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.     

Preparation of triethylamine stabilized silver nanoparticles for low-temperature sintering

In this article, silver nanoparticles were synthesized by chemical reduction from silver nitrate using triethylamine as the protecting and reducing agents simultaneously. The average size of the silver nanoparticles was about 2.10–4.65 nm, which allowed low-temperature sintering of the metal. X-ray diffraction (XRD), thermogravimetric analysis (TGA), and energy dispersive spectrometric (EDS) analysis results indicate that silver nitrate has been converted to silver nanoparticles completely. Using a 20 wt% silver nanoparticles suspension with thermal treatment at 150 °C, silver films with a resistivity of 8.09 × 10⁻⁵ Ω cm have been produced, which is close to the resistivity of bulk silver.     

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.     

Experimental study of nanoparticles penetration through commercial filter media

In this study, nanoparticle penetration was measured with a wide range of filter media using silver nanoparticles from 3 nm to 20 nm at three different face velocities in order to define nanoparticle filtration characteristics of commercial fibrous filter media. The silver particles were generated by heating a pure silver powder source via an electric furnace with a temperature of 870°C, which was found to be the optimal temperature for generating an adequate amount of silver nanoparticles for the size range specified above. After size classification using a nano-DMA, the particle counts were measured by an Ultrafine Condensation Particle Counter (UCPC) both upstream and downstream of the test filter to determine the nanoparticle penetration for each specific particle size. Particle sampling time continued long enough to detect more than 10⁵ counts at the upstream and 10 counts at the downstream sampling point so that 99.99% efficiency can be detected with the high efficiency filter. The results show a very high uniformity with small error bars for all filter media tested in this study. The particle penetration decreases continuously down to 3 nm as expected from the classical filtration theory, and together with a companion modeling paper by␣Wang et al. in this same issue, we found no significant evidence of nanoparticle thermal rebound down to 3 nm.     

Rapid preparation and characterization of chitosan nanoparticles for oligonucleotide

Chitosan is regarded as one of the potential candidates as a gene carrier. However, the poor solubility of chitosan is the major limiting factor in its utilization as a gene carrier. The purpose of this study was to simplify the method of preparing the nanoparticles of chitosan linked with antisense oligonucleotide (asON). The main step was preparing the derivatives of chitosan phosphate (CSP) in order to easily dissolve in aqueous solution. The nanoparticles were formed using a simple mixed method for CSP and asON, and the nanoparticle’s forming condition was optimized so that the nanoparticle’s characterization could be examined. Results showed that it was simple to make the nanoparticles under the optimal condition of 2:1 M proportion of CSP and asON. The size of the nanoparticles was 102.6 ± 12.0 nm, its zeta potential was 1.45 ± 1.75, and the encapsulated ratio of the chitosan crosslinked the asON was 87.6 ± 3.5%. The infrared spectra and electron microscope displayed that chitosan may combine with the asON to form equirotal nanoparticles. In conclusion, it was simple and feasible to form chitosan nanoparticles for asON using the CSP, and the CSP can efficiently encapsulate asON.     

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.     

Fabrication of silver nanoparticles in a continuous flow,low temperature microwave-assisted polyol process

The performed experiments showed that continuous microwave-assisted polyol synthesis at about 70 °C is a viable process to give silver nanoparticles with a narrow size distribution in bulk amounts. The increase of silver precursor concentration in reaction system from 0.0097 to 0.0389 M resulted in the formation of fine nanoparticles 5–10 nm in size, in addition to the larger ones 30–100 nm, and that changed the pattern of particle size distribution from monomodal to bimodal. The effect of specific process variables was found to be the same in the continuous process as in batch operation. An aqueous glycerol solution was found suitable for use as both solvent and reducing agent.     

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.     

Uncapped silver nanoparticles synthesized by DC arc thermal plasma technique for conductor paste formulation

Uncapped silver nanoparticles were synthesized by DC arc thermal plasma technique. The synthesized nanoparticles were structurally cubic and showed wide particle size variation (between 20–150 nm). Thick film paste formulated from such uncapped silver nanoparticles was screen-printed on alumina substrates and the resultant ‘green’ films were fired at different firing temperatures. The films fired at 600 °C revealed better microstructure properties and also yielded the lowest value of sheet resistance in comparison to those corresponding to conventional peak firing temperature of 850 °C. Our findings directly support the role of silver nanoparticles in substantially depressing the operative peak firing temperature involved in traditional conductor thick films technology.     

Electrochemical method for the synthesis of silver nanoparticles

The article deals with a novel electrochemical method of preparing long-lived silver nanoparticles suspended in aqueous solution as well as silver powders. The method does not involve the use of any chemical stabilising agents. The morphology of the silver nanoparticles obtained was studied using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering measurements. Silver nanoparticles suspended in water solution that were produced by the present technique are nearly spherical and their size distribution lies in the range of 2 to 20 nm, the average size being about 7 nm. Silver nanoparticles synthesised by the proposed method were sufficiently stable for more than 7 years even under ambient conditions. Silver crystal growth on the surface of the cathode in the electrochemical process used was shown to result in micron-sized structures consisting of agglomerated silver nanoparticles with the sizes below 40 nm.     

Highly efficient silver particle layers on glass substrate synthesized by the sonochemical method for surface enhanced Raman spectroscopy purposes

A fast method for preparing of silver particle layers on glass substrates with high application potential for using in surface enhanced Raman spectroscopy (SERS) is introduced. Silver particle layers deposited on glass cover slips were generated in one-step process by reduction of silver nitrate using several reducing agents (ethylene glycol, glycerol, maltose, lactose and glucose) under ultrasonic irradiation. This technique allows the formation of homogeneous layers of silver particles with sizes from 80 nm up to several hundred nanometers depending on the nature of the used reducing agent. Additionally, the presented method is not susceptible to impurities on the substrate surface and it does not need any additives to capture or stabilize the silver particles on the glass surface. The characteristics of prepared silver layers on glass substrate by the above mentioned sonochemical approach was compared with chemically prepared ones. The prepared layers were tested as substrates for SERS using adenine as a model analyte. The factor of Raman signal enhancement reached up to 5·10⁵. On the contrary, the chemically prepared silver layers does not exhibit almost any pronounced Raman signal enhancement. Presented sonochemical approach for preparation of silver particle layers is fast, simple, robust, and is better suited for reproducible fabrication functional SERS substrates than chemical one.     

Ultra-short pulse laser ablation of metals: threshold fluence, incubation coefficient and ablation rates

In this paper we present femtosecond laser ablation studies of the metals copper, silver and tungsten. Measurements of the threshold fluence determined from the hole diameters versus fluence provide incubation coefficients of the three materials, which are found to be equal within one standard deviation. Furthermore, we have determined the single-shot threshold fluences to be 1.7±0.3 J/cm², 1.5±0.4 J/cm² and 0.44±0.02 J/cm² for copper, silver and tungsten, respectively. These are in good agreement with theoretical values calculated neglecting heat diffusion.     

In vitro characterization and in vivo analgesic and anti-allodynic activity of PLGA-bupivacaine nanoparticles

An injectable controlled release system containing local anesthetics able to provide long-lasting analgesia in nociceptive and neuropathic pain could have a marked impact in pain management. In order to address this issue, bupivacaine, a widely used local anesthetic, has been nanoencapsulated using poly(lactic-co-glycolic acid) from an oil-in-water emulsion by the solvent evaporation technique. Nanoparticles were evaluated in vitro studying their drug release mechanism by fitting different model equations, and in vivo by testing its analgesic and anti-allodynic activity in front of heat-induced nociceptive pain and sciatic nerve chronic constriction injury in rats, respectively. The particle size of the PLGA nanoparticles obtained was of 453 ± 29 nm, the encapsulation efficiency, drug loading, and burst effect at 30 min were 82.10 ± 0.001, 45.06 ± 0.001, and 4.6 ± 0.6%, respectively. A prolonged release of the drug in comparison to bupivacaine solution was seen. The mean dissolution time (MDT) obtained for nanoparticles was relatively long (9.44 ± 0.56 h) proving the sustained release process, while the dissolution efficiency (DE) (84.10 ± 1.01%) was similar to the maximum percentage of drug released. Korsmeyer–Peppas was the best model that fitted our release data. A non-Fickian mechanism was concluded to be involved in the release of bupivacaine from the nanoparticles, taking into account the value of the diffusional exponent obtained (n = 0.95). After local infiltration in the rat, the antinociceptive and anti-allodynic activity of the nanoencapsulated bupivacaine was longer lasting than that of bupivacaine solution. An increase in the values of the area under the curve (AUC) of the antinociceptive and anti-allodynic effect versus time of 67 and 36%, respectively, was observed when the drug was encapsulated.     

Gold nanorods surface modified with poly(acrylic acid) as a template for the synthesis of metallic nanoparticles

Poly(acrylic acid) (PAA) surface-modified gold nanorods, contained in deionized ultra filtered (DIUF) water, served as templates for the formation of gold (Au), palladium (Pd), and platinum (Pt) nanoparticles upon reduction with NaBH₄. This provided nanoparticles with respective diameters of 7.0 ± 0.7, 4.1 ± 0.4, and 5.1 ± 0.5 nm. Varying amounts of Pt metal salt were used in EG, which acts as both a solvent and a reducing agent, ranging from 0.1, 0.2, and 1.0 mg/mL, to provide control over nanoparticle diameters of 2.0 ± 0.5 nm, to 4.0 ± 0.5 nm, and 6.2 ± 1.9 nm, respectively. Nanoparticle diameter was also controlled in DIUF water by varying the amount of Pt metal salt from 0.1, 0.2, and 1.0 mg/mL, producing Pt particle diameters, respectively, increasing from 2.7 ± 0.3 nm to 4.1 ± 0.5 nm, and 6.0 ± 0.6 nm.     

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.     

Ultrasound-assisted formation of chitosan-glucose Maillard reaction products to fabricate nanoparticles with enhanced antioxidant activity

The influence of ultrasonic processing parameters including reaction temperature (60, 70 and 80 °C), time (0, 15, 30, 45 and 60 min) and amplitude (70, 85 and 100%) on the formation and antioxidant activity of Maillard reaction products (MRPs) in a solution of chitosan and glucose (1.5 wt% at mass ratio of 1:1) was investigated. Selected chitosan-glucose MRPs were further studied to determine the effects of solution pH on the fabrication of antioxidative nanoparticles by ionic crosslinking with sodium tripolyphosphate. Results from FT-IR analysis, zeta-potential determination and color measurement indicated that chitosan-glucose MRPs with improved antioxidant activity were successfully produced using an ultrasound-assisted process. The highest antioxidant activity of MRPs was observed at the reaction temperature, time and amplitude of 80 °C, 60 min and 70%, respectively, with ∼ 34.5 and ∼20.2 μg Trolox mL⁻¹ for DPPH scavenging activity and reducing power, respectively. The pH of both MRPs and tripolyphosphate solutions significantly influenced the fabrication and characteristics of the nanoparticles. Using chitosan-glucose MRPs and tripolyphosphate solution at pH 4.0 generated nanoparticles with enhanced antioxidant activity (∼1.6 and ∼ 1.2 μg Trolox mg⁻¹ for reducing power and DPPH scavenging activity, respectively) with the highest percentage yield (∼59%), intermediate particle size (∼447 nm) and zeta-potential ∼ 19.6 mV. These results present innovative findings for the fabrication of chitosan-based nanoparticles with enhanced antioxidant activity by pre-conjugation with glucose via the Maillard reaction aided by ultrasonic processing.     

Preparation of starch stabilized silver nanoparticles with spatial self-phase modulation properties by laser ablation technique

Silver nanoparticles inside the starch solution have been successfully fabricated by laser ablation of a silver plate immersed in starch solution. The ablation has been done using a Q-switched Nd:YAG laser at 10 Hz repetition rate. The starch solution allows for the formation of silver nanoparticles with uniform particle diameters and well dispersed. The ablation was performed at different time durations to study the influence of the laser ablation time on efficiency of particle formation and sizes. The Spatial Self-phase modulation phenomena which can determine the nonlinear optical property of the samples were also investigated for starch solutions containing silver nanoparticles.     

Temperature‐driven directional coalescence of silver nanoparticles

Silver nanoparticles were synthesized with a chemical reduction method in the presence of polyvinylpyrrolidone as stabilizing agent. The thermal stability behavior of the silver nanoparticles was studied in the temperature range from 25 to 700°C. Thermal gravimetric analysis was used to measure the weight loss of the silver nanoparticles. Scanning electron microscopy and high‐resolution transmission electron microscopy were used to observe the morphology and the change in shape of the silver nanoparticles. In situ temperature‐dependent small‐angle X‐ray scattering was used to detect the increase in particle size with temperature. In situ temperature‐dependent X‐ray diffraction was used to characterize the increase in nanocrystal size and the thermal expansion coefficient. The results demonstrate that sequential slow and fast Ostward ripening are the main methods of nanoparticle growth at lower temperatures (<500°C), whereas successive random and directional coalescences are the main methods of nanoparticle growth at higher temperatures (>500°C). A four‐stage model can be used to describe the whole sintering process. The thermal expansion coefficient (2.8 × 10^?5 K^?1) of silver nanoparticles is about 30% larger than that of bulk silver. To our knowledge, the temperature‐driven directional coalescence of silver nanocrystals is reported for the first time. Two possible mechanisms of directional coalescence have been proposed. This study is of importance not only in terms of its fundamental academic interest but also in terms of the thermal stability of silver nanoparticles.     

Multi-nozzle electrohydrodynamic inkjet printing of silver colloidal solution for the fabrication of electrically functional microstructures

In this paper, multi-nozzle electrohydrodynamic (EHD) inkjet printing of a colloidal solution containing silver nanoparticles in a fully controlled fashion is reported. For minimizing interaction, i.e. cross-talk, between neighboring jets, the distance between the nozzles was optimized numerically by investigating the magnitude of the electric field strength around the tip of each nozzle. A multi-nozzle EHD inkjet printing head consisting of three nozzles was fabricated and successfully tested by simultaneously printing electrically conductive lines of a colloidal solution containing silver nanoparticles onto a glass substrate. The printed results show electrical resistivity of 5.05×10⁻⁸ Ω m, which is almost three times larger than that of bulk silver. These conductive microtracks demonstrate the feasibility of the multi-nozzle EHD inkjet printing process for industrial fabrication of microelectronic devices.     

Green synthesis of finely-dispersed highly bactericidal silver nanoparticles via modified Tollens technique

In this article, we represent a versatile and effective technique which using non-toxic chemicals to prepare stable aqueous dispersions of silver nanoparticles (NPs) via modified Tollens process. It was shown that as-prepared silver colloids consisted of finely-dispersed NPs with average diameter about 10 nm and a relatively narrow size distribution. Moreover, they could be stored very stable after several months without observation of aggregates or sedimentation. In comparison with previous works where Tollens process was being used, we for the first time applied UV-irradiation simultaneously with glucose reduction of silver salt through NPs preparation. The colloidal solutions of silver NPs were found to exhibit a high antibacterial activity against gram-negative Escherichia coli. The concentration of silver leading to a complete inhibition of bacteria growth was revealed as low as at 1.0 μg ml⁻¹ and found much lower compared to earlier reports. These advantages of aqueous dispersions of silver NPs make them ideal for green industrial, medicinal, microbiological and other applications.