LiNbO3 Thin Films through a Sol-Gel/Spin-Coating Approach Using a Novel Heterobimetallic Lithium-Niobium Precursor.

Lithium niobate is a lead-free material which has attracted considerable attention due to its excellent optical, piezoelectric, and ferroelectric properties. This research is devoted to the synthesis through an innovative sol-gel/spin-coating approach of polycrystalline LiNbO3 films on Si substrates. A novel single-source hetero-bimetallic precursor containing lithium and niobium was synthesized and applied to the sol-gel synthesis. The structural, compositional, and thermal characteristics of the precursor have been tested through attenuated total reflection, X-ray photoelectron spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The LiNbO3 films have been characterized from a structural point of view with combined X-ray diffraction and Raman spectroscopy. Field-emission scanning electron microscopy, energy dispersive X-ray analysis, and X-ray photoelectron spectroscopy have been used to study the morphological and compositional properties of the deposited films.

Self-assembled BiFeO3@MIL-101 nanocomposite for antimicrobial applications under natural sunlight.

In this paper, we report on the synthesis of a new hybrid photocatalytic material activated by natural sunlight irradiation. The material consists of multiferroic nanoparticles of bismuth ferrite (BFO) modified through the growth of the Fe-based MIL-101 framework. Material characterization, conducted using various techniques (X-ray diffraction, transmission electron microscopy, FTIR, and X-ray photoelectron spectroscopies), confirmed the growth of the MIL-101 metal-organic framework on the BFO surface. The obtained system possesses the intrinsic photo-degradative properties of BFO nanoparticles significantly enhanced by the presence of MIL-101. The photocatalytic activity of this material was tested in antibacterial experiments conducted under natural sunlight exposure within the nanocomposite concentration range of 100-0.20 µg/ml. The MIL-modified BFO showed a significant decrease in both Minimum Inhibiting Concentration and Minimum Bactericide Concentration values compared to bare nanoparticles. This confirms the photo-activating effect of the MIL-101 modification. In particular, they show an increased antimicrobial activity against the tested Gram-positive species and the ability to begin to inhibit the growth of the four Escherichia coli strains, although at the maximum concentration tested. These results suggest that the new nanocomposite BiFeO3@MOF has been successfully developed and has proven to be an effective antibacterial agent against a wide range of microorganisms and a potential candidate in disinfection processes.

Synthesis of MIL-Modified Fe3O4 Magnetic Nanoparticles for Enhancing Uptake and Efficiency of Temozolomide in Glioblastoma Treatment.

A nanometric hybrid system consisting of a Fe3O4 magnetic nanoparticles modified through the growth of Fe-based Metal-organic frameworks of the MIL (Materials Institute Lavoiser) was developed. The obtained system retains both the nanometer dimensions and the magnetic properties of the Fe3O4 nanoparticles and possesses increased the loading capability due to the highly porous Fe-MIL. It was tested to load, carry and release temozolomide (TMZ) for the treatment of glioblastoma multiforme one of the most aggressive and deadly human cancers. The chemical characterization of the hybrid system was performed through various complementary techniques: X-ray-diffraction, thermogravimetric analysis, FT-IR and X-ray photoelectron spectroscopies. The nanomaterial showed low toxicity and an increased adsorption capacity compared to bare Fe3O4 magnetic nanoparticles (MNPs). It can load about 12 mg/g of TMZ and carry the drug into A172 cells without degradation. Our experimental data confirm that, after 48 h of treatment, the TMZ-loaded hybrid nanoparticles (15 and 20 µg/mL) suppressed human glioblastoma cell viability much more effectively than the free drug. Finally, we found that the internalization of the MIL-modified system is more evident than bare MNPs at all the used concentrations both in the cytoplasm and in the nucleus suggesting that it can be capable of overcoming the blood-brain barrier and targeting brain tumors. In conclusion, these results indicate that this combined nanoparticle represents a highly promising drug delivery system for TMZ targeting into cancer cells.

Dual-Functional Nano-Functionalized Titanium Scaffolds to Inhibit Bacterial Growth and Enhance Osteointegration.

Implantable biomaterials play a key role for the success of orthopedic surgery procedures. However, infections remain one of the most damaging post-operative complications that lead to the implant failure. Recently, several approaches have been proposed to avoid or manage implant-associated infections. Among these, an appropriate surface functionalization to confer intrinsic antibacterial properties preserving the osteo-integration ability represents an appealing strategy for the development of innovative implant materials. Titanium and its alloys are the most used materials for manufacturing of both articular and bone skull prostheses as well as dental implants. However, to date there is still a significant clinical need to improve their bioactivity, osseointegration and antibacterial activity. In this study, titanium biomimetic scaffolds are prepared by nano-functionalization with TiO2 (Ti_TiO2) and γFe2O3 (Ti_γFe2O3). Both cytocompatibility and antibacterial activity have been evaluated. Data show that both nano-functionalized scaffolds exhibit a good antibacterial activity towards Staphylococcus aureus, reducing colony number to 99.4% (Ti_TiO2) and 99.9% (Ti_γFe2O3), respectively. In addition, an increase of both human adipose-derived mesenchymal stem cells (hADSCs) cell proliferation (up to 4.3-fold for Ti_TiO2 and 3.7-fold for Ti_γFe2O3) and differentiation has been observed. These data suggest that these nano-functionalized titanium substrates represent promising prototypes for new antimicrobial and osteoconductive biomaterials to be used in the orthopedic field to reconstruct significant bone defect.

Fabrication of Cu(II) oxide-hydroxide nanostructures onto graphene paper by laser and thermal processes for sensitive nano-electrochemical sensing of glucose.

Glucose electrochemical sensors based on nanostructures of CuO/Cu(OH)2onto graphene paper were prepared by thermal (solid) and nanosecond pulsed laser (molten phase) dewetting of a CuO layer 6 nm thin deposited by sputtering. Dewetted systems, obtained without the use of any binder, act as array of nanoelectrodes. Solid state and molten phase dewetting produce nanostructures of copper oxide-hydroxide with different average size, shape and surface composition. Molten phase dewetting originates particles with size below 100 nm, while solid state dewetting produces particles with average size of about 200 nm. Moreover, molten phase dewetting produce drop-shaped nanostructures, conversely nanostructures derived from solid state dewetting are multifaceted. X-ray photoelectron spectroscopy (XPS) characterization revealed that the surface of nanostructures is formed by a copper(II) species CuO and Cu(OH)2. Shape of anodic branch of the cyclic voltammograms of glucose in alkali solution evidenced a convergent diffusion mechanism. Analytical performances in amperometric mode are as good as or better than other sensors based on copper oxide. Amperometric detection of glucose was done at potential as low as 0.4 V versus saturated calomel electrode by both types of electrodes. Linear range from 50µM to 10 mM, sensitivity ranging from 7 to 43µA cm-2mM-1and detection limit of 7µM was obtained. Good analytical performances were obtained by laser dewetted electrodes with a low copper content up to 1.2 by atoms percentage of the surface. Analytical performance of the proposed electrodes is compliant for the determination of glucose both in blood serum, saliva or tear.

The Interplay between Fe3O4 Superparamagnetic Nanoparticles, Sodium Butyrate, and Folic Acid for Intracellular Transport.

Combined treatments which use nanoparticles and drugs could be a synergistic strategy for the treatment of a variety of cancers to overcome drug resistance, low efficacy, and high-dose-induced systemic toxicity. In this study, the effects on human colon adenocarcinoma cells of surface modified Fe3O4 magnetic nanoparticles (MNPs) in combination with sodium butyrate (NaBu), added as a free formulation, were examined demonstrating that the co-delivery produced a cytotoxic effect on malignant cells. Two different MNP coatings were investigated: a simple polyethylene glycol (PEG) layer and a mixed folic acid (FA) and PEG layer. Our results demonstrated that MNPs with FA (FA-PEG@MNPs) have a better cellular uptake than the ones without FA (PEG@MNPs), probably due to the presence of folate that acts as an activator of folate receptors (FRs) expression. However, in the presence of NaBu, the difference between the two types of MNPs was reduced. These similar behaviors for both MNPs likely occurred because of the differentiation induced by butyrate that increases the uptake of ferromagnetic nanoparticles. Moreover, we observed a strong decrease of cell viability in a NaBu dose-dependent manner. Taking into account these results, the cooperation of multifunctional MNPs with NaBu, taking into consideration the particular cancer-cell properties, can be a valuable tool for future cancer treatment.

Piezoelectric BiFeO3 Thin Films: Optimization of MOCVD Process on Si.

This paper presents a simple and optimized metal organic chemical vapor deposition (MOCVD) protocol for the deposition of perovskite BiFeO3 films on silicon-based substrates, in order to move toward the next generation of lead-free hybrid energy harvesters. A bi-metal mixture that is composed of Bi(phenyl)3, and Fe(tmhd)3 has been used as a precursor source. BiFeO3 films have been grown by MOCVD on IrO2/Si substrates, in which the conductive IrO2 functions as a bottom electrode and a buffer layer. BiFeO3 films have been analyzed by X-ray diffraction (XRD) for structural characterization and by field-emission scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray (EDX) analysis for the morphological and chemical characterizations, respectively. These studies have shown that the deposited films are polycrystalline, pure BiFeO3 phase highly homogenous in morphology and composition all over the entire substrate surface. Piezoelectric force microscopy (PFM) and Piezoelectric Force Spectroscopy (PFS) checked the piezoelectric and ferroelectric properties of the film.

New Synthetic Route for the Growth of α-FeOOH/NH2-Mil-101 Films on Copper Foil for High Surface Area Electrodes.

A novel metal organic framework (MOF)-based composite was synthesized on a Cu substrate via a two-step route. An amorphous iron oxide/hydroxide layer was first deposited on a Cu foil through a sol-gel process; then, Fe-NH2-Mil-101 was grown using both the iron oxide/hydroxide matrix, which provided the Fe3+ centers needed for MOF formation, and 2-aminoterephthalic acid ethanol solution. This innovative synthetic strategy is a convenient approach to grow metal oxide/hydroxide and MOF composite films. Structural, chemical, and morphological characterizations suggest that the obtained composite is made up of both the α-FeOOH goethite and the NH2-Mil-101 phases featuring a hybrid heterostructure. The electrochemical features of the composite structure were investigated using electrochemical impedance spectroscopy. The impedance behavior of the α-FeOOH/NH2-Mil-101 films indicates that they can be used as efficient high surface area metal hydroxide/MOF-based electrodes for applications such as energy storage and sensing.

Multi-Scale-Porosity TiO2 scaffolds grown by innovative sputtering methods for high throughput hybrid photovoltaics.

We propose an up-scalable, reliable, contamination-free, rod-like TiO2 material grown by a new method based on sputtering deposition concepts which offers a multi-scale porosity, namely: an intra-rods nano-porosity (1-5 nm) arising from the Thornton's conditions and an extra-rods meso-porosity (10-50 nm) originating from the spatial separation of the Titanium and Oxygen sources combined with a grazing Ti flux. The procedure is simple, since it does not require any template layer to trigger the nano-structuring, and versatile, since porosity and layer thickness can be easily tuned; it is empowered by the lack of contaminations/solvents and by the structural stability of the material (at least) up to 500 °C. Our material gains porosity, stability and infiltration capability superior if compared to conventionally sputtered TiO2 layers. Its competition level with chemically synthesized reference counterparts is doubly demonstrated: in Dye Sensitized Solar Cells, by the infiltration and chemisorption of N-719 dye (∼1 × 1020 molecules/cm3); and in Perovskite Solar Cells, by the capillary infiltration of solution processed CH3NH3PbI3 which allowed reaching efficiency of 11.7%. Based on the demonstrated attitude of the material to be functionalized, its surface activity could be differently tailored on other molecules or gas species or liquids to enlarge the range of application in different fields.

Similar Structural Dynamics for the Degradation of CH3 NH3 PbI3 in Air and in Vacuum.

We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X-ray diffraction, spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2 . We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3 NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.

Elusive Presence of Chloride in Mixed Halide Perovskite Solar Cells.

The role of chloride in the MAPbI3-xClx perovskite is still limitedly understood, albeit subjected of much debate. Here, we present a combined angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and first-principles DFT modeling to investigate the MAPbI3-xClx/TiO2 interface. AR-XPS analyses carried out on ad hoc designed bilayers of MAPbI3-xClx perovskite deposited onto a flat TiO2 substrate reveal that the chloride is preferentially located in close proximity to the perovskite/TiO2 interface. DFT calculations indicate the preferential location of chloride at the TiO2 interface compared to the bulk perovskite due to an increased chloride-TiO2 surface affinity. Furthermore, our calculations clearly demonstrate an interfacial chloride-induced band bending, creating a directional "electron funnel" that may improve the charge collection efficiency of the device and possibly affecting also recombination pathways. Our findings represent a step forward to the rationalization of the peculiar properties of mixed halide perovskite, allowing one to further address material and device design issues.

Shaping ability of four nickel-titanium rotary instruments in simulated S-shaped canals.

INTRODUCTION: The purpose of this study was to compare the shaping ability of ProTaper, Mtwo, BioRaCe, and BioRaCe + S-Apex instruments in simulated canals with an S-shaped curvature. METHODS: Canal transportation and aberrations were assessed by comparing the preinstrumentation and postinstrumentation images under a stereomicroscope. Analysis of variance and post hoc Student-Newman-Keuls test were used for statistical analysis. RESULTS: ProTaper instruments caused more pronounced canal transportation in the apical curvature (P < .01) than all other instruments. The use of ProTaper, Mtwo, and BioRaCe instruments resulted in more canal aberrations compared with BioRaCe + S-Apex (P < .05). CONCLUSIONS: NiTi systems including less tapered and more flexible instruments like S-Apex seem to be favorable when preparing S-shaped canals.

Chemical analysis of nickel-titanium rotary instruments with and without electropolishing after cleaning procedures with sodium hypochlorite.

The aim of this study was to chemically analyze rotary nickel-titanium instruments with and without electropolishing after cleaning procedures with NaOCl. To evaluate the effect of 5.25% NaOCl on electropolished RaCe instruments, a total of 18 instruments were tested. A control group of 18 nonelectropolished RaCe instruments was used. The surface of each instrument was analyzed before and after cleaning in NaOCl by using energy dispersive x-ray analysis, Auger electron spectroscopy, and scanning electron microscopy. Surface defects were recorded, and a chi(2) test was used for statistical analysis. After immersion in NaOCl, the nonelectropolished and electropolished files showed a significant increase of iron deposits as a result of galvanic corrosion of the shaft (P < .05). The nonelectropolished files showed marked presence of NaCl deposits in the machining marks and microcracks. As regards the chemical nature of the surface, the electropolished files had an oxide increase compared with the low oxide concentration (mainly TiO2) before cleaning. The nonelectropolished files already possessed higher oxides concentration (TiO2 and NiO) before NaOCl cleaning. NaOCl treatment affects the chemical composition of the surface and, in particular for nonelectropolished instruments, of the bulk exposed through machining marks and fabrication microcracks.

Pitting corrosion resistance of nickel-titanium rotary instruments with different surface treatments in seventeen percent ethylenediaminetetraacetic Acid and sodium chloride solutions.

This study evaluated the pitting corrosion resistance of nickel-titanium (NiTi) rotary instruments with different surface treatments in 17% ethylenediaminetetraacetic acid (EDTA) and NaCl solutions. Electropolished RaCe instruments were allocated to group A, non-electropolished RaCe instruments to group B, and physical vapor deposition (PVD)-coated Alpha files to group C (10 instruments per group). Electrochemical measurements were carried out by using a potentiostat for galvanic current measurements. On the basis of electrochemical tests, no localized corrosion problems are to be expected in EDTA. In NaCl, pitting potential occurred at higher values for the electropolished and PVD instruments, indicating an increased corrosion resistance. There appears to be a risk of corrosion for NiTi instruments without surface treatments in contact with NaCl. NiTi files with PVD and electropolishing surface treatments showed an increase corrosion resistance.

Cyclic fatigue of different nickel-titanium endodontic rotary instruments.

OBJECTIVE: A comparative study of the fatigue resistance of rotary nickel-titanium endodontic instruments was performed with the aim of assessing the influence of both instrument design and surface treatment on flexural fracture. STUDY DESIGN: To evaluate fatigue resistance of different rotary instruments, a total of 120 instruments were tested; these came from different sources: ProFile, RaCe, K3, Hero, and Mtwo. To compare the effect of electro-polishing procedures on fatigue resistance, a group of RaCe instruments (which are normally electro-polished) without surface treatment was used. A scanning electron microscope (SEM) study for each instrument was performed before and after fatigue study to determine the mode of fracture and the aspect of tips and cross-sectional surface areas. RESULTS: ProFile instruments gave the best values for fatigue resistance. It was seen that for RaCe instruments the surface treatment reduces the presence of micro-cracks, surface debris, and machining damage. CONCLUSIONS: This study shows that the instrument design often proves to be an important factor in the fatigue resistance of NiTi rotary instruments. In RaCe instruments the electro-polishing surface treatment increases the fracture-related fatigue resistance.

Fabrication of hard coatings on NiTi instruments.

The present study was designed to compare the nature of modified surface layers obtained by two different procedures on endodontic files made of NiTi alloy: the procedures were arc evaporation physical vapor deposition and thermal metal organic chemical vapor deposition (MOCVD). Experimental samples were GT Rotary Instruments. The first method was based on the physical deposition of elemental titanium in the presence of nitrogen. The second technique is a typical MOCVD procedure which adopts Ti(Et2N)4 as a titanium and nitrogen precursor. Control samples were not exposed to any process. The chemical composition of the surface and in-depth layers of each sample were examined by X-ray photoelectron spectroscopy and X-ray diffraction measurements. The instruments showed surface chemical compositions that were different from those seen in the control group; samples treated with the first method show a surface Nitrogen/Titanium ratio of 1; MOCVD instruments show a surface Nitrogen/Titanium ratio of 1.7; control samples show a Nitrogen/Titanium ratio of 0.2. Both techniques can produce a high nitrogen concentration on the surface. However, data showed that the morphologies, the in-depth nitrogen distribution, and the chemical nature of the coatings obtained with the two procedures were different. The paper also reports the effects of the two deposition procedures on the nickel/titanium ratio of the surface.