TiO2-MoS2-PMMA Nanocomposites for an Efficient Water Remediation.

An improvement of water supply and sanitation and better management of water resources, especially in terms of water reuse, is one of the priorities of the European Green Deal. In this context, it is crucial to find new strategies to recycle wastewater efficiently in a low-cost and eco-friendly manner. The immobilization of inorganic nanomaterials on polymeric matrices has been drawing a lot of attention in recent years due to the extraordinary properties characterizing the as-obtained nanocomposites. The hybrid materials, indeed, combine the properties of the polymers, such as flexibility, low cost, mechanical stability, high durability, and ease of availability, with the properties of the inorganic counterpart. In particular, if the inorganic fillers are nanostructured photocatalysts, the materials will be able to utilize the energy delivered by light to catalyze chemical reactions for efficient wastewater treatment. Additionally, with the anchoring of the nanomaterials to the polymers, the dispersion of the nanomaterials in the environment is prevented, thus overcoming one of the main limits that impede the application of nanostructured photocatalysts on a large scale. In this work, we will present nanocomposites made of polymers, i.e., polymethyl methacrylate (PMMA), and photocatalytic semiconductors, i.e., TiO2 nanoparticles (Evonik). MoS2 nanoflakes were also added as co-catalysts to improve the photocatalytic performance of the TiO2. The hybrid materials were prepared using the sonication and solution casting method. The nanocomposites were deeply characterized, and their remarkable photocatalytic abilities were evaluated by the degradation of two common water pollutants: methyl orange and diclofenac. The relevance of the obtained results will be discussed, opening the route for the application of these materials in photocatalysis and especially for novel wastewater remediation.

RGD-tagging of star-shaped PLA-PEG micellar nanoassemblies enhances doxorubicin efficacy against osteosarcoma.

We developed cyclic RGD-tagged polymeric micellar nanoassemblies for sustained delivery of Doxorubicin (Dox) endowed with significant cytotoxic effect against MG63, SAOS-2, and U2-OS osteosarcoma cells without compromising the viability of healthy osteoblasts (hFOBs). Targeted polymeric micellar nanoassemblies (RGD-NanoStar@Dox) enabled Dox to reach the nucleus of MG63, SAOS-2, and U2-OS cells causing the same cytotoxic effect as free Dox, unlike untargeted micellar nanoassemblies (NanoStar@Dox) which failed to reach the nucleus and resulted ineffective, demonstrating the crucial role of cyclic RGD peptide in driving cellular uptake and accumulation mechanisms in osteosarcoma cells. Micellar nanoassemblies were obtained by nanoformulation of three-armed star PLA-PEG copolymers properly synthetized with and without decoration with the cyclic-RGDyK peptide (Arg-Gly-Asp-D-Tyr-Lys). The optimal RGD-NanoStar@Dox nanoformulation obtained by nanoprecipitation method (8 % drug loading; 35 % encapsulation efficiency) provided a prolonged and sustained drug release with a rate significantly lower than the free drug under the same experimental conditions. Moreover, the nanosystem preserved Dox from the natural degradation occurring under physiological conditions (i.e., dimerization and consequent precipitation) serving as a slow-release "drug reservoir" ensuring an extended biological activity over the time.

Ultra-Low Loading of Gold on Nickel Foam for Nitrogen Electrochemistry.

Ammonia (NH3) is widely used in various fields, and it is also considered a promising carbon free energy carrier, due to its high hydrogen content. The nitrogen reduction reaction (NRR), which converts nitrogen into ammonia by using protons from water as the hydrogen source, is receiving a lot of attention, since effective process optimization would make it possible to overcome the Haber-Bosch method. In this study, we used a solution-based approach to obtain functionalized porous Ni foam substrates with a small amount of gold (<0.1 mg cm-1). We investigated several deposition conditions and obtained different morphologies. The electrochemical performance of various catalysts on the hydrogen evolution reaction (HER) and NRR has been characterized. The ammonia production yield was determined by chronoamperometry experiments at several potentials, and the results showed a maximum ammonia yield rate of 20 µg h-1 mgcat-1 and a Faradaic efficiency of 5.22%. This study demonstrates the potential of gold-based catalysts for sustainable ammonia production and highlights the importance of optimizing deposition conditions to improve the selectivity toward HER.

Model of Chronoamperometric Response towards Glucose Sensing by Arrays of Gold Nanostructures Obtained by Laser, Thermal and Wet Processes.

Non-enzymatic electrochemical glucose sensors are of great importance in biomedical applications, for the realization of portable diabetic testing kits and continuous glucose monitoring systems. Nanostructured materials show a number of advantages in the applications of analytical electrochemistry, compared to macroscopic electrodes, such as great sensitivity and little dependence on analyte diffusion close to the electrode-solution interface. Obtaining electrodes based on nanomaterials without using expensive lithographic techniques represents a great added value. In this paper, we modeled the chronoamperometric response towards glucose determination by four electrodes consisting of nanostructured gold onto graphene paper (GP). The nanostructures were obtained by electrochemical etch, thermal and laser processes of thin gold layer. We addressed experiments obtaining different size and shape of gold nanostructures. Electrodes have been characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and chronoamperometry. We modeled the current-time response at the potential corresponding to two-electrons oxidation process of glucose by the different nanostructured gold systems. The finest nanostructures of 10-200 nm were obtained by laser dewetting of 17 nm thin and 300 °C thermal dewetting of 8 nm thin gold layers, and they show that semi-infinite linear diffusion mechanism predominates over radial diffusion. Electrochemical etching and 17 nm thin gold layer dewetted at 400 °C consist of larger gold islands up to 1 µm. In the latter case, the current-time curves can be fitted by a two-phase exponential decay function that relies on the mixed second-order formation of adsorbed glucose intermediate followed by its first-order decay to gluconolactone.

Molecule Clustering Dynamics in the Molecular Doping Process of Si(111) with Diethyl-propyl-phosphonate.

The molecular doping (MD) process is based on the deposition of dopant-containing molecules over the surface of a semiconductor substrate, followed by the thermal diffusion step. Previous studies suggest that, during the deposition, the molecules nucleate clusters, and at prolonged deposition times, they grow into self-assembled layers on the sample to be doped. Little is known about the influence of nucleation kinetics on the final properties of these layers and how they change when we modify the solution properties. In this work, we examine the nucleation rate and the molecular surface coverage kinetics of diethyl-propyl phosphonate on silicon at different solution concentrations and how these conditions influence the final electrical properties of the doped samples. We present a high-resolution morphological characterization of the as-deposited molecules together with the electrical results of the final doped samples. The experimental results show a non-obvious behavior, explained through understanding of the competition between the molecules' physisorption and chemisorption mechanisms. As a consequence, due to the deeper knowledge of the deposition phase, a finer tuning of the conductive properties of MD-doped samples is achieved.

Alkaline Electro-Sorption of Hydrogen Onto Nanoparticles of Pt, Pd, Pt80Pd20 and Cu(OH)2 Obtained by Pulsed Laser Ablation.

Recently, hydrogen evolution reaction (HER) in alkaline media has received a renewed interest both in the fundamental research as well as in practical applications. Pulsed Laser Ablation in Liquid (PLAL) has been demonstrated as a very useful technique for the unconventional preparation of nanomaterials with amazing electro-catalyst properties toward HER, compared to those of nanomaterials prepared by conventional methods. In this paper, we compared the electro-sorption properties of hydrogen in alkaline media by Pt, Pd, Pt80Pd20, and Cu(OH)2 nanoparticles (NPs) prepared by PLAL. The NPs were placed onto graphene paper (GP). Noble metal particles have an almost spherical shape, whereas Cu(OH)2 presents a flower-bud-like shape, formed by very thin nanowalls. XPS analyses of Cu(OH)2 are compatible with a high co-ordination of Cu(II) centers by OH and H2O. A thin layer of perfluorosulfone ionomer placed onto the surface of nanoparticles (NPs) enhances their distribution on the surface of graphene paper (GP), thereby improving their electro-catalytic properties. The proposed mechanisms for hydrogen evolution reaction (HER) on noble metals and Cu(OH)2 are in line with the adsorption energies of H, OH, and H2O on the surfaces of Pt, Pd, and oxidized copper. A significant spillover mechanism was observed for the noble metals when supported by graphene paper. Cu(OH)2 prepared by PLAL shows a competitive efficiency toward HER that is attributed to its high hydrophilicity which, in turn, is due to the high co-ordination of Cu(II) centers in very thin Cu(OH)2 layers by OH- and H2O. We propose the formation of an intermediate complex with water which can reduce the barrier energy of water adsorption and dissociation.

Enhancement of biological effects of oxidised nano- and microplastics in human professional phagocytes.

Micro and nanoplastics are ubiquitous pollutants that can cause adverse health effects even in humans. Effects of virgin and oxidised (simulating the aging processes) polystyrene nano (nPS) and micro particles (mPS) with diameters of 0.1 and 1 µm were studied on human professional phagocytes (i.e., monocyte cells THP-1 and macrophage-like mTHP-1 cells). After characterization by ATR-FTIR, UV-Vis spectroscopy, SEM and dynamic light-scattering analyses, the particles were FITC functionalised to quantify cellular uptake. Changes in the cell compartments were studied by acrydine orange and the pro-oxidant, cytotoxic and genotoxic effects were assessed. Phagocytosis was dose- and time- dependent and at 24 h 52% of nPS and 58% of mPS were engulfed. Despite the high homeostasis of professional phagocytes, significant ROS increases and DNA damage were observed after exposure to oxidised particles. The results highlight that the environmental aging processes enhances the adverse health effects of micro and nanoplastics.

AZO Nanoparticles-Decorated CNTs for UV Light Sensing: A Structural, Chemical, and Electro-Optical Investigation.

Nanocomposites formed by aluminum-doped zinc oxide nanoparticles (AZO-NP) and multiwall carbon nanotubes (CNT) are proposed here as a promising material for UV light sensing applications, with the great advantage of operating in air, at room temperature, and at low voltage. Nanocomposite layers were prepared with different AZO:CNT weight ratios by a simple methodology at room temperature. They were characterized by means of UV-Vis spectroscopy, scanning and transmission electron microscopies (SEM and TEM), and X-ray photoelectron spectroscopy (XPS). The interaction between the two nanomaterials was demonstrated by comparing the properties of the nanocomposite with the ones shown by the AZO-NPs. Dense AZO-CNT nanocomposite layers were deposited between two metal electrodes on a SiO2/Si substrate, and the electrical properties were investigated in dark condition and under UV light irradiation. The electrical response to the UV light was a sudden current increase that reduced when the light was switched off. Several UV on/off cycles were performed, showing good repeatability and stability of the response. The mechanisms involved in the electrical response are discussed and compared to the ones previously reported for ZnO-CNT nanocomposites.

Sulfonated Pentablock Copolymer Coating of Polypropylene Filters for Dye and Metal Ions Effective Removal by Integrated Adsorption and Filtration Process.

In this work, we coated polypropylene (PP) fibrous filters with sulfonated pentablock copolymer (s-PBC) layers and tested them for the removal of cationic organic dyes, such as methylene blue (MB), and heavy metal ions (Fe3+ and Co2+) from water by adsorption and filtration experiments. Some of the coated filters were irradiated by UV light before being exposed to contaminated water and then were tested with unirradiated filters in the same adsorption and filtration experiments. Polymer-coated filters showed high efficiency in removing MB from an aqueous solution in both absorption and filtration processes, with 90% and 80% removal, respectively. On the other hand, for heavy metal ions (Fe3+ and Co2+), the coated filters showed a better removal performance in the filtration process than for the adsorption one. In fact, in the adsorption process, controlled interaction times allow the ionic species to interact with the surface of the filters leading to the formation and release of new species in solution. During filtration, the ionic species are easily trapped in the filters, in particular by UV modified filters, and we observed for Fe3+ ions a total removal (>99%) in a single filtration process and for Co2+ ions a larger removal with respect to the untreated filter. The mechanisms involved in the removal of the contaminants processes were investigated by characterizing the filters before and after use by means of scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis and Fourier transform infrared spectroscopy (FT-IR).

Orange-Peel-Derived Nanobiochar for Targeted Cancer Therapy.

Cancer-targeted drug delivery systems (DDS) based on carbon nanostructures have shown great promise in cancer therapy due to their ability to selectively recognize specific receptors overexpressed in cancer cells. In this paper, we have explored a green route to synthesize nanobiochar (NBC) endowed with graphene structure from the hydrothermal carbonization (HTC) of orange peels and evaluated the suitability of this nanomaterial as a nanoplatform for cancer therapy. In order to compare the cancer-targeting ability of different widely used targeting ligands (TL), we have conjugated NBC with biotin, riboflavin, folic acid and hyaluronic acid and have tested, in vitro, their biocompatibility and uptake ability towards a human alveolar cancer cell line (A549 cells). The nanosystems which showed the best biological performances-namely, the biotin- and riboflavin- conjugated systems-have been loaded with the poorly water-soluble drug DHF (5,5-dimethyl-6a-phenyl-3-(trimethylsilyl)-6,6a-dihydrofuro[3,2-b]furan-2(5H)-one) and tested for their anticancer activity. The in vitro biological tests demonstrated the ability of both systems to internalize the drug in A549 cells. In particular, the biotin-functionalized NBC caused cell death percentages to more than double with respect to the drug alone. The reported results also highlight the positive effect of the presence of oxygen-containing functional groups, present on the NBC surface, to improve the water dispersion stability of the DDS and thus make the approach of using this nanomaterial as nanocarrier for poorly water-soluble drugs effective.

Innovative Antibiofilm Smart Surface against Legionella for Water Systems.

Legionella pneumophila contamination of water systems is a crucial issue for public health. The pathogen is able to persist in water as free-living planktonic bacteria or to grow within biofilms that adhere to and clog filters and pipes in a water system, reducing its lifespan and, in the case of hospital buildings, increasing the risk of nosocomial infections. The implementation of water management is considered to be the main prevention measure and can be achieved from the optimization of water system architecture, notably introducing new materials and strategies to contrast Legionella biofilm proliferation and so prolong the water system functionality. In this research, we propose a new smart surface against L. pneumophila biofilm formation. This is based on an innovative type of coating consisting of a sulfonated pentablock copolymer (s-PBC, commercially named Nexar™) deposited on top of a polypropylene (PP) coupon in a sandwich filter model. The covering of PP with s-PBC results in a more hydrophilic, acid, and negatively charged surface that induces microbial physiological inhibition thereby preventing adhesion and/or proliferation attempts of L. pneumophila prior to the biofilm formation. The antibiofilm property has been investigated by a Zone of Inhibition test and an in vitro biofilm formation analysis. Filtration tests have been performed as representative of possible applications for s-PBC coating. Results are reported and discussed.

Early Stages of Aluminum-Doped Zinc Oxide Growth on Silicon Nanowires.

Aluminum-doped zinc oxide (AZO) is an electrically conductive and optically transparent material with many applications in optoelectronics and photovoltaics as well as in the new field of plasmonic metamaterials. Most of its applications contemplate the use of complex and nanosized materials as substrates onto which the AZO forms the coating layer. Its morphological characteristics, especially the conformality and crystallographic structure, are crucial because they affect its opto-electrical response. Nevertheless, it was difficult to find literature data on AZO layers deposited on non-planar structures. We studied the AZO growth on silicon-nanowires (SiNWs) to understand its morphological evolution when it is formed on quasi one-dimensional nanostructures. We deposited by sputtering different AZO thicknesses, leading from nanoclusters until complete incorporation of the SiNWs array was achieved. At the early stages, AZO formed crystalline nano-islands. These small clusters unexpectedly contained detectable Al, even in these preliminary phases, and showed a wurtzite crystallographic structure. At higher thickness, they coalesced by forming a conformal polycrystalline shell over the nanostructured substrate. As the deposition time increased, the AZO conformal deposition led to a polycrystalline matrix growing between the SiNWs, until the complete array incorporation and planarization. After the early stages, an interesting phenomenon took place leading to the formation of hook-curved SiNWs covered by AZO. These nanostructures are potentially very promising for optical, electro-optical and plasmonic applications.

Study of the Molecule Adsorption Process during the Molecular Doping.

Molecular Doping (MD) involves the deposition of molecules, containing the dopant atoms and dissolved in liquid solutions, over the surface of a semiconductor before the drive-in step. The control on the characteristics of the final doped samples resides on the in-depth study of the molecule behaviour once deposited. It is already known that the molecules form a self-assembled monolayer over the surface of the sample, but little is known about the role and behaviour of possible multiple layers that could be deposited on it after extended deposition times. In this work, we investigate the molecular surface coverage over time of diethyl-propyl phosphonate on silicon, by employing high-resolution morphological and electrical characterization, and examine the effects of the post-deposition surface treatments on it. We present these data together with density functional theory simulations of the molecules-substrate system and electrical measurements of the doped samples. The results allow us to recognise a difference in the bonding types involved in the formation of the molecular layers and how these influence the final doping profile of the samples. This will improve the control on the electrical properties of MD-based devices, allowing for a finer tuning of their performance.

Structural Characterization and Adsorption Properties of Dunino Raw Halloysite Mineral for Dye Removal from Water.

In this work, raw halloysite mineral from Dunino (Poland) has been characterized and tested as an efficient and low-cost adsorbent for dye removal from water. The morphology and structure of this clay were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and the chemical composition was evaluated by means of X-ray fluorescence spectroscopy (XRF), energy dispersive X-ray spectroscopy (EDX), and electron energy loss spectroscopy (EELS). The results showed that it is made up of both platy and tubular structures, mainly composed of Si, Al, and O. Iron oxide particles covering the platy structures were also observed. The surface charge of halloysite was measured by z-potential measurements and by the evaluation of the point of zero charge. The clay was tested as an adsorbent for the removal of positively and negatively charged dye molecules, i.e., methylene blue (MB) and methyl orange (MO), both separately and in a mixed-dye solution. Halloysite showed the ability to efficiently and selectively remove MB molecules by adsorption, both in a single-dye solution and in a mixed one. The adsorption of positive dyes on the clay surface mainly occurred through ion exchange at negatively charged sites on its surface. The possibility of regenerating the clay for further dye removal processes is also shown.

Environmental Management of Legionella in Domestic Water Systems: Consolidated and Innovative Approaches for Disinfection Methods and Risk Assessment.

Legionella is able to remain in water as free-living planktonic bacteria or to grow within biofilms that adhere to the pipes. It is also able to enter amoebas or to switch into a viable but not culturable (VBNC) state, which contributes to its resistance to harsh conditions and hinders its detection in water. Factors regulating Legionella growth, such as environmental conditions, type and concentration of available organic and inorganic nutrients, presence of protozoa, spatial location of microorganisms, metal plumbing components, and associated corrosion products are important for Legionella survival and growth. Finally, water treatment and distribution conditions may affect each of these factors. A deeper comprehension of Legionella interactions in water distribution systems with the environmental conditions is needed for better control of the colonization. To this purpose, the implementation of water management plans is the main prevention measure against Legionella. A water management program requires coordination among building managers, health care providers, and Public Health professionals. The review reports a comprehensive view of the state of the art and the promising perspectives of both monitoring and disinfection methods against Legionella in water, focusing on the main current challenges concerning the Public Health sector.

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.

Antimicrobial s-PBC Coatings for Innovative Multifunctional Water Filters.

Biological contamination is a typical issue in water treatment. Highly concentrated microbial suspensions in a water flow may cause filter occlusion and biofilm formation, affecting the lifespan and quality of water purification systems and increasing the risk of nosocomial infections. In order to contrast the biofilm formation, most of the conventional strategies rely on the water chemical modification and/or on the use of filters functional coatings. The former is unsafe for huge chemicals spilling required; therefore, we focus on the second approach and we propose the use of a sulfonated pentablock copolymer (s-PBC, commercially named Nexar™) as innovative multifunctional coating for improving the performance of commercial water filters. S-PBC-coated polypropylene (PP) samples were tested against the pathogen Pseudomonas aeruginosa. The covering of PP with s-PBC results in a more hydrophilic, acid, and negatively charged surface. These properties avoid the adhesion and proliferation attempts of planktonic bacteria, i.e., the biofilm formation. Inhibition tests were performed on the as-modified filters and an evident antibacterial activity was observed. The results point out the possibility of using NexarTM as coating layer for filters with antifouling properties and a simultaneous ability to remove bacteria and cationic dyes from water.

Sulfonated Pentablock Copolymer Membranes and Graphene Oxide Addition for Efficient Removal of Metal Ions from Water.

Nowadays heavy metals are among the higher environmental priority pollutants, therefore, the identification of new, effective, reusable and easy-to-handle adsorbent materials able to remove metal ions from water is highly desired. To this aim, in this work for the first time, sulfonated pentablock copolymer (s-PBC, Nexar™) membranes and s-PBC/graphene oxide (GO) nanocomposite membranes were investigated for the removal of heavy metals from water. Membranes were prepared by drop casting and their chemical, structural and morphological properties were characterized using scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic mechanical analysis (DMA) and small-angle X-ray scattering (SAXS). The adsorption abilities and adsorption kinetics of both the polymer and the s-PBC/GO nanocomposite were investigated for the removal of different heavy metal ions (Ni2+, Co2+, Cr3+ and Pb2+) from aqueous solutions containing the corresponding metal salts at different concentrations. The investigated s-PBC membrane shows a good efficiency, due to the presence of sulfonic groups that play a fundamental role in the adsorption process of metal ions. Its performance is further enhanced by embedding a very low amount of GO in the polymer allowing an increase by at least three times of the adsorption efficiencies of the polymer itself. This can be ascribed to the higher porosity, higher roughness and higher lamellar distances introduced by GO in the s-PBC membrane, as evidenced by the SEM and SAXS analysis. Both the polymeric materials showed the best performance in removing Pb2+ ions.

Ni foam electrode solution impregnated with Ni-Fe X (OH) Y catalysts for efficient oxygen evolution reaction in alkaline electrolyzers.

Oxygen evolution reaction (OER) is a demanding step within the water splitting process for its requirement of a high overpotential. Thus, to overcome this unfavourable kinetics, an efficient catalyst is required to expedite the process. In this context, we report on Ni foam functionalised with low cost iron (Fe) and iron hydroxide (Fe(OH) X ), wet chemically synthesized as OER catalysts. The prepared catalyst based on iron hydroxide precipitate shows a promising performance, exhibiting an overpotential of 270 mV (at a current density of 10 mA cm-2 in 1 M KOH solution), an efficient Tafel slope of ∼50 mV dec-1 and stable chronopotentiometry. The promising performance of the anode was further reproduced in the overall water splitting reaction with a two electrode cell. The overall reaction requires a lower potential of 1.508 V to afford 10 mA cm-2, corresponding to 81.5% electrical to fuel efficiency.

Chemical Vapor Deposition Growth of Silicon Nanowires with Diameter Smaller Than 5 nm.

Quantum confinement effects in silicon nanowires (SiNWs) are expected when their diameter is less than the size of the free exciton (with a Bohr radius ∼5 nm) in bulk silicon. However, their synthesis represents a considerable technological challenge. The vapor-liquid-solid (VLS) mechanism, mediated by metallic nanoclusters brought to the eutectic liquid state, is most widely used for its simplicity and control on the SiNWs size, shape, orientation, density, and surface smoothness. VLS growth is often performed within high-vacuum physical vapor deposition systems, where the eutectic composition and the pressure conditions define the minimum diameter of the final nanowire usually around 100 nm. In this article, we present and discuss the SiNWs' growth by the VLS method in a plasma-based chemical vapor deposition system, working in the mTorr pressure range. The purpose is to demonstrate that it is possible to obtain nanostructures with sizes well beyond the observed limit by modulating the deposition parameters, like chamber pressure and plasma power, to find the proper thermodynamic conditions for nucleation. The formation of SiNWs with sub-5 nm diameter is demonstrated.