Supramolecular Sensing of a Chemical Warfare Agents Simulant by Functionalized Carbon Nanoparticles.

Real-time sensing of chemical warfare agents by optical sensors is today a crucial target to prevent terroristic attacks by chemical weapons. Here the synthesis, characterization and detection properties of a new sensor, based on covalently functionalized carbon nanoparticles, are reported. This nanosensor exploits noncovalent interactions, in particular hydrogen bonds, to detect DMMP, a simulant of nerve agents. The nanostructure of the sensor combined with the supramolecular sensing approach leads to high binding constant affinity, high selectivity and the possibility to reuse the sensor.

Optimization of ZnO Nanorods Growth on Polyetheresulfone Electrospun Mats to Promote Antibacterial Properties.

Zinc oxide (ZnO) nanorods grown by chemical bath deposition (CBD) on the surface of polyetheresulfone (PES) electrospun fibers confer antimicrobial properties to the obtained hybrid inorganic-polymeric PES/ZnO mats. In particular, a decrement of bacteria colony forming units (CFU) is observed for both negative (Escherichia coli) and positive (Staphylococcus aureus and Staphylococcus epidermidis) Grams. Since antimicrobial action is strictly related to the quantity of ZnO present on surface, a CBD process optimization is performed to achieve the best results in terms of coverage uniformity and reproducibility. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) provide morphological and compositional analysis of PES/ZnO mats while thermogravimetric analysis (TGA) is useful to assess the best process conditions to guarantee the higher amount of ZnO with respect to PES scaffold. Biocidal action is associated to Zn2+ ion leaching in solution, easily indicated by UV-Vis measurement of metallation of free porphyrin layers deposited on glass.

Polyethersulfone Mats Functionalized with Porphyrin for Removal of Para-nitroaniline from Aqueous Solution.

The dispersion of para-nitroaniline (p-NA) in water poses a threat to the environment and human health. Therefore, the development of functional adsorbents to remove this harmful compound is crucial to the implementation of wastewater purification strategies, and electrospun mats represent a versatile and cost-effective class of materials that are useful for this application. In the present study, we tested the ability of some polyethersulfone (PES) nanofibers containing adsorbed porphyrin molecules to remove p-NA from water. The functional mats in this study were obtained by two different approaches based on fiber impregnation or doping. In particular, meso-tetraphenyl porphyrin (H2TPP) or zinc(II) meso-tetraphenyl porphyrin (ZnTPP) were immobilized on the surface of PES fiber mats by dip-coating or added to the PES electrospun solution to obtain porphyrin-doped PES mats. The presence of porphyrins on the fiber surfaces was confirmed by UV-Vis spectroscopy, fluorescence measurements, and XPS analysis. p-NA removal from water solutions was spectrophotometrically detected and evaluated.

Conjugated Gold-Porphyrin Monolayers Assembled on Inorganic Surfaces.

Gold nanoparticles show important properties owing to their electronic structures. A limitation of some gold nanoparticles is that they either show surface plasmons or luminescence. The increase in size of the gold nanoparticles, and the appearance of the surface plasmons may result in the disappearance of luminescence. The aim of our study is the nanoscale assembly of Au nanoparticles on a monolayer of porphyrin molecules anchored to functionalized inorganic surfaces. This functional architecture not only exhibits a strong surface plasmon due to the gold nanoparticles, but also a strong luminescence signal from the porphyrin molecules. Finally we observed a long-range order in the Au nanoparticles conjugated to the porphyrin monolayer.

Chemical and Morphological Modifications Induced by Argon Plasma Treatments on Fluorinated Polybenzoxazole Films.

Fluorinated photodefinable polymers are widely employed as re-distribution layers in wafer-level packaging to produce microelectronic devices because of their suitable low dielectric constant and moisture absorption, high mechanical toughness, thermal conductivity and stability, and chemical inertness. Typically, fluorinated photodefinable polybenzoxazoles (F-PBOs) are the most used in this field. In the present work, we investigated by atomic force microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy the morphological and chemical modifications induced by Ar plasma treatments on F-PBO films. This process, used to remove surface contaminant species, as well as increase the polymeric surface roughness, to improve the adhesion to the other components during electronic packaging, is a crucial step during the manufacturing of some microelectronic devices. We found that argon plasma treatments determine the wanted drastic increase of the polymer surface roughness but, in the presence of a patterned silver layer on F-PBO, needed for the fabrication of electric contacts in microelectronic devices, also induce some unwanted formation of silver fluoride species.

Synthesis, Characterization and Photocatalytic Behavior of SiO2 @nitrized-TiO2 Nanocomposites Obtained by a Straightforward Novel Approach.

We report on the facile synthesis of SiO2 @nitrized-TiO2 nanocomposite (NST) by calcination of TiO2 xerogel with OctaAmmonium POSS® (N-POSS; POSS=polyhedral oligomeric silsesquioxanes). The as-obtained nanoporous mixed oxide is constituted by uniformly distributed SiO2 and nitrized-TiO2 , where the silica component is present in an amorphous state and TiO2 in an anatase/rutile mixed phase (92.1 % vs. 7.9 %, respectively) with very small anatase crystallites (3.7 nm). The TiO2 lattice is nitrized both at interstitial and substitutional positions. NST features a negatively charged surface with a remarkable surface area (406 m2 g-1 ), endowed with special adsorption capabilities towards cationic dyes. Its photocatalytic behavior was tested by following the degradation of standard aqueous methylene blue and methyl orange solutions under UV and visible light irradiation, according to ISO 10678:2010. For comparison, analogous investigations were carried out on a silica-free N-TiO2 , obtained by using NH4 Cl as nitrogen source.

Systematic Characterization of Plasma-Etched Trenches on 4H-SiC Wafers.

Silicon carbide power semiconductors overcome some limitations of silicon chips, and therefore, SiC is an attractive candidate for next-generation power electronics. In addition, the number of possible vertical devices that can be obtained on a given surface using the trench technique is significantly larger than that attainable using a planar setup. Moreover, a SiC trench power metal oxide semiconductor field-effect transistor (power MOSFET) structure removes the junction field-effect transistor (JFET) region (that would decrease the current flow width) and improves the channel density, thus reducing the specific electrical resistance. Consequently, in the present study, we report on the chemical bonding state of elements and structural characterization of trenches, obtained using SF6-based plasma etching, on the 4H-SiC polytype substrate. An interferometric algorithm that finds the endpoint to stop etching governed the trench depth. Scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy analyses stated the high quality and uniformity of the trenches. These materials are particularly promising for the fabrication of the SiC MOSFET to be implemented in the manufacturing of power devices.

Covalently Conjugated Gold-Porphyrin Nanostructures.

Gold nanoparticles show important electronic and optical properties, owing to their size, shape, and electronic structures. Indeed, gold nanoparticles containing no more than 30-40 atoms are only luminescent, while nanometer-sized gold nanoparticles only show surface plasmon resonance. Therefore, it appears that gold nanoparticles can alternatively be luminescent or plasmonic and this represents a severe restriction for their use as optical material. The aim of our study was the fabrication of nanoscale assembly of Au nanoparticles with bi-functional porphyrin molecules that work as bridges between different gold nanoparticles. This functional architecture not only exhibits a strong surface plasmon, due to the Au nanoparticles, but also a strong luminescence signal due to porphyrin molecules, thus, behaving as an artificial organized plasmonic and fluorescent network. Mutual Au nanoparticles-porphyrin interactions tune the Au network size whose dimension can easily be read out, being the position of the surface plasmon resonance strongly indicative of this size. The present system can be used for all the applications requiring plasmonic and luminescent emitters.

Eco-Friendly 1,3-Dipolar Cycloaddition Reactions on Graphene Quantum Dots in Natural Deep Eutectic Solvent.

Due to their outstanding physicochemical properties, the next generation of the graphene family-graphene quantum dots (GQDs)-are at the cutting edge of nanotechnology development. GQDs generally possess many hydrophilic functionalities which allow their dispersibility in water but, on the other hand, could interfere with reactions that are mainly performed in organic solvents, as for cycloaddition reactions. We investigated the 1,3-dipolar cycloaddition (1,3-DCA) reactions of the C-ethoxycarbonyl N-methyl nitrone 1a and the newly synthesized C-diethoxyphosphorylpropilidene N-benzyl nitrone 1b with the surface of GQDs, affording the isoxazolidine cycloadducts isox-GQDs 2a and isox-GQDs 2b. Reactions were performed in mild and eco-friendly conditions, through the use of a natural deep eutectic solvent (NADES), free of chloride or any metal ions in its composition, and formed by the zwitterionic trimethylglycine as the -bond acceptor, and glycolic acid as the hydrogen-bond donor. The results reported in this study have for the first time proved the possibility of performing cycloaddition reactions directly to the p-cloud of the GQDs surface. The use of DES for the cycloaddition reactions on GQDs, other than to improve the solubility of reactants, has been shown to bring additional advantages because of the great affinity of these green solvents with aromatic systems.

Fast and Efficient Sun Light Photocatalytic Activity of Au_ZnO Core-Shell Nanoparticles Prepared by a One-Pot Synthesis.

Gold nanostructures absorb visible light and show localized surface plasmon resonance bands in the visible region. Semiconducting ZnO nanostructures are excellent for ultraviolet detection, thanks to their wide band gap, large free exciton binding energy, and high electron mobility. Therefore, the coupling of gold and ZnO nanostructures represents the best-suited way to boost photodetection. With the above perspective, we report on the high photocatalytic activity of some Au_ZnO core-shell nanoparticles (NPs) recently prepared by a one-pot synthesis in which a [zinc citrate]- complex acted as the ZnO precursor, a reducing agent for Au3+, and a capping anion for the obtained Au NPs. The overall nanostructures proved to be Au(111) NPs surrounded by a thin layer of [zinc citrate]- that evolved to Au_ZnO core-shell nanostructures. Worthy of note, with this photocatalyst, sun light efficiently decomposes a standard methylene blue solution according to ISO 10678:2010. We rationalized photodetection, reaction rate, and quantum efficiency.

High-Mobility Hydrogenated Fluorine-Doped Indium Oxide Film for Passivating Contacts c-Si Solar Cells.

Broadband transparent conductive oxide layers with high electron mobility (µe) are essential to further enhance crystalline silicon (c-Si) solar cell performances. Although metallic cation-doped In2O3 thin films with high µe (>60 cm2 V-1 s-1) have been extensively investigated, the research regarding anion doping is still under development. In particular, fluorine-doped indium oxide (IFO) shows promising optoelectrical properties; however, they have not been tested on c-Si solar cells with passivating contacts. Here, we investigate the properties of hydrogenated IFO (IFO:H) films processed at low substrate temperature and power density by varying the water vapor pressure during deposition. The optimized IFO:H shows a remarkably high µe of 87 cm2 V-1 s-1, a carrier density of 1.2 × 1020 cm-3, and resistivity of 6.2 × 10-4 Ω cm. Then, we analyzed the compositional, structural, and optoelectrical properties of the optimal IFO:H film. The high quality of the layer was confirmed by the low Urbach energy of 197 meV, compared to 444 meV obtained on the reference indium tin oxide. We implemented IFO:H into different front/back-contacted solar cells with passivating contacts processed at high and low temperatures, obtaining a significant short-circuit current gain of 1.53 mA cm-2. The best solar cell shows a conversion efficiency of 21.1%.

Sb-Doped Titanium Oxide: A Rationale for Its Photocatalytic Activity for Environmental Remediation.

The problem of water purification is one of the most urgent issues in developing countries, where large infrastructures and energy resources are limited. Among the possibilities for a cheap route to clean water, photocatalytic materials in the form of coatings or nanostructures are among the most promising. The most widely studied photocatalytic material is titanium dioxide (TiO2). Here, we investigate the photocatalytic properties of 1.5% Sb-doped TiO2 and laser-irradiated Sb-doped TiO x . Calcined Sb-doped TiO2 was found to adopt the rutile structure, but it turned amorphous after laser irradiation. Photocatalytic tests for Sb-doped TiO2 showed an activity 1 order of magnitude higher than that of an undoped TiO2 control sample under both ultraviolet and visible irradiation. A further sizeable enhancement resulted from laser irradiation. The increased photocatalytic activity is ascribed to both enhanced visible region absorption associated with Sb-induced lone pair surface electronic states and trapping of the holes at the lone pair surface sites, thus inhibiting the recombination of the electrons and holes generated in the initial photoexcitation step. This study shows the first rationalization of the photocatalytic properties of Sb-TiO2 in terms of its electronic structure.

Recognition and optical sensing of amines by a quartz-bound 7-chloro-4-quinolylazopillar[5]arene monolayer.

Covalent bonding of 7-chloro-4-quinolylazo-octamethoxypillar[5]arene molecules to silylated quartz substrates readily produced a new chromogenic reusable pillararene-coated quartz slide, for the direct UV detection of "transparent" analytes in solution. This device provides an analyte-selective optical response towards linear (di)amines with a highly reproducible optical read-out.

Long-term hematologic reconstitution after autologous peripheral blood progenitor cell transplantation: a comparison between controlled-rate freezing and uncontrolled-rate freezing at 80 degrees C.

BACKGROUND: The most widely used system for peripheral blood progenitor cell (PBPC) cryopreservation is controlled-rate freezing (CRF). Uncontrolled-rate freezing (URF) at -80 degrees C has also been used, but its clinical impact has not been studied sufficiently yet. STUDY DESIGN AND METHODS: Two groups of patients were compared: Group A consisted of 69 patients autotransplanted with PBPCs cryopreserved with CRF; Group B consisted of 192 patients autotransplanted with PBPCs cryopreserved with URF at -80 degrees C. The same cryoprotectant solution and storage system were used. RESULTS: A significant delay of hematologic reconstitution (HR) in the URF group was observed for neutrophils greater than 0.5 x 10(9) per L and for platelets greater than 20 x 10(9) per L and greater than 50 x 10(9) per L; we did not observe any differences in the clinical course. The long-term HR was comparable in the two groups, all patients showed stable engraftment, and no late graft failures were observed. CONCLUSION: Our study confirms that URF is safe and allows sustained long-term engraftment without increasing the risks of transplantation, even though the early engraftment after URF is slower.