Developing Iron Nanochelating Agents: Preliminary Investigation of Effectiveness and Safety for Central Nervous System Applications.

Excessive iron levels are believed to contribute to the development of neurodegenerative disorders by promoting oxidative stress and harmful protein clustering. Novel chelation treatments that can effectively remove excess iron while minimizing negative effects on the nervous system are being explored. This study focuses on the creation and evaluation of innovative nanobubble (NB) formulations, shelled with various polymers such as glycol-chitosan (GC) and glycol-chitosan conjugated with deferoxamine (DFO), to enhance their ability to bind iron. Various methods were used to evaluate their physical and chemical properties, chelation capacity in diverse iron solutions and impact on reactive oxygen species (ROS). Notably, the GC-DFO NBs demonstrated the ability to decrease amyloid-ß protein misfolding caused by iron. To assess potential toxicity, in vitro cytotoxicity testing was conducted using organotypic brain cultures from the substantia nigra, revealing no adverse effects at appropriate concentrations. Additionally, the impact of NBs on spontaneous electrical signaling in hippocampal neurons was examined. Our findings suggest a novel nanochelation approach utilizing DFO-conjugated NBs for the removal of excess iron in cerebral regions, potentially preventing neurotoxic effects.

Step-by-Step Design of New Theranostic Nanoformulations: Multifunctional Nanovectors for Radio-Chemo-Hyperthermic Therapy under Physical Targeting.

While investigating the possible synergistic effect of the conventional anticancer therapies, which, taken individually, are often ineffective against critical tumors, such as central nervous system (CNS) ones, the design of a theranostic nanovector able to carry and deliver chemotherapy drugs and magnetic hyperthermic agents to the target radiosensitizers (oxygen) was pursued. Alongside the original formulation of polymeric biodegradable oxygen-loaded nanostructures, their properties were fine-tuned to optimize their ability to conjugate therapeutic doses of drugs (doxorubicin) or antitumoral natural substances (curcumin). Oxygen-loaded nanostructures (diameter = 251 ± 13 nm, ζ potential = -29 ± 5 mV) were finally decorated with superparamagnetic iron oxide nanoparticles (SPIONs, diameter = 18 ± 3 nm, ζ potential = 14 ± 4 mV), producing stable, effective and non-agglomerating magnetic nanovectors (diameter = 279 ± 17 nm, ζ potential = -18 ± 7 mV), which could potentially target the tumoral tissues under magnetic driving and are monitorable either by US or MRI imaging.

High-Density Sb2 Te3 Nanopillars Arrays by Templated, Bottom-Up MOCVD Growth.

Sb2 Te3 exhibits several technologically relevant properties, such as high thermoelectric efficiency, topological insulator character, and phase change memory behavior. Improved performances are observed and novel effects are predicted for this and other chalcogenide alloys when synthetized in the form of high-aspect-ratio nanostructures. The ability to grow chalcogenide nanowires and nanopillars (NPs) with high crystal quality in a controlled fashion, in terms of their size and position, can boost the realization of novel thermoelectric, spintronic, and memory devices. Here, it is shown that highly dense arrays of ultrascaled Sb2 Te3 NPs can be grown by metal organic chemical vapor deposition (MOCVD) on patterned substrates. In particular, crystalline Sb2 Te3 NPs with a diameter of 20 nm and a height of 200 nm are obtained in Au-functionalized, anodized aluminum oxide (AAO) templates with a pore density of ≈5 × 1010 cm-2 . Also, MOCVD growth of Sb2 Te3 can be followed either by mechanical polishing and chemical etching to produce Sb2 Te3 NPs arrays with planar surfaces or by chemical dissolution of the AAO templates to obtain freestanding Sb2 Te3 NPs forests. The illustrated growth method can be further scaled to smaller pore sizes and employed for other MOCVD-grown chalcogenide alloys and patterned substrates.

Magnetic Shape Memory Turns to Nano: Microstructure Controlled Actuation of Free-Standing Nanodisks.

Magnetic shape memory materials hold a great promise for next-generation actuation devices and systems for energy conversion, thanks to the intimate coupling between structure and magnetism in their martensitic phase. Here novel magnetic shape memory free-standing nanodisks are proposed, proving that the lack of the substrate constrains enables the exploitation of new microstructure-controlled actuation mechanisms by the combined application of different stimuli-i.e., temperature and magnetic field. The results show that a reversible areal strain (up to 5.5%) can be achieved and tuned in intensity and sign (i.e., areal contraction or expansion) by the application of a magnetic field. The mechanisms at the basis of the actuation are investigated by experiments performed at different length scales and directly visualized by several electron microscopy techniques, including electron holography, showing that thermo/magnetomechanical properties can be optimized by engineering the martensitic microstructure through epitaxial growth and lateral confinement. These findings represent a step forward toward the development of a new class of temperature-field controlled nanoactuators and smart nanomaterials.

Influence of an Overshoot Layer on the Morphological, Structural, Strain, and Transport Properties of InAs Quantum Wells.

InAs quantum wells (QWs) are promising material systems due to their small effective mass, narrow bandgap, strong spin-orbit coupling, large g-factor, and transparent interface to superconductors. Therefore, they are promising candidates for the implementation of topological superconducting states. Despite this potential, the growth of InAs QWs with high crystal quality and well-controlled morphology remains challenging. Adding an overshoot layer at the end of the metamorphic buffer layer, i.e., a layer with a slightly larger lattice constant than the active region of the device, helps to overcome the residual strain and provides optimally relaxed lattice parameters for the QW. In this work, we systematically investigated the influence of overshoot layer thickness on the morphological, structural, strain, and transport properties of undoped InAs QWs on GaAs(100) substrates. Transmission electron microscopy reveals that the metamorphic buffer layer, which includes the overshoot layer, provides a misfit dislocation-free InAs QW active region. Moreover, the residual strain in the active region is compressive in the sample with a 200 nm-thick overshoot layer but tensile in samples with an overshoot layer thicker than 200 nm, and it saturates to a constant value for overshoot layer thicknesses above 350 nm. We found that electron mobility does not depend on the crystallographic directions. A maximum electron mobility of 6.07 × 105 cm2/Vs at 2.6 K with a carrier concentration of 2.31 × 1011 cm-2 in the sample with a 400 nm-thick overshoot layer has been obtained.

Enforcing luminescence at organic nanointerfaces: luminescence spatial confinement and amplification in molecular-based core-shell nanoparticles.

Fully organic core-shell nanoparticles that promote luminescence spatial confinement and enhancement at the core-shell nanointerface are designed and prepared. These molecular-based bicomponent nanostructures give rise to very efficient directional excitation energy transfer from the shell to acceptor molecules in the core located at the core-shell nanointerface. A striking luminescence enhancement is observed with respect to the corresponding single-component nanoparticles, which is ascribed to large local electric fields generated at the nanointerface between the polarizable molecular core and shell.

High performance platinum contacts on high-flux CdZnTe detectors.

The need for direct X-ray detection under high photon flux with moderate or high energies (30-100 keV range) has strongly increased with the rise of the 4th Generation Synchrotron Light Sources, characterised by extremely brilliant beamlines, and of other applications such as spectral computed tomography in medicine and non-destructive tests for industry. The novel Cadmium Zinc Telluride (CZT) developed by Redlen Technologies can be considered the reference material for high-flux applications (HF-CZT). The enhanced charge transport properties of the holes allow the mitigation of the effects of radiation induced polarization phenomena, typically observed in standard CZT materials (LF-CZT) under high photon flux. However, standard LF-CZT electrical contacts led to inacceptable high dark leakage currents on HF-CZT devices. In this work, a detailed study on the characteristics of new optimized sputtered platinum electrical contacts on HF-CZT detectors is reported. The results from electrical and spectroscopic investigations, showed the best performances on HF-CZT detectors with platinum anode, coupled with both platinum or gold cathode. The morphology, structure, and composition of Pt/CZT contact have been analysed by means of Transmission Electron Microscopy (TEM) on microscopic lamellas obtained by Focused Ion Beam (FIB), highlighting the presence of CdTeO3 oxide at the metal semiconductor interface.

Epitaxy of nanocrystalline silicon carbide on Si(111) at room temperature.

Silicon carbide (SiC) has unique chemical, physical, and mechanical properties. A factor strongly limiting SiC-based technologies is the high-temperature synthesis. In this work, we provide unprecedented experimental and theoretical evidence of 3C-SiC epitaxy on silicon at room temperature by using a buckminsterfullerene (C(60)) supersonic beam. Chemical processes, such as C(60) rupture, are activated at a precursor kinetic energy of 30-35 eV, far from thermodynamic equilibrium. This result paves the way for SiC synthesis on polymers or plastics that cannot withstand high temperatures.

Growth of InAs/InAsSb heterostructured nanowires.

We report the growth of InAs/InAs(1-x)Sb(x) single and double heterostructured nanowires by Au-assisted chemical beam epitaxy. The InAs(1-x)Sb(x) nanowire segments have been characterized in a wide range of antimony compositions. Significant lateral growth is observed at intermediate compositions (x ~ 0.5), and the nucleation and step-flow mechanism leading to this lateral growth has been identified and described. Additionally, CuPt ordering of the alloy has been observed with high resolution transmission electron microscopy, and it is correlated to the lateral growth process. We also show that it is possible to regrow InAs above the InAsSb alloy segment, at least up to an intermediate antimony composition. Such double heterostructures might find applications both as mid-infrared detectors and as building blocks of electronic devices taking advantage of the outstanding electronic and thermal properties of antimonide compound semiconductors.

Driving up the Electrocatalytic Performance for Carbon Dioxide Conversion through Interface Tuning in Graphene Oxide-Bismuth Oxide Nanocomposites.

The integration of graphene oxide (GO) into nanostructured Bi2O3 electrocatalysts for CO2 reduction (CO2RR) brings up remarkable improvements in terms of performance toward formic acid (HCOOH) production. The GO scaffold is able to facilitate electron transfers toward the active Bi2O3 phase, amending for the high metal oxide (MO) intrinsic electric resistance, resulting in activation of the CO2 with smaller overpotential. Herein, the structure of the GO-MO nanocomposite is tailored according to two synthetic protocols, giving rise to two different nanostructures, one featuring reduced GO (rGO) supporting Bi@Bi2O3 core-shell nanoparticles (NP) and the other GO supporting fully oxidized Bi2O3 NP. The two structures differentiate in terms of electrocatalytic behavior, suggesting the importance of constructing a suitable interface between the nanocarbon and the MO, as well as between MO and metal.

OBP-functionalized/hybrid superparamagnetic nanoparticles for Candida albicans treatment.

Infections caused by the opportunistic yeast Candida albicans are one of the major life threats for hospitalized and immunocompromised patients, as a result of antibiotic and long-term antifungal treatment abuse. Odorant binding proteins can be considered interesting candidates to develop systems able to reduce the proliferation and virulence of this yeast, because of their intrinsic antimicrobial properties and complexation capabilities toward farnesol, the major quorum sensing molecule of Candida albicans. In the present study, a hybrid system characterized by a superparamagnetic iron oxide core functionalized with bovine odorant binding protein (bOBP) was successfully developed. The nanoparticles were designed to be suitable for magnetic protein delivery to inflamed areas of the body. The inorganic superparamagnetic core was characterized by an average diameter of 6.5 ± 1.1 nm and a spherical shape. Nanoparticles were functionalized by using 11-phosphonoundecanoic acid as spacer and linked to bOBP via amide bonds, resulting in a concentration level of 26.0 ± 1.2 mg bOBP/g SPIONs. Finally, both the biocompatibility of the developed hybrid system and the fungistatic activity against Candida albicans by submicromolar OBP levels were demonstrated by in vitro experiments.

Hierarchical self-assembly on silicon.

A set of modular components was designed, synthesized, and combined to yield an innovative, robust, and reliable methodology for the self-assembly of large supramolecular structures on silicon wafers. Specific host-guest and H-bonding motifs were embedded in a single molecule by exploiting the remarkable complexing properties of tetraphosphonate cavitands toward methylammonium and methylpyridinium salts and the outstanding homo- and hetero-dimerization capability of the ureidopyrimidone moiety. An assembly/disassembly sequence in solution was devised to assess the orthogonality and reversibility of H-bonding and host-guest interactions. The entire process was fully tested and characterized in solution and then successfully transferred to the solid state. The selected binding motifs resulted to be fully compatible in the assembly mode and individually addressable in the disassembly mode. The complete orthogonality of the two interactions allows the molecular level control of each step of the solid-state assembly and the predictable response to precise external stimuli. Complementary surface analysis techniques, such as atomic force microscopy (AFM), ellipsometry, and fluorescence, provided the univocal characterization of the realized structures in the solid state.

Improved electroless platinum contacts on CdZnTe X- and γ-rays detectors.

Platinum is a promising candidate for the realization of blocking electrical contacts on cadmium-zinc-telluride (CdZnTe or CZT) radiation detectors. However, the poor mechanical adhesion of this metal often shortens the lifetime of the final device. In this work, a simple and effective procedure to obtain robust platinum contacts by electroless deposition is presented. Microscopical analysis revealed the final thickness and composition of the contact layer and its adhesion to the bulk crystal. The blocking nature of the Pt-CdZnTe junction, essential to obtain low noise devices, was confirmed by current-voltage measurements. The planar Pt-CdZnTe-Pt detectors showed good room temperature spectroscopic performance with energy resolution of 4% (2.4 keV) and 3% (3.7 keV) FWHM at 59.5 and 122.1 keV, respectively. Finally, we showed, for the first time, that platinum contacts allow the estimation of the carrier lifetime and mobility of both holes and electrons by using current transient measurements. This demonstrated the optimal hole extraction capability of such contacts.

Epitaxial and large area Sb2Te3 thin films on silicon by MOCVD.

Antimony telluride (Sb2Te3) thin films were prepared by a room temperature Metal-Organic Chemical Vapor Deposition (MOCVD) process using antimony chloride (SbCl3) and bis(trimethylsilyl)telluride (Te(SiMe3)2) as precursors. Pre-growth and post-growth treatments were found to be pivotal in favoring out-of-plane and in-plane alignment of the crystallites composing the films. A comprehensive suite of characterization techniques were used to evaluate their composition, surface roughness, as well as to assess their morphology, crystallinity, and structural features, revealing that a quick post-growth annealing triggers the formation of epitaxial-quality Sb2Te3 films on Si(111).

Following the Martensitic Configuration Footprints in the Transition Route of Ni-Mn-Ga Magnetic Shape Memory Films: Insight into the Role of Twin Boundaries and Interfaces.

Magnetic shape memory Heuslers have a great potential for their exploitation in next-generation cooling devices and actuating systems, due to their "giant" caloric and thermo/magnetomechanical effects arising from the combination of magnetic order and a martensitic transition. Thermal hysteresis, broad transition range, and twinning stress are among the major obstacles preventing the full exploitation of these materials in applications. Using Ni-Mn-Ga seven-modulated epitaxial thin films as a model system, we investigated the possible links between the phase transition and the details of the twin variants configuration in the martensitic phase. We explored the crystallographic relations between the martensitic variants from the atomic-scale to the micro-scale through high-resolution techniques and combined this information with the direct observation of the evolution of martensitic twin variants vs. temperature. Based on our multiscale investigation, we propose a route for the martensitic phase transition, in which the interfaces between different colonies of twins play the major role of initiators for both the forward and reverse phase transition. Linking the martensitic transition to the martensitic configuration sheds light onto the possible mechanisms influencing the transition and paves the way towards microstructure engineering for the full exploitation of shape memory Heuslers in different applications.

All-Inorganic CsPbBr3 Perovskite Films Prepared by Single Source Thermal Ablation.

Hybrid organo-lead halide perovskites are becoming the benchmark material for next generation photovoltaics and a very important player for other applications such as photodetectors and light emitting diodes. Nevertheless, the most important issue hindering the large-scale application of these materials remains their intrinsic instability due to the organic cation. Although the substitution with inorganic cesium (Cs) enhances stability, in most cases solution deposition methods of fully inorganic perovskites result in high surface roughness and poor surface coverage. This work reports on the evaporation of the CsPbBr3 precursor by Single Source Thermal Ablation, showing that just after deposition films consist of a mixture of CsPbBr3, CsPb2Br5, and Cs4PbBr6 due to a vertical composition gradient. We point out that mild post deposition treatments lead to the conversion of CsPb2Br5 and Cs4PbBr6 into CsPbBr3 due to its higher thermodynamic stability. Conversion results into smooth and pinhole-free CsPbBr3 films with good light absorption and emission properties. We demonstrate the suitability of obtained films for planar devices by preparing perovskite-based pure-green light emitting diodes, thus promoting Single Source Thermal Ablation as a promising alternative deposition technique for all-inorganic perovskite-based devices.

Light-driven, heterogeneous organocatalysts for C-C bond formation toward valuable perfluoroalkylated intermediates.

The favorable exploitation of carbon nitride (CN) materials in photocatalysis for organic synthesis requires the appropriate fine-tuning of the CN structure. Here, we present a deep investigation of the structure/activity relationship of CN in the photocatalytic perfluoroalkylation of organic compounds. Four types of CN bearing subtle structural differences were studied via conventional characterization techniques and innovative nuclear magnetic resonance (NMR) experiments, correlating the different structures with the fundamental mechanistic nexus and especially highlighting the importance of the halogen bond strength between the reagent and the catalyst surface. The optimum catalyst exhibited an excellent performance, with a very wide reaction scope, and could prominently trigger the model reaction using natural sunlight. The work lays a platform for establishing a new approach in the development of heterogeneous photocatalysts for organic synthesis related to medical, agricultural, and material chemistry.

Superparamagnetic Oxygen-Loaded Nanobubbles to Enhance Tumor Oxygenation During Hyperthermia.

Tumor oxygenation is a critical issue for enhancing radiotherapy (RT) effectiveness. Alternating RT with hyperthermia improves tumor radiosensitivity by inducing a massive vasodilation of the neoangiogenic vasculature provided the whole tumor is properly heated. The aim of this work was to develop superparamagnetic oxygen-loaded nanobubbles (MOLNBs) as innovative theranostic hyperthermic agents to potentiate tumor oxygenation by direct intracellular oxygen administration. Magnetic oxygen-loaded nanobubbles were obtained by functionalizing dextran-shelled and perfluoropentane-cored nanobubbles with superparamagnetic iron oxide nanoparticles. Magnetic oxygen-loaded nanobubbles with sizes of about 380 nm were manufactured, and they were able to store oxygen and in vitro release it with prolonged kinetics. In vitro investigation showed that MOLNBs can increase tissue temperature when exposed to radiofrequency magnetic fields. Moreover, they are easily internalized by tumor cells, herein releasing oxygen with a sustained kinetics. In conclusion, MOLNBs can be considered a multimodal theranostic platform since, beyond their nature of contrast agent for magnetic resonance imaging due to magnetic characteristics, they showed echogenic properties and can be visualized using medical ultrasound.

Selective Electrocatalytic H2 O2 Generation by Cobalt@N-Doped Graphitic Carbon Core-Shell Nanohybrids.

Electrocatalytic oxygen reduction (ORR) is an emerging synthetic strategy to prepare H2 O2 in a sustainable fashion. N-doped graphitic carbon with embedded cobalt nanoparticles was selected as an advanced material able to selectively trigger the ORR to form H2 O2 with a faradaic efficiency of almost 100 % at very positive applied potentials. The production of H2 O2 proceeded with high rates as calculated by bulk electrolysis (49 mmol g-1 h-1 ) and excellent current densities (≈-0.8 mA cm-2 at 0.5 V vs. reversible hydrogen electrode). The totally selective behavior depended on the combination of concomitant material features, such as the textural properties, the nature of the metal, the distribution of N moieties, the acidic environment, and the applied potential.

Macroalgae to nanoparticles: Study of Ulva lactuca L. role in biosynthesis of gold and silver nanoparticles and of their cytotoxicity on colon cancer cell lines.

Marine bio-resources are being widely studied as an invaluable source of compounds with therapeutic applicability. In particular, macroalgae contain an extended variety of bioactive compounds with different structures and promising biological applications. In this work, Ulva lactuca L. (hereafter UL) was utilyzed for the synthesis of gold and silver nanoparticles. Full characterization by UV-Vis spectroscopy, TEM, HRTEM and STEM miscroscopies, Z Potential and FTIR spectroscopy was performed. The first time in the scientific literature, the composition of carbohydrates of UL extract and their changes observed after nanoparticles synthesis were explored in order to investigate their possible role in the biosynthetic process. The reducing power, total phenolic content and DPPH scavenging activity of UL extract, Au@UL and Ag@UL nanoparticles were determined. The effects of UL extract, Au@UL and Ag@UL were tested in vitro on the colon cancer cell lines HT-29 and Caco-2, on normal primary neonatal dermal fibroblast cell line PCS-201-010, as well as on normal colon cell line CCD-112CoN. Lastly, the apoptotic activity and cellular uptake evaluation was determined for Au@UL and Ag@UL.