In Situ Optical Extinction Measurement for Locally Control of Surface Plasmon Resonance During Nanosecond Laser Irradiation of Silver Ion Exchanged Silicate Glass

Online UV/visible extinction measurement have been achieved during nanosecond Nd:YAG laser irradiation at 532 nm of a silver-exchanged silicate glass after each shot. We have explained the evolution of the integrated spectral evolution with the help of a few observed spots after the laser/glass interaction and completed them by optical and surface measurements. This optical method allows to in situ follow silver ions precipitation in nanoparticles (NPs) and the consequently surface plasmon resonance evolution (SPR). In this study, we focus on the interest of this method for one silver-exchanged soda-lime glass by direct observation of the sample surface. Scanning electron microscopy measurement and optical microscopy were used to identify the various ablation mechanisms. Profilometry was used to evaluate the material distribution and the surface roughness evolution (Rms parameter). Thus, we explain the silver NPs effect on glass matrix at various micrometric scales according to the deposited fluence and silver concentration.     

Structural Changes of Ag+�CNa+ Annealed Ion-Exchanged Silicate Glasses Scanning Electron Microscopy, Far-Infrared Reflectivity, UV-Visible Absorption, and TEM Investigation

The effect of silver ionic exchange on the glass structure in a molten bath at 350 °C was presented in a previous paper Catan et al. [1] (J NonCryst Solids 354:1026–1031, 2008). In this paper, the experiment is driven for a temperature near 310 °C, the eutectic of a 10% AgNO₃–NaNO₃ molten salt. The various exchanged silicate glasses are further annealed to obtain silver particles in the matrix. Infrared spectroscopy combined with UV/Visible spectroscopy and scanning electron microscopy analysis allowed to correlate the silver-ion penetration and particle formation with the degree of polymerisation of the silicate network. The previous results have demonstrated an insertion of silver ions in the glass structure that is about 10% higher than the departure of sodium ions. Infrared results obtained after ion exchange have proved that local alterations lead to a higher degree of depolymerisation of the silicate network. Here, the annealing of the samples promotes the formation of silver nanoparticles, the infrared measurements prove that the aggregation is correlated to a repolymerisation of the silicate network. Transmission electron microscopy (TEM) is used to evaluate the distribution size of the silver particles after annealing and to correlate it to the evolution of the absorption curves. The TEM observations prove that the particle are below the incident wavelength but shape factor could lead to scattering contribution when particle growths and to absorption spectra evolution.     

Biosynthesis of silver nanoparticles by the endophytic fungus Epicoccum nigrum and their activity against pathogenic fungi

There is an enormous interest in developing safe, cost-effective and environmentally friendly technologies for nano-materials synthesis. In the present study, extracellular biosynthesis of silver nanoparticles was achieved by Epicoccum nigrum, an endophytic fungus isolated from the cambium of Phellodendron amurense. The reduction of the silver ions was monitored by UV–visible spectrophotometry, and the characterization of the Ag NPs was carried out by X-ray diffraction and transmission electron microscopy. The synthesized Ag NPs were exceptionally stable. It was found that an alkaline pH favored the formation of Ag NPs and elevated temperature accelerated the reduction process. Furthermore, the antifungal activity of the Ag NPs was assessed using a microdilution method. The biosynthesized Ag NPs showed considerable activity against the pathogenic fungi. The current research opens a new path for the green synthesis of Ag NPs and the process is easy to scale up for biomedical applications.     

Laser-Driven Precipitation and Modification of Silver Nanoparticles in Soda Lime Glass Matrix Monitored by On-line Extinction Measurements

In this work, we investigated the effect of nanosecond laser irradiation at 532?nm on precipitation of Ag nanoparticles (NPs) in soda lime glasses doped with silver in the Ag^?+??CNa^?+? ion-exchange process. Formation and subsequent modification of Ag NPs during laser irradiation were studied by on-line extinction measurements making use of the localized surface plasmon resonance (LSPR). These investigations were further completed using scanning and transmission electron microscopies to examine the average size and distribution of nanoparticles within the sample. It has been shown that formation of NPs, its kinetics and the particle size strongly depend on the fluence and the total number of deposited laser pulses. It has been found that Ag NPs form after some specific number of pulses and they rapidly grow in size and number until some maximal value of extinction has been reached. Further irradiation of such samples only results in destruction of precipitated NPs due to photo-breakup, laser ablation confirmed by strong plasma emission observation. Moreover, due to strong irradiation, the host matrix can also be affected by changing its refractive index which manifests as the blue shift of the LSPR.     

Luminescence Study of Silver Nanoparticles Obtained by Annealed Ionic Exchange Silicate Glasses

The photoluminescence of silver nanoparticles glasses obtained by ionic exchange and annealing is investigated for various ionic exchange times. These glasses are prepared by immersion of silicate glass samples in a molten salt bath of molar concentration 10% AgNO₃ in NaNO₃ at T = 320 °C. Scanning electron microscopy measurement in electron diffraction scattering (EDS) configuration confirms the silver presence in the various glasses, and the UV/visible absorption gives the evolution of the spectra after ionic exchange and plasmon resonance apparition after annealing. After annealing at 450 °C, both diagnostics inform us about the particles’ formation and the silver rediffusion. Silver nanoparticle growth after annealing prior leads to photoluminescence exaltation and quenching for the longest exchange samples. Subsequently, we propose potential mechanisms of the nanoparticle formation with an initial depolymerization of the silicate network during the ionic exchange and repolymerization during annealing.     

Biomimetic synthesis and characterisation of protein capped silver nanoparticles

A controlled and up-scalable route for the biosynthesis of silver nanopartilces (NPs) mediated by fungal proteins of Coriolus versicolor has been undertaken for the first time. The fungus when challenged with silver nitrate solution accumulated silver NPs on its surface in 72h which could be reduced to 1h by tailoring the reaction conditions. Under alkaline conditions, the reaction was much faster and could easily proceed at room temperature even without stirring. The resulting Ag NPs displayed controllable structural and optical properties depending on the experimental parameters such as pH and reaction temperatures. The average size, morphology, and structure of particles were determined by AFM, TEM, XRD and UV/Visible absorption spectrophotometry. Fourier transform infrared study disclosed that the amino groups were bound to the particles, which was accountable for the stability of NPs. It further confirmed the presence of protein as the stabilizing and capping agent surrounding the silver NPs. Experiments were conducted both with, media in which fungus was initially harvested and that of pristine fungal mycelium alone. Under normal conditions, in the case of media extracellular synthesis took place whereby other than the fungal proteins, glucose was also responsible for the reduction. In the case of fungal mycelium, the intracellular formation of Ag NPs, could be tailored to give both intracellular and extracellular Ag NPs under alkaline conditions whereby the surface S-H groups of the fungus played a major role.     

Use of ZnO:Tb down‐conversion phosphor for Ag nanoparticle plasmon absorption using a He–Cd ultraviolet laser

Although noble metal nanoparticles (NPs) have attracted some attention for potentially enhancing the luminescence of rare earth ions for phosphor lighting applications, the absorption of energy by NPs can also be beneficial in biological and polymer applications where local heating is desired, e.g. photothermal applications. Strong interaction between incident laser light and NPs occurs only when the laser wavelength matches the NP plasmon resonance. Although lasers with different wavelengths are available and the NP plasmon resonance can be tuned by changing its size and shape or the dielectric medium (host material), in this work, we consider exciting the plasmon resonance of Ag NPs indirectly with a He–Cd UV laser using the down‐conversion properties of Tb³⁺ ions in ZnO. The formation of Ag NPs was confirmed by X‐ray diffraction, transmission electron microscopy and UV–vis diffuse reflectance measurements. Radiative energy transfer from the Tb³⁺ ions to the Ag NPs resulted in quenching of the green luminescence of ZnO:Tb and was studied by means of spectral overlap and lifetime measurements. The use of a down‐converting phosphor, possibly with other rare earth ions, to indirectly couple a laser to the plasmon resonance wavelength of metal NPs is therefore successfully demonstrated and adds to the flexibility of such systems. Copyright © 2016 John Wiley & Sons, Ltd.     

Pine cone-mediated green synthesis of silver nanoparticles and their antibacterial activity against agricultural pathogens

The medicinal and physicochemical properties of nanoscale materials are strong functions of the particle size and the materials used in their synthesis. The nanoparticle shape also contributes significantly to their medicinal properties. Several shapes ranging from oval, spherical, rods, to teardrop structures may be obtained by chemical methods. Triangular and hexagonal nanoparticles have been synthesized by using a pine cone extract (PCE). Here, we report the discovery that PCE, when reacted with silver nitrate ions, yields a high percentage of thin, flat, single-crystalline nanohexagonal and nanotriangular silver nanoparticles. The nanohexagonal and nanotriangular nanoparticles appear to grow by a process involving rapid reduction with assembly at room temperature at a high pH. The nanoparticles were characterized by UV–Vis absorption spectroscopy, SEM-EDS, TEM, FTIR, and X-ray diffraction analyses. The anisotropy of the nanoparticle shape results in large near-infrared absorption by the particles. Highly anisotropic particles are applicable in various fields, including agriculture and medicine. The obtained silver nanoparticles (Ag NPs) had significant antibacterial action on both Gram classes of bacteria associated with agriculture. Because the Ag NPs are encapsulated with functional group-rich PCE, they can be easily integrated in various applications.     

Synthesis of Silver and Gold Nanoparticles Using Cashew Nut Shell Liquid and Its Antibacterial Activity Against Fish Pathogens

This study reveals a green process for the production of multi-morphological silver (Ag NPs) and gold (Au NPs) nanoparticles, synthesized using an agro-industrial residue cashew nut shell liquid. Aqueous solutions of Ag⁺ ions for silver and chloroaurate ions for gold were treated with cashew nut shell extract for the formation of Ag and Au NPs. The nano metallic dispersions were characterized by measuring the surface plasmon absorbance at 440 and 546 nm for Ag and Au NPs. Transmission electron microscopy showed the formation of nanoparticles in the range of 5–20 nm for silver and gold with assorted morphologies such as round, triangular, spherical and irregular. Scanning electron microscopy with energy dispersive spectroscopy and X-ray diffraction analyses of the freeze-dried powder confirmed the formation of metallic Ag and Au NPs in crystalline form. Further analysis by Fourier transform infrared spectroscopy provided evidence for the presence of various biomolecules, which might be responsible for the reduction of silver and gold ions. The obtained Ag and Au NPs had significant antibacterial activity, minimum inhibitory concentration and minimum bactericidal concentration on bacteria associated with fish diseases.     

Zur Abbaubeschleunigung von Pflanzenschutzmittel-Wirkstoffen im Boden

In the current investigation, we report the biosynthesis of silver nanoparticles (Ag NPs) employing extract of Alternaria alternata, which is an eco-friendly process for the synthesis of metallic nanoparticles. Ag NPs were synthesised through the reduction of aqueous Ag⁺ ion using the cell extract of fungus A. alternata in the dark conditions. The synthetic process was relatively fast and Ag NPs were formed within 24 h. UV–visible spectrum of the aqueous medium containing silver ion showed a peak at 435?nm corresponding to the plasmon absorbance of Ag NPs and another peak at 280?nm refers to tyrosine amino acid. The nanoparticles were characterised by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The morphology of nanoparticles is found to be spherical mostly, with ranging size of 27–79?nm; as revealed by SEM. The FTIR spectrum analysis indicated that biomolecules were involved in the synthesis of Ag NPs. The presence of the amino groups is expected to pack differently around the Ag NPs. This in turn will influence the self-assembly of nanoparticles on substrates as well as their stability. The present study demonstrates the possible use of biologically synthesised Ag NPs in the field of agriculture, when A. alternata could be used for simple, nonhazardous and efficient synthesis of Ag NPs.     

Photoreduction of Silver Salts Using Au Nanoparticles to Form a Core-Shell-Type Nanostructure: Insight into the Reaction Mechanism

In this paper, we highlight the formation of Ag/Au core-shell nanoparticles at room temperature by using a low-power laser. We have investigated the plasmon-induced reduction of Ag⁺ ions on bare Au nanoparticles synthesized by laser ablation technique, and citrate-capped Au nanoparticles synthesized by chemical method. It is demonstrated that citrate plays an important role for the reduction of silver ions. The citrate gets oxidized by the ‘hot’ holes produced due to the surface plasmon resonance (SPR) of the Au nanoparticles which then reduces the Ag⁺ ions to Ag. The importance of excitation laser wavelength is also demonstrated to facilitate the reduction process.

     

Antimicrobial cellulose acetate nanofibers containing silver nanoparticles

It was found for the first time that polymer nanofibers containing Ag nanoparticles on their surface could be produced by UV irradiation of polymer nanofibers electrospun with small amounts of silver nitrate (AgNO₃). When the cellulose acetate (CA) nanofibers electrospun from CA solutions with 0.5 wt% of AgNO₃ were irradiated with UV light at 245 nm, Ag nanoparticles were predominantly generated on the surface of the CA nanofibers. The number and size of the Ag nanoparticles were continuously increased up to 240 min. The Ag⁺ ions and Ag clusters diffused and aggregated on the surface of the CA nanofibers during the UV irradiation. The Ag nanoparticles with an average size of 21 nm exhibited strong antimicrobial activity.     

Synthesis,characterization and kinetics of formation of silver nanoparticles by reduction with adrenaline in the micellar media

The present paper describes about the easy, simple and convenient procedure for the synthesis of silver nanoparticles (Ag-NPs) in aqueous solutions by the reduction of silver nitrate with adrenaline. The surfactant molecules of cetyltrimethylammonium bromide (CTABr) and sodium dodecyl ate (SDS) behaved differently during the reduction of Ag⁺ ions by adrenaline. The obtained data suggest that the variation of [CTABr] gave a maxima-like curve for rate constant versus [CTABr], while, the values of rate constant decreased with the increase in [SDS]. The addition of surfactant molecules stabilized the Ag-NPs. The UV–Visible spectra were analyzed to deduce the particle size. The calculated sizes of the nanoparticles were further compared by the TEM images. The XRD spectrum confirmed the crystalline nature of silver nanoparticles having the face-centered cubic crystal structure. The edge length of unit cell was found 4.076 Å. The kinetics of formation of Ag-NPs was performed at different concentrations of adrenaline, AgNO₃, NaOH and [surfactant]. The values of rate constant were independent on [adrenaline] and [AgNO₃]. The increase in [NaOH] increased the rate of agglomeration of silver particles to form Ag-NPs. A linear relationship was obtained for the plot of rate constant versus [NaOH].     

Antioxidant,antibacterial and cytotoxic potential of silver nanoparticles synthesized using terpenes rich extract of Lantana camara L. leaves

Several attempts have been made for green synthesis of silver nanoparticles (AgNPs) using different plant extracts. Present study revealed that, antioxidant, antibacterial and cytotoxic AgNPs were synthesized using terpenes-rich extract (TRE) of environmentally notorious Lantana camara L. leaves. AgNPs were characterized by advanced techniques like UV–Visible and Infra red spectroscopy; XRD, SEM techniques as terpenes coated sphere shaped NPs with average diameter 425 nm. Further, on evaluation, AgNPs were found to exhibit dose – dependent antioxidant potential, good to moderate antibacterial activity against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa; and toxicity on Brine shrimp (A. salinanauplii) with LD₅₀ value 514.50 µg/ml.     

Towards an understanding of the behavior of silanes on glass: an atomistic simulation study of glass surfaces

The present work attempts to develop a better understanding of the glass substrates upon which silane molecules are deposited. Experimentally, when a sodium silicate substrate is used, the silane layer does not bind as well compared to an alkaline earth borosilicate glass (AEBS). Molecular dynamics simulated annealing procedures were used to create atomistic models of these glasses and their surfaces. In sodium silicate glass, we see segregation of sodium ions to the surface and formation of sodium-rich regions. For the AEBS glass, we see a more homogenous distribution of ions. Boron, aluminium, silicon and oxygen form a connected framework structure. The barium and calcium ions are distributed throughout the structure and show no evidence of segregation. We speculate the poor performance of sodium silicate, compared to the AEBS, as a silane substrate could be attributed to its compositionally inhomogeneous surface.     

Assessment of antibacterial activity of silver nanoparticles on Pseudomonas aeruginosa and its mechanism of action

Antimicrobial activity of silver nanoparticles is gaining importance due its broad spectrum of targets in cell compared to conventional antimicrobial agents. In this context, a UV photo-reduction method was used for the synthesis and the nanoparticles were characterized by UV–Visible spectroscopy, transmission electron microscopy, atomic force microscopy and thermogravimetric analysis techniques. The antibacterial activity of the synthesized silver nanoparticles was evaluated both in liquid and solid growth media employing various susceptibility assays on Pseudomonas aeruginosa, a ubiquitous bacterium. The dose dependent growth suppression by nanoparticles was studied with well diffusion method. By broth dilution method, the minimum inhibitory concentration (MIC) was found to be 2 μg/ml. It was observed that the bactericidal effect depends both on nanoparticle concentration and number of bacteria present. In our study, we could demonstrate the complete antibiofilm activity of silver nanoparticles at a concentration as low as 1 μg/ml. Our observations substantiated the association of reactive oxygen species and cell membrane damage in the antibacterial mechanism of silver nanoparticles. Our findings suggested that these nanoparticles can be exploited towards the development of potential antibacterial coatings for various biomedical and environmental applications.     

Green synthesis and physiochemical characterization of nickel oxide nanoparticles: Interaction studies with Calf thymus DNA

One of the most promising applications of nanomaterials is that of nanobiosensors, using biomolecules such as nucleic acids as receptors. This study aimed to synthesize nickel oxide nanoparticles (NiO NPs) by an environmentally friendly green synthesis, using the extract of the herb Coriandrum sativum (coriander). The synthesized NPs were characterized using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, X‐ray photon spectroscopy, field emission scanning electron microscopy coupled with energy dispersive spectroscopy, dynamic light scattering, zeta potential and transmission electron microscopy. All results confirmed the synthesis of pure, spherical, positively charged NiO NPs of around 95 nm in diameter with prominent hydroxyl groups attached to the surface. Furthermore, interaction studies of synthesized NiO NPs with calf thymus DNA (CT DNA) were performed using UV–Visible spectroscopy, UV–thermal melting, circular dichroism, and fluorescence spectroscopy. CT DNA served as a substitute for nucleic acid biosensors. All experimental studies indicated that the NiO NPs bound electrostatically with CT DNA. These studies may facilitate exploring the potential of NiO NP–nucleic acid conjugated materials to be used as nanobiosensors for various applications, especially in pharmacological, epidemiological, and environmental diagnostic applications, and in detection.     

Bioengineered silver nanoparticles using Curvularia pallescens and its fungicidal activity against Cladosporium fulvum

Microorganisms based biosynthesis of nanomaterials has triggered significant attention, due to their great potential as vast source of the production of biocompatible nanoparticles (NPs). Such biosynthesized functional nanomaterials can be used for various biomedical applications. The present study investigates the green synthesis of silver nanoparticles (Ag NPs) using the fungus Curvularia pallescens (C. pallescens) which is isolated from cereals. The C. pallescens cell filtrate was used for the reduction of AgNO₃ to Ag NPs. To the best of our knowledge C. pallescens is utilized first time for the preparation of Ag NPs. Several alkaloids and proteins present in the phytopathogenic fungus C. pallescens were mainly responsible for the formation of highly crystalline Ag NPs. The as-synthesized Ag NPs were characterized by using UV–Visible spectroscopy, X-ray diffraction and transmission electron microscopy (TEM). The TEM micrographs have revealed that spherical shaped Ag NPs with polydisperse in size were obtained. These results have clearly suggested that the biomolecules secreted by C. pallescens are mainly responsible for the formation and stabilization of nanoparticles. Furthermore, the antifungal activity of the as-prepared Ag NPs was tested against Cladosporium fulvum, which is the major cause of a serious plant disease, known as tomato leaf mold. The synthesized Ag NPs displayed excellent fungicidal activity against the tested fungal pathogen. The extreme zone of reduction occurred at 50 μL, whereas, an increase in the reduction activity is observed with increasing the concentration of Ag NPs. These encouraging results can be further exploited by employing the as synthesized Ag NPs against various pathogenic fungi in order to ascertain their spectrum of fungicidal activity.     

Handling of Iron Oxide and Silver Nanoparticles by Astrocytes

Metal-containing nanoparticles (NPs) are currently used for various biomedical applications. Since such NPs are able to enter the brain, the cells of this organ have to deal with NPs and with NP-derived metal ions. In brain, astrocytes are considered to play a key function in regulating metal homeostasis and in protecting other brain cells against metal toxicity. Thus, among the different types of brain cells, especially astrocytes are of interest regarding the uptake and the handling of metal-containing NPs. This article summarizes the current knowledge on the consequences of an exposure of astrocytes to NPs. Special focus will be given to magnetic iron oxide nanoparticles (IONPs) and silver nanoparticles (AgNPs), since the biocompatibility of these NPs has been studied for astrocytes in detail. Cultured astrocytes efficiently accumulate IONPs and AgNPs in a time-, concentration- and temperature-dependent manner by endocytotic processes. Astrocytes are neither acutely damaged by the exposure to high concentrations of NPs nor by the prolonged intracellular presence of large amounts of accumulated NPs. Although metal ions are liberated from accumulated NPs, NP-derived iron and silver ions are not exported from astrocytes but are rather stored in proteins such as ferritin and metallothioneins which are synthesized in NP-treated astrocytes. The efficient accumulation of large amounts of metal-containing NPs and the upregulation of proteins that safely store NP-derived metal ions suggest that astrocytes protect the brain against the potential toxicity of metal-containing NPs.     

Single-Step Synthesis and Surface Plasmons of Bismuth-Coated Spherical to Hexagonal Silver Nanoparticles in Dichroic Ag:Bismuth Glass Nanocomposites

Here, we report for the first time the synthesis of bismuth-coated silver nanoparticles in dichroic bismuth glass nanocomposites by a novel and simple one-step melt quench technique without using any external reducing agent. The metallic silver nanoparticles (Ag NPs) were generated first, and subsequently, metallic bismuth was deposited on the Ag NPs and formed a thick layer. The reduction of Bi³⁺ to Bi^o and subsequently its deposition on the Ag NPs (which were formed earlier than Bi^o) in the K₂O–Bi₂O₃–B₂O₃ (KBB) glass system have been explained by their standard reduction potentials. The UV–vis absorption spectra show a prominent surface plasmon resonance (SPR) absorption band at 575 nm at lower concentrations (up to 0.01 wt%); three bands at 569, 624 and 780 nm at medium concentration (0.02–0.03 wt%); and two weak bands at 619 and 817 nm at highest concentration (0.06 wt%) of silver. They have been explained by the electrodynamics theories. TEM images reveal the conversion of spheroidal (5–15 nm) to hexagonal (10–35 nm) shaped Ag NPs with the increase in concentration of silver (up to 0.06 wt%). SAED pattern confirms the crystalline planes of rhombohedral bismuth and cubic silver. Thermal treatment at 360 °C, which is the glass transformation temperature (T _g) of the sample containing lower concentration of silver (0.007 wt%), shows red-shifted SPR band due to increase in size of NPs. Whereas the sample containing higher concentration (0.06 wt%) of silver under similar treatment exhibited changes in SPR spectral profile happened due to conversion to spherical NPs from hexagonal shape and reduction in size (10–20 nm) of NPs after heat treatment for 65 h. HRTEM images corroborate the different orientations of the NPs. FESEM images reveal hexagonal disk like structure having different orientations. Dichroic nature of the nanocomposites has been explained with the size and shape of Ag nanoparticles. We believe that this work will create new avenues in the area of nanometal–glass hybrid nanocomposites and the materials have significant applications in the field of optoelectronics and nanophotonics.