UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

Accurate controlled deposition of silver nanoparticles on porous silicon by drifted ions in electrolytic solution

In this study, a low-cost, simple, single-step low-voltage operation and a well-controlled method for deposition of uniformed and unique size distributions of silver nanoparticles (AgNPs) on the porous silicon (PS) layer were achieved via controlling the drift velocity of electrons in an aqueous solution of AgNO₃. The laser diode of 530 nm and 60 mW/cm² laser wavelength and illumination power density was employed to prepare PS layer by a laser-assisted etching process. The PS layer was incorporated on the platinum disk cathode electrode, and a stainless steel plate as an anode was employed. Low applied operating voltage of about 3V DC at different drift currents of 10, 20, 30 and 40 mA for 2 min was applied to sustain the drift motion of Ag²⁺. Structural properties of AgNPs layer were examined via the field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) pattern. These measurements exposed that AgNPs were adjusted by controlling the drift current, and a uniform AgNPs with specific unique sizes were obtained. Grain size, specific surface area and nucleation sites of metallic AgNPs were intensely influenced by the drift current.     

Chitosan loaded with silver nanoparticles,CS‐AgNPs,using thymus syriacus,wild mint,and rosemary essential oil extracts as reducing and capping agents

The present study describes the green method for the preparation of chitosan loaded with silver nanoparticles (CS‐AgNPs) in the presence of 3 different extracted essential oils. The essential oils play dual roles as reductant and capping agents. The reducing power and DPPH (2,2‐diphenyl‐1‐picrylhydrazyl) assay for the 3 essential oils—Thymus syriacus (T), wild mint (M), and rosemary (R)—have been reported. The preparation of CS‐AgNPs was performed by 2 steps. The 3 previously extracted essential oils have been used as reducing and capping agent in the first step, while in the second step, silver nanoparticles were integrated in chitosan. The integration of AgNPs in the structure of chitosan was confirmed by ultraviolet‐visible, Fourier transform infrared spectroscopy, scanning electron microscopy techniques, and energy dispersive X‐ray. Surface plasmon resonance confirmed the formation of CS‐AgNPs with maximum absorbance at λ_max between 405 ‐ 410 and 410 ‐ 430 nm for colloidal and films of CS‐AgNPs, respectively. The intensity of bands at 3408 cm^?1 in the fourier transform infrared spectroscopy measurements was decreased substantially and shifted slightly to lower frequency (?υ = 43 cm^?1). Scanning electron microscopy shows a spherical morphology of AgNPs with size of 62 nm for both colloidal and film samples, and energy dispersive X‐ray analysis shows peaks confirming AgNPs formation.     

Effect of surface charge on the colloidal stability and in vitro uptake of carboxymethyl dextran-coated iron oxide nanoparticles

An easy and novel routine are reported for the preparation of metallic silver nanoparticles (AgNPs) with controlled morphology, using Na⁺–magadiite swelled with hexadecyltrimethylammonium bromide (CTA⁺–magadiite) and a layered aluminophosphate with kanemite-type structure modified with n-dodecylammonium and n-butylammonium (but,dod-AlPO-kan) as hosts. For the preparation of the metallic AgNPs (Ag⁰) in the interlamellar space, the CTA⁺–magadiite and but,dod-AlPO-kan hosts were dispersed in N,N-dimethylformamide (DMF) solution with different AgNO₃ concentrations. DMF acts as reducing agent of Ag⁺ ions leading to nanoparticles with disk-like morphology of magadiite silicate; these were characterized by TEM and UV–Vis spectroscopy. On the other hand, the AgNPs are intercalated in but,dod-AlPO-kan showing spherical-like morphology. The UV–Vis spectra of the nanocomposites based on Ag⁰ and magadiite silicate show bands at 565 nm that can be attributed to Ag⁰ nanodisks. The Ag-but,dod-AlPO-kan-based nanocomposites present a band at 422 nm attributed to the surface plasmon resonance of Ag⁰ nanospheres. The results of transmission electron microscopy agree very well with XRD and UV–Vis analysis, indicating the formation of AgNPs with different morphologies using the two kinds of lamellar materials. The magadiite host has an important role in the synthesis of Ag nanodisks, because it controls the growth of nanoparticles inside the interlayer region with disk-like morphology due the high interlayer interactions of the silicate, leading to the growth of nanoparticles in only two directions (xy plane). On the other hand, when but,dod-AlPO-kan is used a sphere-like morphology is preferred due the best accommodation of AgNPs between the layers of aluminophosphate host.     

Preparation of AgBr Nanoparticles in Microemulsions Via Reaction of AgNO<Subscript>3</Subscript> with CTAB Counterion

Nanoparticles of AgBr were prepared by precipitating AgBr in the water pools of microemulsions consisting of CTAB, n-butanol, isooctane and water. An aqueous solution of AgNO₃ added to the microemulsion was the source of Ag⁺ ions. The formation of AgBr nanoparticles in microemulsions through direct reaction with the surfactant counterion is a novel approach aimed at decreasing the role of intermicellar nucleation on nanoparticle formation for rapid reactions. The availability of the surfactant counterion in every reverse micelle and the rapidity of the reaction with the counterion trigger nucleation within individual reverse micelles. The effect of the following variables on the particle size and size distribution was investigated: the surfactant and cosurfactant concentrations, moles of AgNO₃ added, and water to surfactant mole ratio, R. High concentration of the surfactant or cosurfactant, or high water content of the microemulsion favored intermicellar nucleation and resulted in the formation of large particles with broad size distribution, while high amounts of AgNO₃ favored nucleation within individual micelles and resulted in small nanoparticles with narrow size distribution. A blue shift in the UV absorption threshold corresponding to a decrease in the particle size was generally observed. Notably, the variation of the absorption peak size with the nanoparticle size was opposite to those reported by us in previous studies using different surfactants.     

Synthesis of monodisperse spherical AgNPs by ultrasound-intensified Lee-Meisel method,and quick evaluation via machine learning

Due to the high reactivity of Ag⁺ and uncontrolled growth process, the AgNPs produced by conventional Lee-Meisel method always exhibited larger particle size (30–200 nm) and polydisperse morphology (including spherical, triangular, and rod-like shape). An ultrasound-intensified Lee-Meisel (UILM) method is developed in this study to environmental-friendly and controllable synthesize monodisperse spherical AgNPs (~3.7 nm). Effects of Ag:citrate ratio (1:3 or 5:4), ultrasound power (300 to 1200 W) and reaction time (4 to 24 min) on the physical–chemical properties of AgNPs are investigated systematically. The transmission electron microscope (TEM) images, UV–Vis spectra, average particle size, zeta potential and pH value all demonstrate that crystallization and digestive ripening processes are facilitated in the presence of ultrasound irradiation. Therefore, both chemical reaction rate and mass transfer rate are enhanced to accelerate primary nucleation and inhibit uncontrolled particle growth, leading to the formation of monodisperse spherical AgNPs. Moreover, a machine learning approach - Decision Tree Regressor in conjunction with Shapley value analysis reveal the concentration of reactants is a more important feature affecting the particle.     

Immobilization of silver nanoparticles on silica microspheres

The silver nanoparticles (Ag NPs) have been immobilized onto silica microspheres through the adsorption and subsequent reduction of Ag⁺ ions on the surfaces of the silica microspheres. The neat silica microspheres that acted as the core materials were prepared through sol–gel processing; their surfaces were then functionalized using 3-mercaptopropyltrimethoxysilane (MPTMS). The major aims of this study were to immobilize differently sized Ag particles onto the silica microspheres and to understand the mechanism of formation of the Ag nano-coatings through the self-assembly/adsorption behavior of Ag NPs/Ag⁺ ions on the silica spheres. The obtained Ag NP/silica microsphere conglomerates were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy-dispersive spectroscopy (EDS). Their electromagnetic wave shielding effectiveness were also tested and studied. The average particle size of the obtained Ag NPs on the silica microsphere was found that could be controllable (from 2.9 to 51.5 nm) by adjusting the ratio of MPTMS/TEOS and the amount of AgNO₃.     

Preparation of poly(?-caprolactone)-based polyurethane nanofibers containing silver nanoparticles

In this study, poly(?-caprolactone)-based polyurethane (PCL-PU) nanofibers containing Ag nanoparticles for use in antimicrobial nanofilter applications were prepared by electrospinning 8 wt% PCL-PU solutions containing different amounts of AgNO₃ in a mixed solvent consisting of DMF/THF (7/3 w/w). The average diameter of the pure PCL-PU nanofibers was 560 nm and decreased with increasing concentration of AgNO₃. The PCL-PU nanofiber mats electrospun with AgNO₃ exhibited higher tensile strength, tensile modulus, and lower elongation than the pure PCL-PU nanofiber mats. Small Ag nanoparticles were produced by the reduction of Ag⁺ ions in the PCL-PU solutions. The average size and number of the Ag nanoparticles in the PCL-PU nanofibers were considerably increased after being annealed at 100 °C for 24 h. They were all sphere-shaped and evenly distributed in the PCL-PU nanofibers, indicating that the PCL-PU chains stabilized the Ag nanoparticles well.     

Synthesis of dendritic silver nanostructures by means of ultrasonic irradiation

In this paper, a simple and effective route for the synthesis of silver dendritic nanostructures by means of ultrasonic irradiation has been developed. Well-defined silver dendritic nanostructures were obtained by sonicating the aqueous solution of 0.04 mol/L silver nitrate with 4.0 mol/L isopropanol as reducing agent and 0.01 mol/L PEG400 as disperser for 2 h. The effects of the irradiation time, the concentration of Ag⁺ and the molar ratio of PEG to AgNO₃ on the morphology of silver nanostructures were discussed. The structures of the obtained samples were characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray powder diffraction (XRD), and the chemical composition of the dendrites was examined by energy-dispersive X-ray spectrum (EDS).     

The Ag+ induced solution–liquid–solid growth, photoluminescence and photocatalytic activity of twinned ZnSe nanowires

Cubic ZnSe nanowires with periodically alternating twins along the wire growth direction are synthesized in the ZnCl₂–Na₂SeO₃–AgNO₃–ethylenediamine (EN)-ethylene glycol (EG)-polyvinyl–pyrrolidone (PVP) solvothermal system at 180°C for 12 h. The twinned ZnSe nanowires have diameters of 75±10 nm and lengths of >10 micrometers, and grow along 〈111〉 direction. The role of AgNO₃ in the formation of ZnSe nanowires was investigated, and an Ag⁺ induced solution–liquid–solid growth mechanism is also proposed to account for the conversion of microspheres assembled from ZnSe nanocrystallites into ZnSe nanowires. Compared with ZnSe microspheres, the as-prepared twinned ZnSe nanowires exhibit stronger band edge emissions of the wurtzite- and zinc-blende-structured ZnSe and lower deep defect related emission, and their photocatalytic ability is weaker than that of ZnSe microspheres. The results suggest that this simple, mild, one-step solution approach to fabricate ZnSe nanowires may be employed for the synthesis of other selenium compounds with one dimensional nanostructures, and provides opportunities for both fundamental research and technological applications.     

Hydrothermal synthesis of ultra-highly concentrated,well-stable Ag nanoparticles and their application for enzymeless hydrogen peroxide detection

In this article, we have reported on the synthesis of ultra-highly concentrated (5.88 M), well-stable Ag nanoparticles (AgNPs). The AgNPs were formed by hydrothermal heat treatment of an aqueous solution of poly [(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (PQ11), a kind of cationic polyeletrolyte, in the presence of AgNO₃ powder at 170 °C, without the additional step of introducing other reducing agents and protective agents. Transmission electron microscopy (TEM) observations reveal that the as-formed AgNPs mainly consist of small nanoparticles about 10 nm in diameter. Most importantly, it was found that such dispersion can form stable films on bare electrode surfaces and the AgNPs contained therein still exhibit notable catalytic performance for reduction of hydrogen peroxide (H₂O₂). This H₂O₂ sensor has a fast amperometric response time of less than 3 s. Its linear range is estimated to be from 0.1 to 60 mM (r = 0.993), and the detection limit is estimated to be 1.6 μM at a signal-to-noise ratio of 3.     

Dynamic templating role of polynaphtalene sulphonate in the formation of silver nanocrystals in aqueous solution

We have used time resolved small angle X-ray scattering (SAXS) for investigating the early stages of the formation of crystalline colloidal Ag particles by AgNO₃ reduction with ascorbic acid in an aqueous acidic solution of a polynaphthalene sulphonate polymer (Daxad). In order to exploit the polymer role in silver crystallization, the measurements have been performed at different polymer concentrations. Data analysis suggests that the nucleation and growth of primary particles of about 20 nm in diameter, occurring in a surface-fractal arrangement of the dynamic polymeric template, is assisted by the development of long range spatial correlations. These correlations could be a sign of polymer-induced liquid fluctuations as intermediate precursors of Ag crystallization.     

The mechanism of metal nanoparticle formation in plants: limits on accumulation

Metal nanoparticles have many potential technological applications. Biological routes to the synthesis of these particles have been proposed including production by vascular plants, known as phytoextraction. While many studies have looked at metal uptake by plants, particularly with regard to phytoremediation and hyperaccumulation, few have distinguished between metal deposition and metal salt accumulation. This work describes the uptake of AgNO₃, Na₃Ag(S₂O₃)₂, and Ag(NH₃)₂NO₃ solutions by hydroponically grown Brassica juncea and the quantitative measurement of the conversion of these salts to silver metal nanoparticles. Using X-ray absorption near edge spectroscopy (XANES) to determine the metal speciation within the plants, combined with atomic absorption spectroscopy (AAS) for total Ag, the quantity of reduction of Ag^I to Ag⁰ is reported. Transmission electron microscopy (TEM) showed Ag particles of 2–35 nm. The factors controlling the amount of silver accumulated are revealed. It is found that there is a limit on the amount of metal nanoparticles that may be deposited, of about 0.35 wt.% Ag on a dry plant basis, and that higher levels of silver are obtained only by the concentration of metal salts within the plant, not by deposition of metal. The limit on metal nanoparticle accumulation, across a range of metals, is proposed to be controlled by the total reducing capacity of the plant for the reduction potential of the metal species and limited to reactions occurring at an electrochemical potential greater than 0 V (verses the standard hydrogen electrode).     

Fabrication and characterization of double-diffused waveguides

An experimental study of two-step Ag⁺/Na⁺ ion exchange in BK-7 glass substrates in molten solutions consisting of AgNO₃/NaNO₃ mixtures is presented. This paper describes a method for evaluating the measured mode index spectra and the index profile of double-diffused semiburied waveguides. They are first diffused at 320°C in 2% melt and are then converted to semiburied waveguides by a second diffusion step consisting of a short-time reimmersion in a 0.25% melt.     

Sonochemical nitrogen fixation for the generation of NO2− and NO3− ions under high-powered ultrasound in aqueous medium

Sonochemical species such as nitrite (NO₂⁻) and nitrate (NO₃⁻) were detected in ultrapure aqueous medium with 28 kHz low frequency ultrasound (US) in the range of 200–1200 W output power. The concentration of their anionic ions monitored with a high-performance liquid chromatography increased with increasing US power especially under air atmosphere. When the generation of NO₂⁻ and NO₃⁻ ions under US exposure was investigated for N₂, O₂ and Ar-bubbled solutions, no trace of NO₂⁻ was observed while NO₃⁻ was slightly generated. Under air atmosphere, the concentration of dissolved oxygen in the aqueous medium increased especially when 1200 W power was used. In addition, the bulk pH shifted towards the acidic side with an increase in exposure time, which indicated that NO₂⁻ was formed. The formation of oxidizing species under 28 kHz low frequency ultrasonic treatment was confirmed with an absorption spectrum which was dominated by two maxima peaks at 288 nm and 352 nm representing triiodide I₃⁻ anion.     

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.     

Microwave-assisted rapid synthesis of Ag nanoparticles/graphene nanosheet composites and their application for hydrogen peroxide detection

Abstract  

Ag nanoparticles/graphene nanosheet (AgNPs/GN) composites have been rapidly prepared by a one-pot microwave-assisted reduction method, carried out by microwave irradiation of a N,N-dimethylformamide (DMF) solution of graphene oxide (GO) and AgNO₃. Several analytical techniques including UV–vis spectroscopy, FT-IR spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) have been used to characterize the resulting AgNPs/GN composites. It suggests that such composites exhibit good catalytic activity toward reduction of hydrogen peroxide (H₂O₂), leading to a H₂O₂ sensor with a fast amperometric response time of less than 2 s. The linear detection range is estimated to be from 0.1 to 100 mM (r = 0.999), and the detection limit is estimated to be 0.5 μM at a signal-to-noise ratio of 3.     

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.     

Improved modification of clinoptilolite with silver using ultrasonic radiation

The modification of natural clinoptilolite with silver ions using ultrasound has been investigated in the current work. The modification process was performed using clinoptilolite of different fractions (0–3.0 mm) over the temperature range of 25–55 °C, ultrasonic power range of 8.0–12.5 W and AgNO₃ concentration range of 0.01–0.1 M. The zeolite modification was performed in the presence of sonication and mechanical stirring in separate runs for comparison. Fundamental analysis demonstrated that the use of ultrasound ensures desorption of air from clinoptilolite particles and accelerates the diffusion of Ag⁺ ions and subsequent ion exchange. Increasing the particle size of clinoptilolite led to a natural decrease in its sorption capacity. A slight increase in the sorption capacity with an increase in the equivalent particle diameter from 0.081 to 0.35 mm was seen due to changes in the structure of clinoptilolite particles during mechanical grinding. The calculated temperature coefficient of the sorption process of Ag⁺ ions as <1.47 means that the modification takes place with dominant control in the intradiffusion region. Increasing the power of ultrasonic irradiation did not provide a monotonous change in the sorption capacity of clinoptilolite. Increasing the concentration of argentum nitrate solution provided an increase in the content of silver ions in clinoptilolite. In general, the advantage of using ultrasonic vibrations to modify the natural clinoptilolite of different fractions with Ag⁺ ions was demonstrated in terms of achieving higher sorption capacity, also elucidating the effect of different operating conditions.     

Ferroelectricity associated with the metastable phase “III” of AgNO3

The dielectric constant, dc resistance, D-E ferroelectric hysteresis loop and dilatometric analysis of the three phases I, II, and III of AgNO₃ single crystals has been studied over the temperature range 100–200° C. A ferroelectric behaviour of the metastable phase III was detected here for the first time similar to what happened in KNO₃. The ferroelectric is attributed here to Ag⁺-ion vacancy formation in the unit cell of AgNO₃. The energy activating the process of vacancy formation was found to beE _v=2.6 eV. It was found that an ionic shift from one lattice point to another requires an amount of energy to overcome a potential barrierE _m=0.1 eV. A model is suggested to explain such behaviour. Dilatometric analysis indicated that this metastable phase transition III is accompanied by an expansion of the unit cell.