Electrochemical Mechanism of Oxidative Dissolution of Silver Nanoparticles in Water: Effect of Size on Electrode Potential and Solubility.

For the first time, an electrochemical mechanism of oxidative dissolution of silver nanoparticles in aqueous solutions is suggested and substantiated. The dissolution is caused by the occurrence of two interrelated electrochemical processes: (1) silver oxidation on a microanode and (2) oxygen reduction on a microcathode. According to the suggested model, the standard electrode potential of a nanoparticle decreases with a decrease in its size, which leads to an increase in the electromotive force of the oxidative dissolution of silver. A proportional dependence of the solubility of nanoparticles on their standard potential is revealed. An empirical equation is derived that relates the solubility of AgNPs to their electrode potential and size. In the course of oxidation, silver nanoparticles undergo aggregation with a gradual increase in the potential to the value characteristic of the bulk metal. This leads to the deceleration and practical cessation of the dissolution.

Special Aspects of Nitrocellulose Molar Mass Determination by Dynamic Light Scattering.

The dynamic light scattering method was successfully applied to determine the molar mass of nitrocellulose. The methodology of nitrocellulose fractionation in acetonic solutions is described in detail; six polymer fractions with monomodal distribution were obtained. It was shown that the unfractionated colloxylin with polymodal molar mass distribution had mass average molecular mass values of 87.3 ± 14.1, 28.3 ± 7.3, and 0.54 ± 0.17 kDa when investigated by the dynamic light scattering method. The viscometric method only provided integral viscosity average molar mass equal to 56.7 ± 5.8 kDa.

Natural Radioactivity and Chemical Evolution on the Early Earth: Prebiotic Chemistry and Oxygenation.

It is generally recognized that the evolution of the early Earth was affected by an external energy source: radiation from the early Sun. The hypothesis about the important role of natural radioactivity, as a source of internal energy in the evolution of the early Earth, is considered and substantiated in this work. The decay of the long-lived isotopes 232Th, 238U, 235U, and 40K in the Global Ocean initiated the oxygenation of the hydro- and atmosphere, and the abiogenesis. The content of isotopes in the ocean and the kinetics of their decay, the values of the absorbed dose and dose rate, and the efficiency of sea water radiolysis, as a function of time, were calculated. The ocean served as both a "reservoir" that collected components of the early atmosphere and products of their transformations, and a "converter" in which further chemical reactions of these compounds took place. Radical mechanisms were proposed for the formation of simple amino acids, sugars, and nitrogen bases, i.e., the key structures of all living things, and also for the formation of oxygen. The calculation results confirm the possible important role of natural radioactivity in the evolution of terrestrial matter, and the emergence of life.

Determination of the Concentration of Silver Atoms in Hydrosol Nanoparticles.

In this work, we propose a new method for determining the concentration of silver atoms in hydrosols of nanoparticles (NPs) stabilized with various capping agents. The proposed method is based on the determination of IBT absorption in the UV region (a broad band with a weakly pronounced shoulder at ~250 nm). To determine the extinction coefficient at 250 nm, we synthesized silver nanoparticles with average sizes of 5, 10, and 25 nm, respectively. The prepared nanoparticles were characterized by TEM, HRTEM, electron diffraction, XRD, DLS, and UV-Vis spectroscopy. It has been shown that the absorption characteristics of spherical NPs are not significantly influenced by the hydrosol preparation method and the type of stabilizer used. For particles with a size of 5-25 nm, the molar extinction coefficient of Ag0 atoms was found to be equal to 3500 ± 100 L mol-1 cm-1 at a wavelength of 250 nm. The results of the theoretical calculations of the molar extinction coefficients for spherical nanoparticles are in good agreement with the experimental values. ICP-MS analysis confirmed the applicability of this method in the concentration range of 5 × 10-7-1 × 10-4 mol L-1.

Photochemical Synthesis of Silver Hydrosol Stabilized by Carbonate Ions and Study of Its Bactericidal Impact on Escherichia coli: Direct and Indirect Effects.

The great attention paid to silver nanoparticles is largely related to their antibacterial and antiviral effects and their possible use as efficient biocidal agents. Silver nanoparticles are being widely introduced into various areas of life, including industry, medicine, and agriculture. This leads to their spreading and entering the environment, which generates the potential risk of toxic effect on humans and other biological organisms. Proposed paper describes the preparation of silver hydrosols containing spherical metal nanoparticles by photochemical reduction of Ag+ ions with oxalate ions. In deaerated solutions, this gives ~10 nm particles, while in aerated solutions, ~20 nm particles with inclusion of the oxide Ag2O are obtained. Nanoparticles inhibit the bacterium Escherichia coli and suppress the cell growth at concentrations of ~1 × 10-6-1 × 10-4 mol L-1. Silver particles cause the loss of pili and deformation and destruction of cell membranes. A mechanism of antibacterial action was proposed, taking into account indirect suppressing action of Ag+ ions released upon the oxidative metal dissolution and direct (contact) action of nanoparticles on bacterial cells, resulting in a change in the shape and destruction of the bacteria.

Physicochemical and Sorptive Properties of a Phosphorylated Mercerized Cotton Fabric.

A process of phosphorylation for a mercerized cotton kersey fabric was investigated. After wet oxidation, the phosphorus content in each sample was determined by spectrophotometric analysis. The range was 0.179 to 0.950 mmol g-1. A significant decrease in the tensile strength of samples resulted from an increase of phosphoric acid concentration in the phosphorylating solution. The mercerization has a positive impact on the process of phosphorylation, as the phosphorus content was found to be three times higher in the samples that underwent mercerization. The sorption properties of phosphorylated cotton fabric were studied using the Cu2+ sorption process as a reference. The value of the static exchange capacity for the phosphorylated fabric was determined to reach its maximum when the concentration of the H3PO4 in the phosphorylating solution was 1.40 M, and was found to be 1.48 ± 0.11 mmol g-1 with the phosphorus content equal to 0.898 ± 0.090 mmol g-1. The sorption of Cu2+ by a single phosphorus-containing group occurred for samples with phosphorus content not exceeding 0.80 mmol g-1. The preliminary studies of micro-quantities of 241Am, 233U, and 239Pu radionuclide sorption from aqueous solutions with phosphorylated textile demonstrated the high efficiency.

Evolution of Electronic State and Properties of Silver Nanoparticles during Their Formation in Aqueous Solution.

The electron density of a nanoparticle is a very important characteristic of the properties of a material. This paper describes the formation of silver nanoparticles (NPs) and the variation in the electronic state of an NP's surface upon the reduction in Ag+ ions with oxalate ions, induced by UV irradiation. The calculations were based on optical spectrophotometry data. The NPs were characterized using Transmission electron microscopy and Dynamic light scattering. As ~10 nm nanoparticles are formed, the localized surface plasmon resonance (LSPR) band increases in intensity, decreases in width, and shifts to the UV region from 402 to 383 nm. The interband transitions (IBT) band (≤250 nm) increases in intensity, with the band shape and position remaining unchanged. The change in the shape and position of the LSPR band of silver nanoparticles in the course of their formation is attributable to an increasing concentration of free electrons in the particles as a result of a reduction in Ag+ ions on the surface and electron injection by CO2- radicals. The ζ-potential of colloids increases with an increase in electron density in silver nuclei. A quantitative relationship between this shift and electron density on the surface was derived on the basis of the Mie-Drude theory. The observed blue shift (19 nm) corresponds to an approximately 10% increase in the concentration of electrons in silver nanoparticles.

Features of Hydrogen Reduction of Fe(CN)63- Ions in Aqueous Solutions: Effect of Hydrogen Dissolved in Palladium Nanoparticles.

Preliminary saturation of 2.6 nm palladium nanoparticles with hydrogen accelerates the reduction of Fe(CN)63- ions in aqueous solution three to four-fold. An analytical equation was derived describing the hydrogen saturation of palladium nanoparticles and the dependence of their catalytic activity on the hydrogen content in the metal. The specific rate constants of reduction do not depend on the content of palladium nanoparticles in the solution. A change in the temperature and pH or stirring of the solution do not affect the rate of catalytic reaction. Approaches to optimization of palladium-catalyzed reactions involving hydrogen are substantiated.

Ozonation of Decalin as a Model Saturated Cyclic Molecule: A Spectroscopic Study.

Ozonolysis is used for oxidation of a model cyclic molecule-decalin, which may be considered as an analog of saturated cyclic molecules present in heavy oil. The conversion of decalin exceeds 50% with the highest yield of formation of acids about 15-17%. Carboxylic acids, ketones/aldehydes, and alcohols are produced as intermediate products. The methods of UV-visible, transmission IR, attenuated total reflection IR-spectroscopy, NMR and mass-spectrometry were used to identify reaction products and unravel a possible reaction mechanism. The key stage of the process is undoubtedly the activation of the first C-H bond and the formation of peroxide radicals.

Microwave-Assisted Synthesis of Water-Dispersible Humate-Coated Magnetite Nanoparticles: Relation of Coating Process Parameters to the Properties of Nanoparticles.

Nowadays, there is a demand in the production of nontoxic multifunctional magnetic materials possessing both high colloidal stability in water solutions and high magnetization. In this work, a series of water-dispersible natural humate-polyanion coated superparamagnetic magnetite nanoparticles has been synthesized via microwave-assisted synthesis without the use of inert atmosphere. An impact of a biocompatible humate-anion as a coating agent on the structural and physical properties of nanoparticles has been established. The injection of humate-polyanion at various synthesis stages leads to differences in the physical properties of the obtained nanomaterials. Depending on the synthesis protocol, nanoparticles are characterized by improved monodispersity, smaller crystallite and grain size (up to 8.2 nm), a shift in the point of zero charge (6.4 pH), enhanced colloidal stability in model solutions, and enhanced magnetization (80 emu g-1).

The Green Method in Water Management: Electron Beam Treatment.

During the prebiotic era, radiolytic transformations in the oceans played a key role in purifying water from toxic impurities and, thus, played a role in the formation of the aquatic environment of our planet, making it suitable for the emergence of life. Today, the planet again faces the challenge of how to provide people with clean water. Therefore, it is reasonable to look back at past historical stages and again consider the possibility of neutralizing pollutants in water by means of radiolysis, which has already been tested by time. Modern radiolytic treatments can be much faster and safer thanks to the advent of powerful electron accelerators and high-rate electron beam treatment (ELT) of water and wastewater. Radiolytic treatment of water using accelerated electrons corresponds to the essence of advanced oxidative technologies and green chemistry. The ELT of water instantly generates a high concentration of short-lived radicals that can quickly neutralize and decompose chemical and bacterial pollutants. Due to the ability of accelerated electrons to penetrate into a substance, ELT provides the decomposition of both dissolved and suspended pollutants. The cleaning effect of ELT is due to the ability to inactivate toxic and chromophore functional groups, transform impurities into an easily removable form, damage the DNA of microorganisms and their spore forms, and increase the biodegradability of organic impurities. The use of ELT in water treatment provides significant savings in chemical reagents, thereby improving quality and reducing the number of cleaning steps. The compactness, high degree of automation of the equipment used, energy efficiency, high productivity, and excellent compatibility with traditional water treatment methods are important advantages of ELT. Unlike conventional chemicals, the excess radicals generated in the ELT process are converted back to water and hydrogen; thus, the chemical and corrosive activity of water does not increase. Equipping research institutes with electron accelerators, developing cheaper accelerators, and granting government support for pilot projects are key conditions for introducing ELT into water treatment practice.

Spectrophotometric determination of ozone in solutions: Molar absorption coefficient in the visible region.

A new approach for the determination of ozone concentration in solutions in organic liquids based on spectrophotometric absorbance measurements in the visible region was proposed and substantiated. The molar absorption coefficient of ozone in the absorption maximum at ~600nm is 8.0mol-1 L cm-1 for hydrocarbons (hexane, heptane, isooctane), CHCl3 and CCl4, and 5.3mol-1 L cm-1 for methanol and 4.5mol-1 L cm-1 for water (±10%). The coefficient monotonically decreases with increasing dielectric constant of the liquid. The low molar absorption coefficient allows the use of spectrophotometric measurements for determination of high ozone concentrations ranging from approximately 1·10-2mol L-1 up to 1.0mol L-1.

Ecotoxicity of different-shaped silver nanoparticles: Case of zebrafish embryos.

As the worldwide application of silver nanomaterials in commercial products increases every year, and concern about the environmental risks of such nanoparticles also grows. A clear understanding of how different characteristics of nanoparticles contribute in their toxic behavior to organisms are imperative for predicting and control nanotoxicity. Within our research, we investigated the toxic effect of two types of silver nanoparticles (spherical and flat Ag nanoparticles) on zebrafish (Danio rerio) embryos. Particular interest was paid to proper characterization of Ag nanoparticles initially and during the experiment. A proper test medium was found and used for ecotoxicity evaluation. The behavior of flat silver nanoparticles with respect to embryos of zebrafish was analyzed and compared to the ecotoxicity of silver ionic form (AgNO3). Both types of nanoparticles showed a more pronounced toxic effect to Danio rerio embryos than silver ions (AgNO3), while silver nanoplates were more harmful than Ag nanospheres. While previous investigations showed that toxicity of Ag nanoparticles can be explained by the presence of Ag+ in solution of silver nanoparticles, our results demonstrate that the harmful effects of nanosilver may be associated with silver nanoparticles themselves than with ionic silver released into solution.

Chemical and spectral behavior of nitric acid in aqueous sulfuric acid solutions: Absorption spectrum and molar absorption coefficient of nitronium ion.

The chemical species formed from nitric acid in aqueous solutions of sulfuric acid (up to 18.0molL-1) were studied by optical spectroscopy method. The concentration region of nitronium ion formation was identified and NO2+ ion absorption spectrum was measured (λmax≤190nm and ε190=1040±50mol-1Lcm-1).

Adsorption of ozone and plasmonic properties of gold hydrosol: the effect of the nanoparticle size.

The impact of the size of gold nanoparticles on the magnitude of the bathochromic shift of their plasmon resonance peak upon ozone adsorption is revealed and analyzed. Namely, the plasmon band position of 7, 10, 14 and 32 nm nanoparticles shifts toward longer wavelengths by 51, 35, 23 and 9 nm respectively, i.e. the smaller the nanoparticles, the greater the shift of the band. Thus, the sensor efficiency of gold hydrosol increases with a decrease in the nanoparticle size. The shift of the Fermi level is a linear function of the inverse radius of nanoparticles. The observed alterations in the gold nanoparticle plasmonic properties and the Fermi level position are explained by a decrease in the electron density of nanoparticles caused by the electrons' partial binding by adsorbed O3 molecules. The insignificance of oxygen and nitrous oxide effects on plasmonic properties of gold hydrosol is observed.

Radiation-induced high-temperature conversion of cellulose.

Thermal decomposition of cellulose can be upgraded by means of an electron-beam irradiation to produce valuable organic products via chain mechanisms. The samples being irradiated decompose effectively at temperatures below the threshold of pyrolysis inception. Cellulose decomposition resembles local "explosion" of the glucopyranose unit when fast elimination of carbon dioxide and water precede formation of residual carbonyl or carboxyl compounds. The dry distillation being performed during an irradiation gives a liquid condensate where furfural and its derivatives are dominant components. Excessively fast heating is adverse, as it results in a decrease of the yield of key organic products because pyrolysis predominates over the radiolytic-controlled decomposition of feedstock. Most likely, conversion of cellulose starts via radiolytic formation of macroradicals do not conform with each other, resulting in instability of the macroradical. As a consequence, glucosidic bond cleavage, elimination of light fragments (water, carbon oxides, formaldehyde, etc.) and formation of furfural take place.