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1.
Inorg Chem ; 2020 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-32453586

RESUMO

The electronic structures of V-intercalated TiSe2 and substitutionally doped dichalcogenides Ti1-xVxSe2 have been studied using soft X-ray photoelectron, resonant photoelectron, and absorption spectroscopies. In the case of the substitution of Ti by V, the formation of coherently oriented structural fragments VSe2 and TiSe2 is observed and a small charge transfer between these fragments is found. Intercalation of the V atoms into TiSe2 leads to charge transfer from the V atoms to the Ti atoms with the formation of covalent complexes Ti-Se3-V-Se3-Ti.

2.
Inorg Chem ; 58(8): 4935-4944, 2019 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-30920816

RESUMO

Iron is an essential nutrient for nearly all forms of life, although scarcely available due to its poor solubility in nature and complex formation in higher eukaryotes. Microorganisms have evolved a vast array of strategies to acquire iron, the most common being the production of high-affinity iron chelators, termed siderophores. The opportunistic bacterial pathogen Pseudomonas aeruginosa synthesizes and secretes two siderophores, pyoverdine (PVD) and pyochelin (PCH), characterized by very different structural and functional properties. Due to its chemical similarity with Fe(III), Ga(III) interferes with several iron-dependent biological pathways. Both PVD and PCH bind Fe(III) and Ga(III). However, while the Ga-PCH complex is more effective than Ga(III) in inhibiting P. aeruginosa growth, PVD acts as a Ga(III) scavenger and protects bacteria from Ga(III) toxicity. To gain more insight into the different outcomes of the biological paths observed for the Fe(III) and Ga(III)-siderophore complexes, better knowledge is needed of their coordination geometries that directly influence the metal complexes chemical stability. The valence state and coordination geometry of the Ga-PCH and Fe-PCH complexes has recently been investigated in detail; as for PVD complexes, several NMR structural studies of Ga(III)-PVD are reported in the literature, using Ga(III) as a diamagnetic isosteric substitute for Fe(III). In this work, we applied up-to-date spectroscopic techniques as synchrotron-radiation-induced X-ray photoelectron spectroscopy (SR-XPS) and X-ray absorption fine structure (XAFS) spectroscopy coupled with molecular modeling to describe the electronic structure and coordination chemistry of Fe and Ga coordinative sites in PVD metal complexes. These techniques allowed us to unambiguously determine the oxidation state of the coordinative ions and to gather interesting information about the similarities and differences between the two coordination compounds as induced by the different metal.

3.
Chem Sci ; 10(6): 1857-1865, 2019 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-30842854

RESUMO

The space between a metal surface and a two-dimensional cover can be regarded as a nanoreactor, where confined molecule adsorption and surface reactions may occur. In this work, we report CO intercalation and reactivity between a graphene-hexagonal boron nitride (h-BNG) heterostructure and Pt(111). By employing high resolution X-ray photoemission spectroscopy (XPS) we demonstrate the molecular intercalation of the full h-BNG overlayer and stabilization of a dense R23.4°-13CO layer on Pt(111) under ultra-high vacuum at room temperature. We provide experimental evidence of a weakened CO-metal bond due to the confinement effects of the 2D cover. Temperature-programmed XPS results reveal that CO desorption is kinetically delayed and occurs at a higher temperature than on bare Pt(111). Moreover, CO partially reacts with the h-BNG layer to form boron-oxide species, which affect repeated CO intercalation. Finally, we found that the properties of the system towards interaction with CO can be considerably recovered using high temperature treatment.

4.
Phys Chem Chem Phys ; 20(41): 26161-26172, 2018 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-30311617

RESUMO

The structure and electronic properties of carbon-based nanostructures obtained by metal surface assisted synthesis is highly dependent on the nature of the precursor molecule. Here, we report on a combined scanning tunneling microscopy, soft X-ray spectroscopy and density functional theory investigation on the surface assisted polymerization of Br-corannulene at Ag(110) and on the possibility of building a mesh of π-conjugated polymers starting from buckyball shaped molecules. Indeed, the corannulene units form one-molecule-wide ribbons in which the natural concavity of the precursor molecule is maintained. These C-based nanostructures are corrugated and merge into a covalent network on the surface.

5.
Langmuir ; 34(30): 8887-8897, 2018 07 31.
Artigo em Inglês | MEDLINE | ID: mdl-29975548

RESUMO

The performance of devices containing colloidal quantum dot (CQD) films is strongly dependent on the surface chemistry of the CQDs they contain. Multistep surface treatments, which combine two or more strategies, are important for creating films with high carrier mobility that are well passivated against trap states and oxidation. Here, we examine the effect of a number of these surface treatments on PbS CQD films, including cation exchange to form PbS/CdS core/shell CQDs, and solid-state ligand-exchange treatments with Cl, Br, I, and 1,2-ethanedithiol (EDT) ligands. Using laboratory-based and synchrotron-radiation-excited X-ray photoelectron spectroscopy (XPS), we examine the compositions of the surface layer before and after treatment, and correlate this with the performance data and stability in air. We find that halide ion treatments may etch the CQD surfaces, with detrimental effects on the air stability and solar cell device performance caused by a reduction in the proportion of passivated surface sites. We show that films made up of PbS/CdS CQDs are particularly prone to this, suggesting Cd is more easily etched from the surface than Pb. However, by choosing a less aggressive ligand treatment, a good coverage of passivators on the surface can be achieved. We show that halide anions bind preferentially to surface Pb (rather than Cd). By isolating the part of XPS signal originating from the topmost surface layer of the CQD, we show that air stability is correlated with the total number of passivating agents (halide + EDT + Cd) at the surface.

6.
Nanomaterials (Basel) ; 8(7)2018 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-30004404

RESUMO

Silver nanoparticles capped with 3-mercapto-1propanesulfonic acid sodium salt (AgNPs-3MPS), able to interact with Ni2+ or Co2+, have been prepared to detect these heavy metal ions in water. This system works as an optical sensor and it is based on the change of the intensity and shape of optical absorption peak due to the surface plasmon resonance (SPR) when the AgNPs-3MPS are in presence of metals ions in a water solution. We obtain a specific sensitivity to Ni2+ and Co2+ up to 500 ppb (part per billion). For a concentration of 1 ppm (part per million), the change in the optical absorption is strong enough to produce a colorimetric effect on the solution, easily visible with the naked eye. In addition to the UV-VIS characterizations, morphological and dimensional studies were carried out by transmission electron microscopy (TEM). Moreover, the systems were investigated by means of dynamic light scattering (DLS), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and high-resolution X-ray photoelectron spectroscopy (HR-XPS). On the basis of the results, the mechanism responsible for the AgNPs-3MPS interaction with Ni2+ and Co2+ (in the range of 0.5⁻2.0 ppm) looks like based on the coordination compounds formation.

7.
Sci Rep ; 8(1): 8740, 2018 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-29880895

RESUMO

The effects of Cr on local environment and electronic structure of rutile TiO2 are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities CrTi0 and CrTi1- as well as Cr-oxygen vacancy complex 2CrTi + VO are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO2 at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t2g states of the Cr ions in order to reach the stable oxidation state of Cr3+. Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO2 cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO2 are very sensitive to the concentration of Cr.

8.
Chem Sci ; 9(4): 990-998, 2018 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-29629166

RESUMO

The nature of the oxygen species active in ethylene epoxidation is a long-standing question. While the structure of the oxygen species that participates in total oxidation (nucleophilic oxygen) is known the atomic structure of the selective species (electrophilic oxygen) is still debated. Here, we use both in situ and UHV X-ray Photoelectron Spectroscopy (XPS) to study the interaction of oxygen with a silver surface. We show experimental evidence that the unreconstructed adsorbed atomic oxygen (Oads) often argued to be active in epoxidation has a binding energy (BE) ≤ 528 eV, showing a core-level shift to lower BE with respect to the O-reconstructions, as previously predicted by DFT. Thus, contrary to the frequent assignment, adsorbed atomic oxygen cannot account for the electrophilic oxygen species with an O 1s BE of 530-531 eV, thought to be the active species in ethylene epoxidation. Moreover, we show that Oads is present at very low O-coverages during in situ XPS measurements and that it can be obtained at slightly higher coverages in UHV at low temperature. DFT calculations support that only low coverages of Oads are stable. The highly reactive species is titrated by background gases even at low temperature in UHV conditions. Our findings suggest that at least two different species could participate in the partial oxidation of ethylene on silver.

9.
J Am Chem Soc ; 139(26): 8960-8970, 2017 07 05.
Artigo em Inglês | MEDLINE | ID: mdl-28598604

RESUMO

Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co3O4/Co(OH)2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH)2 and partial conversion of the spinel Co3O4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co3O4 catalyst supports this interpretation and reveals that the presence of Co(OH)2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.

10.
Nanoscale ; 9(18): 6056-6067, 2017 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-28443889

RESUMO

Achieving control of the surface chemistry of colloidal quantum dots (CQDs) is essential to fully exploit their properties in solar cells, but direct measurement of the chemistry and electronic structure in the outermost atomic layers is challenging. Here we probe the surface oxidation and passivation of cation-exchanged PbS/CdS core/shell CQDs with sub nm-scale precision using synchrotron-radiation-excited depth-profiling photoemission. We investigate the surface composition of the topmost 1-2.5 nm of the CQDs as a function of depth, for CQDs of varying CdS shell thickness, and examine how the surface changes after prolonged air exposure. We demonstrate that the Cd is localized at the surface of the CQDs. The surface-localized products of oxidation are identified, and the extent of oxidation quantified. We show that oxidised sulfur species are progressively eliminated as Cd replaces Pb at the surface. A sub-monolayer surface 'decoration' of Cd is found to be effective in passivating the CQDs. We show that the measured energy-level alignments at PbS/CdS colloidal quantum dot surfaces differ from those expected on the basis of bulk band offsets, and are strongly affected by the oxidation products. We develop a model for the passivating action of Cd. The optimum shell thickness (of around 0.1 nm, previously found to give maximised power conversion efficiency in PbS/CdS solar cells) is found to correspond to a trade-off between the rate of oxidation and the introduction of a surface barrier to charge transport.

11.
Phys Chem Chem Phys ; 18(48): 33233-33239, 2016 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-27892576

RESUMO

In this paper, we study the magnetic and chemical properties of Fe/graphene vertically stacked ultrathin films by means of X-ray magnetic circular dichroism and X-ray photoelectron spectroscopy. We compare two systems: an iron layer deposited directly on top of the Pt(111) surface, and an intercalated Fe film sandwiched between graphene and Pt(111). The system composed of a submonolayer Fe deposited directly on Pt(111) maintains an out-of-plane easy magnetization axis, even if it has been covered by graphene that quenches effectively the magnetic orbital moment of Fe. However, when the Fe coverage is increased above 1 ML the easy magnetization axis flips in the in-plane direction.

12.
Nanoscale ; 8(41): 17843-17853, 2016 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-27714142

RESUMO

By a combination of scanning tunneling microscopy, X-ray spectroscopic techniques and density functional theory calculations, we prove the formation of extended patterns of parallel, graphene nanoribbons with alternate zig-zag and armchair edges and selected width by surface-assisted Ullmann coupling polymerization and dehydrogenation of 1,6-dibromopyrene (C16H8Br2). Besides the relevance of these nanostructures for their possible application in nanodevices, we demonstrate the peculiarity of halogenated pyrene derivatives for the formation of nanoribbons, in particular on Ag(110). These results open the possibility of tuning the shape and dimension of nanoribbons (and hence the correlated electronic properties) by choosing suitably tailored or on-purpose designed molecular precursors.

13.
Sci Rep ; 6: 21629, 2016 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-26899926

RESUMO

The mesenchymal state in cancer is usually associated with poor prognosis due to the metastatic predisposition and the hyper-activated metabolism. Exploiting cell glucose metabolism we propose a new method to detect mesenchymal-like cancer cells. We demonstrate that the uptake of glucose-coated magnetic nanoparticles (MNPs) by mesenchymal-like cells remains constant when the glucose in the medium is increased from low (5.5 mM) to high (25 mM) concentration, while the MNPs uptake by epithelial-like cells is significantly reduced. These findings reveal that the glucose-shell of MNPs plays a major role in recognition of cells with high-metabolic activity. By selectively blocking the glucose transporter 1 channels we showed its involvement in the internalization process of glucose-coated MNPs. Our results suggest that glucose-coated MNPs can be used for metabolic-based assays aimed at detecting cancer cells and that can be used to selectively target cancer cells taking advantage, for instance, of the magnetic-thermotherapy.


Assuntos
Neoplasias da Mama/tratamento farmacológico , Transportador de Glucose Tipo 1/genética , Glucose/administração & dosagem , Nanopartículas de Magnetita/administração & dosagem , Neoplasias da Mama/diagnóstico , Neoplasias da Mama/patologia , Células Epiteliais/efeitos dos fármacos , Células Epiteliais/patologia , Feminino , Glucose/química , Glucose/metabolismo , Transportador de Glucose Tipo 1/antagonistas & inibidores , Humanos , Hipertermia Induzida , Células MCF-7 , Nanopartículas de Magnetita/química , Mesoderma/metabolismo , Mesoderma/patologia
14.
ACS Appl Mater Interfaces ; 7(46): 25685-92, 2015 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-26517577

RESUMO

Aerosol processing enables the preparation of hierarchical graphene nanocomposites with special crumpled morphology in high yield and in a short time. Using modular insertion of suitable precursors in the starting solution, it is possible to synthesize different types of graphene-based materials ranging from heteroatom-doped graphene nanoballs to hierarchical nanohybrids made up by nitrogen-doped crumpled graphene nanosacks that wrap finely dispersed MoS2 nanoparticles. These materials are carefully investigated by microscopic (SEM, standard and HR TEM), diffraction (grazing incidence X-ray diffraction (GIXRD)) and spectroscopic (high resolution photoemission, Raman and UV-visible spectroscopy) techniques, evidencing that nitrogen dopants provide anchoring sites for MoS2 nanoparticles, whereas crumpling of graphene sheets drastically limits aggregation. The activity of these materials is tested toward the photoelectrochemical production of hydrogen, obtaining that N-doped graphene/MoS2 nanohybrids are seven times more efficient with respect to single MoS2 because of the formation of local p-n MoS2/N-doped graphene nanojunctions, which allow an efficient charge carrier separation.

15.
Chemistry ; 21(15): 5826-35, 2015 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-25711882

RESUMO

Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions.

16.
Langmuir ; 30(5): 1336-42, 2014 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-24443819

RESUMO

Despite the relevance of carbohydrates as cues in eliciting specific biological responses, the covalent surface modification of collagen-based matrices with small carbohydrate epitopes has been scarcely investigated. We report thereby the development of an efficient procedure for the chemoselective neoglycosylation of collagen matrices (patches) via a thiol-ene approach, between alkene-derived monosaccharides and the thiol-functionalized material surface. Synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS), Fourier transform-infrared (FT-IR), and enzyme-linked lectin assay (ELLA) confirmed the effectiveness of the collagen neoglycosylation. Preliminary biological evaluation in osteoarthritic models is reported. The proposed methodology can be extended to any thiolated surface for the development of smart biomaterials for innovative approaches in regenerative medicine.


Assuntos
Materiais Biocompatíveis/química , Carboidratos/química , Química Click , Colágeno/química , Compostos de Sulfidrila/química , Animais , Sequência de Carboidratos , Modelos Animais de Doenças , Ensaio de Imunoadsorção Enzimática , Glicosilação , Masculino , Estrutura Molecular , Osteoartrite/terapia , Espectroscopia Fotoeletrônica , Ratos , Ratos Wistar , Espectroscopia de Infravermelho com Transformada de Fourier
17.
J Med Chem ; 51(11): 3250-60, 2008 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-18484716

RESUMO

The synthesis of the Fe(III), Co(II), Mn(II), and Ru(III) complexes with two polyamine-polycarboxylate ligands, N-(2-hydroxyethyl)ethylenediamine-N, N', N'-triacetic acid (H3L1) and ethylene bisglycol tetraacetic acid (H4L2) is reported. Potentiometric studies showed that these ligands form stable complexes in aqueous solution and no metal release occurs, thus accounting for their low toxicity in cultured RAW 264.7 macrophages. X-ray characterization of the [Co(L1)](-) complex showed that binding sites are available at the metal for NO binding. Efficiency of these compounds to bind NO was studied by UV-vis spectrophotometry. Then their NO-scavenging properties were assayed in a cell-free system under physiological conditions, using S-nitroso-N-acetyl-D,L-penicillamine (SNAP) as NO source. The L1 complexes caused the most effective reduction of free NO, [Mn(L1)](-) being the most efficient. Conversely, in NOS II induced RAW 264.7 macrophages, the Ru(III) and Co(II) complexes with L2 were the most effective compounds. [Ru(L2)](-) also afforded significant protection against lipopolysaccharide-induced endotoxic shock in the mouse in vivo.


Assuntos
Quelantes/química , Cobalto , Ácido Edético/análogos & derivados , Ácido Egtázico/análogos & derivados , Ácido Egtázico/química , Ferro , Manganês , Óxido Nítrico/metabolismo , Rutênio , Animais , Linhagem Celular , Quelantes/farmacologia , Cristalografia por Raios X , Ácido Edético/química , Ácido Edético/farmacologia , Ácido Egtázico/farmacologia , Ligantes , Lipopolissacarídeos/farmacologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Modelos Moleculares , Doadores de Óxido Nítrico/química , Potenciometria , S-Nitroso-N-Acetilpenicilamina/farmacologia , Choque/tratamento farmacológico , Relação Estrutura-Atividade
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