Fusarium solani: a novel biological agent for the extracellular synthesis of silver nanoparticles

We report extracellular biosynthesis of silver nanoparticles by Fusarium solani (USM-3799), a phytopathogen causing disease in onion, when challenged with 1 mM silver nitrate (AgNO₃). The formation of nanoparticles was characterized by visual observation followed by UV–Vis spectrophotometric analysis, which showed a peak at about 420 nm, which is very specific for silver nanoparticles. Further analysis carried out by Fourier Transform Infrared Spectroscopy (FTIR), provides evidence for the presence of proteins as capping agent, which helps in increasing the stability of the synthesized silver nanoparticles. Transmission Electron Microscopy (TEM) investigations confirmed that silver nanoparticles were formed. The synthesized silver nanoparticles were found to be polydispersed, spherical in the range of 5–35 nm with average diameter of 16.23 nm. Extracellular synthesis of nanoparticles could be highly advantageous from the point of view of synthesis in large quantities and easy downstream processing.     

Self-assembled gold nanochains hybrid based on insulin fibrils

We reported a facile method for preparing self-assembly gold nanochains by using insulin fibrils as biotemplate in aqueous environment. The gold nanochains hybrid nanostructures, which are insulin fibrils coated by gold nanoparticles, can be fabricated by simply reducing the salt precursors using DMAB. By increasing the molar ratio between salt precursors and insulin, denser hybrid nanochains can be obtained, meanwhile the mean diameter of gold nanoparticles is changing from 8 to 10 nm and then to 12 nm. The fabricated gold nanochains hybrid had helix structure, which was confirmed by circular dichroism spectra. The hybrid nanostructures were also investigated by transmission electron microscope, atomic force microscope, Fourier transform infrared spectra, and UV–Visible spectroscopy. As the wire-like structure become denser, the suspensions show color-changing, corresponding to the surface plasmon resonance red shift, which is attributed to the increasing mean size of nanoparticles. Based on the characterizations, a hypothetic mechanism was suggested to describe the formation processing of hybrid gold nanochains.     

A novel method for synthesis of colloidal silver nanoparticles by arc discharge in liquid

This paper presents a novel, inexpensive and one-step approach for synthesis of silver nanoparticles (Ag NPs) using arc discharge between titanium electrodes in AgNO₃ solution. The resulting nanoparticles were characterized using UV–Vis spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Silver nanoparticles of 18 nm diameter were formed during reduction of AgNO₃ in plasma discharge zone. Optical absorption spectroscopy of as prepared samples at 15 A arc current in AgNO₃ solution shows a surface plasmon resonance around 410 nm. It was found that sodium citrate acts as a stabilizer and surface capping agent of the colloidal nanoparticles. SEM images exhibit the increase of reduced nanoparticles in 6 min arc duration compared with 1 min arc duration. TEM image of the sample prepared at 6 min arc duration shows narrow size distribution with 18 nm mean particle size. Antibacterial activities of silver nanoparticles were investigated at the presence of Escherichia coli (E-coli) bacteria.     

Seed-mediated shape evolution of gold nanomaterials: from spherical nanoparticles to polycrystalline nanochains and single-crystalline nanowires

We studied the kinetics of the reduction of a gold precursor (HAuCl₄) and the effect of the molar ratio (R) of sodium citrate, which was introduced from a seed solution, and the gold precursor on the shape evolution of gold nanomaterials in the presence of preformed 13 nm gold nanoparticles as seeds. The reduction of the gold precursor by sodium citrate was accelerated due to the presence of gold seeds. Nearly single-crystalline gold nanowires were formed at a very low R value (R = 0.16) in the presence of the seeds as a result of the oriented attachment of the growing gold nanoparticles. At a higher R value (R = 0.33), gold nanochains were formed due to the non-oriented attachment of gold nanoparticles. At a much higher R value (R = 1.32), only larger spherical gold nanoparticles grown from the seeds were found. In the absence of gold seeds, no single-crystalline nanowires were formed at the same R value. Our results indicate that the formation of the 1D nanostructures (nanochains and nanowires) at low R values is due to the attachment of gold nanoparticles along one direction, which is driven by the surface energy reduction, nanoparticle attraction, and dipole–dipole interaction between adjacent nanoparticles.     

Size-tuneable synthesis of nickel nanoparticles

A facile method is described for synthesising nickel nanoparticles via the thermal decomposition of an organometallic precursor in the presence of excess n-trioctylphosphine as a capping ligand. For the first time, alkylamines with different chain lengths were employed as size-limiting agents in this synthesis. A direct correlation is demonstrated between the size of the alkylamine ligands used and the mean diameter of the nickel nanoparticles obtained. The use of bulky oleylamine as a size-limiting agent over a reaction period of 30 min led to the growth of nickel nanoparticles with a mean diameter of 2.8 ± 0.9 nm. The employment of less bulky N,N-dimethylhexadecylamine groups led to the growth of nickel nanoparticles with a mean diameter of 4.4 ± 0.9 nm. By increasing the reaction time from 30 to 240 min, while employing oleylamine as the size-limiting agent, the mean diameter of the nickel nanoparticles was increased from 2.8 ± 0.9 to 5.1 ± 0.7 nm. Decreasing the amount of capping ligand present in the reaction system allowed further growth of the nickel nanoparticles to 17.8 ± 1.3 nm. The size, structure and morphology of the nanoparticles synthesised were characterised by transmission electron microscopy and powder X-ray diffraction; while magnetic measurements indicated that the particles were superparamagnetic in nature.     

Photoinduced formation and aggregation of silver nanoparticles at the surface of carboxymethylcellulose films

Formation and aggregation of photolytic silver nanoparticles at the surface of silver salt of carboxymethylcellulose films (CMCAg films) have been investigated. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize silver nanoparticles at the film surface. When the CMCAg films were irradiated with UV light in wet air at room temperature for 30–60 min, silver nanoparticles of ca. 10 nm size were formed at the irradiated surface. According to the FE-SEM observation, the growth of the particle diameter and aggregation of nanoparticles took place after prolonged irradiation, and finally, the irradiated side of the film surface was densely covered with the silver nanoparticles of ca. 35 nm size. Chemical composition analysis by the XPS measurements has confirmed the increase in the atomic concentration of silver with irradiation time. It is suggested that silver atoms and clusters can move in the film and precipitate at the irradiated surface.     

Controlled synthesis of titanium nanochains using a template

Nanochains have unique properties due to their organized structures. We synthesized nanochains of titanium using crown ether as a template exploiting a simple sliding technique. The nanochains of Ti were formed with an average diameter of the sphere nodes around 80 nm separated by organic molecules with a space of 1–5 nm. The method developed here is the simplest reported to date. This process can be used for making nanostructures of different metallic materials. Trapping titanium ion particles is important to reduce the risk of the same material in the biomedical applications. The metallic nanochains are potentially applicable for making electronic and optical devices.     

One-step synthesis and antibacterial property of water-soluble silver nanoparticles by CGJ bio-template

In this article, a new synthetic method of nanoparticles with fresh Chinese gooseberry juice (CGJ) as bio-template was developed. One-step synthesis of highly water-soluble silver nanoparticles at room temperature without using any harmful reducing agents and special capping agent was fulfilled with this method. In the process, the products were obtained by adding AgNO₃ to CGJ, which was used as reducing agent, capping agent, and the bio-template. The products of silver nanoparticles with diameter of 10–30 nm have strong water solubility and excellent antibiotic function. With the same concentration 0.047 μg mL⁻¹, the antibacterial effect of water-soluble silver particles by fresh CGJ was 53%, whereas only 27% for silver nanoparticles synthesized using the template method of fresh onion inner squama coat (OISC). The excellent water solubility of the products would enable them have better applications in the bio-medical field. The synthetic method would also have potential application in preparing other highly water-soluble particles, because of its simple apparatus, high yield, mild conditions, and facile operation.     

Synthesis and characterization of silver nanoparticles: effect on phytopathogen <Emphasis Type="Italic">Colletotrichum gloesporioides</Emphasis>

Colloidal silver nanoparticles were synthesized by reducing silver nitrate solutions with glucose, in the presence of gelatin as capping agent. The obtained nanoparticles were characterized by means of UV–Vis spectroscopy, transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The response surface methodology (RSM) was also used to determine the influence of the variables on the size of the nanoparticles. The antifungal activity of the silver nanoparticles was evaluated on the phytopathogen Colletotrichum gloesporioides, which causes anthracnose in a wide range of fruits. The UV–Vis spectra indicated the formation of silver nanoparticles preferably spherical and of relatively small size (<20 nm). The above-mentioned was confirmed by TEM, observing a size distribution of 5–24 nm. According to RSM the synthesis variables influenced on the size of the silver nanoparticles. By means of FTIR spectroscopy it was determined that gelatin, through their amide and hydroxyl groups, interacts with nanoparticles preventing their agglomeration. The growth of C. gloesporioides in the presence of silver nanoparticles was significantly delayed in a dose dependent manner.     

Highly bacterial resistant silver nanoparticles: synthesis and antibacterial activities

In this article, we describe a simple one-pot rapid synthesis route to produce uniform silver nanoparticles by thermal reduction of AgNO₃ using oleylamine as reducing and capping agent. To enhance the dispersal ability of as-synthesized hydrophobic silver nanoparticles in water, while maintaining their unique properties, a facile phase transfer mechanism has been developed using biocompatible block co-polymer pluronic F-127. Formation of silver nanoparticles is confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–vis spectroscopy. Hydrodynamic size and its distribution are obtained from dynamic light scattering (DLS). Hydrodynamic size and size distribution of as-synthesized and phase transferred silver nanoparticles are 8.2 ± 1.5 nm (σ = 18.3%) and 31.1 ± 4.5 nm (σ = 14.5%), respectively. Antimicrobial activities of hydrophilic silver nanoparticles is tested against two Gram positive (Bacillus megaterium and Staphylococcus aureus), and three Gram negative (Escherichia coli, Proteus vulgaris and Shigella sonnei) bacteria. Minimum inhibitory concentration (MIC) values obtained in the present study for the tested microorganisms are found much better than those reported for commercially available antibacterial agents.     

Mycogenic synthesis of silver nanoparticles by the Japanese environmental isolate <Emphasis Type="Italic">Aspergillus tamarii</Emphasis>

In this study, an environmental friendly process for the synthesis of silver nanoparticles (AgNPs) using a fungus Aspergillus tamarii has been investigated. The process of silver ion reduction by the fungal extracellular filtrate was spontaneous which lead to the development of an easy process for synthesis of silver nanoparticles. The AgNPs formed were characterized using UV–Visible spectrum, FTIR, and SEM. The results revealed that silver ions reduction by the fungal extracellular filtrate started at 420 nm after 0.5 h of incubation time. The FTIR peaks were observed at 1393, 1820, 2727, and 3545 cm⁻¹. The SEM result showed the distribution of spherical AgNPs ranging from 25 to 50 nm.     

Importance of poly(ethylene glycol) conformation for the synthesis of silver nanoparticles in aqueous solution

Silver nanoparticles (NPs) were prepared using silver nitrate (AgNO₃) as a precursor in an aqueous solution of poly(ethylene glycol) (PEG), which acted as both a reducing and stabilizing agent. The UV/Vis spectra showed that PEG 100 (100 kg/mol) has a remarkable capability to produce silver NPs at 80 °C, but the production of silver NPs by both PEG 2 (2 kg/mol) and PEG 35 (35 kg/mol) was negligible. This difference was explained by the conformation of PEG in the reaction solution: the entangled conformation for PEG 100 and the single-coiled conformation for PEG 2 and PEG 35, which were confirmed by pulse-field-gradient ¹H NMR and viscosity measurements. In an aqueous solution, the entangled conformation of PEG 100 facilitated the reduction reaction by caging silver ions and effectively prevented the agglomeration of formed NPs. The reaction in an aqueous PEG 100 solution was observed to be stable under the conditions of a prolonged reaction time or an increased temperature, while no reduction reaction occurred in the PEG 2 solution. The synthesis of silver NPs by PEG 100 was well controlled to produce fine silver NPs with 3.68 ± 1.03 nm in diameter, the size of which remained relatively constant throughout the reaction.     

Core–shell nanostructures and nanocomposites of Ag@TiO2: effect of capping agent and shell thickness on the optical properties

Two different shell-forming reagents viz. titanium isopropoxide and titanium hydroxyacylate, have been employed to obtain core–shell nanostructures of Ag@TiO₂. However, nanocomposites were formed when the shell-forming agent, titanium isopropoxide, was added before breaking the micelles. Titanium hydroxyacylate has been used for the first time as a shell-forming agent which resulted in uniform core–shell structures of Ag@TiO₂ with core diameter ranging from 10 to 40 nm and a shell thickness of 10–50 nm. The low rate of hydrolysis of titanium hydroxyacylate than titanium isopropoxide (used in other methods) appears to be responsible for the uniform shell thickness. The presence of capping agent (2-mercaptoethanol) disrupts the formation of a uniform shell structure of Ag@TiO₂. HRTEM, IR, and XPS studies of Ag@TiO₂ synthesized using capping agent show the formation of Ag₂S coated with an amorphous layer of TiO₂. A red shift of 25 and 10 nm was observed in the surface plasmon band of silver for Ag@TiO₂ core–shell structures (compared with that of silver nanoparticles) synthesized using titanium hydroxyacylate and titanium isopropoxide, respectively. The presence of capping agent (2-mercaptoethanol) masks the surface plasmon peak. Photoluminescence studies show an increase in the emission intensity for the core–shell structures when compared to that of TiO₂ nanoparticles.     

Formation of fractal aggregates during green synthesis of silver nanoparticles

The aggregation behavior of silver nanoparticles (AgNPs) prepared by a green synthesis procedure using starch as the stabilizer was studied by the small angle X-ray scattering (SAXS) technique. The protecting ability of starch was affected by the presence of NaOH leading to different aggregation behaviors. In all the samples, mass as well as surface fractal regimes were observed. Assuming spherical form, the radii of nanoparticles were in the range of 11–17 nm.     

Use of a silver ion selective electrode to assess mechanisms responsible for biological effects of silver nanoparticles

For a detailed analysis of the biological effects of silver nanoparticles, discrimination between effects related to the nano-scale size of the particles and effects of released silver ions is required. Silver ions are either present in the initial particle dispersion or released by the nanoparticles over time. The aim of this study is to monitor the free silver ion activity {Ag⁺} in the presence of silver nanoparticles using a silver ion selective electrode. Therefore, silver in the form of silver nanoparticles, 4.2 ± 1.4 nm and 2–30 nm in size, or silver nitrate was added to cell culture media in the absence or presence of A549 cells as a model for human type II alveolar epithelial cells. The free silver ion activity measured after the addition of silver nanoparticles was determined by the initial ionic silver content. The p {Ag⁺} values indicated that the cell culture media decrease the free silver ion activity due to binding of silver ions by constituents of the media. In the presence of A549 cells, the free silver ion activity was further reduced. The morphology of A549 cells, cultivated in DME medium containing 9.1% (v/v) FBS, was affected by adding AgNO₃ at concentrations of ≥30 μM after 24 h. In comparison, silver nanoparticles up to a concentration of 200 μM Ag did not affect cellular morphology. Our experiments indicate that the effect of silver nanoparticles is mainly mediated by silver ions. An effect of silver on cellular morphology was observed at p {Ag⁺} ≤ 9.2.     

Silver nanoparticles with gelatin nanoshells: photochemical facile green synthesis and their antimicrobial activity

In the current study, a facile green synthesis of silver-gelatin core–shell nanostructures (spherical, spherical/cubic hybrid, and cubic, DLS diameter: 4.1–6.9 nm) is reported via the wet chemical synthesis procedure. Sunlight-UV as an available reducing agent cause mild reduction of silver ions into the silver nanoparticles (Ag-NPs). Gelatin protein, as an effective capping/shaping agent, was used in the reaction to self-assemble silver nanostructures. The formation of silver nanostructures and their self-assembly pattern was confirmed by SEM, AFM, and TEM techniques. Further investigations were carried out using zeta-potential, UV–Vis, FTIR, GPC, and TGA/DTG/DTA data. The prepared Ag-NPs showed proper and acceptable antimicrobial activity against three classes of microorganisms (Escherichia coli Gram-negative bacteria, Staphylococcus aureus Gram-positive bacteria, and Candida albicans fungus). The antibacterial and antifungal Ag-NPs exhibit good stability in solution and can be considered as promising candidates for a wide range of biomedical applications.     

Processes in resonant domains of metal nanoparticle aggregates and optical nonlinearity of aggregates in pulsed laser fields

Optical nonlinearities in aggregates of nanoparticles formed in silver hydrosols (SHs) are studied under pico- and nanosecond pulsed laser excitation. The dependence of the nonlinear refractive index n ₂ on the degree of hydrosol aggregation is studied experimentally at the wavelength λ=1.064 μm. It is found that n ₂ changes sign when the degree of hydrosol aggregation is increased. Various physical effects occurring in resonant domains of the aggregates are analyzed using a simple physical model of two bound silver nanoparticles. The theory takes into account thermal, elastic, electrostatic, and light-induced effects. Experimental results are discussed in the context of this theory.     

Silver nanowires electrodeposited into nanoporous templates: Study of the influence of sizes on crystallinity and structural properties

In this work, results on the study of the influence of silver nanowire dimensions on the crystallinity and structural properties are presented. Silver nanowire arrays with high aspect ratios were prepared in the hollow structures of nanoporous templates using potentiostatic electrodeposition. Two types of material were employed as a template: commercial porous anodic aluminum oxide (with a mean pore diameter of 180 nm) and track-etched polycarbonate membranes (with a mean pore diameter of 15, 30 and 80 nm). Characterization of the silver nanowires has been done by EDS, XRD, TEM and electron diffraction. The degree of preferred crystallographic orientation (along the (1 1 1), (2 0 0) or (2 2 0) crystallographic planes) and the crystallite size of the silver nanowires as a function of template pore diameter are given and discussed.     

Application of calixarene to high active surface‐enhanced Raman scattering (SERS) substrates suitable for in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater

The characteristics of the sol–gel matrix embedding Ag nanoparticles functionalized with 25,27‐dimercaptoacetic acid‐26,28‐dihydroxy‐4‐tert‐butylcalix[4]arene (DMCX) suitable for the in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater is presented. The DMCX‐functionalized silver nanoparticles were produced by the thermal reduction method in xerogel film. The silver colloid blocks were formed in the sol–gel matrix, with a diameter ranging from 50 to 120 nm. DMCX forming the monolayer on the silver nanoparticle surface contributes to the surface‐enhanced Raman scattering (SERS) activity due to the aggregation of silver nanoparticles and the preconcentration of PAH molecules within the zone of electromagnetic enhancement. When selected, PAH molecules e.g. pyrene and naphthalene were adsorbed onto the SERS substrate; Raman band positions of PAH were slightly shifted. A calibration procedure reveals that this type of SERS substrate has a limit of detection of 3 × 10⁻¹⁰ mol/l for pyrene and 13 × 10⁻⁹ mol/l for naphthalene in artificial seawater. The Raman signal response on a pyrene concentration change in artificial seawater was evaluated using a 671‐nm Raman setup with a flow‐through cell. This type of SERS substrate will be suitable for the in situ trace detection of pollutant chemicals in seawater. Copyright © 2012 John Wiley & Sons, Ltd.     

Extracellular biosynthesis of monodispersed gold nanoparticles by a SAM capping route

Monodispersed gold nanoparticles capped with a self-assembled monolayer of dodecanethiol were biosynthesized extracellularly by an efficient, simple, and environmental friendly procedure, which involved the use of Bacillus megatherium D01 as the reducing agent and the use of dodecanethiol as the capping ligand at 26 °C. The kinetics of gold nanoparticle formation was followed by transmission electron microscope (TEM) and UV-vis spectroscopy. It was shown that reaction time was an important parameter in controlling the morphology of gold nanoparticles. The effect of thiol on the shape, size, and dispersity of gold nanoparticles was also studied. The results showed that the presence of thiol during the biosynthesis could induce the formation of small size gold nanoparticles (<2.5 nm), hold the shape of spherical nanoparticles, and promote the monodispersity of nanoparticles. Through the modulation of reaction time and the use of thiol, monodispersed spherical gold nanoparticles capped with thiol of 1.9 ± 0.8 nm size were formed by using Bacillus megatherium D01.