Ag modified ZnS for photocatalytic water pollutants degradation: Influence of metal loading and preparation method.

In this paper, the photocatalytic degradation of organic pollutants was investigated using Ag/ZnS nanoparticles at different noble metal loadings. The photocatalysts were prepared at room temperature by two different methods: photodeposition and chemical reduction. The obtained samples were characterized by Specific surface area measurement, X-ray photoelectron spectroscopy, X-ray Powder diffraction, ultraviolet-visible diffuse reflectance and Raman spectroscopy. The X-ray photoelectron spectroscopy spectra showed that Ag is present on ZnS surface as intermediate state between nanostructured Ag0 and Ag2O. Moreover, the addition of silver caused a significant change of the absorption spectrum of bare ZnS, resulting in higher absorbance in the visible region, due to the Ag surface plasmon band. Methylene blue (MB) was used to evaluate the photocatalytic activity of the prepared samples. The best photocatalytic activity was observed using the sample at 0.1 wt% Ag loading prepared by chemical reduction method. In particular, the almost complete MB degradation was achieved using UV-LEDs as light sources and 6 g L-1 of catalyst dosage. Finally, the optimized photocatalyst was also effective in the degradation of phenol in aqueous solution under UV irradiation.

Inhibiting P. fluorescens biofilms with fluoropolymer-embedded silver nanoparticles: an in-situ spectroscopic study.

Surface colonization by microorganisms leads to the formation of biofilms, i.e. aggregates of bacteria embedded within a matrix of extracellular polymeric substance. This promotes adhesion to the surface and protects bacterial community, providing an antimicrobial-resistant environment. The inhibition of biofilm growth is a crucial issue for preventing bacterial infections. Inorganic nanoparticle/Teflon-like (CFx) composites deposited via ion beam sputtering demonstrated very efficient antimicrobial activity. In this study, we developed Ag-CFx thin films with tuneable metal loadings and exceptional in-plane morphological and chemical homogeneity. Ag-CFx antimicrobial activity was studied via mid-infrared attenuated total reflection spectroscopy utilizing specifically adapted multi-reflection waveguides. Biofilm was sampled by carefully depositing the Ag-CFx film on IR inactive regions of the waveguide. Real-time infrared spectroscopy was used to monitor Pseudomonas fluorescens biofilm growth inhibition induced by the bioactive silver ions released from the nanoantimicrobial coating. Few hours of Ag-CFx action were sufficient to affect significantly biofilm growth. These findings were corroborated by atomic force microscopy (AFM) studies on living bacteria exposed to the same nanoantimicrobial. Morphological analyses showed a severe bacterial stress, leading to membrane leakage/collapse or to extended cell lysis as a function of incubation time.

MALDI-TOF mass spectrometry analysis of proteins and lipids in Escherichia coli exposed to copper ions and nanoparticles.

Escherichia coli (E. coli) is one of the most important foodborne pathogens to the food industry responsible for diseases as bloody diarrhea, hemorrhagic colitis and life-threatening hemolytic-uremic syndrome. For controlling and eliminating E. coli, metal nano-antimicrobials (NAMs) are frequently used as bioactive systems for applications in food treatments. Most NAMs provide controlled release of metal ions, eventually slowing down or completely inhibiting the growth of undesired microorganisms. Nonetheless, their antimicrobial action is not totally unraveled and is strongly dependent on metal properties and environmental conditions. In this work, we propose the use of matrix-assisted laser desorption ionization time-of-flight (MALDI TOF) mass spectrometry as a powerful tool for direct, time efficient, plausible identification of the cell membrane damage in bacterial strains exposed to copper-based antimicrobial agents, such as soluble salts (chosen as simplified AM material) and copper nanoparticles. E. coli ATCC 25922 strain was selected as 'training bacterium' to set up some critical experimental parameters (i.e. cell concentration, selection of the MALDI matrix, optimal solvent composition, sample preparation method) for the MS analyses. The resulting procedure was then used to attain both protein and lipid fingerprints from E. coli after exposure to different loadings of Cu salts and NPs. Interestingly, bacteria exposed to copper showed over-expression of copper binding proteins and degradation of lipids when treated with soluble salt. These findings were completed with other investigations, such as microbiological experiments. Copyright © 2016 John Wiley & Sons, Ltd.

Surface chemical and biological characterization of flax fabrics modified with silver nanoparticles for biomedical applications.

Silver nanophases are increasingly used as effective antibacterial agent for biomedical applications and wound healing. This work aims to investigate the surface chemical composition and biological properties of silver nanoparticle-modified flax substrates. Silver coatings were deposited on textiles through the in situ photo-reduction of a silver solution, by means of a large-scale apparatus. The silver-coated materials were characterized through X-ray Photoelectron Spectroscopy (XPS), to assess the surface elemental composition of the coatings, and the chemical speciation of both the substrate and the antibacterial nanophases. A detailed investigation of XPS high resolution regions outlined that silver is mainly present on nanophases' surface as Ag2O. Scanning electron microscopy and energy dispersive X-ray spectroscopy were also carried out, in order to visualize the distribution of silver particles on the fibers. The materials were also characterized from a biological point of view in terms of antibacterial capability and cytotoxicity. Agar diffusion tests and bacterial enumeration tests were performed on Gram positive and Gram negative bacteria, namely Staphylococcus aureus and Escherichia coli. In vitro cytotoxicity tests were performed through the extract method on murine fibroblasts in order to verify if the presence of the silver coating affected the cellular viability and proliferation. Durability of the coating was also assessed, thus confirming the successful scaling up of the process, which will be therefore available for large-scale production.

Reduction of spectral interferences using ultraclean gold nanowire arrays in the LDI-MS analysis of a model peptide.

The surface chemistry of gold nanowires (AuNWs) has been systematically assessed in terms of contamination and cleaning processes. The nanomaterial's surface quality was correlated to its performance in the matrix-free laser desorption ionization mass spectrometry (LDI-MS) analysis of low molecular weight analytes. Arrays of AuNWs were deposited on glass slides by means of the lithographically patterned nanowire electrodeposition technique. AuNWs were then characterized in terms of surface chemical composition and morphology using X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy. AuNWs were subjected to a series of well-known cleaning procedures with the aim of producing the best performing surfaces for the LDI-MS detection of leucine enkephalin, chosen as a model analyte with a molar mass below 1,000 g/mol. Prolonged cyclic voltammetry in 2 M sulfuric acid and, most of all, oxygen plasma cleaning for 5 min provided the best results in terms of simpler (interference-free) and more intense mass spectrometry spectra of the reference compound. The analyte always ionized as the sodiated adduct, and leucine enkephalin limits of detection of 0.5 and 2.5 pmol were estimated for the positive and negative analysis modes, respectively. This study points out the tight correlation existing between the chemical status of the nanostructure surface and the AuNW-assisted LDI-MS performance in terms of reproducibility of spectra, intensity of analyte ions and reduction of interferences.

Analytical characterization of laser-generated copper nanoparticles for antibacterial composite food packaging.

A new type of nanomaterial has been developed as antibacterial additive for food packaging applications. This nanocomposite is composed of copper nanoparticles embedded in polylactic acid, combining the antibacterial properties of copper nanoparticles with the biodegradability of the polymer matrix. Metal nanoparticles have been synthesised by means of laser ablation, a rising and easy route to prepare nanostructures without any capping agent in a liquid environment. As prepared, nanoparticle suspensions have been easily mixed to a polymer solution. The resulting hybrid solutions have been deposited by drop casting, thus obtaining self-standing antibacterial packages. All samples have been characterized by UV-Vis spectroscopy, X-ray photoelectron spectroscopy and electro-thermal atomic absorption spectroscopy. Ion release data have been matched with bioactivity tests performed by Japanese Industrial Standard (JIS) method (JIS Z 2801:2000) against Pseudomonas spp., a very common Gram-negative microbial group able to proliferate in processed food.

Silver nanofractals: electrochemical synthesis, XPS characterization and application in LDI-MS.

Silver nanofractals (Ag-NFs) have been electrosynthesized and characterized by means of morphological and spectroscopic analytical techniques. In particular, X-ray photoelectron spectroscopy has been used to assess the nanomaterial surface chemical state. Ag-NFs show interesting perspectives in bioanalytical applications, particularly as non-conventional desorption and ionization promoters in laser desorption ionization mass spectrometry.

Analytical characterization of chitosan nanoparticles for peptide drug delivery applications.

Chitosan-cyclodextrin hybrid nanoparticles (NPs) were obtained by the ionic gelation process in the presence of glutathione (GSH), chosen as a model drug. NPs were characterized by means of transmission electron microscopy and zeta-potential measurements. Furthermore, a detailed X-ray photoelectron spectroscopy study was carried out in both conventional and depth-profile modes. The combination of controlled ion-erosion experiments and a scrupulous curve-fitting approach allowed for the first time the quantitative study of the GSH in-depth distribution in the NPs. NPs were proven to efficiently encapsulate GSH in their inner cores, thus showing promising perspectives as drug carriers.

Analytical investigations of poly(acrylic acid) coatings electrodeposited on titanium-based implants: a versatile approach to biocompatibility enhancement.

A polyacrylic acid film was synthesized on titanium substrates from aqueous solutions via an electroreductive process for the first time. This work was done in order to develop a versatile coating for titanium-based orthopaedic implants that acts as both an effective bioactive surface and an effective anti-corrosion barrier. The chemical structure of the PAA coating was investigated by X-ray photoelectron spectroscopy (XPS). Scanning electron microscopy (SEM) was employed to evaluate the effect of annealing treatment on the morphology of the coatings in terms of their uniformity and porosity. Inductively coupled plasma mass spectrometry was used to measure ion concentrations in ion release tests performed on Ti-6Al-4V sheets modified with PAA coatings (annealed and unannealed). Results indicate that the annealing process produces coatings that possess considerable anti-corrosion performance. Moreover, the availability and the reactivity of the surface carboxylic groups were exploited in order to graft biological molecules onto the PAA-modified titanium implants. The feasibility of the grafting reaction was tested using a single aminoacid residue. A fluorinated aminoacid was selected, and the grafting reaction was monitored both by XPS, using fluorine as a marker element, and via quartz crystal microbalance (QCM) measurements. The success of the grafting reaction opens the door to the synthesis of a wide variety of PAA-based coatings that are functionalized with selected bioactive molecules and promote positive reactions with the biological system interfacing the implant while considerably reducing ion release into surrounding tissues.

Synthesis, analytical characterization and bioactivity of Ag and Cu nanoparticles embedded in poly-vinyl-methyl-ketone films.

The electrosynthesis of copper and silver core-shell nanoparticles (NPs) by the sacrificial anode technique, employing tetraoctylammonium (TOA) salts as base electrolyte for the first time, is described. These surfactants were selected because they combine high NP stabilizing power with useful disinfecting properties. The resulting colloids were mixed with a solution of an inert dispersing polymer and used to prepare nanostructured composite thin films. The morphologies and chemical compositions of the nanomaterials were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The TEM reveals that the average core diameter of the metal NPs ranges between 1.7 and 6.3 nm, as a function of the nature of the metal and of the electrosynthesis conditions, and does not change significantly upon inclusion in the polymer matrix. An appreciable concentration of the metal is detected on the nanoparticle surface by XPS. High-resolution XP spectra indicate that both copper and silver are present at zero oxidation state in all of the materials (colloids and composite films). This demonstrates the high efficiency of the surfactant at controlling the morphology and the chemical composition of the nanodispersed metal in both the as-synthesized colloid and in the polymeric dispersion. The nanocoatings are shown to exert a marked inhibitory effect on the growth of eukaryote and prokaryote target microrganisms, and experimental evidence of a synergic disinfecting effect due to the surfactant and the nanodispersed metal is provided. On the basis of these stability and bioactivity results, it is clear that Cu-NPs and Ag-NPs are suitable for application in disinfecting or antifouling paint and coating formulations.

Analytical characterization of bioactive fluoropolymer ultra-thin coatings modified by copper nanoparticles.

Copper-fluoropolymer (Cu-CFx) nano-composite films are deposited by dual ion-beam sputtering. The extensive analytical characterization of these layers reveals that inorganic nanoparticles composed of Cu(II) species are evenly dispersed in a branched fluoropolymer matrix. In particular, X-ray photoelectron spectroscopy has been employed to study the surface chemical composition of the material and to assess how it changes on increasing the copper loading in the composite. Transmission electron microscopy reveals that the copper nanoclusters have a mean diameter of 2-3 nm and are homogeneously in-plane distributed in the composite films. Electrothermal atomic absorption spectroscopy has been used to study the kinetics of copper release in the solutions employed for the biological tests. The Cu-CFx layers are employed as bioactive coatings capable of inhibiting the growth of target microorganisms such as Saccharomyces cerevisiae, Escherichia coli, Staphylococcus aureus, and Lysteria. The results of the analytical characterization enable a strict correlation to be established among the chemical composition of the material surface, the concentration of copper dissolved in the microorganisms broths, and the bioactivity of the nano-structured layer.

An electrospray ionization ion trap mass spectrometric (ESI-MS-MSn) study of dehydroascorbic acid hydrolysis at neutral pH.

The hydrolysis of dehydroascorbic acid (DAAH) at neutral pH and 27 degrees C was investigated by direct infusion electrospray ionisation ion trap mass spectrometry (ESI-MS). This approach permitted derivatisation and elution procedures to be avoided, reducing to the minimum extent sample manipulation and allowing a rapid and direct observation of the species involved in the reaction. Six main peaks, related to hydrated dehydroascorbate (HyDAA-) and diketogulonate (HyDKG-) anions, were observed in the mass spectra of DAAH solutions at different times of incubation and were characterised by MSn experiments. The relevant signal intensities changed with time and a model, based on the irreversible pseudo-first order HyDAA(-)-->HyDKG- conversion, fitted successfully the data obtained for dehydroascorbate. The kinetic constant of the process was (3.2 +/- 0.5) x 10(-2) min-1. The influence of metal ion traces on the hydrolysis rate was also checked, performing experiments in the presence of EDTA, and was found to be negligible.