Fate of silver nanoparticles in constructed wetlands : a microcosm study

Nano-enabled materials are produced at growing volumes which increases the likelihood of nanoparticles being released into the environment. Constructed wetlands (CWs) are likely to receive wastewater containing nanoparticles leaching from products during usage. Therefore, we investigate the retention of silver nanoparticles (Ag-NPs) in microcosms simulating CWs treating domestic wastewater. The effects of aeration and organic matter content on the Ag-NP removal efficiencies are studied in particular. CWs remove most of the Ag (80-90%) and the largest fraction of Ag is found in/on the biofilm. Detailed electron microscopy analyses suggest that Ag-NPs are transformed into Ag2S in all microcosm experiments. The good correlation between total suspended solids (TSS) and the Ag concentration measured in the effluent indicates that Ag-NPs are bound to the solids in the effluent. Aeration of the microcosms does not affect the release of Ag-NPs from the systems but increasing organic matter leads to increased amounts of Ag passing the CWs, correlating with the increased release of TSS from the CWs. These results suggest that Ag-NPs are retained with the (suspended) solids in CWs and that the removal efficiency of TSS is an important factor determining the discharge of Ag-NPs from CWs

Facile preparation of agarose-chitosan hybrid materials and nanocomposite ionogels using an ionic liquid via dissolution, regeneration and sol-gel transition

We report simultaneous dissolution of agarose (AG) and chitosan (CH) in varying proportions in an ionic liquid (IL), 1-butyl-3-methylimidazolium chloride [C4mim][Cl]. Composite materials were constructed from AG-CH-IL solutions using the antisolvent methanol, and IL was recovered from the solutions. Composite materials could be uniformly decorated with silver oxide (Ag2O) nanoparticles (Ag NPs) to form nanocomposites in a single step by in situ synthesis of Ag NPs in AG-CH-IL sols, wherein the biopolymer moiety acted as both reducing and stabilizing agent. Cooling of Ag NPs-AG-CH-IL sols to room temperature resulted in high conductivity and high mechanical strength nanocomposite ionogels. The structure, stability and physiochemical properties of composite materials and nanocomposites were characterized by several analytical techniques, such as Fourier transform infrared (FTIR), CD spectroscopy, differential scanning colorimetric (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), and scanning electron micrography (SEM). The result shows that composite materials have good thermal and conformational stability, compatibility and strong hydrogen bonding interactions between AG-CH complexes. Decoration of Ag NPs in composites and ionogels was confirmed by UV-Vis spectroscopy, SEM, TEM, EDAX and XRD. The mechanical and conducting properties of composite ionogels have been characterized by rheology and current-voltage measurements. Since Ag NPs show good antimicrobial activity, Ag NPs -AG-CH composite materials have the potential to be used in biotechnology and biomedical applications whereas nanocomposite ionogels will be suitable as precursors for applications such as quasi-solid dye sensitized solar cells, actuators, sensors or electrochromic displays

Synthesis of Al and Ag nanoparticles through ultra-sonic dissociation of thermal evaporation deposited thin films for promising clinical applications as polymer nanocomposite

Nanoparticles (NPs) having well-defined shape, size and clean surface serve as ideal model system to investigate surface/interfacial reactions. Ag and Al NPs are receiving great interest due to their wide applications in bio-medical field, aerospace and space technology as combustible additives in propellants and hydrogen generation. Hence, in this study, we have synthesized Ag and Al NPs using an innovative approach of ultra-sonic dissociation of thin films. Phase and particle size distributions of the Ag and Al NPs have been determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thin film dissociation/dissolution mechanism, hence conversion into NPs has been characterized by SEM- scanning electron microscope. EDXA & ICPMS have been performed for chemical analysis of NPs. Optical properties have been characterized by UV-Vis and PL spectroscopy. These NPs have also been investigated for their anti-bacterial activity against Escherichia coli bacteria. To the best of our knowledge, this is the first time when NPs has been synthesized by ultra-sonic dissociation of thin films. As an application, these NPs were used further for synthesis of nanocomposite polymer membranes, which show excellent activity against bio film formation

Embedded layer of Ag nanoparticles prepared by a combined PECVD/PVD process producing SiOxCy-Ag nanocomposite thin films.

Structural properties of SiOxCy–Ag nanocomposite thin films prepared by a dual process PVD–PECVD in the same reactor have been investigated. The experimental results have demonstrated the influence of a PECVD process carried out at room temperature for the growth of a dielectric matrix on the size and the distribution density of Ag nanoparticles (NPs) deposited beforehand by magnetron sputtering. The plasma during the growth of the encapsulation SiOxCy layer caused a diffusion of silver from NPs through the SiOxCy matrix associated with a decrease in the average size of nanoparticles and an increase of their distribution density. Silver diffusion is blocked at a barrier interface to form a buried layer of individual Ag NPs which, for instance, can find plasmonic applications. Silver also diffuses toward the outer surface inducing antibacterial properties. In both cases initial Ag NPs act as reservoirs for multifunctional properties of advanced nanostructured films

Yeast-derived biosynthesis of silver/silver chloride nanoparticles and their antiproliferative activity against bacteria

Here, we provide the first evidence of yeast strains assisted Ag/AgCl-NPs production in vitro. The formed nanoparticles were characterized by spectroscopic and electron microscopy approaches. UV-vis supported the biosynthesis. TEM analysis evidenced that the nanoparticles mainly presented a circular shape and their diameters varied mostly being in the range 2 to 10 nm. XRD analysis showed a crystalline structure, with diffraction peaks corresponding to metallic silver and silver chloride nanoparticles, and when analyzed by high-resolution transmission electron microscopy (HRTEM), instead of being round, (111) (octahedral) and (200) (cubic) symmetry facets appeared systematically in one side of the nanoparticles. Analysis of ultra-thin sections by TEM indicated that the domain of the synthesis of Ag/AgCl-NPs was mainly between the cell wall and the plasma membrane. By using 3D reconstruction obtained from focused ion beam scanning electron microscopy (FIB/SEM) the spatial distribution of the domains of nanoparticle synthesis was mapped and nanoaggregates of Ag/AgCl-NPs up 35 nm in diameter were observed. Extracellular synthesis also occurred; in accordance with the fact that conditioned media from yeast isolates were as efficient at producing Ag/AgCl-NPs as live-cell cultures. Exposure of Gram-positive Staphylococcus aureus and Gram-negative Klebsiella pneumoniae cultures to Ag/AgCl-NPs led to a strong growth inhibition as shown by optical density measurements. The Ag/AgCl-NPs described here have characteristics compatible with a strong potential for use in the biotechnology industry, particularly for biomedical applications

Synthesis, Characterization and Antibacterial Properties of Silver Nanoparticles in Clay and Organic Polymers as Nanocomposites

In this study, silver nanoparticles (Ag NPs) with the small size (2.12–30.63 nm) were successfully synthesized in the lamellar space of montmorillonite (MMT), montmorillonite/chitosan (MMT/Cts), porous zeolite framework and external surface layer of talc by chemical reducing agent in the absence of heat treatment. The most favourable experimental condition for the synthesis of Ag NPs in the MMT, talc, zeolite nanocomposites (NCs) and silver/montmorillonite/chitosan bionanocomposites (Ag/MMT/Cts BNCs) are described in terms of the initial concentrations of AgNO3. The mean diameters and standard deviation of Ag NPs in all of solid supports increased gradually with the increase of silver ions concentration. The external morphologies indicate that there are no noteworthy morphological distinctions between solid substrates and Ag NPs incorporated to them. The Ag NPs by the physical synthetic route were synthesized in the lamellar space of MMT/Cts utilising the UV-irradiation reduction method in the absence of reducing agent or heat treatment. The properties of Ag/MMT/Cts BNCs were studied as the function of UV-irradiation times. UV-irradiation disintegrated the Ag NPs into smaller size until a relatively stable size and size distribution were achieved. The silver nanocrystals were also synthesized by another physical method into the interlamellar space of MMT by using ƴ-irradiation in the absence of reducing agent or heat treatment. The properties of Ag/MMT NCs and the diameters of Ag NPs were studied as a function of ƴ-irradiation doses. The results from the UV-visible spectroscopy and TEM demonstrated that increasing the ƴ-irradiation doses enhanced the concentration of Ag NPs. In addition, the particle size of Ag NPs gradually increased from 1 until 20 kGy. When the ƴ-irradiation doses increased from 20 to 40 kGy, the particle diameters decreased suddenly as a result of the induced fragmentation for Ag NPs. Moreover silver/poly(lactic acid) nanocomposites (Ag/PLA NCs) films were investigated, while Ag NPs were synthesized into the biodegradable PLA as a polymeric matrix and stabilizer in the presence of sodium borohydride as a chemical reduction agent in diphase solvent. In all preparation, MMT, talc and zeolite were used as the inorganic solid supports and poly(lactic acid) was used as organic polymeric matrix. The silver nitrate, chitosan, and sodium borohydride were used as the silver precursor, natural and biodegradable polymeric stabilizer, and the reduction agent respectively. The crystalline structure of Ag NPs for all of samples, average size and size distributions, surface plasmon resonance, surface morphology, and functional groups were studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible spectroscopy (UVvis), scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) respectively. The XRD analysis confirmed that the crystallographic planes of the silver crystals were the face-centred cubic (fcc) types. The UV-visible absorption spectra showed the peaks characteristic of the surface plasmon resonance (SPR) bonds of Ag NPs. The antibacterial activities of Ag NPs were investigated against Gram-negative and Gram-positive bacteria by the disk diffusion method using Mueller-Hinton Agar (MHA) at different sizes and amounts of Ag NPs. Results show that the antibacterial activity of Ag NPs can be modified with the particle size of Ag NPs

Near-field interactions between metal nanoparticle surface plasmons and molecular excitons in thin-films: part I: absorption

In this and the following paper (parts I and II, respectively), we systematically study the interactions between surface plasmons of metal nanoparticles (NPs) with excitons in thin-films of organic media. In an effort to exclusively probe near-field interactions, we utilize spherical Ag NPs in a size-regime where far-field light scattering is negligibly small compared to absorption. In part I, we discuss the effect of the presence of these Ag NPs on the absorption of the embedding medium by means of experiment, numerical simulations, and analytical calculations, all shown to be in good agreement. We observe absorption enhancement in the embedding medium due to the Ag NPs with a strong dependence on the medium permittivity, the spectral position relative to the surface plasmon resonance frequency, and the thickness of the organic layer. By introducing a low index spacer layer between the NPs and the organic medium, this absorption enhancement is experimentally confirmed to be a near field effect In part II, we probe the impact of the Ag NPs on the emission of organic molecules by time-resolved and steady-state photoluminescence measurements

In situ synthesis of size-controlled, stable silver nanoparticles within ultrashort peptide hydrogels and their anti-bacterial properties

We have developed a silver-releasing biomaterial with promising potential for wound healing applications. The material is made of ultrashort peptides which can self-assemble in water to form hydrogels. Silver nanoparticles (Ag NPs) were synthesized in situ within the biomaterial, using only UV irradiation and no additional chemical reducing agents. The synthetic strategy allows precise control of the nanoparticle size, with the network of peptide fibers preventing aggregation of Ag NPs. The biomaterial shows increased mechanical strength compared to the hydrogel control. We observed a sustained release of Ag NPs over a period of 14 days. This is a crucial prerequisite for effective anti-bacterial therapy. The ability to inhibit bacterial growth was tested using different bacterial strains, namely gram-negative Escherichia coli and Pseudomonas aeruginosa and gram-positive Staphylococcus aureus. Inhibition of bacterial growth was observed for all strains. The best results were obtained for Pseudomonas aeruginosa which is known for exhibiting multidrug resistance. Biocompatibility studies on HDFa cells, using Ag NP-containing hydrogels, did not show any significant influence on cell viability. We propose this silver-releasing hydrogel as an excellent biomaterial with great potential for applications in wound healing due to its low silver content, sustained silver nanoparticle release and biocompatibility

White light-activated antimicrobial surfaces: effect of nanoparticles type on activity

Toluidine blue O (TBO) dye together with either silver (Ag) nanoparticles (NPs), gold (Au) NPs, or a mixture of Ag and Au NPs (Mix Ag–Au NPs) were incorporated into polyurethane to make antimicrobial surfaces using a swell-encapsulation-shrink process. Antimicrobial testing against Escherichia coli showed that inclusion of the NPs significantly enhanced the antimicrobial activities of the TBO polyurethane samples. In particular, samples containing Ag NPs exhibited potent antimicrobial activity under white light and surprisingly, also in the dark. The numbers of viable bacteria decreased below the detection limit on the TBO/Ag NPs incorporated samples within 3 h and 24 h under white light and dark conditions. A mechanistic study using furfuryl alcohol indicated that the enhanced photobactericidal activity was most likely due to a type I photochemical reaction. To the best of our knowledge, this is the first report of an antimicrobial surface comprised of a combination of Ag NPs and a light activated agent to provide a dual kill mechanism. These surfaces are promising candidates for use in healthcare environments to reduce the incidence of hospital-acquired infections