Lanthanum (La) and cerium (Ce) are one of the most abundant rare earth elements (REEs). In spite of quite extensive studying of the effects of these lanthanides on biota, some contradictions remain ...in the results. Also little is known about the effect of lanthanum and cerium on plant cells and their mitotic cycle, especially in soils. In this study, the effects of La and Ce in solutions and soil samples on root growth, mitotic index (MI) and frequency of aberrant cells (FAC) were assayed using one of the most convenient objects for testing of cytotoxicity – onion Allium cepa L. Bulbs were germinated on media containing La and Ce in concentrations 0–200 mg/l and 0–50 mg/l respectively for solutions and 0–200 mg/kg for soil samples. After 5 days of germination in solutions, a significant decrease in root elongation and MI in apical meristem cells are shown. We have also observed an increase in the number of cells with aberrations at 50 mg/l La and Ce concentration. The number of observed stickiness and disturbed metaphase has increased significantly. Soil samples turned out to be less toxic compared to the solutions probably due to the decreased availability of REEs. In spite of this, significant cytotoxicity of soil samples containing the highest concentration of La and Ce (200 mg/kg) is observed. The latter may indicate the importance of considering the cytotoxicity of soils containing high lanthanides concentrations – in extraction and production areas and actively fertilized fields.
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•La and Ce inhibit cell division in onion root tips.•La and Ce increase the frequency of aberrant cells.•Cytotoxic effects of Ce is observed at lower concentration compared to La.•Toxic effects of La and Ce are less pronounced in the soil than in the solution.•La and Ce cause the disturbed metaphase and chromosome stickiness.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
This study aims to compare photoacoustic (FTIR–PAS), diffuse reflectance (DRIFT), and attenuated total reflection (ATR) FTIR modalities in the wide wavenumber range from NIR (7500 cm−1) to FIR (150 ...cm−1) for the same silicate soil samples under the same conditions. The possibilities of non-destructive rapid qualitative analysis of soils by these modalities without comprehensive data treatment were compared. The assignment of more than 100 bands for the chernozem and sod-podzolic as common types of silicate types of soil was made. The following groups of bands of organic matter and inorganic matrix were reliably found in spectra of all or at least two modalities: 3690–3680 cm−1 (hydrogen-bonded SiO–H…H2O stretch, not ATR), 2930–2910 cm−1 and 2860–2850 cm−1 (methylene stretch), 1390–1380 cm−1, (symmetric stretch carboxylate, DRIFT and FTIR–PAS); 2000–1990 cm−1, 1885 cm−1, and 1790–1783 cm−1 (SiO2 overtones, DRIFT and FTIR–PAS), 1163–1153 cm−1, SiO2 lattice (not FTIR–PAS), 1037 cm−1 (Si–O or Al–O stretch), 796 cm−1 (lattice symmetrical Si–O–Si stretch); 697 cm−1, SiO2; and 256 cm−1 (not FTIR–PAS). Amide I, II, and III bands appear in DRIFT and FTIR–PAS spectra while not in ATR. Except for methylene and carboxylate groups, CH vibrations (3100–2900 cm−1) are not seen in ATR. Bands at 1640–1630 cm−1, 1620–1610 cm−1, 1600–1598 cm−1 (primary water bands and probably carboxylate) appear in the spectra of all three modalities but are unresolved and require data treatment. It is preferable to use all three modalities to characterize both soil organic matter and mineral composition. DRIFT provides the maximum number of bands in all three modalities and should be selected as a primary technique in the NIR and 4000–2000 cm−1 regions for hydrogen-bonding bands, CHX groups, and the silicate matrix. ATR–FTIR complements DRIFT and provides a good sensitivity for soil water and the matrix in 2000–400 cm−1. FTIR–PAS in 4000–1500 cm−1 reveals more bands than DRIFT and shows the highest sensitivity for absorption bands that do not appear in DRIFT or ATR-IR spectra. Thus, FTIR–PAS is expedient for supporting either DRIFT or ATR–FTIR. This modality comparison can be a basis for methodological support of IR spectroscopy of soils and similar organomineral complexes.
High-resolution mass spectra of natural organic matter (NOM) contain a large number of noise signals. These signals interfere with the correct molecular composition estimation during nontargeted ...analysis because formula-assignment programs find empirical formulas for such peaks as well. Previously proposed noise filtering methods that utilize the profile of the intensity distribution of mass spectrum peaks rely on a histogram to calculate the intensity threshold value. However, the histogram profile can vary depending on the user settings. In addition, these algorithms are not automated, so they are handled manually. To overcome the mentioned drawbacks, we propose a new algorithm for noise filtering in mass spectra. This filter is based on Gaussian Mixture Models (GMMs), a machine learning method to find the intensity threshold value. The algorithm is completely data-driven and eliminates the need to work with a histogram. It has no customizable parameters and automatically determines the noise level for each individual mass spectrum. The algorithm performance was tested on mass spectra of natural organic matter obtained by averaging a different number of microscans (transients), and the results were compared with other noise filters proposed in the literature. Finally, the effect of this noise filtering approach on the fraction of peaks with assigned formulas was investigated. It was shown that there is always an increase in the identification rate, but the magnitude of the effect changes with the number of microscans averaged. The increase can be as high as 15%.
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IJS, KILJ, NUK, PNG, UL, UM
Rare earth elements (REEs) have received enormous attention in recent years. However, there are many gaps in the understanding of their behavior in the soil-plant system. The aim of this study is to ...investigate the behavior of three most common REEs (La, Ce, Nd) in the soil-plant system directly on soil samples using barley (Hordeum vulgare L.) in a vegetation experiment. We attribute the absence of significant changes in plant biomass and photosynthetic pigment content to the reduced availability of REEs in soil samples. The concentration of water-soluble forms of La, Ce and Nd didn't exceed 1 mg/kg, while the concentration of exchangeable forms varied and decreased in a row La > Ce > Nd. The transfer factor (TF) from soil to above-ground biomass was low for all three elements (<1). The stem-to-leaf TF increased with the increase in REEs concentration in soil. The concentration in plant material increased in the row Ce < Nd < La. REEs concentrations in barley leaves didn't exceed 1–3% of the corresponding element concentration in soil samples. REEs concentration in plant tissues is in close direct correlation with the REEs total concentration in soil, water-soluble and exchange forms. REEs concentration in barley leaves is 3–4 times higher than in the stems and for the group with extraneous concentration of 200 mg/kg for La, Ce and Nd was 6.20 ± 1.48, 2.10 ± 0.51, 6.90 ± 3.00 mg/kg, respectively. We show that there were no major changes in barley plants, but further study is needed of the relationship between the absorption of lanthanides by plants and the content of various forms of lanthanides in the soil.
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•No changes in barley plants biomass due to extraneous La, Ce and Nd in soil.•No changes in chlorophyll content in plants grown on soil with extraneous REE's.•Introduction of REEs into soil samples promotes REEs inflow into barley plants.•Barley leaves accumulate more lanthanides than stems.•La, Ce, Nd show different degrees of extraction of exchange forms from the soil.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
FTIR photoacoustic spectroscopy was used to approach inorganic matrix components and organic-matter constituents of chernozem size fractions (1–5000 μm, by dry sieving) with a different history of ...use (from intact steppe to permanent bare fallow, a continuous long-term field experiment). The conditions of FTIR photoacoustic measurements in continuous-scan modes were compared with attenuated total reflection measurements, the advantages of photoacoustic measurements resulting from a higher intensity of the incident radiation and signal-generating volume were discussed. Overtone peaks of quartz as a soil matrix component at 2000–1700 cm–1 were selected as a possible internal-standard (guide) bands for the comparison of photoacoustic spectra. For different land-use samples, differences in the composition were found, which are differently manifested in normalized spectra of size fractions, with millimeter-size, 20–100 μm, and silt fraction bearing the maximum information.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Granulometric aggregate fractions (20 µm–2 mm) of chernozem soils with different agriculture-use histories (native steppe, permanent bare fallow, arable land, and shelterbelt) were investigated in ...mid-IR and far IR regions (4000–100 cm−1) by heating in the air from 25 to 215 °C, using ATR FTIR and linear discriminant analysis to differentiate the land-use samples without chemical perturbation. The temperature dependences of the band maxima significantly differed for bands of silicate matrix and bands with the contribution of soil organic matter and were more stable to experimental conditions compared to the absolute positions. The thermal behavior of the integral intensities of the IR bands at 790–750 cm−1 and 440–420 cm−1 that was different compared to pure quartz, may be attributed to –C–H bending of alkanes and (poly)aromatic structures and skeletal bending, and could be used to distinguish intact soils from agriculturally used samples. The different temperature behaviors of the bands for fractions of soils with different land use are shown, with the maximum difference in fractions below 20–50 µm and medium fractions (50–200 µm). Changes in the band-maximum frequencies and the integral intensities of the bands were reversible for a heating–cooling cycle. The linear discriminant analysis of the spectra obtained for granulometric fractions of chernozem soils made it possible to separate the samples of native steppe, arable land, bare fallow, and shelterbelt with a high probability based on the type of vegetation and agrogenic load, mainly on the basis of the spectral ranges associated with biogenic forms of quartz and phytoliths.
Nanoparticles based on biocompatible methoxy poly(ethylene glycol)-
-poly(D,L-lactide) (mPEG
-
-P(D,L)LA
) copolymers as potential vehicles for the anticancer agent oxaliplatin were prepared by a ...nanoprecipitation technique. It was demonstrated that an increase in the hydrophobic PLA block length from 62 to 173 monomer units leads to an increase of the size of nanoparticles from 32 to 56 nm. Small-angle X-ray scattering studies confirmed the "core-corona" structure of mPEG
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-P(D,L)LA
nanoparticles and oxaliplatin loading. It was suggested that hydrophilic oxaliplatin is adsorbed on the core-corona interface of the nanoparticles during the nanoprecipitation process. The oxaliplatin loading content decreased from 3.8 to 1.5% wt./wt. (with initial loading of 5% wt./wt.) with increasing PLA block length. Thus, the highest loading content of the anticancer drug oxaliplatin with its encapsulation efficiency of 76% in mPEG
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-P(D,L)LA
nanoparticles can be achieved for block copolymer with short hydrophobic block.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
A 68-element survey study was carried out on micro-impurities from 20 commercial nanodiamond samples from eight international manufacturers. The measurements were made using inductively coupled ...plasma atomic emission spectroscopy with detection limits for most elements below 1ppm. Various methods of sample preparation were compared: direct introduction of suspensions, ashing with microwave-assisted acid digestion, and microwave-assisted acid extraction, and their advantages and disadvantages evaluated. The work demonstrates the feasibility of nanodiamond analysis by direct slurry nebulization, which provides a multi-element, rapid, simple, and relatively low-cost route for nanodiamond purity estimation. Most of the samples contain relatively high amounts of Fe, Na, Ca, Si, Cu, Al, S, and Ti (>100ppm), while Pb, Zn, K, Mn, B, Cr, Mg, Mo, Sn, W, Ba, Sb, Co, and Sr are at low but significant amounts. In addition, in several samples, we found some uncommon elements like Ag, Ce, Y, Hf, Zr, and Hg. This study provides new possibilities for certifying nanodiamond purity, understanding their properties and behavior, and advancing their production technology.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Fourier-transform infrared (FTIR) spectroscopy provides rapid, reliable, quantitative, and qualitative analysis of samples in different aggregation states, i.e., gases, thin films, solids, liquids, ...etc. However, when analyzing aqueous solutions, particular issues associated with the rather pronounced IR absorption characteristics of water appear to interfere with the solute determination. In this review, Fourier-transform infrared spectroscopic techniques and their analytical capabilities for analyzing aqueous solutions are reviewed, and highlight examples are discussed.
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BFBNIB, GIS, IJS, KISLJ, NUK, PNG, UL, UM, UPUK
TldD and TldE proteins are involved in the biosynthesis of microcin B17 (MccB17), an Escherichia coli thiazole/oxazole-modified peptide toxin targeting DNA gyrase. Using a combination of biochemical ...and crystallographic methods we show that E. coli TldD and TldE interact to form a heterodimeric metalloprotease. TldD/E cleaves the N-terminal leader sequence from the modified MccB17 precursor peptide, to yield mature antibiotic, while it has no effect on the unmodified peptide. Both proteins are essential for the activity; however, only the TldD subunit forms a novel metal-containing active site within the hollow core of the heterodimer. Peptide substrates are bound in a sequence-independent manner through β sheet interactions with TldD and are likely cleaved via a thermolysin-type mechanism. We suggest that TldD/E acts as a “molecular pencil sharpener”: unfolded polypeptides are fed through a narrow channel into the active site and processively truncated through the cleavage of short peptides from the N-terminal end.
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•E. coli proteins TldD and TldE form a heterodimeric metalloprotease•Binding of peptides within the active-site cleft is not sequence-specific•Specificity is controlled through the access of substrates via a narrow channel•Peptides enter the channel N-terminus first and are processively digested
Ghilarov et al. crystallized the microcin-processing E. coli metalloprotease TldD/E in complex with various substrates, and used this structural information to explain the unusual specificity of the enzyme.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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