Vibrational properties of metastable orthorhombic Bi2Se3.

Chalcogenide materials are being considered as some of the most promising systems for energy harvesting and energy conversion. Among them, the orthorhombic family of compounds X2Y3 (with X = Bi, Sb and Y = S, Se) has attracted special attention due to its interesting atomic structure and thermoelectric and optical properties. While Bi2S3 and Sb2Se3 have already been applied to solar cells, practical application of the new metastable Bi2Se3 is still a challenge due to the lack of data and knowledge on its properties. Here, the vibrational and structural properties of the orthorhombic metastable phase of Bi2Se3 are investigated by using Raman spectroscopy and ab initio calculations. We perform Raman spectroscopy measurements along with in situ thermal treatment on samples grown by electrochemical deposition. We show that by increasing the temperature an improved crystallization occurs in the orthorhombic structure, followed by recrystallization to the usual rhombohedral phase. Our results point out specific Raman modes of the orthorhombic phase. First principles computational results based on the density functional theory support the experimental data and describe three singlet Raman active vibrational modes, such as B(2)3g, B(2)2g and A(6)g.

Resistive Switching in Electrodeposited Prussian Blue Layers.

Prussian blue (PB) layers were electrodeposited for the fabrication of Au/PB/Ag stacks to study the resistive switching effect. The PB layers were characterized by different techniques to prove the homogeneity, composition, and structure. Electrical measurements confirmed the bipolar switching behavior with at least 3 orders of magnitude in current and the effect persisting for the 200 cycles tested. The low resistance state follows the ohmic conduction with an activation energy of 0.2 eV.

Multifunctional hybrid nanoparticles as magnetic delivery systems for siRNA targeting the HER2 gene in breast cancer cells.

Breast cancer is a major cause of death among women worldwide. Resistance to conventional therapies has been observed in HER2-positive breast cancer patients, indicating the need for more effective treatments. Small interfering RNA (siRNA) therapy is an attractive strategy against HER2-positive tumors, but its success depends largely on the efficient delivery of agents to target tissues. In this study, we prepared a magnetic hybrid nanostructure composed of iron oxide nanoparticles coated with caffeic acid and stabilized by layers of calcium phosphate and PEG-polyanion block copolymer for incorporation of siRNA. Transmission electron microscopy images showed monodisperse, neutrally charged compact spheres sized <100 nm. Dynamic light scattering and nanoparticle tracking analysis revealed that the nanostructure had an average hydrodynamic diameter of 130 nm. Nanoparticle suspensions remained stable over 42 days of storage at 4 and 25 °C. Unloaded caffeic acid-magnetic calcium phosphate (Caf-MCaP) nanoparticles were not cytotoxic, and loaded nanoparticles were successfully taken up by the HER2-positive breast cancer cell line HCC1954, even more so under magnetic guidance. Nanoparticles escaped endosomal degradation and delivered siRNA into the cytoplasm, inducing HER2 gene silencing.

Morphology and Structure of Electrodeposited Prussian Blue and Prussian White Thin Films.

The compound Prussian Blue (PB), and its reduced form Prussian White (PW) are nowadays considered, in applied and fundamental research groups, as potential materials for sustainable energy storage devices. In this work, these compounds were prepared by potentiostatic electrochemical synthesis, by using different deposition voltages and thicknesses. Thick, compact and uniform layers were characterized by scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. Results have shown a well-defined transition voltage for growing Prussian Blue phases and a strong dependence of the morphology/growing orientation of the samples as a function of applied potential and thickness. For the negative potential tested of -0.10 V vs. SCE, a mixture of cubic and rhombohedral phases was observed.

Influence of substrate on the structure of predominantly anatase TiO2 films grown by reactive sputtering.

TiO2 films are grown on LaAlO3 (001), Si (100) and SiO2 substrates by reactive radio frequency sputtering. X-ray diffraction (XRD) pole figures revealed important characteristics about the texture and phase distribution on those films. Combined with spectroscopic ellipsometry, the pole figures allowed the analysis of the growth characteristics over the whole volume of the layers. Details in the microstructure of the films were probed using transmission electron spectroscopy. Anatase is the dominating phase in the films grown on all substrates. On TiO2/LaAlO3 fims, the mosaicity is very low, so that the pole figure closely resembles that of anatase monocrystals. Detailed inspection of XRD pole figures reveals a small amount of rutile in the TiO2/LaAlO3 films. For the growth of TiO2 onto SiO2, rutile and brookite phases are also detected. Transmission electron microscopy and XRD results show the formation of anatase {112} twins in films grown on the different substrates, suggesting that the anatase {112} twin mediates the growth of rutile and brookite phases. Optical results are in agreement with the XRD observations: the optical properties of TiO2/LaAlO3 films are similar to the ordinary values of bulk anatase crystals, indicating the orientation of the film in the [001] direction, whereas results for TiO2/SiO2 are compatible with lower crystalline ordering.

Probing the spinor nature of electronic states in nanosize non-collinear magnets.

Non-collinear magnetization textures provide a route to novel device concepts in spintronics. These applications require laterally confined non-collinear magnets (NCM). A crucial aspect for potential applications is how the spatial proximity between the NCM and vacuum or another material impacts the magnetization texture on the nanoscale. We focus on a prototypical exchange-driven NCM given by the helical spin order of bilayer Fe on Cu(111). Spin-polarized scanning tunnelling spectroscopy and density functional theory reveal a nanosize- and proximity-driven modification of the electronic and magnetic structure of the NCM in interfacial contact with a ferromagnet or with vacuum. An intriguing non-collinearity between the local magnetization in the sample and the electronic magnetization probed above its surface results. It is a direct consequence of the spinor nature of electronic states in NCM. Our findings provide a possible route for advanced control of nanoscale spin textures by confinement.

The role of interstitial native defects in the topological insulator Bi2Se3.

Bi2Se3 is a prominent narrow gap semiconductor with a rhombohedral crystal structure and potential applications in thermoelectric and spintronic technologies. Its electrical conduction is ruled by native point defects inducing an n-type degenerate behavior. Here, we present a first principles study of the point defects in Bi2Se3, focusing on the relevance of the interstitial sites. A density functional methodology was employed with van der Waals correction and spin-orbit coupling in order to achieve a better description of the defects. The results indicate that interstitial Bi atoms in octahedral sites between two consecutive quintuple layers have a lower formation energy than selenium vacancies and that these interstitials could act as a possible source of free electron carriers. In addition, we show that the utilization of an experimental or strained lattice constant in the calculations may lead to an under- or overestimation of the defect formation energies.

Toxicity and inflammatory response in Swiss albino mice after intraperitoneal and oral administration of polyurethane nanoparticles.

In this work in vivo experiments were conducted in order to characterize the biocompatibility of polyurethane nanoparticles (PU-NPs) after intraperitoneal (i.p.) and oral administration. Additionally, ex vivo assays were performed to assess human blood compatibility as well as in vitro assays to assess protein binding. Our results indicated that administration of three different concentrations of PU-NPs induced a significant increase in visceral fat accumulation after oral dosing. In addition, fat tissue of mice intraperitoneally treated with the highest concentration of nanoparticles showed diffuse mononuclear inflammatory infiltrate in the fat tissue. Histopathological assessment showed inflammatory infiltrate and hepatocyte vacuolization in the liver, inflammatory infiltration and vascular congestion in the lung and glomerular necrosis in the kidney. Hepatic enzymes related with liver function were significantly increased in both groups of mice treated with PU-NPs. The PU-NPs did not affect the human blood cells number as well as coagulation time but showed a susceptibility to bind in proteins commonly found in the blood stream. In addition, increased amounts of pro inflammatory cytokines in vivo, as well as ex vivo in human cells were observed. Further studies to establish the consequences of long-term exposure to PU-NPs are warranted.

Superparamagnetic iron-oxide nanoparticles mPEG350- and mPEG2000-coated: cell uptake and biocompatibility evaluation.

Superparamagnetic iron oxide nanoparticles (SPIONS) were synthesized by thermal decomposition of an organometallic precursor at high temperature and coated with a bi-layer composed of oleic acid and methoxy-polyethylene glycol-phospholipid. The formulations were named SPION-PEG350 and SPION-PEG2000. Transmission electron microscopy, X-ray diffraction and magnetic measurements show that the SPIONs are near-spherical, well-crystalline, and have high saturation magnetization and susceptibility. FTIR spectroscopy identifies the presence of oleic acid and of the conjugates mPEG for each sample. In vitro biocompatibility of SPIONS was investigated using three cell lines; up to 100µg/ml SPION-PEG350 showed non-toxicity, while SPION-PEG2000 showed no signal of toxicity even up to 200µg/ml. The uptake of SPIONS was detected using magnetization measurement, confocal and atomic force microscopy. SPION-PEG2000 presented the highest internalization capacity, which should be correlated with the mPEG chain size. The in vivo results suggested that SPION-PEG2000 administration in mice triggered liver and kidney injury. FROM THE CLINICAL EDITOR: The potential use of superparamagnetic iron oxide nanoparticles (SPIONS) in the clinical setting have been studied by many researchers. The authors synthesized two types of SPIONS here and investigated the physical properties and biological compatibility. The findings should provide more data on the design of SPIONS for clinical application in the future.

Peroxidase immobilized on phospholipid bilayers supported on Au (111) by DTT self-assembled monolayers: application to dopamine determination.

In this work, horseradish peroxidase (HRP) was immobilized on dimyristoylphosphatidylcholine (DMPC) bilayers supported on Au (111) by dithiotreitol (DTT) self-assembled monolayers and used as a nanostructured electrochemical biosensor to dopamine determination. The morphology of the phospholipid bilayers and the immobilization of HRP to these layers were characterized by atomic force microscopy (AFM). Square-wave voltammetry (SWV) experiments were done to investigate the performance of the HRP-modified electrode. The AFM images indicate that the enzyme is adsorbed at the external layer of the lipid bilayer and, although the electrical charges on the surface were not measured, the enzyme and phospholipids surface interaction occurs probably by electrostatic forces due to the pH used in the experiments. Interestingly, the present system can be used as one-shot sensor for the rapid detection of dopamine. The analytical performance of this system was linear for dopamine concentrations from 3.3 × 10⁻5 to 1.3 × 10⁻³ mol L⁻¹ (r = 0.9997) with a detection limit of 2.0 × 10⁻6 mol L⁻¹. Our results indicate that the use of HRP-DMPC bilayer system may be useful not only in developing new nanostructured materials for technological purposes, but could be very useful in fundamental studies to investigate the interactions between different micro-and macromolecules, even with soluble proteins, and lipid membranes.

Sulfidization of Au(111) from thioacetic acid: an experimental and theoretical study.

We have studied the adsorption of thioacetic acid (TAAH) on Au(111) from solution deposition. The close proximity of the SH groups to CO groups makes this molecule very attractive for exploring the effect of the functional group on the stability of the S-C and S-Au bonds. Although thioacetic acid was supposed to decompose slowly in water by hydrolysis supplying hydrogen sulfide, this behavior is not expected in nonpolar solvents such as toluene or hexane. Therefore, we have used these solvents for TAAH self-assembly on the Au(111) surface. The characterization of the adsorbates has been done by electrochemical techniques, X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM). We have found that even in nonpolar solvents thioacetic acid decomposes to S. The results have been discussed on the basis that the adsorbed species suffer a cleavage on the Au surface, leaving the S attached to it. The dissociation is a spontaneous process that reaches the final state very fast once it is energetically favorable, as can be interpreted from DFT calculations. The thioacetic acid adsorption reveals the strong effect that produces a functional group and the key role of the S-H bond cleavage in the self-assembly process.

Influence of melatonin on the order of phosphatidylcholine-based membranes.

The effect of melatonin was evaluated on three phosphatidylcholine-based membrane models. Changes in liposome dynamics were monitored by fluorescence, following the response of the probe merocyanine-540, as well as by differential scanning calorimetry (DSC). Langmuir monolayers were investigated using molecular area measurements, as well as by Brewster angle microscopy (BAM). Mica-supported bilayers were observed via atomic force microscopy (AFM). Fluorescence results demonstrating that melatonin increases the affinity between MC-540 and lipid molecules possibly because of an increase in the membrane fluidity in liposomes. DSC analyses showed that melatonin promoted a reduction in enthalpy in the lipid nonpolar chains. Melatonin also promoted an increase in the molecular area of Langmuir monolayers, as well as a decrease in membrane thickness. Consequently, melatonin appeared to induce re-ordering effects in liposome and Langmuir monolayers. AFM images of bilayers immobilized on mica suggested that melatonin induced a gel state predominance or a delay in the main phase transition. At experimental conditions, melatonin interacted actively with all membranes models tested and induced changes in their physico-chemical properties. The data presented here may contribute to the understanding of melatonin physiologic properties, as well as the development of therapeutic advanced systems, such as drug delivery systems and biosensors.

Self-assembled dithiothreitol on Au surfaces for biological applications: phospholipid bilayer formation.

Self-assembly of dithiothreitol (DTT) on Au(111) from solution deposition has been studied by X-ray photoelectron spectroscopy and electrochemical data. DTT molecules self-assemble on Au(111) in a lying-down configuration irrespective of the concentration and temperature. XPS and electrochemical data indicate a DTT surface coverage of theta approximately 0.16 with two S-head-Au covalent bonds per DTT molecule. The DTT monolayer turns the Au surface hydrophilic enough to allow the formation of fluid dimyristoylphosphatidylcholine (DMPC) bilayer domains by vesicle fusion as revealed by in situ atomic force imaging. Methylene blue (MB) and flavin adenine dinucleotide (FAD) have been used as probes to study molecule transport across the bilayer.