humic acid (HA).
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Published toxicology data on chitosan nanoparticles (NP) often lack direct correlation to the in situ size and surface characteristics of the nanoparticles, and the repeated NP assaults as experienced in chronic use. The aim of this paper was to breach these gaps. Chitosan nanoparticles synthesized by spinning disc processing were characterised for size and zeta potential in HBSS and EMEM at pHs 6.0 and 7.4. Cytotoxicity against the Caco-2 cells was evaluated by measuring the changes in intracellular mitochondrial dehydrogenase activity, TEER and sodium fluorescein transport data and cell morphology. Cellular uptake of NP was observed under the confocal microscope. Contrary to established norms, the collective data suggest that the in vitro cytotoxicity of NP against the Caco-2 cells was less influenced by positive surface charges than by the particle size. Particle size was in turn determined by the pH of the medium in which the NP was dispersed, with the mean size ranging from 25 to 333 nm. At exposure concentration of 0.1%, NP of 25 ± 7 nm (zeta potential 5.3 ± 2.8 mV) was internalised by the Caco-2 cells, and the particles were observed to inflict extensive damage to the intracellular organelles. Concurrently, the transport of materials along the paracellular pathway was significantly facilitated. The Caco-2 cells were, however, capable of recovering from such assaults 5 days following NP removal, although a repeat NP exposure was observed to produce similar effects to the 1st exposure, with the cells exhibiting comparable resiliency to the 2nd assault.
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Células CACO-2/efeitos dos fármacos , Quitosana/toxicidade , Nanopartículas/toxicidade , Quitosana/administração & dosagem , Humanos , Concentração de Íons de Hidrogênio , Microscopia Confocal , Microscopia Eletrônica de Transmissão , Mitocôndrias/efeitos dos fármacos , Mitocôndrias/enzimologia , Nanopartículas/administração & dosagem , Nanopartículas/ultraestrutura , Oxirredutases/efeitos dos fármacos , Tamanho da PartículaRESUMO
Gold nanoclusters are deposited directly on silicon by sputtering of a target of metallic gold using an argon plasma to provide a semiconductor-based plasmonic platform. The effects of annealing and substrate temperatures during the nanoparticles deposition and of the silicon surface energy on the shape of the nanoparticles and resulting surface plasmon resonance are investigated. The Au nanoparticles are characterized optically, structurally and morphologically using spectroscopic ellipsometry, transmission electron microscopy and atomic force microscopy to establish a correlation among the Au/Si interface reactivity, the Au nanoparticles shape and plasmonic resonance properties. It is found that post-growth annealing up to 600 degrees C of nanoparticles deposited at 60 degrees C causes aggregation of nanoparticles. Increasing the temperature of the substrate during the sputtering of gold on Si yields pancake-like nanoparticles with a large Si/Au interface reactivity forming a gold-silicides interface layer. The O2 plasma treatment of the Si surface forming a thin intentional SiO2 interface layer prevents the Au/Si interdiffusion yielding polyedrical nanoparticles whose plasmon resonance can be shifted down to 1.5 eV.
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Ouro/química , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Gases em Plasma/química , Semicondutores , Silício/química , Prata/química , Cristalização/métodos , Temperatura Alta , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
OBJECTIVE: The aim of this study was to synthesize and characterize reduced nano graphene oxide (RGO) and graphene nanoplatelets (GNPs) doped with silver nanoparticles (nAg) and to prepare an experimental dentin adhesive modified with RGO/nAg and GNP/nAg nanofillers for studying various biological and mechanical properties after bonding to tooth dentin. METHODS: Nanoparticles were characterized for their morphology and chemical structure using electron microscopy and infrared spectroscopy. Experimental dentin adhesive was modified using two weight percentage (0.25% and 0.5%) of RGO/nAg and GNP/nAg to study its degree of conversion (DC), antimicrobial potential, and cytotoxicity. The effect and significance of these modified bonding agents on resin-dentin bonded interface were investigated by evaluating interfacial nanoleakage, micropermeability, nanodynamic mechanical analysis, micro-tensile bond strength (µTBS), and four-point bending strength (BS), RESULTS: Both 0.25% and 0.5% GNP/nAg graphene-modified adhesives showed comparable DC values to the commercial and experimental adhesive (range: 42-46%). The bacterial viability of the groups 0.25% and 0.5% GNP-Ag remained very low under 25% compared to RGO/nAg groups with low cytotoxicity profiles (cell viability>85%). Resin-bonded dentin interface created with GNP/nAg showed homogenous, well-defined hybrid layer and regularly formed long resin tags devoid of any microporosity as evidenced by SEM and confocal microscopy. The lowest nanoleakage and highest bending strength and µTBS was recorded for 0.25% GNP/nAg after 12 months of ageing. A significantly increased nanoelasticity was seen for all experimental groups except for control groups. SIGNIFICANCE: The addition of 0.25% GNP/nAg showed optimized anti-biofilm properties without affecting the standard adhesion characteristics.