Selective Removal of Chlorophyll and Isolation of Lutein from Plant Extracts Using Magnetic Solid Phase Extraction with Iron Oxide Nanoparticles.

In recent years, there has been a growing interest in plant pigments as readily available nutraceuticals. Photosynthetic pigments, specifically chlorophylls and carotenoids, renowned for their non-toxic antioxidant properties, are increasingly finding applications beyond their health-promoting attributes. Consequently, there is an ongoing need for cost-effective methods of isolation. This study employs a co-precipitation method to synthesize magnetic iron oxide nanoparticles. Scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) confirms that an aqueous environment and oxidizing conditions yield nanosized iron oxide with particle sizes ranging from 80 to 140 nm. X-ray photoelectron spectroscopy (XPS) spectra indicate the presence of hydrous iron oxide FeO(OH) on the surface of the nanosized iron oxide. The Brunauer-Emmett-Teller (BET) surface area of obtained nanomaterial was 151.4 m2 g-1, with total pore volumes of pores 0.25 cm3 g-1 STP. The material, designated as iron oxide nanoparticles (IONPs), serves as an adsorbent for magnetic solid phase extraction (MSPE) and isolation of photosynthetic pigments (chlorophyll a, lutein) from extracts of higher green plants (Mentha piperita L., Urtica dioica L.). Sorption of chlorophyll a onto the nanoparticles is confirmed using UV-vis spectroscopy, Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS), and high-performance liquid chromatography (HPLC). Selective sorption of chlorophyll a requires a minimum of 3 g of IONPs per 12 mg of chlorophyll a, with acetone as the solvent, and is dependent on a storage time of 48 h. Extended contact time of IONPs with the acetone extract, i.e., 72 h, ensures the elimination of remaining components except lutein, with a spectral purity of 98%, recovered with over 90% efficiency. The mechanism of chlorophyll removal using IONPs relies on the interaction of the pigment's carbonyl (C=O) groups with the adsorbent surface hydroxyl (-OH) groups. Based on molecular dynamics (MD) simulations, it has been proven that the selective adsorption of pigments is also influenced by more favorable dispersion interactions between acetone and chlorophyll in comparison with other solutes. An aqueous environment significantly promotes the removal of pigments; however, it results in a complete loss of selectivity.

Chemical Studies of Multicomponent Kidney Stones Using the Modern Advanced Research Methods.

Defining the kidney stone composition is important for determining a treatment plan, understanding etiology and preventing recurrence of nephrolithiasis, which is considered as a common, civilization disease and a serious worldwide medical problem. The aim of this study was to investigate the morphology and chemical composition of multicomponent kidney stones. The identification methods such as infrared spectroscopy (FTIR), X-ray diffraction (XRD), and electron microscopy with the EDX detector were presented. The studies by the X-ray photoelectron spectroscopy (XPS) were also carried out for better understanding of their chemical structure. The chemical mapping by the FTIR microscopy was performed to show the distribution of individual chemical compounds that constitute the building blocks of kidney stones. The use of modern research methods with a particular emphasis on the spectroscopic methods allowed for a thorough examination of the subject of nephrolithiasis.

Binary Co-Crystals of Quercetin: Synthesis, Structure, and Spectroscopic Characterization.

A mechanochemical method was used to obtain four new quercetin (QUE) co-crystals. Three co-formers have the systems of the heterocyclic rings with the oxygen and nitrogen atoms and they form co-crystals at the stoichiometric ratio of 1 : 2. In contrast, the QUE : o-dianisidine co-crystal represents the 1 : 1 stoichiometry and the former molecule is the aniline derivative. The X-ray crystallography and FT-IR and FT-Raman spectra revealed formation of the intermolecular O-H…N or N-H…O hydrogen bonds. The dynamics of the hydrogen bonds was investigated using the XPS method. The N 1s XPS spectra showed no proton transfer in the QUE : FEN and QUE : O-DIA co-crystal systems. The QUE : BZFP and QUE : EBZFP show the two-site static disorder across the proton transfer pathway to the pyridine ring, with the occupancies (C=N : C=NH+ ) of 72 : 28 and 77 : 23, respectively.

Reduced Graphene Oxide Modulates the FAK-Dependent Signaling Pathway in Glioblastoma Multiforme Cells In Vitro.

Aggressive invasiveness is a common feature of malignant gliomas, despite their high level of tumor heterogeneity and possible diverse cell origins. Therefore, it is important to explore new therapeutic methods. In this study, we evaluated and compared the effects of graphene (GN) and reduced graphene oxides (rGOs) on a highly invasive and neoplastic cell line, U87. The surface functional groups of the GN and rGO flakes were characterized by X-ray photoelectron spectroscopy. The antitumor activity of these flakes was obtained by using the neutral red assay and their anti-migratory activity was determined using the wound healing assay. Further, we investigated the mRNA and protein expression levels of important cell adhesion molecules involved in migration and invasiveness. The rGO flakes, particularly rGO/ATS and rGO/TUD, were found highly toxic. The migration potential of both U87 and Hs5 cells decreased, especially after rGO/TUD treatment. A post-treatment decrease in mobility and FAK expression was observed in U87 cells treated with rGO/ATS and rGO/TUD flakes. The rGO/TUD treatment also reduced ß-catenin expression in U87 cells. Our results suggest that rGO flakes reduce the migration and invasiveness of U87 tumor cells and can, thus, be used as potential antitumor agents.

Effect of Various Surface Treatments on Wettability and Morphological Properties of Titanium Oxide Thin Films.

The effect of three popular surface activation methods for a titanium oxide (titania) surface was thoroughly investigated to identify the most effective protocol for the enhancement of hydrophilicity. All the methods, namely H2O2 activation, UV irradiation and oxygen plasma treatment resulted in an enhanced hydrophilic titania surface, which was evidenced by the reduced contact angle values. To study in detail the chemical and morphological features responsible for the increased hydrophilicity, the treated surfaces were submitted to inspection with atomic force microscopy and X-ray photoelectron spectroscopy. The correlation between the treatment and titania surface hydroxylation as well as hydrophilic behavior have been discussed.

Immobilization mechanism of Cd2+/HCrO4-/CrO42- ions and carboxin on montmorillonite modified with Rhizobium leguminosarum bv. trifolii exopolysaccharide.

The modification of clay minerals by exopolysaccharides (EPSs) may significantly increase their adsorption capacity. Therefore, this study focused on the impact of the EPS synthesised by the soil bacterium Rhizobium leguminosarum bv. trifolii on the adsorptive features of montmorillonite relative to two heavy metal ions (cadmium/Cd(II) and chromium/Cr(VI)) and a pesticide (carboxin). The characterization of montmorillonite was carried out using various methods: X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy. The adsorption/desorption data were modelled using theoretical equations (Langmuir-Freundlich, Redlich-Peterson, etc.). The obtained results showed that EPS promoted the accumulation of heavy metals on the clay mineral and, simultaneously, contributed to a lower degree of their desorption. This resulted from complexation between the biopolymer and the Cd(II)/Cr(VI) ions. After montmorillonite modification with 100 mg/L EPS, the maximum noted growth in Cd(II) adsorption was 26.10%, whereas it was 20.30% for Cr(VI). The adsorbed amounts of Cd(II) and Cr(VI) were then 24.24 and 14.45 mg/g, respectively. In the case of carboxin, the EPS effect on its adsorption/desorption rates was opposite - its adsorption level decreasing by 10.80%, was 0.27 mg/g. Thus, the presence of EPS-producing bacteria could reduce the bioavailability of the heavy metals, but not of the selected pesticide.

How the Duration and Mode of Photopolymerization Affect the Mechanical Properties of a Dental Composite Resin.

Composite materials are the most common materials in use in modern dentistry. Over the years, the methods of photopolymerization of composite materials have been improved with the use of various devices, such as quartz tungsten halogen lamps (QTHs), light-emitting diode units (LEDs), plasma-arc lamps and argon-ion lasers. This study aimed to compare the mechanical properties of a composite material, depending on the time and mode of photopolymerization. One hundred and forty rectangular specimens (25 × 2 × 2 mm) and forty-two disc-shaped samples (5 mm diameter and 2 mm thickness) were prepared from shade A2 Boston composite resin. Samples were cured using the following seven photopolymerization protocols: four fast-cure modes (full power for 3, 5, 10, and 20 s), two pulse-cure modes (5 and 10 shots of 1 s exposures at full power), and one step-cure mode (soft start with a progressive cycle lasting 9 s). Specimens were subjected to a flexural strength test, Vickers microhardness test, and FTIR spectroscopy test. A 2-factor ANOVA and post-hoc tests were carried out to assess the differences in the flexural strength parameter between the tested groups of samples before and after aging. A mixed-model ANOVA was carried out to assess the differences in the Vickers microhardness parameter between the tested groups of samples before and after aging. The lowest values of flexural strength (p < 0.001) and Vickers microhardness (p < 0.001) were obtained for the 3 s mode for the pre- and post-aging groups. The FTIR mapping tests showed a much more homogeneous chemical structure of the composite after 20 s of continuous irradiation, compared to the sample irradiated for 5 s in the continuous mode. The mode and cure time affects the mechanical properties of the composite resin. Appropriate selection of the cure mode and time ensures better mechanical properties of composite resin. This suggests that the survival of dental restorations within the oral cavity could be extended by using longer photopolymerization durations.

Carboxin and Diuron Adsorption Mechanism on Sunflower Husks Biochar and Goethite in the Single/Mixed Pesticide Solutions.

The study focused on the adsorption mechanism of two selected pesticides: carboxin and diuron, on goethite and biochar, which were treated as potential compounds of mixed adsorbent. The authors also prepared a simple mixture of goethite and biochar and performed adsorption measurements on this material. The adsorbents were characterized by several methods, inter alia, nitrogen adsorption/desorption, Boehm titration, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The adsorption study included kinetics and equilibrium measurements, in the solution containing one or two pesticides simultaneously. The adsorption data were fitted to selected theoretical models (e.g., Langmuir, Freudlich, Redlich-Peterson, pseudo first-order and pseudo second-order equations). Based on the obtained results, it was stated that, among all tested adsorbents, biochar had the highest adsorption capacity relative to both carboxin and diuron. It equaled 0.64 and 0.52 mg/g, respectively. Experimental data were best fitted to the pseudo second-order and Redlich-Peterson models. In the mixed systems, the adsorption levels observed on biochar, goethite and their mixture were higher for diuron and lower for carboxin, compared to those noted in the single solutions. The presented results may enable the development of new mixed adsorbent for remediation of soils polluted with pesticides.

The concentration and changes in freely dissolved polycyclic aromatic hydrocarbons in biochar-amended soil.

The presence of polycyclic aromatic hydrocarbons (PAHs) in biochars hinders their environmental use. The aim of this study was to determine the freely dissolved (Cfree) PAH content in soil amended with biochar in a long-term (851 days) field experiment. Biochar was added to the soil at a rate of 30 and 45 t/ha. The addition of biochar to the soil resulted in a decrease in Σ13 Cfree PAHs by 25 and 22%, in the soil with the addition of biochar at the rate of 30 and 45 t/ha, respectively. As far as individual PAHs are concerned, in most cases a reduction in Cfree was also observed (from 3.6 to 66%, depending on the biochar rate). During the first 105 days of the experiment, the content of Σ13 Cfree in the biochar-amended soil significantly decreased by 26% (30 t/ha) and 36% (45 t/ha). After this period of time until the end of the experiment, no significant changes in Cfree were observed, regardless of the biochar rate. However, the behavior of individual PAH groups differed depending on the number of rings and experimental treatment. Ultimately, after 851 days of the experiment the content of Σ13 Cfree PAHs was lower by 29% (30 t/ha) and 35% (45 t/ha) compared to the beginning of the study as well as lower by 40% (30 t/ha) and 42% (45 t/ha) than in the control soil. The log KTOC coefficients calculated for the biochar-amended soils were higher immediately after adding biochar and subsequently they gradually decreased, indicating the reduced strength of the interaction between biochar and the studied PAHs. The obtained results show that the addition of biochar to soil does not create a risk in terms of the content of Cfree PAHs.

Persistence of polycyclic aromatic hydrocarbons (PAHs) in biochar-amended soil.

In the present study the persistence of polycyclic aromatic hydrocarbons (PAHs) applied with biochar to acidic soil (loamy sand) was studied in two and half year field experiment. An experiment was carried out in three experimental plots (15 m(2) each). The biochar was introduced in the following doses: soil without fertilization - control (C-BC00), soil with 30 t ha(-1) (B-BC30) and soil with 45 t ha(-1) (A-BC45) of biochar. Biochar addition to soils resulted in an increase in the PAHs content from 0.239 µg g(-1) in control soil to 0.526 µg g(-1) and 1.310 µg g(-1) in 30 and 45 t ha(-1) biochar-amended soil respectively. However during the experimental period the PAHs content decreased to a level characteristic for the control soil. The highest losses of PAHs were observed during the first 105 days of the experiment. Three and four rings PAHs were the most susceptible for degradation and leaching. Migration of PAHs from 0-10 cm to 10-20 cm soil horizon was also observed.

Biochar production increases the polycyclic aromatic hydrocarbon content in surrounding soils and potential cancer risk.

The objectives of the study were the identification of the source of contamination of soils and estimation of the potential cancer risk that may be caused by contact with soils situated in the vicinity of biochar production sites. Samples of soils collected in the immediate vicinity of traditional biochar-producing plants, located within the area of the Bieszczady National Park (Poland), were analysed for the content of polycyclic aromatic hydrocarbons (PAHs). The sum of the content of 16 PAHs varied within the range of 1.80-101.3 µg/g, exceeding the norms permitted in many European countries. The calculated coefficients on the basis of which one can determine the origin of PAHs (molecular diagnostic ratios) demonstrated that the potential source of PAHs in the soils may be processes related with the production of biochar. Estimation on the basis of the results of incremental lifetime cancer risks (ILCRs) within the range of 2.33 · 10(-4)-1.05 · 10(-1) indicated that the soils studied may constitute a significant cancer risk for persons who have contact with them. The values of ILCRS should be considered as at least high, which permits the conclusion that sites of that type may create a hazard to human health.

Biochar properties regarding to contaminants content and ecotoxicological assessment.

The objective of the study was the determination of the content of contaminants and toxicity of four different biochars. The properties of the biochars, content of trace metals and polycyclic aromatic hydrocarbons (16 PAHs) were determined. Toxicological estimation of the biochars was performed on the basis of a battery of biotests with plants (Lepidium sativum), bacteria (Vibrio fischeri and 11 different strains from MARA), alga (Selenastrum capricornutum), protozoa (Tetrahymena thermophila) and crustaceans (Daphnia magna). The content of trace metals depended on the biochar and was comparable to uncontaminated soils. PAHs sum varied from 1124 to 28,339 µg/kg. The toxicity of the biochars depended both on their kind and on the test applied. The most sensitive organism was D. magna. Relatively the least sensitive to extracts from the biochars proved to be S. capricornutum and T. thermophila. A significant correlation between the content of PAHs and toxicity was noted only in the case of D. magna.