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Silver nanoparticles synthesized using laser ablation synthesis in isopropanol, in absence of additional capping agents, were found to be stable with respect to both aggregation and silver oxidation over several months. The rationale for this extreme stability of metal nanoparticles suspended in organic solvents was challenging. On the basis of theoretical considerations and basic experiments it is proposed that the stabilization of silver nanoparticles involves the formation of an organic coating generated by the interaction of isopropanol molecules with the pulsed, high-energy laser beam. This coating prevents, on the one hand, any chemical reaction on colloidal nanoparticles (e.g. silver oxidation); on the other hand, the presence of the organic shell with a nature akin to that of the organic solvent led to weaker Van der Walls interactions between approaching nanoparticles enabling a larger stability than for naked metallic nanoparticles.

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.

ZnO nanoparticles were prepared with a green, cheap, and easy aqueous electrochemical process. The electrolyte was made of a stabilizing cationic surfactant (cetyltrimethylammonium bromide, CTAB) dissolved in NaHCO3 at pH = 8. The electrosynthesis was carried out galvanostatically at 10 mA/cm2, at room temperature or at 80 °C for 1 h. Gel-like pristine colloids, made of mixed Zn carbonates and hydroxides, underwent post-synthesis thermal treatments to allow a compete conversion to ZnO. Calcination was carried out at 300 or 600 °C for 1 h. All nanomaterials were characterized at each step of their production by transmission electron microscopy, UV–Vis, infrared (FT–IR) and X-ray photoelectron spectroscopies. Electrochemical synthesis at 80 °C followed by calcination at 300 °C for 1 h allowed preparing ZnO submicron structures with good morphology and stoichiometry.

In this work, novel hybrid nanostructured surfaces, consisting of dense arrays of silicon nanowires (SiNWs) functionalized by Ag nanoparticles (AgNP/SiNWs), were used for the laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) analysis of some typical unsaturated food components (e.g. squalene, oleic acid) to assess their MS performance. The synthesis of the novel platforms is an easy, cost-effective process based on the maskless wet-etching preparation at room temperature of SiNWs followed by their decoration with AgNPs, produced by pulsed laser deposition. No particular surface pretreatment or addition of organic matrixes/ionizers was necessary. Moreover, oil extracts (e.g. extra virgin olive oil, peanut oil) could be investigated on AgNP/SiNWs surfaces, revealing their different MS profiles. It was shown that such substrates operate at reduced laser energy, typically generating intense silver cluster ions and analyte adducts. A comparison with bare SiNWs was also performed, indicating the importance of AgNP density on NW surface. In this case, desorption/ionization on silicon was invoked as probable LDI mechanism. Finally, the influence of SiNW length and surface composition on MS results was assessed. The combination of typical properties of SiNWs (hydrophobicity, antireflectivity) with ionization ability of metal NPs can be a valid methodology for the further development of nanostructured surfaces in LDI-TOF MS applications. Copyright © 2016 John Wiley & Sons, Ltd.

Silver nanoparticles (AgNPs) are well-known for their antimicrobial effects and several groups are proposing them as active agents to fight antimicrobial resistance. A wide variety of methods is available for nanoparticle synthesis, affording a broad spectrum of chemical and physical properties. In this work, we report on AgNPs produced by laser ablation synthesis in solution (LASiS), discussing the major features of this approach. Laser ablation synthesis is one of the best candidates, as compared to wet-chemical syntheses, for preparing Ag nano-antimicrobials. In fact, this method allows the preparation of stable Ag colloids in pure solvents without using either capping and stabilizing agents or reductants. LASiS produces AgNPs, which can be more suitable for medical and food-related applications where it is important to use non-toxic chemicals and materials for humans. In addition, laser ablation allows for achieving nanoparticles with different properties according to experimental laser parameters, thus influencing antibacterial mechanisms. However, the concentration obtained by laser-generated AgNP colloids is often low, and it is hard to implement them on an industrial scale. To obtain interesting concentrations for final applications, it is necessary to exploit high-energy lasers, which are quite expensive. In this review, we discuss the pros and cons of the use of laser ablation synthesis for the production of Ag antimicrobial colloids, taking into account applications in the food packaging field.

Silicon nanowires (SiNWs) decorated by pulsed laser ablation with gold or copper nanoparticles (labeled as AuNPs@SiNWs and CuNPs@SiNWs) were investigated for their catalytic properties. Results demonstrated high catalytic performances in the Caryl–N couplings and subsequent carbonylations for gold and copper catalysts, respectively, that have no precedents in the literature. The excellent activity, attested by the very high turn over number (TON) values, was due both to the uniform coverage along the NW length and to the absence of the chemical shell surrounding the metal nanoparticles (MeNPs). A high recyclability was also observed and can be ascribed to the strong covalent interaction at the Me–Si interface by virtue of metal “silicides” formation.

Surface modification treatments able to confer antistain/antibacterial properties to natural or synthetic materials are receiving increasing attention among scientists. Ion beam co-sputtering (IBS) of zinc oxide (ZnO) and poly-tetrafluoroethylene (PTFE) targets allows for the preparation of novel multifunctional coatings composed of antimicrobial ZnO nanoparticles (NPs) finely dispersed in an antistain PTFE polymeric matrix. Remarkably, IBS has been proved to be successful in the controlled deposition of thin nanocoatings as an alternative to wet methods. Moreover, tuning IBS deposition parameters allows for the control of ZnONP loadings, thus modulating the antibacterial/antistain coating’s final properties. All the deposited coatings were fully characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and transmission electron microscopy (TEM) in order to obtain information on the materials’ surface composition, with deep insight into the nanocoatings’ morphology as a function of the ZnONP loadings. An analysis of high-resolution XP spectra evidenced a high degree of polymer defluorination along with the formation of inorganic fluorides at increasing ZnO volume ratios. Hence, post-deposition treatments for fluorides removal, performed directly in the deposition chamber, were successfully developed and optimized. In this way, a complete stoichiometry for inorganic nanophases was obtained, allowing for the conversion of fluorides into ZnO.

ZnO nanoparticles have been prepared via a green electrochemical synthesis method in the presence of a polymeric anionic stabilizer (poly-sodium-4-styrenesulfonate, PSS), and then applied as inorganic component in poly-3-hexyl-thiophene thin-film transistor active layers. Different parameters (i.e. current density, electrolytic media, PSS concentration, and temperature) influencing nanoparticle synthesis have been studied. The resulting nanomaterials have been investigated by transmission electron microscopy (TEM) and spectroscopic techniques (UV-Vis, infrared, and x-ray photoelectron spectroscopies), assessing the most suitable conditions for the synthesis and thermal annealing of nanostructured ZnO. The proposed ZnO nanoparticles have been successfully coupled with a poly-3-hexyl-thiophene thin-film resulting in thin-film transistors with improved performance.

Designing bioactive materials, with controlled metal ion release, exerting significant bioactivity and associated low toxicity for humans, is nowadays one of the most important challenges for the scientific community. In this work, we propose a new material combining the well-known antimicrobial properties of copper nanoparticles (CuNPs) with those of bioactive chitosan (CS), a cheap natural polymer widely exploited for its biodegradability and nontoxicity. Here, we used ultrafast femtosecond laser pulses to finely fragment, via laser ablation, a Cu solid target immersed into aqueous CS solutions. Homogeneously dispersed copper-chitosan (Cu-CS) colloids were obtained by tuning the Cu/CS molar ratios, according to the initial chitosan concentration, as well as other experimental parameters. Cu-CS colloids were characterized by several techniques, like UV-Vis and X-ray Photoelectron spectroscopies (XPS). Transmission Electron Microscopy (TEM) was used to morphologically characterize the novel nanocomposites.

In this study, a preventive method for fighting bio-deterioration of stone substrates is proposed. This is based on the use of bioactive zinc oxide nanoparticles (ZnO-NPs), which are able to exert a marked biological activity over a long period of time due to their peculiar structure. ZnO-NPs are synthesised by a simple and reproducible electrochemical procedure. The nanomaterials are embedded in consolidant/water-repellent matrices to obtain nanostructured coatings. Commonly used products based on tetraethoxysilane and/or polysiloxanes were tested. The resulting nanomaterials were fully characterised by X-ray photoelectron spectroscopy (XPS) to investigate the amount and composition of the NPs and the behaviour of the nanocomposites. Inductively coupled plasma mass spectrometry (ICP-MS) was used for the study of the release of metal from the composites when put in contact with artificial rainwater. The nanocomposites were applied to specimens composed of three different types of stone and chromatic changes upon curing were measured by spectrophotocolorimetry. Finally, morphological characterization by scanning electron microscopy (SEM) was performed. The bioactivity of ZnO-NPs nanocomposites was also assessed in preliminary tests against Aspergillus niger fungus.

In this work, the unique capability of femtosecond laser pulses to finely fragment via laser ablation a Cu solid target immersed into CS-HAc solutions was exploited in order to obtain a homogeneously dispersed colloid of Cu-CS nanocomposites with different Cu/CS molar ratios according to the initial chitosan concentration. Using these hybrid nanocolloids as solvents, well-dispersed nanocomposite polymer films were produced after spin-coating on glass substrates. Both Cu-CS colloids and coatings were characterized by several techniques, including UV-Vis, FTIR, DLS, TEM and XPS aiming to analyse the surface and bulk chemical composition as well as the morphology of the novel nanocomposite. The antimicrobial properties of the proposed hybrid Cu-CS nanomaterial, which in the intention combines the bioactivity of both components, have been assessed by biological experiments using selected microorganism strains including samples from hospitalized dermatology patients.

The development of antibacterial coatings is of great interest from both industry and the consumer’s point of view. In this study, we characterized tanned leather and polyurethane leatherette, typically employed in the automotive and footwear industries, which were modified by photo-deposition of antibacterial silver nanoparticles (AgNPs). Material surface chemical composition was investigated in detail by X-ray photoelectron spectroscopy (XPS). The material’s antibacterial capability was checked against Escherichia coli and Staphylococcus aureus, as representative microorganisms in cross transmissions. Due to the presence of silver in a nanostructured form, nanosafety issues were considered, as well. Ionic release in contact media, as well as whole nanoparticle release from treated materials, were quantitatively evaluated, thus providing specific information on potential product nanotoxicity, which was further investigated through cytocompatibility MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays, also after surface abrasion of the materials. The proved negligible nanoparticle release, as well as the controlled release of antibacterial ions, shed light on the materials’ potentialities, in terms of both high activity and safety.

Nanomaterials are frequently used in laser desorption ionization mass spectrometry (LDI-MS) as DI enhancers, providing excellent figures of merit for the analysis of low molecular weight organic molecules. In recent years, literature on this topic has benefited from several studies assessing the fundamental aspects of the ion desorption efficiency and the internal energy transfer, in the case of model analytes. Several different parameters have been investigated, including the intrinsic chemical and physical properties of the nanophase (chemical composition, thermal conductivity, photo-absorption efficiency, specific heat capacity, phase transition point, explosion threshold, etc.), along with morphological parameters such as the nanophase size, shape, and interparticle distance. Other aspects, such as the composition, roughness and defects of the substrate supporting the LDI-active nanophases, the nanophase binding affinity towards the target analyte, the role of water molecules, have been taken into account as well. Readers interested in nanoparticle based LDI-MS sub-techniques (SALDI-, SELDI-, NALDI- MS) will find here a concise overview of the recent findings in the specialized field of fundamental and mechanistic studies, shading light on the desorption ionization phenomena responsible of the outperforming MS data offered by these techniques.

Silver nanophases are routinely used as bioactive additives in commercial products. Besides their antimicrobial activity, nanosafety issues regarding the application of (silver-based) nanoantimicrobials should be considered, as well. In this study, we modified polyurethane foams, typically employed in air filtration and stuffing, by photodeposited silver nanoparticles for preparing hybrid materials (Ag-PU) with antibacterial properties. The composite materials were characterized in terms of morphology, surface chemical composition, ionic release in contact media, bioactivity, as well as whole nanoparticle release. Cytocompatibility was also assessed on 3T3 mouse fibroblasts. The proposed systematic approach allows for defining suitable composite final properties, in terms of bioactivity and safety, by properly tuning the deposition parameters.

ZnO nanoparticles were prepared by a green electrochemical synthesis method applying low current densities followed by a thermal treatment. Sodium polystyrene sulphonate (PSS) was used as stabilizer in the electrolytic aqueous medium due to its biocompatibility and stability. The as-prepared nanocolloids were then annealed to improve their stability, and then converted via hydroxide species into stoichiometric oxide. Different calcination temperatures were studied. ZnO@PSS nanomaterials were deposited onto SiO2/Si substrates, in part in combination with an organic semiconductor layer to evaluate their influence on organic field effect transistors (OFETs). All nanomaterials and composite layers were characterized by morphological and spectroscopic techniques. Promising results regarding the use of ZnO@PSS in OFETs could be demonstrated.

In this article is proposed a new preparation method for composite ultra-thin films for photovoltaic application. Compounds such as Kesterites (CZTS, ternary and quaternary copper and zinc sulfides) could be used in virtue of their semiconductor behavior in conjunction with electrodeposition from aqueous media methodologies; in particular E-ALD (Electrochemical Atomic Layer Deposition) method seems a legitimate alternative to the high pressure and temperature methods used since today. We studied the feasibility of the electrodeposition process of two layers of semiconductors (Cux Zny S, with p electronic proprieties, and CdS with n electronic proprieties), one above the other, by means of E-ALD. Preliminary electrochemical studies revealed the complex nature of the composite film, impairing the anodic stripping of Cd. In order to confirm that the Cd electrodeposition is surface limited, two sets of samples were compared using different conventional and charge controlled potentiostatic electrodeposition methodologies. SEM and XPS characterization was then performed to characterize morphologically and quantitatively the samples. Consequently, the conditions for the surface limited deposition of Cd over Cux Zny S have been reckoned through the electrochemical and spectroscopical analysis. The layered (p-n) structure of the thin film has been confirmed.

Antimicrobial copper nanoparticles (CuNPs) were electrosynthetized and applied to the controlled impregnation of industrial polyurethane foams used as padding in the textile production or as filters for air conditioning systems. CuNP-modified materials were investigated and characterized morphologically and spectroscopically, by means of Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS). The release of copper ions in solution was studied by Electro-Thermal Atomic Absorption Spectroscopy (ETAAS). Finally, the antimicrobial activity of freshly prepared, as well as aged samples—stored for two months—was demonstrated towards different target microorganisms.

A novel flow cell capable of improving piezoelectric response in system combining Electrochemical Quartz Crystal Microbalance (EQCM) and Flow Injection Analysis is presented. The original design of flow cell modified in shape and position of ports compared to other models for QCM is proposed. Electrochemical and viscoelastic experiments showed focusing of the sample in the central zone between ports and a remarkable enhancement of mass sensitivity compared to Sauerbrey value. Enhancement of mass sensitivity may allow piezoelectric device to be applied to the same concentration range of electrochemical ones and may be used as a tool to develop electrochemical sensors.

A simple and fast microwave-assisted hydrothermal method is proposed for the synthesis of magnetite nanoparticles. The addition of different surfactants (polyvinylpyrrolidone, oleic acid, or trisodium citrate) was studied to investigate the effect on size distribution, morphology, and functionalization of the magnetite nanoparticles. Microwave irradiation at 150 °C for 2 h of aqueous ferrous chloride and hydrazine without additives resulted in hexagonal magnetite nanoplatelets with a facet-to-facet distance of 116 nm and a thickness of 40 nm having a saturation magnetization of ~65 Am2 kg−1. The use of polyvinylpyrrolidone led to hexagonal nanoparticles with a facet-to-facet distance of 120 nm and a thickness of 53 nm with a saturation magnetization of ~54 Am2 kg−1. Additives such as oleic acid and trisodium citrate yielded quasi-spherical nanoparticles of 25 nm in size with a saturation magnetization of ~70 Am2 kg−1 and spheroidal nanoparticles of 60 nm in size with a saturation magnetization up to ~82 Am2 kg−1, respectively. A kinetic control of the crystal growth is believed to be responsible for the hexagonal habit of the nanoparticles obtained without additive. Conversely, a thermodynamic control of the crystal growth, leading to spheroidal nanoparticles, seems to occur when additives which strongly interact with the nanoparticle surface are used. A thorough characterization of the materials was performed. Magnetic properties were investigated by Superconducting Quantum Interference Device and Vibrating Sample magnetometers. Based on the observed magnetic properties, the magnetite obtained using citrate appears to be a promising support for magnetically transportable catalysts.

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.

Ultrasensitive biosensors based on bottom gate organic field-effect transistors can be developed by depositing a functional biological (protein) interlayer directly on the silicon oxide gate dielectric and underneath the organic semiconductor film. However, the deposition methods for assembling the protein biological recognition layer can affect the biosensor analytical performances for the target analyte detection. Here, spin-coating and layer-by-layer techniques were considered as different approaches for streptavidin protein deposition. X-ray photoelectron spectroscopy (XPS) was systematically used in the non-destructive parallel angle resolved mode to characterize the multilayer device at each step of its assembly to gain information on elemental depth profiles. Scanning electron and scanning Helium ion microscopies gave information about stacked layer structure and morphology corroborating XPS results.

Novel Donor-pi-Acceptor triphenylamine-based dyes were synthesized and characterized with regard to their photophysical and photoelectrochemical properties by introducing the ethynyl-2-thienyl moiety as spacer (YS-1). The modification of the donor triphenylamine, performed by intodroducing two p-methoxy groups gave the YS-2 dye. Experimental results showed that the UV-Vis absorption spectra changed exhibiting the increasing of the molar extinction coefficient as well as the red-shift in dichloromethane solution. The maximum power conversion efficiency under standard global AM 1.5 illumination for YS-1 was 4.1% rising to 5.3% when the cell was sensitized with YS-2. The interpretation of the improvement and the discussion of the experimental results were corroborated by Time-Dependent Density-Functional Theory calculations, carried out for the photosensitizers in vacuo and in solution. In particular, the effects on the spectroscopic properties of the dyes due to the presence of the solvent and to the common deprotonation of the carboxylic unit in polar solvents have been investigated.

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.

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.

In this study a conservation treatment of stone monuments meant for consolidation, protection, and inhibition of biofilm formation is proposed. The method is developed as a part of a systematic investigation aimed at producing nanocomposite coatings able to exert a marked biological activity over a long period of time thanks to their peculiar structure. Zinc oxide nanoparticles, synthesised by means of simple and reproducible electrochemical procedures, are embedded in commercially available and commonly used consolidant/water repellent matrices to obtain nanostructured materials. Products based on tetraethoxysilane and/or polysiloxanes were tested. In a first step the nanomaterials were applied on stone samples and studied with scanning electron microscopy and spectrophotocolorimetry. Then, in situ experimentation was undertaken by applying nanocomposite coatings on the exterior of a 12th-century church in the south of Italy. The performances of the ZnO-nanoparticles based composite coating were compared with a previously investigated copper nanoparticles based material, successfully tested and monitored in situ for more than two years. Finally, preliminary tests on the inhibitory effect on the growth of the fungus Aspergillus niger were also carried out. The results showed that in case of zinc oxide a tenfold higher concentration of nanoparticles as compared with Cu-NPs can be utilized in the matrices without affecting the colour of the stone substrate, which means that the new material should be able to exert a long-lasting biocide activity. Laboratory and in situ tests of the developed innovative nanomaterials yielded very promising, though preliminary, results in terms of chromatic changes, morphological characteristics and bioactivity. Constant monitoring of the coatings will be continued in order to obtain all necessary information on their long term behaviour and inhibition of biological colonisation.