Fitting Procedure to Reconstruct the Size Distribution and the Concentration of Silver Colloidal Nanoparticles from UV-Vis Spectra.

In this work, a complete fitting procedure of UV-Vis spectra of silver nanoparticles in colloidal solutions is reported. The fitting function, based on the Beer-Lambert law, Mie theory, and log-normal probability distribution of nanoparticles' sizes, is developed and confirmed by 33 different independent measurements. In order to validate the accuracy of the function's behavior on different spectra, freely accessible measurements were used, proving that the fitting function works independently of the method of their production-laser or chemical synthesis of nanoparticles. The developed fitting function is, to the best of our knowledge, novel and not based on any conventional spectral analysis approaches like the Mie-Gans procedure. Furthermore, since fitted parameters are all physical, it allows determination of the mode diameter of nanoparticles as well as the standard deviation of the log-normal distribution of sizes. It enables the reconstruction of size distribution of nanoparticles in colloidal solution. Step-by-step derivation of the fitting function is provided with a physical explanation of all parameters. The importance of Lorentzian dependence emerging at the core of Beer-Lambert law is physically discussed and linked to harmonic oscillator behavior of localized surface plasmon resonance of silver nanoparticles in a colloidal solution. Size distribution reconstruction from fitted parameters according to a log-normal distribution function is provided and a concentration calculation is presented.

Analytical Model for Determination of Size-Distribution of Colloidal Silver Nanoparticles from Surface Plasmon Resonance Wavelength and Dielectric Functions.

In this work it is shown that the size of silver nanoparticles in a colloidal solution can be determined only from the wavelength of the surface plasmon resonance and material and medium dielectric functions. The size dependence of dielectric functions of silver nanoparticles becomes noticeable in nanoparticles which are smaller than 30 nm in size, which is in accordance with Mie scattering theory applicability. The novelty of this work is in the development of an analytical model for the determination of the size of silver nanoparticles derived from applying shift functions to the UV-Vis spectra, resulting in well-known characteristic diameters of log-normal size distribution function. The purpose of these shift functions is the reconstruction of experimental UV-Vis spectra from simulated ones based on the Beer-Lambert law and log-normal distribution function in order to find the mode diameters of colloidal silver nanoparticles. The introduction of Lagrangian analogue of extinction cross section explains the redshift constant characteristic for given nanoparticle material and the size distribution of nanoparticles. Therefore, the size determination of colloidal silver nanoparticles is possible only through UV-Vis spectroscopy.

Synthesis of Silver, Gold, and Platinum Doped Zinc Oxide Nanoparticles by Pulsed Laser Ablation in Water.

In this paper, we propose a simple two-step method for the synthesis of Ag, Au, and Pt-doped ZnO nanoparticles. The method is based on the fabrication of targets using the pulsed laser deposition (PLD) technique where thin layers of metals (Ag, Pt, Au) have been deposited on a metal-oxide bulk substrate (ZnO). Such formed structures were used as a target for the production of doped nanoparticles (ZnO: Ag, ZnO: Au, and ZnO: Pt) by laser ablation in water. The influence of Ag, Au, and Pt doping on the optical properties, structure and composition, sizing, and morphology was studied using UV-Visible (UV-Vis) and photoluminescence (PL) spectroscopies, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The band-gap energy decreased to 3.06, 3.08, and 3.15 for silver, gold, and platinum-doped ZnO compared to the pure ZnO (3.2 eV). PL spectra showed a decrease in the recombination rate of the electrons and holes in the case of doped ZnO. SEM, TEM, and AFM images showed spherical-shaped nanoparticles with a relatively smooth surface. The XRD patterns confirm that Ag, Au, and Pt were well incorporated inside the ZnO lattice and maintained a hexagonal wurtzite structure. This work could provide a new way for synthesizing various doped materials.

Enhancement of Methylene Blue Photodegradation Rate Using Laser Synthesized Ag-Doped ZnO Nanoparticles.

In this work, Ag-doped ZnO nanoparticles are obtained via pulsed laser ablation of the Ag-coated ZnO target in water. The ratio of Ag dopant in ZnO nanoparticles strongly depends on the thickness of the Ag layer at the ZnO target. Synthesized nanoparticles were characterized by XRD, XPS, SEM, EDS, ICP-OES, and UV-VIS spectrophotometry to obtain their crystal structure, elemental composition, morphology and size distribution, mass concentration, and optical properties, respectively. The photocatalytic studies showed photodegradation of methylene blue (MB) under UV irradiation. Different ratios of Ag dopant in ZnO nanoparticles influence the photodegradation rate. The ZnO nanoparticles doped with 0.32% silver show the most efficient photodegradation rate, with the chemical reaction constant of 0.0233 min-1. It exhibits an almost twice as large photodegradation rate compared to pure ZnO nanoparticles, showing the doping effect on the photocatalytic activity.

Concentration Quantification of TiO2 Nanoparticles Synthesized by Laser Ablation of a Ti Target in Water.

In this work, we present a quantitative method for determining the concentration of metal oxide nanoparticles (NP) synthesized by laser ablation in liquid. The case study was performed with titanium dioxide nanoparticles (TiO2 NP), which were synthesized by laser ablation of a Ti target in water. After synthesis, a colloidal solution was analyzed with UV-Vis spectroscopy. At the same time, the craters that remained on the Ti target after ablation were evaluated with an optical microscope to determine the volume of the ablated material. SEM microscopy was used to determine the TiO2 NP size distribution. It was found that synthesized TiO2 NP followed a Log-Normal diameter distribution with a maximum at about 64 nm. From the volume of ablated material and NP size distribution, under the assumption that most of the ablated material is consumed to form nanoparticles, a concentration of nanoparticles can be determined. The proposed method is verified by comparing the calculated concentrations to the values obtained from the Beer-Lambert law using the Mie scattering theory for the NP cross-section calculation.

Metal oxide nanoparticles as solid contact in ion-selective electrodes sensitive to potassium ions.

In recent years, various types of nanomaterials and nanoparticles have been very popular, also in analytical chemistry for sensors preparation. Ion-selective electrodes with solid contact were constructed, in which a layer of nanoparticles of selected metal oxides (zinc, copper and iron oxides) obtained by pulsed laser liquid ablation (PLAL) was placed between the glassy carbon solid electrode material and the ion-selective membrane. The basic analytical parameters of the obtained sensors were determined using potentiometric methods. Additionally, the electrochemical impedance spectroscopy method (EIS) was also used to investigate the electrical properties of the sensors. The obtained results were compared for all types of electrodes, both modified and unmodified, in order to investigate the effect of the type of nanoparticles and the thickness of their layer used as solid contact. It was found that the addition of metal oxide nanoparticles improved the analytical parameters of the sensors, mainly the potential stability and electrical parameters. The best results were obtained for an electrode with an intermediate layer of zinc oxide nanoparticles. In this case, a slope of -56.07 mV/dec, a linearity range of 1 × 10-5 - 1 × 10-1 mol L-1 and a limit of detection of 3.66 × 10-6 mol L-1 were obtained. Particularly noteworthy is the significant improvement in the stability of the potential of this electrode and the long life of more than 5 months.

Photodegradation of Methylene Blue and Rhodamine B Using Laser-Synthesized ZnO Nanoparticles.

In this paper we examined the photocatalytic efficiency of a laser-synthesized colloidal solution of ZnO nanoparticles synthesized by laser ablation in water. The average size of the obtained colloidal ZnO nanoparticles is about 47 nm. As revealed by electron microscopy, other nanostructures were also present in the colloidal solution, especially nanosheets. A photocatalytic degradation of UV-irradiated Methylene Blue and Rhodamine B solutions of different concentration in the presence of different ZnO catalyst mass concentrations was studied in order to examine their influence on photodegradation rates. ZnO nanoparticles have shown high photocatalytic efficiency, which is limited due to different effects related to UV light transmittivity through the colloidal solution. Therefore, increasing catalyst concentration is effective way to increase photocatalytic efficiency up to some value where photodegradation rate saturation occurs. The photodegradation rate increases as the dye concentration decreases. These findings are important for water purification applications of laser-synthesized ZnO nanoparticles.

Probing the Mode of Antibacterial Action of Silver Nanoparticles Synthesized by Laser Ablation in Water: What Fluorescence and AFM Data Tell Us.

We aim to elucidate the mode of antibacterial action of the laser-synthesized silver colloid against Escherichia coli. Membrane integrity was studied by flow cytometry, while the strain viability of the treated culture was determined by plating. The spectrofluorometry was used to obtain the time development of the reactive oxygen species (ROS) inside the nanoparticle-treated bacterial cells. An integrated atomic force and bright-field/fluorescence microscopy system enabled the study of the cell morphology, Young modulus, viability, and integrity before and during the treatment. Upon lethal treatment, not all bacterial cells were shown to be permeabilized and have mostly kept their morphology with an indication of cell lysis. Young modulus of untreated cells was shown to be distinctly bimodal, with randomly distributed softer parts, while treated cells exhibited exponential softening of the stiffer parts in time. Silver nanoparticles and bacteria have shown a masking effect on the raw fluorescence signal through absorbance and scattering. The contribution of cellular ROS in the total fluorescence signal was resolved and it was proven that the ROS level inside the lethally treated cells is not significant. It was found that the laser-synthesized silver nanoparticles mode of antibacterial action includes reduction of the cell's Young modulus in time and subsequently the cell leakage.

Bacteria Exposed to Silver Nanoparticles Synthesized by Laser Ablation in Water: Modelling E. coli Growth and Inactivation.

This study is aimed to better understand the bactericidal mode of action of silver nanoparticles. Here we present the production and characterization of laser-synthesized silver nanoparticles along with growth curves of bacteria treated at sub-minimal and minimal inhibitory concentrations, obtained by optical density measurements. The main effect of the treatment is the increase of the bacterial apparent lag time, which is very well described by the novel growth model as well as the entire growth curves for different concentrations. The main assumption of the model is that the treated bacteria uptake the nanoparticles and inactivate, which results in the decrease of both the nanoparticles and the bacteria concentrations. The lag assumes infinitive value for the minimal inhibitory concentration treatment. This apparent lag phase is not postponed bacterial growth. It is a dynamic state in which the bacterial growth and death rates are close in value. Our results strongly suggest that the predominant mode of antibacterial action of silver nanoparticles is the penetration inside the membrane.

ZnO@TiO2 Core Shell Nanorod Arrays with Tailored Structural, Electrical, and Optical Properties for Photovoltaic Application.

ZnO has prominent electron transport and optical properties, beneficial for photovoltaic application, but its surface is prone to the formation of defects. To overcome this problem, we deposited nanostructured TiO2 thin film on ZnO nanorods to form a stable shell. ZnO nanorods synthesized by wet-chemistry are single crystals. Three different procedures for deposition of TiO2 were applied. The influence of preparation methods and parameters on the structure, morphology, electrical and optical properties were studied. Nanostructured TiO2 shells show different morphologies dependent on deposition methods: (1) separated nanoparticles (by pulsed laser deposition (PLD) in Ar), (2) a layer with nonhomogeneous thickness (by PLD in vacuum or DC reactive magnetron sputtering), and (3) a homogenous thin layer along the nanorods (by chemical deposition). Based on the structural study, we chose the preparation parameters to obtain an anatase structure of the TiO2 shell. Impedance spectroscopy shows pure electron conductivity that was considerably better in all the ZnO@TiO2 than in bare ZnO nanorods or TiO2 layers. The best conductivity among the studied samples and the lowest activation energy was observed for the sample with a chemically deposited TiO2 shell. Higher transparency in the visible part of spectrum was achieved for the sample with a homogenous TiO2 layer along the nanorods, then in the samples with a layer of varying thickness.

Green Procedure to Manufacture Nanoparticle-Decorated Paper Substrates.

For this study, a paper impregnated with silver nanoparticles (AgNPs) was prepared. To prepare the substrates, aqueous suspensions of pulp fines, a side product from the paper production, were mixed with AgNP suspensions. The nanoparticle (NP) synthesis was then carried out via laser ablation of pure Ag in water. After the sheet formation process, the leaching of the AgNPs was determined to be low while the sheets exhibited antimicrobial activity toward Escherichia coli (E. coli).