Maria Chiara Sportelli

Characterization and behaviour of ZnO-based nanocomposites designed for the control of biodeterioration of patrimonial stoneworks

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.

Investigation of Industrial Polyurethane Foams Modified with Antimicrobial Copper Nanoparticles

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.

Catalytic Activity of Silicon Nanowires Decorated with Gold and Copper Nanoparticles Deposited by Pulsed Laser Ablation

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.

Spectroscopic Characterization of Copper-Chitosan Nanoantimicrobials Prepared by Laser Ablation Synthesis in Aqueous Solutions

Copper-chitosan (Cu-CS) nanoantimicrobials are a novel class of bioactive agents, providing enhanced and synergistic efficiency in the prevention of biocontamination in several application fields, from food packaging to biomedical. Femtosecond laser pulses were here exploited to disrupt a Cu solid target immersed into aqueous acidic solutions containing different CS concentrations. After preparation, Cu-CS colloids were obtained by tuning both Cu/CS molar ratios and laser operating conditions. As prepared Cu-CS colloids were characterized by Fourier transform infrared spectroscopy (FTIR), to study copper complexation with the biopolymer. X-ray photoelectron spectroscopy (XPS) was used to elucidate the nanomaterials’ surface chemical composition and chemical speciation of the most representative elements. Transmission electron microscopy was used to characterize nanocolloids morphology. For all samples, ξ-potential measurements showed highly positive potentials, which could be correlated with the XPS information. The spectroscopic and morphological characterization herein presented outlines the characteristics of a technologically-relevant nanomaterial and provides evidence about the optimal synthesis parameters to produce almost monodisperse and properly-capped Cu nanophases, which combine in the same core-shell structure two renowned antibacterial agents.

Spectroscopic Characterization and Nanosafety of Ag-Modified Antibacterial Leather and Leatherette

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.

Electrosynthesis of ZnO nanomaterials in aqueous medium with CTAB cationic stabilizer

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.Graphical Abstract

The Pros and Cons of the Use of Laser Ablation Synthesis for the Production of Silver Nano-Antimicrobials

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.

Nonconventional Routes to Silver Nanoantimicrobials: Technological Issues, Bioactivity, and Applications**This chapter was prepared by three research groups that equally contributed to the work. The first author listed for each institution represents the first author for his/her own research group. Mauro Pollini and Federica Paladini contributed equally to this chapter.

Silver antimicrobial nanomaterials are the subject of exponentially increasing attention in both academia and industry because of their unprecedented efficiency in preventing biocontamination in several real-life applications. Wet chemical syntheses based on redox processes in micellar media as well as plasma or magnetron sputtering methods are dominating the fields of chemical or physical preparations of silver nanoparticles (AgNPs), respectively. The authors of this chapter are experts in three nonconventional methods producing outperforming AgNPs, either as nanocolloids or as multifunctional thin coatings. Electrochemical synthesis of AgNP colloids, ion beam sputtering, and photo-assisted deposition of AgNP-based coatings are reviewed in the present chapter. Technological insights into the processes are offered to the specialized audience, and an overview of the most widely accepted bioactivity mechanisms and the most promising applications is provided.