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Copper is efficient, has a high conductivity (5.8 × 10 7 S/m), and is cost-effective. The use of copper-based catalysts is promising for the electrocatalytic reduction of nitrates. This work aims to grow and characterize copper micro-crystals on Screen-Printed Electrodes (SPEs) for NO 3 - reduction in water. Copper micro-crystals were grown by cyclic voltammetry. Different cycles (2, 5, 7, 10, 12, 15) of copper electrodeposition were investigated (potential ranges from -1.0 V to 0.0 V, scan rate of 0.1 V s -1 ). Electrodeposition generated different morphologies of copper crystals on the electrodes, as a function of the number of cycles, with various performances. The presence of numerous edges and defects in the copper micro-crystal structures creates highly reactive active sites, thus favoring nitrate reduction. The manufactured material can be successfully employed for environmental applications.

The progressive increase in nitrate's (NO 3 - ) presence in surface and groundwater enhances environmental and human health risks. The aim of this work is the fabrication and characterization of sensitive, real-time, low-cost, and portable amperometric sensors for low NO 3 - concentration detection in water. Copper (Cu) micro-flowers were electrodeposited on top of carbon screen-printed electrodes (SPCEs) via cyclic voltammetry (with voltage ranging from -1.0 V to 0.0 V at a scan rate of 0.1 V s -1 ). The obtained sensors exhibited a high catalytic activity toward the electro-reduction in NO 3 - , with a sensitivity of 44.71 μA/mM. They had a limit of detection of 0.87 µM and a good dynamic linear concentration range from 0.05 to 3 mM. The results were compared to spectrophotometric analysis. In addition, the devices exhibited good stability and a maximum standard deviation (RSD) of 5% after ten measurements; reproducibility, with a maximum RSD of 4%; and repeatability after 10 measurements with the RSD at only 5.63%.

Monitoring of ammonium ion levels in water is essential due to its significant impact on environmental and human health. This work aims to fabricate and characterize sensitive, real-time, low-cost, and portable amperometric sensors for low NH 4 + concentrations in water. Two strategies were conducted by cyclic voltammetry (CV): electrodeposition of Au nanoparticles on a commercial polyaniline/C electrode (Au/PANI/C), and CV of electropolymerized polyaniline on a commercial carbon electrode (Au/PANIep/C). Au NPs increase the electrical conductivity of PANI and its ability to transfer charges during electrochemical reactions. The electrode performances were tested in a concentration range from 0.35 µM to 7 µM in NH 4 + solution. The results show that the Au/PANI/C electrode performs well for high NH 4 + concentrations (0.34 µM LoD) and worsens for low NH 4 + concentrations (0.01 µM LoD). A reverse performance occurs for the electrode Au/PANIep/C, with a 0.03 µM LoD at low NH 4 + concentration and 0.07 µM LoD at high NH 4 + concentration. The electrodes exhibit a good reproducibility, with a maximum RSD of 3.68% for Au/PANI/C and 5.94% for Au/PANIep/C. In addition, the results of the repeatability tests show that the electrochemical reaction of sensing is fully reversible, leaving the electrode ready for a new detection event.

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 LiNbO 3 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 LiNbO 3 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.

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 BiFeO 3 @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., (© 2023. Springer Science+Business Media, LLC, part of Springer Nature.)

A nanometric hybrid system consisting of a Fe 3 O 4 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 Fe 3 O 4 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 Fe 3 O 4 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.

Glucose electrochemical sensors based on nanostructures of CuO/Cu(OH) 2 onto 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 50 μ M to 10 mM, sensitivity ranging from 7 to 43 μ A cm -2 mM -1 and detection limit of 7 μ M 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., (© 2021 IOP Publishing Ltd.)

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 TiO 2 (Ti_TiO 2 ) and γFe 2 O 3 (Ti_γFe 2 O 3 ). 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_TiO 2 ) and 99.9% (Ti_γFe 2 O 3 ), respectively. In addition, an increase of both human adipose-derived mesenchymal stem cells (hADSCs) cell proliferation (up to 4.3-fold for Ti_TiO 2 and 3.7-fold for Ti_γFe 2 O 3 ) 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.

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 Fe 3 O 4 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.

In this work, multiferroic bismuth ferrite (BFO) was functionalized with meso-tetraphenylporphine-4,4',4'',4'''-tetracarboxylic acid (TCPP). This new hybrid organic-inorganic material shows an enhanced photocatalytic activity for the degradation of organic dyes as it combines the properties of BFO which is an efficient visible light photocatalyst with peculiar porphyrin absorption in visible light. The anchoring of TCPP to the OH-terminations of the BFO surface through its carboxylic tethering groups was demonstrated using X-ray photoelectron spectroscopy and FT-IR spectroscopy. The photocatalytic activity of the material was also demonstrated through the photocatalytic degradation of Methylene Blue (MB) and Rhodamine-B (Rhd-B) in water under simulated solar light illumination. The TCPP molecules anchored to BFO slightly decrease (∼0.06 eV) the bandgap energy of the system and act as new catalytic centres, thus improving its photocatalytic activity. A photodegradation mechanism was also proposed. This new material is reusable and stable, as it maintains an unmodified photo-activity after several MB discoloration runs.

This paper presents a simple and optimized metal organic chemical vapor deposition (MOCVD) protocol for the deposition of perovskite BiFeO 3 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. BiFeO 3 films have been grown by MOCVD on IrO 2 /Si substrates, in which the conductive IrO 2 functions as a bottom electrode and a buffer layer. BiFeO 3 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 BiFeO 3 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.

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-NH 2 -Mil-101 was grown using both the iron oxide/hydroxide matrix, which provided the Fe 3+ 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 NH 2 -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/NH 2 -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., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

A novel hybrid photoactive material based on graphene foam (G) coupled with porphyrin-based polymers (Porph rings) was formulated by using a time-saving procedure to remove nickel from the final device. Specifically, Porph rings were spin coated onto the G platform with the double function of a visible-light photocatalyst and protective agent during nickel etching. The characterization of G-Porph rings was assessed by Scanning Electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). The novel material showed photocatalytic ability in degrading different classes of pollutants such as the herbicide 2,4 dichlorophenoxyacetic acid (2,4-D), polyethylene glycol (PEG) as an ingredient of care and health products, and also the methylene blue (MB) dye. UV-Vis spectroscopy, total organic carbon (TOC) and soft mass spectrometry techniques were used to monitor the photocatalytic process. The best performance in terms of photocatalytic efficiency was exhibited versus PEG and MB degradation. Furthermore, to determine the individual contribution of Reactive Oxygen Species (ROS) produced, free radical and hole scavenging tests were also carried out. Finally, a detailed map of the photocatalytic degradation mechanisms was proposed, reporting also the calculation of Porph rings' Highest Occupied Molecular Orbital (HOMO) and Lowest Occupied Molecular Orbital (LUMO) energy level values., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Nanocolumnar Si substrates (porous silicon (PSi)) have been functionalized with a quinoxaline-bridged (EtQxBox) cavitand in which the quinoxaline moieties are bonded to each other through four ethylendioxy bridges at the upper rim of the cavity. The receptor, which is known to selectively complex aromatic volatile organic compounds (VOCs) even in the presence of aliphatic compounds, has been covalently anchored to PSi. The larger surface area of PSi, compared to that of flat substrates, allowed one to study the recognition process of the surface-grafted receptors through different techniques: Fourier-transform infrared spectroscopy, thermal desorption, and X-ray photoelectron spectroscopy. The experiments proved that surface-grafted cavitands retain the recognition capability toward aromatic VOCs. In addition, the affinities of EtQxBox for various aromatic compounds (i.e., benzene, toluene, nitrobenzene, and p -nitrotoluene) have been studied combining density functional theory computations and thermal desorption experiments. Computational data based on the crystal structures of the complexes indicate that this cavitand possesses a higher affinity toward aromatic nitro-compounds compared to benzene and toluene, making this receptor of particular interest for the detection of explosive taggants. The results of computational studies have been validated also for the surface-grafted receptor through competitive recognition experiments. These experiments showed that EtQxBox-functionalized PSi can recognize nitrobenzene in the presence of a significant excess of aromatic vapors such as benzene (1:300) or toluene (1:100)., Competing Interests: The authors declare no competing financial interest.

A versatile synthetic route based on magnetic Fe 3 O 4 nanoparticle (MNP) prefunctionalization with a phosphonic acid monolayer has been used to covalently bind the gH625 peptide on the nanoparticle surface. gH625 is a membranotropic peptide capable of easily crossing the membranes of various cells including the typical human blood-brain barrier components. A similar synthetic route was used to prepare another class of MNPs having a functional coating based on PEG, rhodamine, and folic acid, a well-known target molecule, to compare the performance of the two cell-penetrating systems (i.e., gH625 and folic acid). Our results demonstrate that the uptake of gH625-decorated MNPs in immortalized human brain microvascular endothelial cells after 24 h is more evident compared to folic acid-functionalized MNPs as evidenced by confocal laser scanning microscopy. On the other hand, both functionalized systems proved capable of being internalized in a brain tumor cell line (i.e., glioblastoma A-172). These findings indicate that the functionalization of MNPs with gH625 improves their endothelial cell internalization, suggesting a viable strategy in designing functional nanostructures capable of first crossing the BBB and, then, of reaching specific tumor brain cells.

The complexation between 2-ureido-4[1H]-pyrimidinone (UPy) and 2,7-diamido-1,8-naphthyridine (NaPy) is used to promote the mild chemisorption of a UPy-functionalized terbium(III) double decker system on a silicon surface. The adopted strategy allows the single-molecule magnet behavior of the system to be maintained unaltered on the surface., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We propose an up-scalable, reliable, contamination-free, rod-like TiO 2 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 TiO 2 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 × 10 20 molecules/cm 3 ); and in Perovskite Solar Cells, by the capillary infiltration of solution processed CH 3 NH 3 PbI 3 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.

Conventional and Pulsed Liquid Injection MOCVD processes (C-MOCVD and PLI-MOCVD) have been explored as synthetic routes for the growth of BaMgF 4 on Si (100) and single crystalline SrTiO 3 (100) substrates. For the two applied approaches, the volatile, thermally stable β-diketonate complexes Ba(hfa) 2 tetraglyme and Mg(hfa) 2 (diglyme) 2 (H 2 O) 2 have been used as single precursors (C-MOCVD) or as a solution multimetal source (PLI-MOCVD). Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial BaMgF 4 films on SrTiO 3 substrates. Energy dispersive X-ray (EDX) analyses have been used to confirm composition and purity of deposited films. The impact of process parameters on film properties has been addressed, highlighting the strong influence of precursor ratio, deposition temperature and oxygen partial pressure on composition, microstructure and morphology of the films. Both methods appear well suited for the growth of the BaMgF 4 phase, but while PLI-MOCVD yields a more straightforward control of the precursor composition that reflects on film stoichiometry, C-MOCVD provides easier control of the degree of texturing as a function of temperature.

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., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Calcium-doped praseodymium manganite films (Pr0.7Ca0.3MnO3, PCMO) were prepared by metal-organic chemical vapor deposition (MOCVD) on SrTiO3 (001) and SrTiO3 (110) single-crystal substrates. Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial PCMO phase films. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) characterization was used to confirm lateral and vertical composition and the purity of the deposited films. Magnetic measurements, obtained in zero-field-cooling (ZFC) and field-cooling (FC) modes, provided evidence of the presence of a ferromagnetic (FM) transition temperature, which was correlated to the transport properties of the film. The functional properties of the deposited films, combined with the structural and chemical characterization collected data, indicate that the MOCVD approach represents a suitable route for the growth of pure, good quality PCMO for the fabrication of novel spintronic devices.

In this paper we report the synthesis and characterization of biocompatible multi-functional magnetic nanoparticles (MNPs) able to enhance the intracellular transport of N-methylated drugs. The Fe 3 O 4 magnetic core was first functionalized with a mixed monolayer consisting of two different phosphonic acids having terminal acetylenic and amino groups, which provide an active platform for further functionalization with organic molecules. Then, a tetraphosphonate cavitand receptor (Tiiii) bearing an azide moiety and the N-hydroxysuccinimide (NHS) activated forms of poly(ethylene glycol) (PEG), folic acid (FA) and carboxy-X-rhodamine (Rhod) were covalently anchored on alkyne and amine moieties respectively, through 1,3-dipolar cycloaddition and EDC/NHS coupling reactions. The obtained MNPs are biocompatible and possess magnetic, luminescence and recognition properties which make them suitable for multimodal theranostic applications. In particular, combined confocal microscopy and cytotoxicity experiments showed that these multi-functional MNPs are able to recognize a specific drug "in situ" and promote its cellular internalization, thus enhancing its efficiency.

Free 4-undecenoxyphthalocyanine molecules were covalently bonded to Si(100) and porous silicon through thermic hydrosilylation of the terminal double bonds of the undecenyl chains. The success of the anchoring strategy on both surfaces was demonstrated by the combination of X-ray photoelectron spectroscopy with control experiments performed adopting the commercially available 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine, which is not suited for silicon anchoring. Moreover, the study of the shape of the XPS N 1s band gave relevant information on the interactions occurring between the anchored molecules and the substrates. The spectra suggest that the phthalocyanine ring interacts significantly with the flat Si surface, whilst ring-surface interactions are less relevant on porous Si. The surface-bonded molecules were then metalated in situ with Co by using wet chemistry. The efficiency of the metalation process was evaluated by XPS measurements and, in particular, on porous silicon, the complexation of cobalt was confirmed by the disappearance in the FTIR spectra of the band at 3290 cm(-1) due to -NH stretches. Finally, XPS results revealed that the different surface-phthalocyanine interactions observed for flat and porous substrates affect the efficiency of the in situ metalation process.

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.

The direct, clean, and unbiased transduction of molecular recognition into a readable and reproducible response is the biggest challenge associated to the use of synthetic receptors in sensing. All possible solutions demand the mastering of molecular recognition at the solid-liquid interface as prerequisite. The socially relevant issue of screening amine-based illicit and designer drugs is addressed by nanomechanical recognition at the silicon-water interface. The methylamino moieties of different drugs are all first recognized by a single cavitand receptor through a synergistic set of weak interactions. The peculiar recognition ability of the cavitand is then transferred with high fidelity and robustness on silicon microcantilevers and harnessed to realize a nanomechanical device for label-free detection of these drugs in water., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Single-molecule magnets (SMMs) are among the most promising molecular systems for the development of novel molecular electronics based on spin transport. Going beyond investigations focused on physisorbed SMMs, in this work the robust grafting of terbium(III) bis(phthalocyaninato) complexes to a silicon surface from a diluted solution is achieved by rational chemical design yielding the formation of a partially oriented monolayer on the conducting substrate. Here by exploiting the surface sensitivity of X-ray circular magnetic dichroism, we evidence an enhancement of the magnetic bistability of this SMM, in contrast to the dramatic reduction of the magnetic hysteresis that characterizes monolayer deposits evaporated on noble and ferromagnetic metals. Photoelectron spectroscopy investigations and density functional theory analysis suggest a non-innocent role played by the silicon substrate, evidencing the potentiality of this approach for robust integration of bistable magnetic molecules in electronic devices.

A chiral organic-inorganic hybrid material, based on a porous silicon surface functionalized with a chiral cavitand, was designed and synthesized. The affinity of this device in water toward a bromine-marked alkyl-ammonium salt has been evaluated using XPS detection. UV and CD measurements highlight the enantioselective extraction from a racemic mixture in water of the S-enantiomer of the selected guest (ee ≥ 80%).

We implemented a low-temperature approach to fabricate efficient photoanodes for dye-sensitized solar cells, which combines three different nanoarchitectures, namely, a highly conductive and highly transparent AZO film, a thin TiO2-blocking layer, and a mesoporous TiO2 nanorod-based working electrode. All the components were processed at T≤200°C. Both the AZO and the TiO2 blocking layers were deposited by reactive sputtering, whereas the TiO2 nanorods were synthesized by surfactant-assisted wet-chemical routes and processed into photoelectrodes in which the native geometric features assured uniform mesoporous structure with effective nanocrystal interconnectivity suitable to maximize light harvesting and electron diffusion. Because of the optimized structure of the TiO2-blocking/AZO bilayer, and thanks to the good adhesion of the TiO2 nanorods over it, a significant enhancement of the charge recombination resistance was demonstrated, this laying on the basis of the outstanding power conversion efficiency achievable through the use of this photoanode's architecture: a value of 4.6% (N719) was achieved with a 4-μm-thick electrode processed at T=200°C. This value noticeably overcomes the current literature limit got on AZO-based cells (N719), which instead use Nb-doped and thicker blocking layers, and thicker nanostructured photoanodes, which have been even sintered at higher temperatures (450-500°C).

In this contribution, Fe3O4 magnetic nanoparticles (MNPs) have been functionalized with a tetraphosphonate cavitand receptor (Tiiii), capable of complexing N-monomethylated species with high selectivity, and polyethylene glycol (PEG) via click-chemistry. The grafting process is based on MNP pre-functionalization with a bifunctional phosphonic linker, 10-undecynylphosphonic acid, anchored on an iron surface through the phosphonic group. The Tiiii cavitand and the PEG modified with azide moieties have then been bonded to the resulting alkyne-functionalized MNPs through a "click" reaction. Each reaction step has been monitored by using X-ray photoelectron and FTIR spectroscopies. PEG and Tiiii functionalized MNPs have been able to load N-methyl ammonium salts such as the antitumor drug procarbazine hydrochloride and the neurotransmitter epinephrine hydrochloride and release them as free bases. In addition, the introduction of PEG moieties promoted biocompatibility of functionalized MNPs, thus allowing their use in biological environments.

Chemical vapour deposition (CVD) on catalytic metals is one of main approaches for high-quality graphene growth over large areas. However, a subsequent transfer step to an insulating substrate is required in order to use the graphene for electronic applications. This step can severely affect both the structural integrity and the electronic properties of the graphene membrane. In this paper, we investigated the morphological and electrical properties of CVD graphene transferred onto SiO2 and on a polymeric substrate (poly(ethylene-2,6-naphthalene dicarboxylate), briefly PEN), suitable for microelectronics and flexible electronics applications, respectively. The electrical properties (sheet resistance, mobility, carrier density) of the transferred graphene as well as the specific contact resistance of metal contacts onto graphene were investigated by using properly designed test patterns. While a sheet resistance R sh ≈ 1.7 kΩ/sq and a specific contact resistance ρc ≈ 15 kΩ·μm have been measured for graphene transferred onto SiO2, about 2.3× higher R sh and about 8× higher ρc values were obtained for graphene on PEN. High-resolution current mapping by torsion resonant conductive atomic force microscopy (TRCAFM) provided an insight into the nanoscale mechanisms responsible for the very high ρc in the case of graphene on PEN, showing a ca. 10× smaller "effective" area for current injection than in the case of graphene on SiO2.

A supramolecular approach for the specific detection of sarcosine, recently linked to the occurrence of aggressive prostate cancer forms, has been developed. A hybrid active surface was prepared by the covalent anchoring on Si substrates of a tetraphosphonate cavitand as supramolecular receptor and it was proven able to recognize sarcosine from its nonmethylated precursor, glycine, in water and urine. The entire complexation process has been investigated in the solid state, in solution, and at the solid-liquid interface to determine and weight all the factors responsible of the observed specificity. The final outcome is a Si-based active surface capable of binding exclusively sarcosine. The complete selectivity of the cavitand-decorated surface under these stringent conditions represents a critical step forward in the use of these materials for the specific detection of sarcosine and related metabolites in biological fluids.

This paper reports on the preparation of a porous silicon-based material covalently functionalized with cavitand receptors suited for the detection of organophosphorus vapors. Two different isomeric cavitands, both containing one acid group at the upper rim, specifically designed for covalent anchoring on silicon, were grafted on H-terminated porous silicon (PSi) by thermal hydrosilylation. The covalently functionalized surfaces and their complexation properties were characterized by combining different analytical techniques, namely X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and mass spectroscopy analysis coupled with thermal desorption experiments. Complexation experiments were performed by exposing both active surfaces and a control surface consisting of PSi functionalized with a structurally similar but inactive methylene-bridged cavitand (MeCav) to dimethyl methylphosphonate (DMMP) vapors. Comparison between active and inactive surfaces demonstrated the recognition properties of the new surfaces. Finally, the nature of the involved interactions, the energetic differences between active and inactive surfaces toward DMMP complexation, and the comparison with a true nerve gas agent (sarin) were studied by DFT modeling. The results revealed the successful grafting reaction, the specific host-guest interactions of the PSi-bonded receptors, and the reversibility of the guest complexation.

Metal-Organic Chemical Vapor Deposition (MOCVD) has been applied to the fabrication of BiFeO3 films undoped and doped with Ba or Ti on SrTiO3 (100) and YSZ (100) substrates. The films have been deposited using a multi-metal source, consisting of the Bi(phenyl)3, Fe(tmhd)3 and Ba(hfa)2 tetraglyme or Ti(tmhd)2(O-iPr)2 (phenyl = -C6H5, H-tmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = iso-propoxide; H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = CH3O(CH2CH2O)4CH3) precursor mixture. The structural and morphological characterization of films has been carried out using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Chemical compositional studies have been performed by energy dispersive X-ray (EDX) analysis. Structural and morphological characterizations point to the formation of homogeneous and flat surfaces for both undoped and doped BiFeO3 films.

Aim: To assess the failure mechanism of rotary NiTi instruments by chemical, structural and morphological analyses to provide a rational explanation of the effects of surface and bulk treatments on their resistance to fatigue fracture., Methodology: Thermal treatment (350-500 °C) was performed on electropolished (EP) and non-electropolished (Non-EP) NiTi endodontic instruments. Bulk and surface chemical composition and crystallographic structures were determined by energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) to evaluate the effects of thermal treatment and electropolishing on the NiTi alloy. Fatigue tests of all instruments were performed. Surface morphology before and after the tests, and fractured section were analysed using scanning electron microscopy to determine crack extensions. Results were analysed statistically using analysis of variance (anova) and post hoc Student-Newman-Keuls test., Results: Before thermal treatment, significant differences (P < 0.05) in fatigue resistance between EP and Non-EP instruments (the number of revolutions to failure, N(f) , was 385 and 160, respectively) were attributed to differences in the surface morphology of the instruments. SEM analysis of the fracture surfaces indicated that flexural fatigue fractures occurred in two steps: first by a slow growth of initial cracks and then rapid rupture of the remaining material. Thermal treatment did not affect the surface morphology but resulted in significant changes in the instrument bulk with the appearance of an R-phase and an improved fatigue resistance; indeed after treatment at 500 °C, N(f) increased up to 829 and 474 for EP and Non-EP instruments, respectively., Conclusions: Both thermal treatment and electropolishing improved the resistance of NiTi rotary instruments against fatigue fracture., (© 2010 International Endodontic Journal.)

Selective and reversible complexation of halogen-tagged aromatic VOCs by a quinoxaline cavitand-decorated Si surface is demonstrated. The specific host-guest interactions of the Si-bonded receptors are proved to be responsible of the surface recognition properties, while extracavity non specific adsorptions are totally suppressed compared to the bulk material.

A Si(100) surface featuring molecular recognition properties was obtained by covalent functionalization with a tetraphosphonate cavitand (Tiiii), able to complex positively charged species. Tiiii cavitand was grafted onto the Si by photochemical hydrosilylation together with 1-octene as a spatial spectator. The recognition properties of the Si-Tiiii surface were demonstrated through two independent analytical techniques, namely XPS and fluorescence spectroscopy, during the course of reversible complexation-guest exchange-decomplexation cycles with specifically designed ammonium and pyridinium salts. Control experiments employing a Si(100) surface functionalized with a structurally similar, but complexation inactive, tetrathiophosphonate cavitand (TSiiii) demonstrated no recognition events. This provides evidence for the complexation properties of the Si-Tiiii surface, ruling out the possibility of nonspecific interactions between the substrate and the guests. The residual Si-O(-) terminations on the surface replace the guests' original counterions, thus stabilizing the complex ion pairs. These results represent a further step toward the control of self-assembly of complex supramolecular architectures on surfaces.

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.

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.

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.

The magnetic properties of a monolayer of Mn12 single molecule magnets grafted onto a silicon (Si) substrate have been investigated using depth-controlled beta-detected nuclear magnetic resonance. A low-energy beam of spin-polarized radioactive 8Li was used to probe the local static magnetic field distribution near the Mn12 monolayer in the Si substrate. The resonance line width varies strongly as a function of implantation depth as a result of the magnetic dipolar fields generated by the Mn12 electronic magnetic moments. The temperature dependence of the line width indicates that the magnetic properties of the Mn12 moments in this low-dimensional configuration differ from bulk Mn12.

Bottom-up fabrication of 3D organic nanostructures on Si(100) surfaces has been achieved by a two-step procedure. Tetradentate cavitand 1 was grafted on the Si surface together with 1-octene (Oct) as a spatial spectator by photochemical hydrosilylation. Ligand exchange between grafted cavitand 1 and self-assembled homocage 2, derived from cavitand 5 bearing a fluorescence marker, led to the formation of coordination cages on Si(100). Formation, quantification, and distribution of the nanoscale molecular containers on a silicon surface was assessed by using three complementary analytical techniques (AFM, XPS, and fluorescence) and validated by control experiments on cavitand-free silicon surfaces. Interestingly, the fluorescence of pyrene at approximately 4 nm above the Si(100) surface can be clearly observed.

Cavitand molecules having double bond terminated alkyl chains and different bridging groups at the upper rim have been grafted on H-terminated Si(100) surface via photochemical hydrosilylation of the double bonds. Pure and mixed monolayers have been obtained from mesitylene solutions of either pure cavitand or cavitand/1-octene mixtures. Angle resolved high-resolution X-ray photoelectron spectroscopy has been used as the main tool for the monolayer characterization. The cavitand decorated surface consists of Si-C bonded layers with the upper rim at the top of the layer. Grafting of pure cavitands leads to not-well-packed layers, which are not able to efficiently passivate the Si(100) surface. By contrast, monolayers obtained from cavitand/1-octene mixtures consist of well-packed layers since they prevent silicon oxidation after aging. AFM measurements showed that these monolayers have a structured topography, with objects protruding from the Si(100) surface with average heights compatible with the expected ones for cavitand molecules.

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.

The synthesis and structure of a dipolar nonlinear optical bis(salicylaldiminato)Ni(II)-derivatized Schiff base complex chemisorbed on H-terminated Si(100) surfaces is reported. The existence of a monolayer of the derivatized complex chemisorbed on the Si(100) surface is unambiguously confirmed by high-resolution core-level XPS and AFM/SNOM analyses. The comparison between the optical SNOM images highlights the contribution of the monolayer to the local reflectivity of the sample. Angle-resolved XPS data indicate the presence of chlorine head atoms on the monolayer surface. Altogether, XPS and AFM/SNOM data suggest the formation of a nanoscale uniform, homogeneous, complete, ordered monolayer self-assembled on the Si(100) surface.