Agronomic Investigation of Spray Dispersion of Metal-Based Nanoparticles on Sunflowers in Real-World Environments.

In environmental and agronomic settings, even minor imbalances can trigger a range of unpredicted responses. Despite the widespread use of metal-based nanoparticles (NPs) and new bio-nanofertilizers, their impact on crop production is absent in the literature. Therefore, our research is focused on the agronomic effect of spray application of gold nanoparticles anchored to SiO2 mesoporous silica (AuSi-NPs), zinc oxide nanoparticles (ZnO-NPs), and iron oxide nanoparticles (Fe3O4-NPs) on sunflowers under real-world environments. Our findings revealed that the biosynthetically prepared AuSi-NPs and ZnO-NPs were highly effective in enhancing sunflower seasonal physiology, e.g., the value of the NDVI index increased from 0.012 to 0.025 after AuSi-NPs application. The distribution of leaf trichomes improved and the grain yield increased from 2.47 t ha-1 to 3.29 t ha-1 after ZnO-NPs application. AuSi-NPs treatment resulted in a higher content of essential linoleic acid (54.37%) when compared to the NPs-free control (51.57%), which had a higher determined oleic acid. No NPs or residual translocated metals were detected in the fully ripe sunflower seeds, except for slightly higher silica content after the AuSi-NPs treatment. Additionally, AuSi-NPs and NPs-free control showed wide insect biodiversity while ZnO-NPs treatment had the lowest value of phosphorus as anti-nutrient. Contradictory but insignificant effect on physiology, yield, and insect biodiversity was observed in Fe3O4-NPs treatment. Therefore, further studies are needed to fully understand the long-term environmental and agricultural sustainability of NPs applications.

Mycosynthesis of Metal-Containing Nanoparticles-Fungal Metal Resistance and Mechanisms of Synthesis.

In the 21st century, nanomaterials play an increasingly important role in our lives with applications in many sectors, including agriculture, biomedicine, and biosensors. Over the last two decades, extensive research has been conducted to find ways to synthesise nanoparticles (NPs) via mediation with fungi or fungal extracts. Mycosynthesis can potentially be an energy-efficient, highly adjustable, environmentally benign alternative to conventional physico-chemical procedures. This review investigates the role of metal toxicity in fungi on cell growth and biochemical levels, and how their strategies of resistance, i.e., metal chelation, biomineral formation, biosorption, bioaccumulation, compartmentalisation, and efflux of metals from cells, contribute to the synthesis of metal-containing NPs used in different applications, e.g., biomedical, antimicrobial, catalytic, biosensing, and precision agriculture. The role of different synthesis conditions, including that of fungal biomolecules serving as nucleation centres or templates for NP synthesis, reducing agents, or capping agents in the synthesis process, is also discussed. The authors believe that future studies need to focus on the mechanism of NP synthesis, as well as on the influence of such conditions as pH, temperature, biomass, the concentration of the precursors, and volume of the fungal extracts on the efficiency of the mycosynthesis of NPs.

Current Strategies for Selenium and Iodine Biofortification in Crop Plants.

Selenium and iodine are essential trace elements for both humans and animals. Among other things, they have an essential role in thyroid function and the production of important hormones by the thyroid gland. Unfortunately, in many areas, soils are deficient in selenium and iodine, and their amount is insufficient to produce crops with adequate contents to cover the recommended daily intake; thus, deficiencies have an endemic character. With the introduction of iodized table salt in the food industry, the thyroid status of the population has improved, but several areas remain iodine deficient. Furthermore, due to the strong relationship between iodine and selenium in metabolic processes, selenium deficiency often compromises the desired positive impact of salt iodization efforts. Therefore, a considerable number of studies have looked for alternative methods for the simultaneous supplementation of selenium and iodine in foodstuff. In most cases, the subject of these studies is crops; recently, meat has also been a subject of interest. This paper reviews the most recent strategies in agriculture to fortify selenium and iodine in crop plants, their effect on the quality of the plant species used, and the potential impact of food processing on their stability in fortified crops.

Preconcentration and Separation of Gold Nanoparticles from Environmental Waters Using Extraction Techniques Followed by Spectrometric Quantification.

The quantification of gold nanoparticles (AuNP) in environmental samples at ultratrace concentrations can be accurately performed by sophisticated and pricey analytical methods. This paper aims to challenge the analytical potential and advantages of cheaper and equally reliable alternatives that couple the well-established extraction procedures with common spectrometric methods. We discuss several combinations of techniques that are suitable for separation/preconcentration and quantification of AuNP in complex and challenging aqueous matrices, such as tap, river, lake, brook, mineral, and sea waters, as well as wastewaters. Cloud point extraction (CPE) has been successfully combined with electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma mass spectrometry (ICP-MS), chemiluminescence (CL), and total reflection X-ray fluorescence spectrometry (TXRF). The major advantage of this approach is the ability to quantify AuNP of different sizes and coatings in a sample with a volume in the order of milliliters. Small volumes of sample (5 mL), dispersive solvent (50 µL), and extraction agent (70 µL) were reported also for surfactant-assisted dispersive liquid-liquid microextraction (SA-DLLME) coupled with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). The limits of detection (LOD) achieved using different combinations of methods as well as enrichment factors (EF) varied greatly, being 0.004-200 ng L-1 and 8-250, respectively.

Intragenomic Variability of ITS Sequences in Bjerkandera adusta.

Bjerkandera adusta is a species of common white rot polyporoid fungi found worldwide. Despite playing an important role in deadwood decay, the species strains are used in bioremediation due to its ability to degrade polycyclic hydrocarbons and some of them are important etiological agents of chronic coughs and are associated with lung inflammations. In our experiments, diversity within the species was investigated using molecular approaches and we found that sequence diversity seen at ITS sequence level is not due to cryptic speciation but to intragenomic variability of ITS sequences in this species.

Effects of Foliar Application of ZnO Nanoparticles on Lentil Production, Stress Level and Nutritional Seed Quality under Field Conditions.

Nanotechnology offers new opportunities for the development of novel materials and strategies that improve technology and industry. This applies especially to agriculture, and our previous field studies have indicated that zinc oxide nanoparticles provide promising nano-fertilizer dispersion in sustainable agriculture. However, little is known about the precise ZnO-NP effects on legumes. Herein, 1 mg·L-1 ZnO-NP spray was dispersed on lentil plants to establish the direct NP effects on lentil production, seed nutritional quality, and stress response under field conditions. Although ZnO-NP exposure positively affected yield, thousand-seed weight and the number of pods per plant, there was no statistically significant difference in nutrient and anti-nutrient content in treated and untreated plant seeds. In contrast, the lentil water stress level was affected, and the stress response resulted in statistically significant changes in stomatal conductance, crop water stress index, and plant temperature. Foliar application of low ZnO-NP concentrations therefore proved promising in increasing crop production under field conditions, and this confirms ZnO-NP use as a viable strategy for sustainable agriculture.

Mycosynthesis of Metal-Containing Nanoparticles-Synthesis by Ascomycetes and Basidiomycetes and Their Application.

Fungi contain species with a plethora of ways of adapting to life in nature. Consequently, they produce large amounts of diverse biomolecules that can be generated on a large scale and in an affordable manner. This makes fungi an attractive alternative for many biotechnological processes. Ascomycetes and basidiomycetes are the most commonly used fungi for synthesis of metal-containing nanoparticles (NPs). The advantages of NPs created by fungi include the use of non-toxic fungus-produced biochemicals, energy efficiency, ambient temperature, pressure conditions, and the ability to control and tune the crystallinity, shape, and size of the NPs. Furthermore, the presence of biomolecules might serve a dual function as agents in NP formation and also capping that can tailor the (bio)activity of subsequent NPs. This review summarizes and reviews the synthesis of different metal, metal oxide, metal sulfide, and other metal-based NPs mediated by reactive media derived from various species. The phyla ascomycetes and basidiomycetes are presented separately. Moreover, the practical application of NP mycosynthesis, particularly in the fields of biomedicine, catalysis, biosensing, mosquito control, and precision agriculture as nanofertilizers and nanopesticides, has been studied so far. Finally, an outlook is provided, and future recommendations are proposed with an emphasis on the areas where mycosynthesized NPs have greater potential than NPs synthesized using physicochemical approaches. A deeper investigation of the mechanisms of NP formation in fungi-based media is needed, as is a focus on the transfer of NP mycosynthesis from the laboratory to large-scale production and application.

Fungal Mobilization of Selenium in the Presence of Hausmannite and Ferric Oxyhydroxides.

Bioleaching of mineral phases plays a crucial role in the mobility and availability of various elements, including selenium. Therefore, the leachability of selenium associated with the surfaces of ferric and manganese oxides and oxyhydroxides, the prevailing components of natural geochemical barriers, has been studied in the presence of filamentous fungus. Both geoactive phases were exposed to selenate and subsequently to growing fungus Aspergillus niger for three weeks. This common soil fungus has shown exceptional ability to alter the distribution and mobility of selenium in the presence of both solid phases. The fungus initiated the extensive bioextraction of selenium from the surfaces of amorphous ferric oxyhydroxides, while the hausmannite (Mn3O4) was highly susceptible to biodeterioration in the presence of selenium. This resulted in specific outcomes regarding the selenium, iron, and manganese uptake by fungus and residual selenium concentrations in mineral phases as well. The adverse effects of bioleaching on fungal growth are also discussed.

Impact of Bulk ZnO, ZnO Nanoparticles and Dissolved Zn on Early Growth Stages of Barley-A Pot Experiment.

Zinc is among the most in-demand metals in the world which also means that a considerable amount of this element is released to the environment each year as a result of human activities. A pot experiment was conducted to study the impact of low- and high-dose zinc amendments on plant growth and biomass yield, with Calcic Chernozem as a growing medium and barley (Hordeum vulgare L.) as a model plant. The distribution of zinc in various plant parts was also investigated. Zn (II) was added in powder as bulk ZnO and in solution as ZnO nanoparticles and ZnSO4 in two dosages (3 and 30 mmol kg-1 soil) prior to planting. The plants were harvested after 10 days of growth. The three sets of data were taken under identical experimental conditions. The application of zinc in aqueous solution and in particulate form (having particle sizes in the range of <100 nm to >500 nm) at concentration of 3 and 30 mmol Zn kg-1 to the soil resulted in decreased growth (root length, shoot length) and biomass yield; the only exception was the addition of 30 mmol Zn kg-1 in the form of bulk ZnO, which had a positive effect on the root growth. The dry weight reduction (sprout biomass) was lowest in plants grown in soil treated with dissolved zinc. There were no statistically significant changes in the content of chlorophyll a, chlorophyll b, and total chlorophyll, although flame atomic absorption spectrometry (FAAS) analysis indicated that plants bioaccumulated the zinc applied. This implies that the transport of zinc into the above-ground plant parts is controlled by the presence of effective mechanical and physiological barriers in roots. Crop performance under zinc stress in relation to biomass production and the growth of roots and shoots is also partly a reflection of the effects of soil properties. Our findings emphasize the importance of considering plant-soil interactions in research of potential toxicity and bioavailability of zinc in the environment.

Fungus Aspergillus niger Processes Exogenous Zinc Nanoparticles into a Biogenic Oxalate Mineral.

Zinc oxide nanoparticles (ZnO NPs) belong to the most widely used nanoparticles in both commercial products and industrial applications. Hence, they are frequently released into the environment. Soil fungi can affect the mobilization of zinc from ZnO NPs in soils, and thus they can heavily influence the mobility and bioavailability of zinc there. Therefore, ubiquitous soil fungus Aspergillus niger was selected as a test organism to evaluate the fungal interaction with ZnO NPs. As anticipated, the A. niger strain significantly affected the stability of particulate forms of ZnO due to the acidification of its environment. The influence of ZnO NPs on fungus was compared to the aqueous Zn cations and to bulk ZnO as well. Bulk ZnO had the least effect on fungal growth, while the response of A. niger to ZnO NPs was comparable with ionic zinc. Our results have shown that soil fungus can efficiently bioaccumulate Zn that was bioextracted from ZnO. Furthermore, it influences Zn bioavailability to plants by ZnO NPs transformation to stable biogenic minerals. Hence, a newly formed biogenic mineral phase of zinc oxalate was identified after the experiment with A. niger strain's extracellular metabolites highlighting the fungal significance in zinc biogeochemistry.

Foliar Application of Low Concentrations of Titanium Dioxide and Zinc Oxide Nanoparticles to the Common Sunflower under Field Conditions.

Nano-fertilisers have only recently been introduced to intensify plant production, and there still remains inadequate scientific knowledge on their plant-related effects. This paper therefore compares the effects of two nano-fertilisers on common sunflower production under field conditions. The benefits arising from the foliar application of micronutrient-based zinc oxide fertiliser were compared with those from the titanium dioxide plant-growth enhancer. Both the zinc oxide (ZnO) and titanium dioxide (TiO2) were delivered by foliar application in nano-size at a concentration of 2.6 mg·L-1. The foliar-applied nanoparticles (NPs) had good crystallinity and a mean size distribution under 30 nm. There were significant differences between these two experimental treatments in the leaf surfaces' trichomes diversity, ratio, width, and length at the flower-bud development stage. Somewhat surprisingly, our results established that the ZnO-NPs treatment induced generally better sunflower physiological responses, while the TiO2-NPs primarily affected quantitative and nutritional parameters such as oil content and changed sunflower physiology to early maturation. There were no differences detected in titanium or zinc translocation or accumulation in the fully ripe sunflower seeds compared to the experimental controls, and our positive results therefore encourage further nano-fertiliser research.

Partitioning and stability of ionic, nano- and microsized zinc in natural soil suspensions.

Batch experiments aimed at solid-liquid distribution of 40 nm engineered zinc oxide nanoparticles (ZnO-NP), microparticles (bulk ZnO), and ionic Zn in ZnSO4 solution were conducted on eight field soil samples of different characteristics to identify how the form of Zn affects its distribution in soil. The concentration of Zn in different size fractions present in supernatant solutions obtained from centrifuged soil suspensions was also measured. The distribution between a liquid and a solid was different for the ionic Zn (ZnSO4) and particulate Zn (ZnO-NP and bulk ZnO). In acidic soil solutions, the partitioning coefficient (KdA) of the ionic Zn was in range of 14.7-15.9 compared to 133.4-194.1 for ZnO-NP and bulk ZnO. The situation was reversed under alkaline conditions resulting in a decreased retention of particulate forms of Zn by the solids, with ZnO-NP showing KdA of 8.5-23.4 compared to 160.0-760.1 of ionic Zn. Soil pH thus appears to be the predominant factor influencing the solid-liquid distribution of Zn in different forms. Even the distribution of Zn in different size fractions is heavily affected by the soil pH, causing dissolution of ZnO-NP and bulk ZnO in acidic soils. In alkaline soils, applied ionic Zn (ZnSO4) remained dissolved. This study shows that ZnO-NP are the most mobile of the three tested forms of Zn in alkaline soils. This may affect the spatial distribution of Zn in soil and potentially increase the effectivity of the application of Zn fertilizer when in nanoparticle form.

Effect of Foliar Spray Application of Zinc Oxide Nanoparticles on Quantitative, Nutritional, and Physiological Parameters of Foxtail Millet (Setaria italica L.) under Field Conditions.

It has been shown that the foliar application of inorganic nano-materials on cereal plants during their growth cycle enhances the rate of plant productivity by providing a micro-nutrient source. We therefore studied the effects of foliarly applied ZnO nanoparticles (ZnO NPs) on Setaria italica L. foxtail millet's quantitative, nutritional, and physiological parameters. Scanning electron microscopy showed that the ZnO NPs have an average particle size under 20 nm and dominant spherically shaped morphology. Energy dispersive X-ray spectrometry then confirmed ZnO NP homogeneity, and X-ray diffraction verified their high crystalline and wurtzite-structure symmetry. Although plant height, thousand grain weight, and grain yield quantitative parameters did not differ statistically between ZnO NP-treated and untreated plants, the ZnO NP-treated plant grains had significantly higher oil and total nitrogen contents and significantly lower crop water stress index (CWSI). This highlights that the slow-releasing nano-fertilizer improves plant physiological properties and various grain nutritional parameters, and its application is therefore especially beneficial for progressive nanomaterial-based industries.

Nanogold Biosynthesis Mediated by Mixed Flower Pollen Grains.

Physical and chemical methods for nanoparticle synthesis are disadvantageous to less energy demanding and more efficient and environmentally friendly biological approaches. Thus, in this paper, we designed simple, bottom-up, in vitro, static experiment under laboratory conditions using suspension of mixed flower pollen grains for nanoparticle synthesis. Pollen grains provided template substrates for gold nanoparticles synthesis from dissolved Au(III). Transmission and scanning electron microscopy along with ultraviolet-visible spectra confirmed the gold nanoparticles formation. The biosynthesized/phytosynthesized gold nanoparticles had relative narrow size distribution (from 3 to 11 nm) with dominant spherical morphology with no aggregated forms. Thus, the gold nanoparticles in pollen dispersion provides excellent stability and dispersity.

Increased Colloidal Stability and Decreased Solubility-Sol-Gel Synthesis of Zinc Oxide Nanoparticles with Humic Acids.

Adding the humic acid coating to the nanoparticles of zinc oxide (ZnO-NP) may improve the properties necessary for their colloidal stability. To show how humic acid coating affects the properties of ZnO-NP, three differently sol-gel synthesized ZnO-NP were synthesized: pristine zinc oxide nanoparticles without coating (p-ZnO-NP) and humic acid coated zinc oxide nanoparticles at two different initial concentrations of 20 mg/L (HA20-ZnO-NP) and 200 mg/L (HA200-ZnO-NP) of humic acids in the starting solution. All ZnO-NP were found to be nanocrystals of mineral zincite exhibiting wurtzite crystal symmetry. Transmission electron microscopy showed that capping by humic acids during synthesis decreased the size of HA20-ZnO-NP and HA200-ZnO-NP compared to p-ZnO-NP nanoparticles. Via experiments, HA20-ZnO-NP were found to dissolve less and have a similar or higher stability than both p-ZnO-NP and HA200-ZnO-NP.