O. V. Dement’eva

Effect of Gold Nanoparticles on Mouse Spermatogenesis

The response of the mouse male germ cells exposed to gold nanoparticles (∼2.5 nm) was studied. Our investigation demonstrates that treatment with Au nanoparticles for four days does not impair the architecture of the spermatogenic epithelium. Cytogenetic evaluation using micronucleus assay showed that gold nanoparticles can affect the chromosomes of early primary spermatocytes. However, gold nanoparticles did not induce chromosome abnormalities in spermatogonial stem cells. Further, the cauda epididymal sperm was isolated on the 14th day after treatment and was incubated in SDS solution (Na dodecyl sulphate) and then in a solution containing DTT (dithiothreitol) to induce nuclear chromatin decondensation. Observations showed that after four days of treatment of spermiogenic (postmeiotic) cells with gold nanoparticles the decondensation process had no differences from the control. On the contrary, in the experiment with the same cells and period of fixation but with a single exposure to gold nanoparticles, the number of mature gametes with totally decondensed nuclei reached 100% as opposed to 44% in the controls.

Bovine sperm chromatin is not protected from the effects of ultrasmall gold nanoparticles

The response of ejaculated bovine spermatozoa to gold nanoparticles was studied by the standard method of nuclear chromatin decondensation in vitro. After the treatment of semen samples with a hydrosol containing gold nanoparticles with an average diameter of ∼3.0 nm and a concentration of 1 × 1015 particles/mL, the ability of sperm nuclei to decondense in the presence of sodium dodecyl sulfate (SDS) and dithiothreitol (DTT) dramatically changed compared to the control. The frequencies of gametes with nondecondensed (“intact”), partially decondensed, and completely decondensed nuclei correlated as 40: 32: 28% and 0: 36: 64% in the experiment and the control, respectively. Moreover, the appearance of a sufficiently large number of gametes with destructed and almost completely destroyed nuclei was noticed in the spermatozoa treated with gold nanoparticles. This article suggests the putative mechanisms of action of ultrasmall gold nanoparticles on the structural and functional integrity of the deoxyribonucleoprotein (DNP) complex of mature male gametes.

Colloidal synthesis of new silver-based nanostructures with tailored localized surface plasmon resonance

Silver-based nanostructures with tailored localized surface plasmon resonance are of interest for a number of practical applications. They can conventionally be divided into three main groups: (1) anisotropic silver particles, (2) particles of alloys of silver with other metals, and (3) composite particles with dielectric or magnetic cores and silver shells. Fine “tuning” of plasmon resonance of these particles is ensured by changes in their shapes, composition, and/or structure. Procedures for the colloidal synthesis of nanostructures of all these groups and some fields of their application are described, with the main attention focused on core/shell composite particles.

SiO2-based nanocontainers of a novel type: If the template micelles are functional, why remove them

A new method is proposed for creating containers based on mesoporous silica nanoparticles for diverse amphiphilic compounds. The method is based on the use of the micelles of required functional compound (i.e., the compound that is subsequently loaded into the containers) as a template when synthesizing nanoparticles. The prospects and advantages of this approach are exemplified by the synthesis of SiO2 particles using the micelles of cetyltrimethylammonium bromide (which can be used as an inhibitor of hydrogen sulfide corrosion) as a template.

Comparative study of the properties of silver hydrosols prepared by “citrate” and “citrate-sulfate” procedures

Comparative study of the properties of silver hydrosols prepared with the use of two classical procedures (“citrate” and “citrate-sulfate”) is performed. The possibility of using these procedures for the synthesis of stable monodisperse silver hydrosols with particle diameters of 20 nm and more is studied. The effect of the main parameters of synthesis (the ratio of initial components, the rate of their mixing, etc) on the hydrosol characteristics is investigated. It is revealed that, in the case of “citrate” synthesis, it is quite impossible to realize conditions ensuring the reproducible preparation of colloidal solutions with particles having sufficiently uniform size and shape. The procedure for the one-stage preparation of “citrate-sulfate” hydrosol (without multiple precipitation-redispersion of nanoparticles) is elaborated and it is shown that the thus prepared hydrosol is greatly superior in both the optical characteristics and the morphological uniformity of particles to the citrate sol. An increase in synthesis temperature to 100°C leads to a substantial enhancement of the stability of colloidal solution. The possibility of using “citrate-sulfate” hydrosol for the design of two-dimensional ensembles of silver nanoparticles on the quartz and silicon surfaces modified with poly(2-vinylpyridine) is demonstrated. It is shown that such ensembles possess optical properties that allow to use them in designing “two-dimensional” polymer-metal nanocomposites potentially suitable for using as active media in devices working on the principle of surface plasmon resonance.

Mesostructured SiO2-based nanocontainers synthesized on a functional template: Capacity and rate of unloading

A new approach to template synthesis of mesostructured pH-sensitive SiO2 nanocontainers is developed. The approach combines the stages of synthesis of the nanocontainers and their loading with a targeted functional substance. The structure, capacity, and the rate of “unloading” of the nanocontainers at different pH values of an aqueous medium under static and quasi-dynamic conditions are studied using mesoporous SiO2 nanoparticles as a model. Nanoparticles are synthesized using the micelles of cetyltrimethylammonium bromide as templates. Based on the obtained information, a mechanism is proposed for release of cetyltrimethylammonium cations from SiO2 nanocontainers into the aqueous medium.

The effect of ozone on plasmon absorption of gold hydrosols. Quasi-metal and metal nanoparticles

The character of the interaction between ultrasmall gold nanoparticles and ozone is shown to be mainly governed by the particle structure. For borohydride sols of gold nanoparticles with sizes of ≈3 nm, which are characterized by metallic properties, this interaction is reduced to reversible adsorption of ozone on their surface. At the same time, ozone adsorption on “nonplasmon” Au particles that have a diameter of 2 nm and a very defective structure results in their irreversible structural rearrangement and transition to a metallic state, which is accompanied by the appearance of a surface plasmon resonance. The set of the results obtained shows that nanoparticles of borohydride gold sols are more efficient as possible hemosensors of ozone than are larger particles synthesized by the citrate method.

Copper nanoparticles synthesized by the polyol method and their oxidation in polar dispersion media. The influence of chloride and acetate ions

Copper nanoparticles have been synthesized from Cu(2+) acetate in the medium of dimethylformamide by the polyol method using hydrazine as a reductant and poly(vinylpyrrolidone) as a stabilizer. Optical spectroscopy has been employed to study the influence of chloride and acetate ions on the oxidation of copper nanoparticles by atmospheric oxygen in aqueous and dimethylformamide media, respectively. It has been established that the presence of ions of one of the aforementioned types in a colloidal solution significantly accelerates the oxidation of metal nanoparticles. In the case of acetate ions, copper oxide particles rapidly dissolve to form the corresponding salt. It has been shown that Cu nanoparticles can be repeatedly formed in such a solution by the addition of hydrazine.

Anisotropic particles with different morphologies of silver nanoshell: Synthesis and optical properties

Hydrosols of spindle-shaped composite particles with the core of iron(III) oxyhydroxide and silver shell are synthesized by enlarging metal seeding nanoparticles adsorbed on the surface of the cores in the solution containing silver nitrate and mild reducing agent. It is revealed that the character of the growth of shells on gold seeding particles greatly depends on the type of reducing agent. When using ascorbic acid, seeding particles grow primarily in the direction normal to the core surface due to the blocking of some of the particle faces by ions present in the solution. As a result, the forming shell is characterized by a fairly nonuniform structure. At the same time, when using formaldehyde, the growth of seeding nanoparticles proceeds predominantly in the lateral direction to form first an island-like film, then a continuous thin metal shell on the core surface. It is demonstrated that the position of localized surface plasmon resonance of such structure can be fine tuned to the preset wavelength by controlled variations in the thickness of Ag shell with very small step (up to 1 nm).

Metal nanoparticles on polymer surfaces: 6. Probing of non-glassy polystyrene surface layer

Peculiarities of the state of the surface layer of the amorphous glassy polymer polystyrene are studied with a specially developed experimental approach. The essence of the method consists in the observation via atomic force microscope for the depth and rate of embedding of gold nanoparticles in a polymer after their preliminary adsorption on the polymer surface from hydrosol. It is shown that the polymer glass-transition temperature near the boundary with air is substantially lowered relative to its bulk value. “Equilibrium” thickness of the non-glassy (“melted”) surface layer is determined through analysis of the data on the kinetics of nanoparticle embedding, and it is revealed that the layer thickness increases with temperature, reaching, near the “bulk” glass-transition temperature, the magnitude that is close to the diameter of the macromolecular coil. The results obtained are analyzed with allowance for published data, and the semi-empirical formula describing variations in the thickness of the non-glassy surface layer as a function of temperature in the interval between the “surface” and “bulk” glass-transition temperatures of a polymer is proposed.