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The discovery of ferroelectricity in two-dimensional van der Waals materials has sparked enormous interest from the scientific community, due to its possible applications in next-generation nanoelectronic devices, such as random-access memory devices, digital signal processors, and solar cells, among others. In the present study, we used vapor phase deposition to synthesize ultrathin germanium sulfide nano-flakes on a highly oriented pyrolytic graphite substrate. Nanostructures of variable thicknesses were characterized using scanning tunneling microscopy and spectroscopy. Tunneling currents under forward and backward biases were measured as a function of nano-flake thickness. Remarkably, we clearly observed a hysteresis pattern, which we attributed to surface ferroelectric behavior, consistent with the screening conditions of polarization charges. The effect increases as the number of layers is reduced. This experimental result may be directly applicable to miniaturized memory devices, given the two-dimensional nature of this effect.
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The prediction of semiconductor device performance is a persistent challenge in materials science, and the ability to anticipate useful specifications prior to construction is crucial for enhancing the overall efficiency. In this study, we investigate the constituents of a solar cell by employing scanning tunneling microscopy (STM) and spectroscopy (STS). Through our observations, we identify a spatial distribution of the dopant type in thin films of materials that were designed to present major p-doping for germanium sulfide (GeS) and dominant n-doping for tin disulfide (SnS2). By generating separate STS maps for each semiconductor film and conducting a statistical analysis of the gap and doping distribution, we determine intrinsic limitations for the solar cell efficiency that must be understood prior to processing. Subsequently, we fabricate a solar cell utilizing these materials (GeS and SnS2) via vapor phase deposition and carry out a characterization using standard J-V curves under both dark/illuminated irradiance conditions. Our devices corroborate the expected reduced efficiency due to doping fluctuation but exhibit stable photocurrent responses. As originally planned, quantum efficiency measurements reveal that the peak efficiency of our solar cell coincides with the range where the standard silicon solar cells sharply decline. Our STS method is suggested as a prequel to device development in novel material junctions or deposition processes where fluctuations of doping levels are retrieved due to intrinsic material characteristics such as the occurrence of defects, roughness, local chemical segregation, and faceting or step bunching.
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The goal of this work is to study transformations that occur upon heating Bi2Se3 to temperatures up to 623 K. X-ray diffraction (XRD) and scanning tunneling microscopy (STM) and spectroscopy (STS) techniques were used in our investigation. XRD was measured following the 00L and 01L truncation rods. These measurements revealed that upon heating there is a coexistence of a major Bi2Se3 phase and other ones that present structures of quintuple-layers intercalated with Bismuth bilayers. STM measurements of the surface of this material showed the presence of large hexagonal BixSey domains embedded in a Bi2Se3 matrix. STS experiments were employed to map the local electronic density of states and characterize the modifications imposed by the presence of the additional phases. Finally, density functional theory (DFT) calculations were performed to support these findings.
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In this work we present unique signatures manifested by the local electronic properties of the topological surface state in Bi2Te3 nanostructures as the spatial limit is approached. We concentrate on the pure nanoscale limit (nanoplatelets) with spatial electronic resolution down to 1 nm. The highlights include strong dependencies on nanoplatelet size: (1) observation of a phase separation of Dirac electrons whose length scale decreases as the spatial limit is approached, and (2) the evolution from heavily n-type to lightly n-type surface doping as nanoplatelet thickness increases. Our results show a new approach to tune the Dirac point together with reduction of electronic disorder in topological insulator (TI) nanostructured systems. We expect our work will provide a new route for application of these nanostructured Dirac systems in electronic devices.
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There is a great need for orally active drugs for the treatment of the neglected tropical disease leishmaniasis. Amphiphilic Sb(V) complexes, such as 1:3 Sb-N-octanoyl-N-methylglucamide complex (SbL8), are promising drug candidates. It has been previously reported that SbL8 forms kinetically stabilized nanoassemblies in water and that this simple dispersion exhibits antileishmanial activity when given by oral route to a murine model of visceral leishmaniasis. The main objective of the present work was to interfere in the structural organization of these nanoassemblies so as to investigate their influence on the oral bioavailability of Sb, and ultimately, optimize an oral formulation of SbL8 for the treatment of cutaneous leishmaniasis. The structural organization of SbL8 nanoassemblies was manipulated through addition of propylene glycol (PG) to the aqueous dispersion of SbL8. The presence of 50% (v/v) PG resulted in the loss of hydrophobic microenvironment, as evidenced by fluorescence probing. However, nanostructures were still present, as demonstrated by dynamic light scattering, small-angle X-ray scattering, and atomic force microscopy (AFM). A remarkable property of these nanoassemblies, as revealed by AFM analysis, is the flexibility of their supramolecular organization, which showed changes as a function of the solvent and substrate polarities. The formulation of SbL8 in 1:1 water:PG given orally to mice promoted significantly higher and more sustained serum levels of Sb, when compared to SbL8 in water. The new formulation, when given as repeated doses (200 mg Sb/kg/day) to BALB/c mice infected with Leishmania amazonensis, was significantly more effective in reducing the lesion parasite burden, compared to SbL8 in water, and even, the conventional drug Glucantime(®) given intraperitoneally at the same dose. In conclusion, this work introduces a new concept of polarity-sensitive nanocarrier that was successfully applied to optimize an oral formulation of Sb(V) for treating cutaneous leishmaniasis.
Assuntos
Antimônio/uso terapêutico , Antiprotozoários/uso terapêutico , Portadores de Fármacos/química , Leishmaniose Cutânea/tratamento farmacológico , Nanopartículas/química , Administração Oral , Animais , Antimônio/sangue , Antimônio/farmacocinética , Antiprotozoários/química , Antiprotozoários/farmacocinética , Modelos Animais de Doenças , Feminino , Interações Hidrofóbicas e Hidrofílicas , Meglumina/uso terapêutico , Antimoniato de Meglumina , Camundongos Endogâmicos BALB C , Microscopia de Força Atômica , Nanopartículas/ultraestrutura , Compostos Organometálicos/uso terapêutico , Espalhamento a Baixo Ângulo , Solventes , Resultado do Tratamento , Difração de Raios XRESUMO
Paclitaxel is a potent antimicrotubule chemotherapeutic agent widely used for clinical treatment of a variety of solid tumors. However, the low solubility of the drug in aqueous medium and the toxic effects of the commercially available formulation, Taxol(®), has hindered its clinical application. To overcome these paclitaxel-related disadvantages, several drug delivery approaches have been thoroughly investigated. In this context, our research group has developed long-circulating and pHsensitive liposomes containing paclitaxel composed of dioleylphosphatidylethanolamine, cholesterylhemisuccinate and distearoylphosphatidylethanolamine-polyethylene glycol2000, which have shown to be very promising carriers for this taxane. For the destabilization of pH-sensitive liposomal systems and the release of the encapsulated drug in the cytoplasm of tumor cells, the occurrence of a phase transition from a lamellar to a non-lamellar phase of dioleylphosphatidylethanolamine molecules is essential. Two techniques, differential scanning calorimetry and small angle X-ray scattering, were used to investigate the influence of the liposomal components and paclitaxel in the phase transition process of dioleylphosphatidylethanolamine molecules and to evaluate the pH-sensitivity of the formulation under low hydration conditions. The findings clearly evidence the phase transition of dioleylphosphatidylethanolamine molecules in the presence and absence of PTX indicating that the introduction of the drug in the system does not bring damage to the pH-sensitivity of the system, which resulting in liposome destabilization at low pH regions and encapsulated paclitaxel release preferentially in a desired target tissue.
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Paclitaxel/farmacologia , Transição de Fase , Fosfatidiletanolaminas/química , Concentração de Íons de Hidrogênio , Lipossomos/química , Transição de Fase/efeitos dos fármacos , Espalhamento a Baixo Ângulo , Cloreto de Sódio/química , Difração de Raios XRESUMO
Mucopolysaccharidosis type I (MPS I) is an autosomal disease caused by alpha-L-iduronidase deficiency. This study proposed the use of cationic nanoemulsions as non-viral vectors for a plasmid (pIDUA) containing the gene that codes for alpha-L-iduronidase. Nanoemulsions composed of medium chain triglycerides (MCT)/1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE)/1,2-dioleoyl-sn-glycero-3-trimethylammonium propane (DOTAP)/1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethylene glycol)-2000] (DSPE-PEG) were prepared by high pressure homogenization. Formulations were prepared by the adsorption or encapsulation of preformed pIDUA-DOTAP complexes into the oil core of nanoemulsions at different charge ratios. pIDUA complexed was protected from enzymatic degradation by DNase I. The physicochemical characteristics of complexes in protein-containing medium were mainly influenced by the presence of DSPE-PEG. Bragg reflections corresponding to a lamellar organization were identified for blank formulations by energy dispersive X-ray diffraction, which could not be detected after pIDUA complexation. The intravenous injection of these formulations in MPS I knockout mice led to a significant increase in IDUA activity (fluorescence assay) and expression (RT-qPCR) in different organs, especially the lungs and liver. These findings were more significant for formulations prepared at higher charge ratios (+4/-), suggesting a correlation between charge ratio and transfection efficiency. The present preclinical results demonstrated that these nanocomplexes represent a potential therapeutic option for the treatment of MPS I.
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Terapia Genética , Iduronidase/genética , Mucopolissacaridose I/terapia , Transfecção/métodos , Animais , Modelos Animais de Doenças , Emulsões , Ácidos Graxos Monoinsaturados/química , Expressão Gênica , Humanos , Iduronidase/química , Iduronidase/metabolismo , Rim/metabolismo , Fígado/metabolismo , Pulmão/metabolismo , Masculino , Camundongos Endogâmicos C57BL , Camundongos Knockout , Mucopolissacaridose I/genética , Mucopolissacaridose I/metabolismo , Nanoestruturas/química , Fosfatidiletanolaminas/química , Plasmídeos , Polietilenoglicóis/química , Compostos de Amônio Quaternário/química , Baço/metabolismo , Triglicerídeos/químicaRESUMO
Ursolic acid (UA) is a triterpene found in different plant species that has been shown to possess significant antitumor activity. However, UA presents a low water solubility, which limits its biological applications. In this context, our research group has proposed the incorporation of UA in long-circulating and pH-sensitive liposomes (SpHL-UA).These liposomes, composed of dioleylphosphatidylethanolamine (DOPE), cholesteryl hemisuccinate (CHEMS), and distearoylphosphatidylethanolamine-polyethylene glycol2000 (DSPE-PEG2000), were shown to be very promising carriers for UA. Considering that the release of UA from SpHL-UA and its antitumor activity depend upon the occurrence of the lamellar to non-lamellar phase transition of DOPE, in the present work, the interactions of UA with the components of the liposomes were evaluated, aiming to clarify their role in the structural organization of DOPE. The study was carried out by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) under low hydration conditions. DSC studies revealed that DOPE phase transition temperatures did not shift significantly upon UA addition. On the other hand, in SAXS studies, a different pattern of DOPE phase organization was observed in the presence of UA, with the occurrence of the cubic phase Im3m at 20 °C and the cubic phase Pn3m at 60 °C. These findings suggest that UA interacts with the lipids and changes their self-assembly. However, these interactions between the lipids and UA were unable to eliminate the lamellar to non-lamellar phase transition, which is essential for the cytoplasmic delivery of UA molecules from SpHL-UA.
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Lipossomos/química , Triterpenos/química , Soluções Tampão , Ésteres do Colesterol/química , Concentração de Íons de Hidrogênio , Lipossomos/sangue , Lipossomos/farmacocinética , Modelos Moleculares , Conformação Molecular , Transição de Fase , Fosfatos/química , Fosfatidiletanolaminas/química , Polietilenoglicóis/química , Ácido UrsólicoRESUMO
The determination of the molecular structure of a porphyrin is achieved by using nuclear magnetic resonance (NMR) and scanning tunneling microscopy (STM) techniques. Since macroscopic crystals cannot be obtained in this system, this combination of techniques is crucial to solve the molecular structure without the need for X-ray crystallography. For this purpose, previous knowledge of the flatness of the reagent molecules (a porphyrin and its functionalizing group, a naphthalimide) and the resulting molecular structure obtained by a force-field simulation are used. The exponents of the I-V curves obtained by scanning tunneling spectroscopy (STS) allow us to check whether the thickness of the film of molecules is greater than a monolayer, even when there is no direct access to the exposed surface of the metal substrate. Photoluminescence (PL), optical absorption, infrared (IR) reflectance and solubility tests are used to confirm the results obtained here with this NMR/STM/STS combination.
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Espectroscopia de Ressonância Magnética , Microscopia de Tunelamento , Porfirinas/química , Ouro/química , Conformação Molecular , Naftalimidas/química , Óxidos de Enxofre/químicaRESUMO
Atomic force microscopy image analysis and energy dispersive X-ray diffraction experiments were used to investigate the structural organization of cationic nanoemulsion/oligonucleotide complexes. Oligonucleotides targeting topoisomerase II gene were adsorbed on cationic nanoemulsions obtained by means of spontaneous emulsification procedure. Topographical analysis by atomic force microscopy allowed the observation of the nanoemulsion/oligonucleotide complexes through three-dimensional high-resolution images. Flattening of the oil droplets was observed, which was reduced in the complexes obtained at high amount of adsorbed oligonucleotides. In such conditions, complexes exhibit droplet size in the 600nm range. The oligonucleotides molecules were detected on the surface of the droplets, preventing their fusion during aggregation. A lamellar structure organization was identified by energy dispersive X-ray diffraction experiments. The presence of the nucleic acid molecules led to a disorganization of the lipid arrangement and an expansion in the lattice spacing, which was proportional to the amount of oligonucleotides added.
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Nanoestruturas/química , Oligonucleotídeos Antissenso/química , Cátions , DNA Topoisomerases Tipo II/genética , DNA de Protozoário/genética , Sistemas de Liberação de Medicamentos , Emulsões , Marcação de Genes , Microscopia de Força Atômica , Nanoestruturas/ultraestrutura , Oligonucleotídeos Antissenso/administração & dosagem , Oligonucleotídeos Antissenso/genética , Plasmodium falciparum/enzimologia , Plasmodium falciparum/genética , Difração de Raios XRESUMO
Topological insulators such as Bi2Se3 and Bi2Te3 have extremely promising transport properties, due to their unique electronic behavior: they are insulators in the bulk and conducting at the surface. Recently, the coexistence of two types of surface conducting channels has been observed for Bi2Se3, one being Dirac electrons from the topological state and the other electrons from a conventional two-dimensional gas. As an explanation for this effect, a possible structural modification of the surface of these materials has been hypothesized. Using scanning tunneling microscopy we have directly observed the coexistence of a conducting bilayer and the bare surface of bulk-terminated Bi2Te3. X-ray crystal truncation rod scattering was used to directly show the stabilization of this epitaxial bilayer which is primarily composed of bismuth. Using this information, we have performed density functional theory calculations to determine the electronic properties of the possible surface terminations. They can be used to understand recent angular resolved photoemission data which have revealed this dual surface electronic behavior.
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Amorphous silica nanowires have been produced by thermal annealing of Si/SiO2/Ni substrate structures at 900 degrees C under an atmosphere of hexamethyldisilazane (HMDS) and hydrogen (H2). The wires have diameter ranging from 35 to 55 nm, which are controlled by the Ni particle size. It is demonstrated that the growth occurs through vapor-liquid-solid mechanisms, and it is proposed that the vapor source is volatile SiO generated from the etching of the Si substrate through active oxidation reactions. The role of the HMDS-H2 atmosphere in promoting such reactions is discussed.