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We cross-linked unfractionated heparin (H) using epichlorohydrin (E), in the absence or presence of imidazole (I), using various ratios of H, E, and I substances. The objectives and goals were to use the reaction for the preparation of medical materials suitable for blood sample applications. Nuclear magnetic resonance indicated the involvement of an H-end sequence [H-(1→4)-β-D-GlcA-(1→3)-β-D-Gal-(1→3)-β-D-Gal-(1→4)-β-D-Xyl-α-Ser] in the linkage with the 2-hydroxypropyl bridge. The yields of the individual experiments were found to increase in the following ratios: 1H/1E/3I (24%) < 1H/1E/2I (32%) < 1H/3E (42%) < 1H/1E/1I (46%) < 1H/2E (64%) < 1H/1E (77%). According to size-exclusion chromatography with multiple-angle light scattering (SEC-MALS) analysis, the mass at the peak increased in the following order: H (9292 g/mol) < 1H/1E (9294 g/mol) < 1H/2E (9326 g/mol) < 1H/3E (9708 g/mol) < 1H/1E/2I (11,212 g/mol) < 1H/1E/3I (12,301 g/mol) < 1H/1E/1I (13,800 g/mol) and in the reverse order with the increase in amount of epichlorohydrin and imidazole, i.e., 1H/1E > 1H/2E > 1H/3E and 1H/1E/1I > 1H/1E/2I > 1H/1E/3I. X-ray diffraction revealed that all prepared films were amorphous. An evaluation of the surface morphology using atomic force microscopy (AFM) confirmed a relatively low films roughness (~0.9–3.6 nm). The surface reduced elastic modulus, determined by the PeakForce quantitative nanomechanical mapping (PF-QNM) technique, was found to increase by up to ~63% for films cross-linked with E in the absence of I when compared with the results for the H substrate. A negligible change in modulus was, however, observed for films cross-linked in the presence of I, or was even reduced by ~15% (1H/1E/3I) compared to that for the H substrate. This could be explained by the parallel cross-linking of H only with E within its serine end unit and in competition with only one nitrogen of I. According to the highest yield (77%) of 1H/1E, the preferred product is the following: H-(1→4)-β-D-GlcA-(1→3)-β-D-Gal-(1→3)-β-D-Gal-(1→4)-β-D-Xyl-α-Ser-CH2-CH(OH)-CH2-OH. For the 1H/1E/1I (46% yield), 1H/1E/2I (32%), and 1H/1E/3I (24%) products, the cross-linked motif was the same, and the difference represented the surplus amount of the imidazolium cation ionically bound to the heparin anionic groups.

In this paper, we present the preparation of few-layer MoS2 films on single-crystal sapphire, as well as on heteroepitaxial GaN templates on sapphire substrates, using the pulsed laser deposition (PLD) technique. Detailed structural and chemical characterization of the films were performed using Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction measurements, and high-resolution transmission electron microscopy. According to X-ray diffraction studies, the films exhibit epitaxial growth, indicating a good in-plane alignment. Furthermore, the films demonstrate uniform thickness on large areas, as confirmed by Raman spectroscopy. The lateral electrical current transport of the MoS2 grown on sapphire was investigated by temperature (T)-dependent sheet resistance and Hall effect measurements, showing a high n-type doping of the semiconducting films (ns from ~1 × 1013 to ~3.4 × 1013 cm−2 from T = 300 K to 500 K), with a donor ionization energy of Ei = 93 ± 8 meV and a mobility decreasing with T. Finally, the vertical current injection across the MoS2/GaN heterojunction was investigated by means of conductive atomic force microscopy, showing the rectifying behavior of the I-V characteristics with a Schottky barrier height of ϕB ≈ 0.36 eV. The obtained results pave the way for the scalable application of PLD-grown MoS2 on GaN in electronics/optoelectronics.

One of the challenges in agriculture practices is guaranteeing an adequate and bioavailable phosphorus supply for plants on phosphorus-deficient soils. A promising alternative lies in the utilization of phosphate nano-fertilizers (NFs) through spray applications. Therefore, this short-term study aimed to investigate the yet undetermined widespread impact of P-NFs on crops characterized by broad leaves, an intensive rate of photosynthesis, and belonging to the oilseed plant, sunflower (Helianthus annuus L.). To achieve this, NFs were applied at lower concentrations of various phosphate-based NFs, including (i) nano-hydroxylapatite (nano-Hap) and (ii) a mixture of nano-calcium zinc phosphate and macro-sized parascholzite (nano/macro-ZnPhos), in comparison to the NF-free control. The study was carried out under authentic field conditions during the 2022 vegetation season at the Dolná Malanta site within the Central European Region. The empirical evidence presented herein indicates that the utilization of biocompatible and bioactive nano-Hap, initially engineered for biomedical applications, and nano/macro-ZnPhos, now foliarly applied at reduced concentrations, elicited a statistically significant elevation in quantitative parameters and seasonal physiological responses. The parameters analyzed included head diameter, dry head weight, seed yield per hectare, nutritional seed oiliness, etc. as well as the physiological normalized difference vegetation index (NDVI), stomatal conductance index (Ig), and crop water stress index (CWSI). In terms of agro-ecological terrestrial bio/diversity, it was evident that the nano/macro-ZnPhos was the most hospitable variant for the terrestric insect community, but surprisingly, the agronomically more popular nano-Hap showed only statistically insignificant changes in the diversity of the detected communities. However, the relevance of outcomes highlighted using nano-fertilizers, supporting the concept of precision and sustainable agriculture under field conditions.

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.

In(Ga)N epitaxial layers were grown on on-axis and off-axis (0001) sapphire substrates with an about 1100 nm-thick GaN buffer layer stack using organometallic chemical vapor deposition at 600 °C. The In(Ga)N layers consisted of a thin (~10–25 nm) continuous layer of small conical pyramids in which large conical pyramids with an approximate height of 50–80 nm were randomly distributed. The large pyramids were grown above the edge-type dislocations which originated in the GaN buffer; the dislocations did not penetrate the large, isolated pyramids. The large pyramids were well crystallized and relaxed with a small quantity of defects, such as dislocations, preferentially located at the contact zones of adjacent pyramids. The low temperature (6.5 K) photoluminescence spectra showed one clear maximum at 853 meV with a full width at half maximum (FWHM) of 75 meV and 859 meV with a FWHM of 80 meV for the off-axis and on-axis samples, respectively.

Since the fate of nanoparticles after their release in the environment and their possible transfer in plants and subsequent impacts is still largely unknown, this paper evaluates the potential phytotoxic effects of up to 20% w/w TiO2 nanoparticles (nTiO2) on barley cultivated in hydroponics and agar media. The X-ray diffraction analysis confirmed that nTiO2 powder corresponds to anatase phase. On agar medium only high concentrations of nTiO2 (10% and 20% w/w) induced significant inhibition of shoot growth. However, hydroponics treatment with nTiO2 up to 1000 mg L−1 did not show any adverse effect on the shoot growth. In both experiments, (i) root growth inhibition effects became visible with increasing concentration of nTiO2, (ii) plants treated with nTiO2 showed no change in chlorophyll a and b content, even though the plants absorbed nTiO2, (iii) weight of biomass treated with nTiO2 was not significantly different compared to control. Therefore, we assume that transport of nTiO2 into the aerial parts is limited due to the presence of effective mechanical or physiological barriers in roots. Overall, it appears that early root growth is a relevant indicator of potential effects of nTiO2 exposure. Our results also indicate that synthesized nTiO2 are not significantly toxic to the barley when applied at the concentrations used in this work, even though plants absorb titanium.

The aim of this work was to evaluate the transformation of manganese oxide (hausmannite) by microscopic filamentous fungus Aspergillus niger and the effects of the transformation on mobility and bioavailability of arsenic. Our results showed that the A. niger strain CBS 140837 greatly affected the stability of hausmannite and induced its transformation into biogenic crystals of manganese oxalates—falottaite and lindbergite. The transformation was enabled by fungal acidolysis of hausmannite and subsequent release of manganese ions into the culture medium. While almost 45% of manganese was bioextracted, the arsenic content in manganese precipitates increased throughout the 25-day static cultivation of fungus. This significantly decreased the bioavailability of arsenic for the fungus. These results highlight the unique A. niger strain’s ability to act as an active geochemical factor via its ability to acidify its environment and to induce formation of biogenic minerals. This affects not only the manganese speciation, but also bioaccumulation of potentially toxic metals and metalloids associated with manganese oxides, including arsenic.

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.

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 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.

In this work, the viability of bioaccumulation and bioextraction processes for arsenic removal from contaminated waters, as well as the recycling of arsenate-treated amorphous ferric oxyhydroxide adsorbent (FeOOH) were evaluated using the common soil microscopic filamentous fungus Aspergillus niger. After treating the contaminated arsenate solution (100 mg As L−1) with FeOOH, the remaining solution was exposed to the growing fungus during a static 19-day cultivation period to further decrease the arsenic concentration. Our data indicated that although the FeOOH adsorbent is suitable for arsenate removal with up to 84% removal efficiency, the fungus was capable of accumulating only up to 13.2% of the remaining arsenic from the culture media. This shows that the fungus A. niger, although highly praised for its application in environmental biotechnology research, was insufficient for decreasing the arsenic contamination to an environmentally acceptable level. However, the bioextraction of arsenic from arsenate-treated FeOOH proved relatively effective for reuse of the adsorbent. Due to its production of acidic metabolites, which decreased pH below 2.7, the fungal strain was capable of removing of up to 98.2% of arsenic from the arsenate-treated FeOOH adsorbent.

Nickel-zinc ferrites are very important soft magnetic materials from the point of view of diverse technical applications (such as, e.g., various electronic devices and components) for their high magnetic permeability and permittivity, low core loss, high resistivity, high Curie temperature as well as mechanical strength and chemical stability. Due to their good absorbing properties, they can be used as microwave absorbing and shielding materials with the aim of decreasing the environmental pollution caused by non-ionizing microwave radiation. The ferrite material incorporated into the polymer matrix creates qualitatively new magneto-polymer composite material taking benefits from both components. The properties typical for polymers (elasticity, mouldability, etc.) are combined with good high-frequency magnetic parameters, thus allowing to utilize these materials, e.g., in high-frequency applications where especially flexibility of composite materials plays a key role. Small amounts of selected rare-earth (RE) ions, in particular Y3+, La3+, Eu3+ and Gd3+ have been embedded into the nickel-zinc ferrite that has been used as the magnetic filler in magnetic polymer composites with polyvinylchloride (PVC) acting as the polymeric matrix. The effect of various types of rare-earth ions on the structural as well as quasi-static and dynamic (electro)magnetic properties of the ferrite fillers as well as ferrite/PVC composites, in particular the frequency dispersion of the complex permeability, has been studied.