We report for the first time that the medicinal basidiomycete Lentinula edodes can reduce selenium from inorganic sodium selenite (Se(IV)) and the organoselenium compound 1,5-diphenyl-3-selenopentanedione-1,5 (DAPS-25) to the elemental state, forming spherical nanoparticles. Submerged cultivation of the fungus with sodium selenite or with DAPS-25 produced an intense red coloration of L. edodes mycelial hyphae, indicating accumulation of elemental selenium (Se(0)) in a red modification. Several methods, including transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and X-ray fluorescence, were used to show that red Se(0) accumulated intracellularly in the fungal hyphae as electron-dense nanoparticles with a diameter of 180.51±16.82 nm. Under designated cultivation conditions, shiitake did not reduce selenium from sodium selenate (Se(VI)).
Au, Ag, Se, and Si nanoparticles were synthesized from aqueous solutions of HAuCl4, AgNO3, Na2SeO3, and Na2SiO3 with extra- and intracellular extracts from the xylotrophic basidiomycetes Pleurotus ostreatus, Lentinus edodes, Ganoderma lucidum, and Grifola frondosa. The shape, size, and aggregation properties of the nanoparticles depended both on the fungal species and on the extract type. The bioreduction of the metal-containing compounds and the formation rate of Au and Ag nanoparticles depended directly on the phenol oxidase activity of the fungal extracts used. The biofabrication of Se and Si nanoparticles did not depend on phenol oxidase activity. When we used mycelial extracts from different fungal morphological structures, we succeeded in obtaining nanoparticles of differing shapes and sizes. The cytotoxicity of the noble metal nanoparticles, which are widely used in biomedicine, was evaluated on the HeLa and Vero cell lines. The cytotoxicity of the Au nanoparticles was negligible in a broad concentration range (1–100 µg/mL), whereas the Ag nanoparticles were nontoxic only when used between 1 and 10 µg/mL.
This article analyzes data on the diversity of shapes and sizes of nanoparticles obtained by green synthesis from HAuCl 4 , AgNO 3 , Na 2 SeO 3 , and Na 2 SiO 3 by using xylotrophic and humus basidiomycetes and soil bacteria. The formation of nanoparticles of various shapes and sizes was controlled by changing the bioreduction conditions, including culture type and age, growth medium, culture liquid, mycelial extract, isolated proteins, and incubation time. Biogenic selenium nanoparticles were represented exclusively by spheres whose size varied from 20 to 550 nm, depending on the culture. Autoclaving of selenium nanoparticles fabricated with bacterial cultures yielded nanowires with a width of 20−150 nm and a length of more than 10 μm. With bacterial culture liquids, silicon nanospheres were synthesized, ranging in size from very small (5−15 nm) to relatively large (250 nm) particles. The use of the Agaricus culture liquid made it possible to obtain mesoporous particles with a size of 30−60 nm. The size and shape of the fabricated gold and silver nanoparticles were very diverse, depending on the bioreduction conditions, and were represented by regular and irregular spheres; large balls; hexagonal, tetragonal, and triangular prisms; tetrahedrons; and nanobelts. The particle size ranged from 1−10 to 200−500 nm.
The ability to reduce selenite (SeO(3)(2-)) ions with the formation of selenium nanoparticles was demonstrated in Azospirillum brasilense for the first time. The influence of selenite ions on the growth of A. brasilense Sp7 and Sp245, two widely studied wild-type strains, was investigated. Growth of cultures on both liquid and solid (2 % agar) media in the presence of SeO(3)(2-) was found to be accompanied by the appearance of the typical red colouration. By means of transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS) and X-ray fluorescence analysis (XFA), intracellular accumulation of elementary selenium in the form of nanoparticles (50 to 400 nm in diameter) was demonstrated for both strains. The proposed mechanism of selenite-to-selenium (0) reduction could involve SeO(3)(2-) in the denitrification process, which has been well studied in azospirilla, rather than a selenite detoxification strategy. The results obtained point to the possibility of using Azospirillum strains as endophytic or rhizospheric bacteria to assist phytoremediation of, and cereal cultivation on, selenium-contaminated soils. The ability of A. brasilense to synthesise selenium nanoparticles may be of interest to nanobiotechnology for "green synthesis" of bioavailable amorphous red selenium nanostructures.
The work shows the ability of cultured Basidiomycetes of different taxonomic groups-Lentinus edodes, Pleurotus ostreatus, Ganoderma lucidum, and Grifola frondosa-to recover gold, silver, selenium, and silicon, to elemental state with nanoparticles formation. It examines the effect of these metal and metalloid compounds on the parameters of growth and accumulation of biomass; the optimal cultivation conditions and concentrations of the studied ion-containing compounds for recovery of nanoparticles have been identified. Using the techniques of transmission electron microscopy, dynamic light scattering, X-ray fluorescence and X-ray phase analysis, the degrees of oxidation of the bioreduced elements, the ζ-potential of colloidal solutions uniformity, size, shape, and location of the nanoparticles in the culture fluid, as well as on the surface and the inside of filamentous hyphae have been determined. The study has found the part played by homogeneous chromatographically pure fungal phenol-oxidizing enzymes (laccases, tyrosinases, and Mn-peroxidases) in the recovery mechanism with formation of electrostatically stabilized colloidal solutions. A hypothetical mechanism of gold(III) reduction from HAuCl to gold(0) by phenol oxidases with gold nanoparticles formation of different shapes and sizes has been introduced.
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