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Stabilizing metal nanoparticles is vital for large scale implementations of supported metal catalysts, particularly for a sustainable transition to clean energy, e.g., H2 production. In this work, iridium sub-nanometric particles were deposited on commercial graphite and on graphitic carbon nitride by a wet impregnation method to investigate the metal-support interaction during the hydrous hydrazine decomposition reaction. To establish a structure-activity relationship, samples were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The catalytic performance of the synthesized materials was evaluated under mild reaction conditions, i.e. 323 K and ambient pressure. The results showed that graphitic carbon nitride (GCN) enhances the stability of Ir nanoparticles compared to graphite, while maintaining remarkable activity and selectivity. Simulation techniques including Genetic Algorithm geometry screening and electronic structure analyses were employed to provide a valuable atomic level understanding of the metal-support interactions. N anchoring sites of GCN were found to minimise the thermodynamic driving force of coalescence, thus improving the catalyst stability, as well as to lead charge redistributions in the cluster improving the resistance to poisoning by decomposition intermediates.
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The oxygen stoichiometry of hollandite, KxMnO2-δ, nanorods has been accurately determined from a quantitative analysis of scanning-transmission electron microscopy (STEM) X-Ray Energy Dispersive Spectroscopy (XEDS) experiments carried out in chrono-spectroscopy mode. A methodology combining 3D reconstructions of high-angle annular dark field electron tomography experiments, using compressed-sensing algorithms, and quantification through the so-called ζ-factors method of XEDS spectra recorded on a high-sensitivity detector has been devised to determine the time evolution of the oxygen content of nanostructures of electron-beam sensitive oxides. Kinetic modeling of O-stoichiometry data provided K0.13MnO1.98 as overall composition for nanorods of the hollandite. The quantitative agreement, within a 1% mol error, observed with results obtained by macroscopic techniques (temperature-programmed reduction and neutron diffraction) validate the proposed methodology for the quantitative analysis, at the nanoscale, of light elements, as it is the case of oxygen, in the presence of heavy ones (K, Mn) in the highly compromised case of nanostructured materials which are prone to electron-beam reduction. Moreover, quantitative comparison of oxygen evolution data measured at macroscopic and nanoscopic levels allowed us to rationalize beam damage effects in structural terms and clarify the exact nature of the different steps involved in the reduction of these oxides with hydrogen.
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Marine ancestors of freshwater sponges had to undergo a series of physiological adaptations to colonize harsh and heterogeneous limnic environments. Besides reduced salinity, river-lake systems also have calcium concentrations far lower than seawater. Cell adhesion in sponges is mediated by calcium-dependent multivalent self-interactions of sulfated polysaccharide components of membrane-bound proteoglycans named aggregation factors. Cells of marine sponges require seawater average calcium concentration (10 mM) to sustain adhesion promoted by aggregation factors. We demonstrate here that the freshwater sponge Spongilla alba can thrive in a calcium-poor aquatic environment and that their cells are able to aggregate and form primmorphs with calcium concentrations 40-fold lower than that required by marine sponges cells. We also find that their gemmules need calcium and other micronutrients to hatch and generate new sponges. The sulfated polysaccharide purified from S. alba has sulfate content and molecular size notably lower than those from marine sponges. Nuclear magnetic resonance analyses indicated that it is composed of a central backbone of non- and 2-sulfated α- and ß-glucose units decorated with branches of α-glucose. Assessments with atomic force microscopy/single-molecule force spectroscopy show that S. alba glucan requires 10-fold less calcium than sulfated polysaccharides from marine sponges to self-interact efficiently. Such an ability to retain multicellular morphology with low environmental calcium must have been a crucial evolutionary step for freshwater sponges to successfully colonize inland waters.
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Cálcio/metabolismo , Polissacarídeos/metabolismo , Poríferos/metabolismo , Proteoglicanas/metabolismo , Animais , Cálcio/química , Adesão Celular , Água Doce , Polissacarídeos/química , Poríferos/citologia , Proteoglicanas/químicaRESUMO
Early metazoans had to evolve the first cell adhesion mechanism addressed to maintain a distinctive multicellular morphology. As the oldest extant animals, sponges are good candidates for possessing remnants of the molecules responsible for this crucial evolutionary innovation. Cell adhesion in sponges is mediated by the calcium-dependent multivalent self-interactions of sulfated polysaccharides components of extracellular membrane-bound proteoglycans, namely aggregation factors. Here, we used atomic force microscopy to demonstrate that the aggregation factor of the sponge Desmapsamma anchorata has a circular supramolecular structure and that it thus belongs to the spongican family. Its sulfated polysaccharide units, which were characterized via nuclear magnetic resonance analysis, consist preponderantly of a central backbone composed of 3-α-Glc1 units partially sulfated at 2- and 4-positions and branches of Pyr(4,6)α-Gal1â3-α-Fuc2(SO3)1â3-α-Glc4(SO3)1â3-α-Glcâ4-linked to the central α-Glc units. Single-molecule force measurements of self-binding forces of this sulfated polysaccharide and their chemically desulfated and carboxyl-reduced derivatives revealed that the sulfate epitopes and extracellular calcium are essential for providing the strength and stability necessary to sustain cell adhesion in sponges. We further discuss these findings within the framework of the role of molecular structures in the early evolution of metazoans.
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Evolução Biológica , Cálcio/química , Polissacarídeos/química , Poríferos/química , Sulfatos/química , Animais , Cálcio/metabolismo , Microscopia de Força Atômica , Polissacarídeos/metabolismo , Polissacarídeos/ultraestrutura , Poríferos/metabolismo , Poríferos/ultraestrutura , Sulfatos/metabolismoRESUMO
Phenol is one of the most important fine chemical intermediates in the synthesis of plastics and drugs with a market size of ca. $30b1 and the commercial production is via a two-step selective oxidation of benzene, requiring high energy input (high temperature and high pressure) in the presence of a corrosive acidic medium, and causing serious environmental issues2-5. Here we present a four-phase interface strategy with well-designed Pd@Cu nanoarchitecture decorated TiO2 as a catalyst in a suspension system. The optimised catalyst leads to a turnover number of 16,000-100,000 for phenol generation with respect to the active sites and an excellent selectivity of ca. 93%. Such unprecedented results are attributed to the efficient activation of benzene by the atomically Cu coated Pd nanoarchitecture, enhanced charge separation, and an oxidant-lean environment. The rational design of catalyst and reaction system provides a green pathway for the selective conversion of symmetric organic molecules.
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To boost efficient energy transitions, alternatives to expensive and unsustainable noble metal-based electrocatalysts for the oxygen reduction reaction (ORR) are needed. Having this in mind, carbon black - Black Pearls 2000 (BP) was enriched in active nitrogen-containing centers, including single-atom Fe-N sites surrounded by Fe nanoclusters, through a synthesis methodology employing only broadly available precursors. The methodical approach taken to optimize the synthesis conditions highlighted the importance of (1) a proper choice of the Fe precursor; (2) melamine as an N source to limit the formation of magnetite crystals and modulate the charge density nearby the active sites, and glucose to chelate/isolate Fe atoms and thus allow the Fe-N coordination to be established, with a limiting formation of Fe0 clusters; and (3) a careful dosing of the Fe load. The ORR on the optimized electrocatalyst (Fe0.06-N@BP) proceeds mostly through a four-electron pathway, having an onset potential (0.912 V vs. RHE) and limiting current density (4.757 mA cm-2) above those measured on Pt/C (0.882 V and 4.657 mA cm-2, respectively). Moreover, the current density yielded by Fe0.06-N@BP after 24 h at 0.4 V vs. RHE was still above that of Pt/C at t = 0 (4.44 mA cm-2), making it a promising alternative to noble metal-containing electrocatalysts in fuel cells.
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Methane activation by photocatalysis is one of the promising sustainable technologies for chemical synthesis. However, the current efficiency and stability of the process are moderate. Herein, a PdCu nanoalloy (~2.3 nm) was decorated on TiO2, which works for the efficient, stable, and selective photocatalytic oxidative coupling of methane at room temperature. A high methane conversion rate of 2480 µmol g-1 h-1 to C2 with an apparent quantum efficiency of ~8.4% has been achieved. More importantly, the photocatalyst exhibits the turnover frequency and turnover number of 116 h-1 and 12,642 with respect to PdCu, representing a record among all the photocatalytic processes (λ > 300 nm) operated at room temperature, together with a long stability of over 112 hours. The nanoalloy works as a hole acceptor, in which Pd softens and weakens C-H bond in methane and Cu decreases the adsorption energy of C2 products, leading to the high efficiency and long-time stability.
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OBJECTIVES: Toothbrushing, though aimed at biofilm removal, also affects the lubricative function of adsorbed salivary conditioning films (SCFs). Different modes of brushing (manual, powered, rotary-oscillatory or sonically driven) influence the SCF in different ways. Our objectives were to compare boundary lubrication of SCFs after different modes of brushing and to explain their lubrication on the basis of their roughness, dehydrated layer thickness, and degree of glycosylation. A pilot study was performed to relate in vitro lubrication with mouthfeel in human volunteers. MATERIALS AND METHODS: Coefficient of friction (COF) on 16-h-old SCFs after manual, rotary-oscillatory, and sonically driven brushing was measured using colloidal probe atomic force microscopy (AFM). AFM was also used to assess the roughness of SCFs prior to and after brushing. Dehydrated layer thicknesses and glycosylation of the SCFs were determined using X-ray photoelectron spectroscopy. Mouthfeel after manual and both modes of powered brushing were evaluated employing a split-mouth design. RESULTS: Compared with unbrushed and manually or sonically driven brushed SCFs, powered rotary-oscillatory brushing leads to deglycosylation of the SCF, loss of thickness, and a rougher film. Concurrently, the COF of a powered rotary-oscillatory brushed SCF increased. Volunteers reported a slightly preferred mouthfeel after sonic brushing as compared to powered rotating-oscillating brushing. CONCLUSION: Deglycosylation and roughness increase the COF on SCFs. CLINICAL RELEVANCE: Powered rotary-oscillatory brushing can deglycosylate a SCF, leading to a rougher film surface as compared with manual and sonic brushing, decreasing the lubricative function of the SCF. This is consistent with clinical mouthfeel evaluation after different modes of brushing.
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Lubrificação , Saliva/química , Escovação Dentária/instrumentação , Adulto , Feminino , Glicosilação , Voluntários Saudáveis , Humanos , Masculino , Microscopia de Força Atômica , Espectroscopia Fotoeletrônica , Projetos Piloto , Propriedades de SuperfícieRESUMO
This work reports the ellipsometry analysis of atomic layer deposition (ALD) films of ZnO doped with Zr to determine parameters like free carrier concentration and mobility. Thin films of zinc oxide (ZnO) and Zr-doped ZnO of thickness â¼100 nm were prepared by atomic layer deposition on sapphire, SiO2/Si(100), and Si(100) substrates. Variable-angle spectroscopic ellipsometry was used to study their optical properties in the 0.5-3.5 eV spectral range. The optical constants were accurately obtained using a model that combines Drude and Tauc-Lorentz oscillators with Bruggeman effective medium approximations, allowing the inclusion of a roughness layer in the optical model. The effect of Zr doping (ca. 1.9-4.4 atom %) was then investigated in both as-prepared samples and samples annealed in the temperature range of 100-300 °C. All of the films exhibited good optical transparency (ca. 70-90% in the visible region). For doping levels below 2.7 atom %, the real part of the dielectric permittivity reveals a semiconductor-to-metal transition in the near-infrared (NIR) region, as the permittivity goes from positive to negative. Besides, the plasma energy increases with increasing Zr concentration, and both resistivity and carrier concentration exhibit slightly parabolic behaviors, with a minimum of â¼1.5 × 10-3 Ω cm and a maximum of 2.4 × 1020 cm-3, respectively, at the same critical Zr concentration (2.7 atom %). In contrast, the carrier mobility decreases rapidly from 76.0 to 19.2 cm2/(V s) with increasing Zr content, while conductivities and carrier mobilities worsen when the annealing temperature increases, probably due to the segregation of ZnO crystals. Finally, the optical band gap is very stable, revealing its interesting independence of substrate composition and annealing temperature, as it collapses to a single master curve when band gap energy is plotted versus free carrier concentration, following the Burstein-Moss effect. Overall, the Zr-doped ZnO films studied here would be a highly desirable system for developing thermally stable transparent conductive oxides (TCOs).
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The optical properties of 5wt% Fe3O4-TiO2 thin films were evaluated in detail with the aim of proposing a mechanism for solar photocatalytic processes and highlighting the advantages over the use of bare TiO2. The results showed that the incorporation of 5wt% Fe3O4 enhanced the optical properties by a redshift to a wavelength in the visible range, reducing the anatase/rutile band gap energy from 3.2 eV to 2.8 eV. Photoluminescence studies reveal a superior separation efficiency of photoexcited electron-hole pairs when Fe3O4 nanoparticles (NPs) are present in the photocatalyst. X-ray photoelectron spectroscopy spectra confirm the presence of Fe3O4 and existence of a chemical bonding between TiO2 and Fe3O4 NPs. Moreover, in this study, a mechanism of solar photocatalytic processes involving Fe3O4-TiO2 thin films is proposed and it is supported by experimental results. Finally, solar photocatalytic experiments were carried out, indicating that the effectiveness for the removal of the selected pharmaceutical is considerably improved when the composite material is used as catalyst. Furthermore, it was demonstrated that the photocatalytic activity of the prepared Fe3O4-TiO2 thin films depends on their thickness, achieving the highest pharmaceutical removal yields using the 2 µm thick sample. The stability and reusability of the catalyst was confirmed studying the photocatalytic activity over three cycles.
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A new approach for the preparation of carbohydrate-coated magnetic nanoparticles is reported. In a first step, we show that the pH-driven assembly-disassembly natural process that occurs in apoferritin protein is effective for the encapsulation of maghemite nanoparticles of different sizes: 4 and 6 nm. In a second step, we demonstrate that the presence of functional amine groups in the outer shell of apoferritin allows functionalization with two carbohydrates, N-acetyl-D-glucosamine and d-mannose. High-resolution electron microscopy (HREM), high angle annular dark field scanning electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), and SQUID technique have been used to characterize the magnetic samples, termed herein Apomaghemites. The in vivo magnetic resonance imaging (MRI) studies showed the efficiency in contrasting images for these samples; that is, the r(2) NMR relaxivities are comparable with Endorem (a commercial superparamagnetic MRI contrast agent). The r(2) relaxivity values as well as the pre-contrast and post-contrast T(2)*-weighted images suggested that our systems could be used as perspective superparamagnetic contrast agents for magnetic resonance imaging (MRI). The carbohydrate-functionalized Apomaghemite nanoparticles retained their recognition abilities, as demonstrated by the strong affinity with their corresponding carbohydrate-binding lectins.
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Apoferritinas/química , Compostos Férricos/química , Lectinas/química , Magnetismo , Nanopartículas/química , Subunidades Proteicas/química , Carboidratos/química , Cristalografia por Raios X , Concentração de Íons de Hidrogênio , Imageamento por Ressonância Magnética , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Methanol adsorption over both supported NiSn Nps and analogous NiSn catalyst prepared by impregnation was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to gain insights into the basis of hydrogen production from methanol steam reforming. Different intermediate species such as methoxides with different geometry (bridge and monodentate) and formate species were identified after methanol adsorption and thermal desorption. It is proposed that these species are the most involved in the methanol steam reforming reaction and the major presence of metal-support interface sites in supported NiSn Nps leads to higher production of hydrogen. On the basis of these results, a plausible reaction mechanism was elucidated through the correlation between the thermal stability of these species and the evolution of the effluent gas released. In addition, it was demonstrated that DME is a secondary product generated by condensation of methoxides over the acid sites of alumina support in an acid-catalyzed reaction.
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A family of iron-doped manganese-related hollandites, K x Mn1-y Fe y O2-δ (0 ≤ y ≤ 0.15), with high performance in CO oxidation have been prepared. Among them, the most active catalyst, K0.11Mn0.876Fe0.123O1.80(OH)0.09, is able to oxidize more than 50% of CO at room temperature. Detailed compositional and structural characterization studies, using a wide battery of thermogravimetric, spectroscopic, and diffractometric techniques, both at macroscopic and microscopic levels, have provided essential information about this never-reported behavior, which relates to the oxidation state of manganese. Neutron diffraction studies evidence that the above compound stabilizes hydroxyl groups at the midpoints of the tunnel edges as in isostructural ß-FeOOH. The presence of oxygen and hydroxyl species at the anion sublattice and Mn3+, confirmed by electron energy loss spectroscopy, appears to play a key role in the catalytic activity of this doped hollandite oxide. The analysis of these detailed structural features has allowed us to point out the key role of both OH groups and Mn3+ content in these materials, which are able to effectively transform CO without involving any critical, noble metal in the catalyst formulation.
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Hydrogen production by photocatalytic reforming of aqueous solutions of ethanol and glycerol was studied with the use of impregnated and embedded CuO(x)/TiO(2) photocatalysts. Embedded CuO(x)@TiO(2) was prepared by a water-in-oil microemulsion method, which consists in the formation of Cu nanoparticles in the microemulsion followed by controlled hydrolysis and condensation of tetraisopropyl orthotitanate with the aim of covering the protected metal particles with a surrounding layer of porous titanium oxyhydroxide. Mild calcination leads to the complete removal of the organic residues, the crystallization of TiO(2), and an unavoidable oxidation of copper. Two reference samples were prepared by classical wet impregnation of preformed TiO(2) with different ratios of anatase, rutile, and brookite polymorphs. The two supports were prepared by sol-gel (TiO(2)-SG) and microemulsion (TiO(2)-ME) methods. Superior performances have been observed for the embedded system, which shows higher hydrogen production rates with respect to the impregnated systems using either ethanol or glycerol as sacrificial molecules. Deep structural characterization of the materials has been performed by coupling high resolution transmission electron microscopy (HRTEM), high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), X-ray absorption fine structure (XAFS), and electron paramagnetic resonance (EPR) techniques. Correlation between copper oxidation state and its dispersion and reactivity has been attempted. Finally, the stability of the CuO(x)/TiO(2) catalysts was also studied with respect to carbonaceous deposits and copper leaching.
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The high pollution levels in our cities are producing a significant increase of dust on buildings. An application of photoactive coatings on building materials can produce buildings with self-cleaning surfaces. In this study, we have developed a simple sol-gel route for producing Au-TiO2/SiO2 photocatalysts with application on buildings. The gold nanoparticles (AuNPs) improved the TiO2 photoactivity under solar radiation because they promoted absorption in the visible range. We varied the content of AuNPs in the sols under study, in order to investigate their effect on self-cleaning properties. The sols obtained were sprayed on a common building stone, producing coatings which adhere firmly to the stone and preserve their aesthetic qualities. We studied the decolourization efficiency of the photocatalysts under study against methylene blue and against soot (a real staining agent for buildings). Finally, we established that the coating with an intermediate Au content presented the best self-cleaning performance, due to the role played by its structure and texture on its photoactivity.
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The selective oxidation of veratryl alcohol (VA), a model compound of lignin, with oxygen molecules to produce veratraldehyde (VAld) was studied over monometallic Au, Pd, and bimetallic Au:Pd nanoparticles supported on a Ce0.62Zr0.38O2 mixed oxide for the first time. These bimetallic Au-Pd catalysts with Au:Pd molar ratios from 0.4 to 4.3 were synthesized by the sol-immobilization method. Furthermore, all the catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), N2 physisorption, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) imaging, energy dispersive X-ray spectroscopy (EDXS), and temperature programmed reduction (TPR) techniques. A synergistic effect between gold and palladium was observed over all the bimetallic catalysts in a wide range of studied Au:Pd ratios. Remarkably, the optimum Au:Pd ratio for this reaction was 1.4 with a turnover frequency of almost six times larger than for the monometallic gold and palladium catalysts. Selectivity to veratraldehyde was higher than 99% for the monometallic Au, Pd, and all the bimetallic Au-Pd catalysts, and stayed constant during the reaction time.
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BACKGROUND AND OBJECTIVE: The preoperative planning of bone fractures using information from CT scans increases the probability of obtaining satisfactory results, since specialists are provided with additional information before surgery. The reduction of complex bone fractures requires solving a 3D puzzle in order to place each fragment into its correct position. Computer-assisted solutions may aid in this process by identifying the number of fragments and their location, by calculating the fracture zones or even by computing the correct position of each fragment. The main goal of this paper is the development of an automatic method to calculate contact zones between fragments and thus to ease the computation of bone fracture reduction. METHODS: In this paper, an automatic method to calculate the contact zone between two bone fragments is presented. In a previous step, bone fragments are segmented and labelled from CT images and a point cloud is generated for each bone fragment. The calculated contact zones enable the automatic reduction of complex fractures. To that end, an automatic method to match bone fragments in complex fractures is also presented. RESULTS: The proposed method has been successfully applied in the calculation of the contact zone of 4 different bones from the ankle area. The calculated fracture zones enabled the reduction of all the tested cases using the presented matching algorithm. The performed tests show that the reduction of these fractures using the proposed methods leaded to a small overlapping between fragments. CONCLUSIONS: The presented method makes the application of puzzle-solving strategies easier, since it does not obtain the entire fracture zone but the contact area between each pair of fragments. Therefore, it is not necessary to find correspondences between fracture zones and fragments may be aligned two by two. The developed algorithms have been successfully applied in different fracture cases in the ankle area. The small overlapping error obtained in the performed tests demonstrates the absence of visual overlapping in the figures.
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Fraturas Ósseas/terapia , Terapia Assistida por Computador , Algoritmos , Fraturas Ósseas/diagnóstico por imagem , Humanos , Tomografia Computadorizada por Raios XRESUMO
The therapeutic benefit of local administration of growth factors using controlled release systems for bone regeneration is under study. In the present work, a PDGF release profile from chitosan granules administered into bone defect produced in the femur of Wistar rats was obtained using 125I-PDGF as tracer and a probe-type gamma counter with a suitable collimator for detection. The measurement method was validated by the radioactivity values obtained from the isolated bones using a well-type gamma counter. Both the invasive and the non-invasive measurement methods were linear in the analyzed range, with coefficients of variation around 3% and 15%, respectively. A good correlation between the two methods was found for the 125I-PDGF release profile from the chitosan granules. These results confirm that a reliable release profile can be obtained for a drug incorporated into delivery systems for local bone therapy using this non-invasive measurement method.
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Osso e Ossos/metabolismo , Fator de Crescimento Derivado de Plaquetas/administração & dosagem , Fator de Crescimento Derivado de Plaquetas/análise , Animais , Doenças Ósseas/tratamento farmacológico , Doenças Ósseas/patologia , Osso e Ossos/química , Quitosana , Sistemas de Liberação de Medicamentos , Excipientes , Fêmur/patologia , Radioisótopos do Iodo , Masculino , Tamanho da Partícula , Fator de Crescimento Derivado de Plaquetas/farmacocinética , Pós , Ratos , Ratos Wistar , Reprodutibilidade dos TestesRESUMO
The development of support systems for surgery significantly increases the likelihood of obtaining satisfactory results. In the case of fracture reduction interventions these systems enable surgery planning, training, monitoring and assessment. They allow improvement of fracture stabilization, a minimizing of health risks and a reduction of surgery time. Planning a bone fracture reduction by means of a computer assisted simulation involves several semiautomatic or automatic steps. The simulation deals with the correct position of osseous fragments and fixation devices for a fracture reduction. Currently, to the best of our knowledge there is no computer assisted methods to plan an entire fracture reduction process. This paper presents an overall scheme of the computer based process for planning a bone fracture reduction, as described above, and details its main steps, the most common proposed techniques and their main shortcomings. In addition, challenges and new trends of this research field are depicted and analyzed.