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.

Hydrodynamic Cavitation as a Method of Removing Surfactants from Real Carwash Wastewater.

The present work aimed to evaluate whether the use of an innovative method such as hydrodynamic cavitation (HC) is suitable for the simultaneous removal of surfactants of different chemical natures (non-ionic, anionic and cationic) from actual car wash wastewater at different numbers of passes through the cavitation zone and different inlet pressures. An additional novelty was the use of multi-criteria decision support, which enabled the selection of optimal HC conditions that maximized the removal of each group of surfactants and chemical oxygen demand (COD) with minimal energy input. For the optimal HC variants, Fourier transform infrared spectroscopy (FT-IR/ATR) as well as investigations of surface tension, zeta potential, specific conductivity, system viscosity and particle size were carried out. The highest reduction of non-ionic surfactants was found at 5 bar inlet pressure and reached 35.5% after 120 min. The most favourable inlet pressure for the removal of anionic surfactants was 3 bar and the removal efficiency was 77.2% after 120 min, whereas the most favourable inlet pressure for cationic surfactant removal was 3 bar, with the highest removal of 20% after 120 min. The obtained results clearly demonstrate that HC may constitute an effective, fast and cost-efficient method for removing surfactants from real industrial wastewater.

Hydrophobization of Cold Plasma Activated Glass Surfaces by Hexamethyldisilazane Treatment.

The objective of this study was to investigate the modification of glass surfaces by the synergistic combination of cold plasma and chemical surface modification techniques. Glass surface hydrophobicity was obtained as a result of various plasma and deposition operational conditions. The mechanisms governing the hydrophobization process were also studied. Glass plates were activated with plasma using different gases (oxygen and argon) at different treatment times, ranging from 30 to 1800 s. Then, the plasma-treated surfaces were exposed to hexamethyldisilazane vapors at different temperatures, i.e., 25, 60, and 100 °C. Complete characterization, including contact angle measurements, surface free energy calculations, 3D profilometry, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy, was accomplished. It was found that the extent of the hydrophobicity effect depends on both the plasma pre-treatment and the specific conditions of the hexamethyldisilazane deposition process. Plasma activation led to the formation of active sites on the glass surface, which promoted the adsorption and reaction of hexamethyldisilazane species, thereby inducing surface chemical modification. Longer plasma pre-treatment resulted in stronger modification on the glass surface, resulting in changes in the surface roughness. The largest water contact angle of ≈100° was obtained for the surface activated by argon plasma for 1800 s and exposed to hexamethyldisilazane vapors at 25 °C. The changes in the surface properties were caused by the introduction of the hydrophobic trimethylsilyl groups onto the glass surface as well as roughness development.

Optimization of Cyanocobalamin (Vitamin B12) Sorption onto Mesoporous Superparamagnetic Iron Oxide Nanoparticles.

The techniques used to detect and quantify cyanocobalamin (vitamin B12) vary considerably in terms of detection sensitivity, from the most sensitive, based on radioisotopes and mass spectrometry (MS) with limits of detection (LOD) in fg mL-1, to fluorescence (FL) and surface plasmon resonance (SPR) biosensors with LOD values in the range of a few µg mL-1. For accurate quantification of an analyte present at trace levels in complex biological matrices, a selective separation and enrichment step is required to overcome matrix interferences and ensure sufficient detection sensitivity. In this study, iron oxide magnetic nanoparticles (IONPs) were used for the extraction and initial preconcentration of cyanocobalamin (vitamin B12). In the dependence of the magnetization on the H-field (hysteresis loop), no coercivity and remanence values were found at 300 K, indicating the superparamagnetic properties of the tested IONPs. Perfluorinated acids were used as amphiphilic agents to allow the sorption of cyanocobalamin onto the IONPs. FT-IR/ATR spectroscopy was used to confirm the sorption of cyanocobalamin on the IONPs. The influence of the addition of a homologous series of perfluorinated acids such as trifluoroacetic acid (TFAA), heptafluorobutyric acid (HFBA), and trichloroacetic acid (TCAA) to the extraction mixture was tested considering their type, mass, and time required for effective sorption. The adsorption kinetics and isotherm, described by the Freundlich and Langmuir equations, were analyzed. The maximum adsorption capacity (qm) exceeded 6 mg g-1 and was 8.9 mg g-1 and 7.7 mg g-1 for HFBA and TCAA, respectively, as the most efficient additives. After the desorption process using aqueous KH2PO4 solution, the sample was finally analyzed spectrophotometrically and chromatographically. The IONP-based method was successfully applied for the isolation of cyanocobalamin from human urine samples. The results showed that the developed approach is simple, cheap, accurate, and efficient for the determination of traces of cyanocobalamin in biological matrices.

Antimicrobial and Apoptotic Efficacy of Plant-Mediated Silver Nanoparticles.

Phytogenically synthesised nanoparticle (NP)-based drug delivery systems have promising potential in the field of biopharmaceuticals. From the point of view of biomedical applications, such systems offer the small size, high surface area, and possible synergistic effects of NPs with embedded biomolecules. This article describes the synthesis of silver nanoparticles (Ag-NPs) using extracts from the flowers and leaves of tansy (Tanacetum vulgare L.), which is known as a remedy for many health problems, including cancer. The reducing power of the extracts was confirmed by total phenolic and flavonoid content and antioxidant tests. The Ag-NPs were characterised by various analytical techniques including UV-vis spectroscopy, scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), Fourier transform infrared (FT-IR) spectroscopy, and a dynamic light scattering (DLS) system. The obtained Ag-NPs showed higher cytotoxic activity than the initial extracts against both human cervical cancer cell lines HeLa (ATCC CCL-2) and human melanoma cell lines A375 and SK-MEL-3 by MTT assay. However, the high toxicity to Vero cell culture (ATCC CCL-81) and human fibroblast cell line WS-1 rules out the possibility of their use as anticancer agents. The plant-mediated Ag-NPs were mostly bactericidal against tested strains with MBC/MIC index ≤4. Antifungal bioactivity (C. albicans, C. glabrata, and C. parapsilosis) was not observed for aqueous extracts (MIC > 8000 mg L-1), but Ag-NPs synthesised using both the flowers and leaves of tansy were very potent against Candida spp., with MIC 15.6 and 7.8 µg mL-1, respectively.

Application of Response Surface Methodology to Design and Optimize Purification of Acetone or Aqueous Acetone Extracts of Hop Cones (Humulus lupulus L.) Using Superparamagnetic Iron Oxide Nanoparticles for Xanthohumol Isolation.

Iron oxide nanoparticles (IONPs) are an ideal sorbent for magnetic dispersion extraction due to their superparamagnetic properties and developed and active surface. This work aims to use IONPs, obtained by chemical co-precipitation, to purify 100% acetone and 50% acetone extracts from hop cones (Humulus lupulus L.) obtained by ultrasonic-assisted solvent extraction. The extracts were purified from bitter acids (i.e., humulones, lupulones) to isolate xanthohumol. The sorption conditions were optimized depending on the composition of the extraction mixture, specifically the mass of IONPs and the time needed to achieve effective sorption using response surface methodology (RSM). An analysis of variance (ANOVA) was performed to assess the adequacy of the developed model, and a good agreement was found between the experimental data and the proposed model. The polynomial equation describing the model is highly significant (p < 0.05), with a precision of Adeq (above 4). This indicates the usefulness of the polynomial regression model for prediction in experimental design. The final products of the purification for 100% acetone extracts and 50% acetone contain 40.58 ± 2.84 µg mL-1 and 57.64 ± 0.83 µg mL-1 of xanthohumol, respectively. The use of 50% acetone extract provides more favorable conditions due to the smaller amount of nanoparticles required for extract purification and a higher recovery of xanthohumol. The development of a reliable multivariate model allowed for the optimization of the extract purification process, resulting in high-purity xanthohumol from natural sources.

Characteristics and Antimicrobial Activities of Iron Oxide Nanoparticles Obtained via Mixed-Mode Chemical/Biogenic Synthesis Using Spent Hop (Humulus lupulus L.) Extracts.

Iron oxide nanoparticles (IONPs) have many practical applications, ranging from environmental protection to biomedicine. IONPs are being investigated due to their high potential for antimicrobial activity and lack of toxicity to humans. However, the biological activity of IONPs is not uniform and depends on the synthesis conditions, which affect the shape, size and surface modification. The aim of this work is to synthesise IONPs using a mixed method, i.e., chemical co-precipitation combined with biogenic surface modification, using extracts from spent hops (Humulus lupulus L.) obtained as waste product from supercritical carbon dioxide hop extraction. Different extracts (water, dimethyl sulfoxide (DMSO), 80% ethanol, acetone, water) were further evaluated for antioxidant activity based on the silver nanoparticle antioxidant capacity (SNPAC), total phenolic content (TPC) and total flavonoid content (TFC). The IONPs were characterised via UV-vis spectroscopy, scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and Fourier-transform infrared (FT-IR) spectroscopy. Spent hop extracts showed a high number of flavonoid compounds. The efficiency of the solvents used for the extraction can be classified as follows: DMSO > 80% ethanol > acetone > water. FT-IR/ATR spectra revealed the involvement of flavonoids such as xanthohumol and/or isoxanthohumol, bitter acids (i.e., humulones, lupulones) and proteins in the surface modification of the IONPs. SEM images showed a granular, spherical structure of the IONPs with diameters ranging from 81.16 to 142.5 nm. Surface modification with extracts generally weakened the activity of the IONPs against the tested Gram-positive and Gram-negative bacteria and yeasts by half. Only the modification of IONPs with DMSO extract improved their antibacterial properties against Gram-positive bacteria (Staphylococcus epidermidis, Staphylococcus aureus, Micrococcus luteus, Enterococcus faecalis, Bacillus cereus) from a MIC value of 2.5-10 mg/mL to 0.313-1.25 mg/mL.

Pretreatment of herbal waste using sonication.

The effect of hydrodynamic cavitation (HC) and the manner it affects the biodegradability of herbal waste suspended on municipal wastewater subjected to mechanical pre-treatment was examined in this paper. The HC was performed at an optimal inlet pressure equal to 3.5 bar and with the cavitation number of 0.11; the number of recirculation passes through the cavitation zone amounted to 30.5. The BOD5/COD ratio was enhanced by more than 70% between the 5th and 10th minute of the process, indicating the enhanced biodegradability of herbal waste shortly. Fiber component analysis, FT-IR/ATR, TGA and SEM analysis were conducted to check the findings and to demonstrate changes in the chemical and morphological structure of herbal waste. It confirmed that hydrodynamic cavitation visibly influenced the herbal composition and their structural morphology, decreased hemicellulose, cellulose and lignin content, but did not form the by-products affecting the subsequent biological treatment of herbal waste.

Unveiling of interactions between foliar-applied Cu nanoparticles and barley suffering from Cu deficiency.

The objective of this study was to evaluate nano-Cu-plant interactions under Cu deficiency. Nano-Cu at rates of 100 and 1000 mg L-1 was applied as foliar spray to Hordeum vulgare L. during increased demand for nutrients at tillering stage. Corresponding treatment with CuSO4 was used to exam the nano-specific effects. Cu compounds-plant leaves interactions were analyzed with spectroscopic and microscopic methods (ICP-OES, FTIR/ATR, SEM-EDS). Moreover, the effect of Cu compounds on plants in terms of biomass, pigments content, lipid peroxidation, antiradical properties, the activity of enzymes involved in plant defense against stress (SOD, CAT, POD, GR, PAL, PPO) and the content of non-enzymatic antioxidants (GSH, GSSG, TPC) was determined after 1 and 7 days of exposure. Cu loading to plant leaves increased over time, but the content of Cu under treatment with nano-Cu at 100 mg L-1 was lower by 76% than CuSO4 at 7th day of exposure. The changes induced by applied Cu compounds in biochemical traits were mostly observed after 1 day. Our data showed that CuSO4 exposure induce oxidative stress (increased MDA level and GSSG content) when compared to control and nano-Cu treated plants. Noteworthy, nano Cu at 100 mg L-1 demonstrated enhanced stress tolerance as indicated by boosted GSH content. After 7 days, the antioxidant response was almost same compared to control sample. However, based on other indicators (pigment content, chlorosis sign, biomass), it should be noted that CuSO4 caused serve oxidative burst of plant which may resulted in damage of defense system. Nano-Cu, especially at 100 mg L-1, showed promising effect on plant health, and obtained results may be useful for optimizing of nano-Cu application as fertilizer agent.

Theoretical determination of the infrared spectra of amorphous polymers.

The simple procedure of calculating the infrared spectra of polymers is presented. It is based on selecting the relevant, medium-size representative fragments of a polymer, for which the vibrational frequencies are computed within the harmonic approximation, in conjunction with the multiparameter scaling techniques. Scaling is necessary to predict the reliable fundamentals, which, along with the calculated intensities and properly chosen band widths, reproduce the observed band shapes with high accuracy. Applications to the three polymers: poly(methyl methacrylate), poly(vinyl acetate), and poly(isopropenyl acetate) are presented. The simulated spectra are in good agreement with the experiment. The assignment of bands is reported. The obtained results indicate strong delocalization of the vibrational modes within polymers, which is in accord with the most recent experimental finding [Macromolecules2008, 41, 2494-2501]. Good agreement between the observed and the calculated spectra of deuterated PMMA confirms the correctness of our approach. The preliminary results obtained for the highly irregular macromolecular compound (vinyl-functionalized silica) are also shown.

Thermophilic and mesophilic biogas production from PLA-based materials: Possibilities and limitations.

Recently, the use of bio-based products, including biodegradable poly(lactic acid) (PLA), has increased, causing their rapid growth in municipal waste streams. The presence of PLA in biowaste may increase biogas production (BP). However, the rate of PLA biodegradation, which affects the time frame of anaerobic digestion, is a key parameter for an efficient process. In this study, detailed kinetics of BP from PLA were determined at 58 °C and 37 °C. At both temperatures, lag phases were observed: 40 days at 37 °C, and 10 days at 58 °C. After the lag phase BP proceeded in two phases, differed in process rate. At 58 °C, during the 1st phase (up to day 30), the rate of BP (rB1,58) equaled about 35 L/(kg OM·d). At the end of this phase, the amount of biogas was 710 L/kg OM, which constituted 84% of the maximal BP (831-849 L/kg OM). In the 2nd phase (10 days), only 13% of maximal BP was produced (rB2,58 of 16.1 L/(kg OM·d)). At 37 °C, maximal BP (obtained after 280 days) was 1.5-fold lower (558-570 L/kg OM) than at 58 °C. In the 1st phase (100 days), rB1,37 was 1.4 L/(kg OM·d); at the end of this phase, BP constituted merely 14% of the maximal BP. A majority of biogas was produced in the 2nd phase (the next 180 days), and rB2,37 doubled to 2.6 L/(kg OM·d)). At 58 °C, intensive biogas production took place when PLA pieces were still visible. At 37 °C, in contrast, biogas was mainly produced when the PLA pieces had been disintegrated. Although PLA anaerobically biodegrades and produces a high yield of biogas, the time frame of PLA digestion is much longer than that of biowaste and, in thermophilic conditions requires separate digesters. In mesophilic conditions, however, is unacceptable at technical scale.

Photoacoustic Spectroscopy of Surface-Functionalized Fe3O4-SiO2 Nanoparticles.

A permanent development of hybrid materials based on the highly absorptive or opaque materials has prompted a need of analytical tools, which are able to overcome obstacles connected with their physicochemical features. Iron oxide (II, III) (Fe3O4) nanoparticles gained a huge attention as supporters, as they are not only easily accessible using various synthetic approaches, but they also exhibit homogeneity and paramagnetic properties, which make them easily separable materials. Nevertheless, the classic infrared spectroscopic studies might meet several problems with characterization of such systems. Therefore, infrared spectroscopy in photoacoustic mode using Fourier transform infrared-photoacoustic infrared spectroscopy (FT-IR PAS) can be an extremely sensitive and exact analytical tool for investigation of the magnetite-based hybrid material surface. Herein, we present a synthesis of Fe3O4 nanoparticles using co-precipitation method with their subsequent encapsulation within silica matrix decorated with different silanes containing various terminal functional groups. The proper syntheses of core/shell structures were confirmed using the FT-IR PAS method. Each spectrum exhibited specific bands corresponding to vibrations of magnetite particles, silica lattice, and particular surface functional groups, which strictly indicated successful grafting of silanes onto Fe3O4 surface.

Adsorption of bentazone in the profiles of mineral soils with low organic matter content.

The current laboratory adsorption study aimed at determination of the values of adsorption distribution coefficient (Kd) of bentazone in the profiles of Arenosols, Luvisols, and Cambisols, which are the most common arable mineral soils in Poland. The study attempted to identify the soil components that bind bentazone and the principal adsorption mechanisms of this compound as well as create a model capable of predicting its adsorption in soils. The Kd values determined in batch experiments after 24 h of shaking were very low, and ranged from 0.05 to 0.30 mL/g for the Ap horizon and 0 to 0.07 mL/g for subsoils. The results indicated that the anionic form of bentazone was adsorbed on organic matter, while in acidic soils the neutral form of bentazone was adsorbed on organic matter and sand. The detailed analyses of mineralogical composition revealed that the principal mineral that was responsible for the adsorption of bentazone was quartz, which content was strongly positively correlated with the sand fraction. In soils with pH < 5 and an organic carbon content of < 0.35%, quartz exhibited much greater affinity for the neutral bentazone form than organic matter. Fourier transform infrared photoacoustic spectroscopy analyses supported by computational methods have shown the most probable mechanisms behind the adsorption of bentazone on quartz. The created model, assuming the adsorption of bentazone on organic matter and on sand and using the spectrophotometrically determined dissociation constant of bentazone, very well explained the Kd variance in the 81 examined soils, while correctly predicting the adsorption based on soil properties described in the published data.

Mature landfill leachate utilization using a cost-effective hybrid method.

The main goal of this study was to investigate the co-digestion of sewage sludge and mature landfill leachate pretreated through hydrodynamic cavitation. The process efficiency was analyzed from the aspects of organics removal, biogas production, kinetics and digestate quality. Energy efficiency of the overall treatment was evaluated as well. A dose of hydrodynamically cavitated leachate of 5% v/v was used as a substrate for co-digestion with sewage sludge at a hydraulic retention time of 20 days. This improved the kinetics, biogas production and corresponding yields, as well as digestate quality. Fourier transform infrared photoacoustic spectroscopy analysis seemed to indicate that no new toxic compounds were formed with co-digestion. The investigated two-stage treatment is recommended as a safe and cost-effective method of utilizing mature leachate.

Application of the multi-parameter SQM harmonic force field, and ESFF harmonic frequencies scaling procedures to the determination of the vibrational spectra of silicon- and sulfur(II)-containing compounds.

Multi-parameter scaling techniques, such as Scaled Quantum Mechanical (SQM) force field [J. Am. Chem. Soc. 105 (1983) 7037-7047; J. Phys. Chem. A 102 (1998) 1412-1424] or Effective Scaling Frequency Factor (ESFF) [Chem. Phys. Lett. 446 (2007) 191-198; J. Mol. Spectrosc. 264 (2010) 66-74] techniques, are very powerful in the theoretical prediction of the vibrational spectra of complex molecules. In the present work sets of transferable SQM and ESFF scaling factors (within the valence coordinates based schemes) that can be applied to silicon- and sulfur(II)-containing compounds have been determined. A number of VDZ- and VTZ-quality basis sets were used in conjunction with the B3LYP density functional. Eight molecules typically used in the synthesis of silica-based materials were chosen, and theoretical modes were assigned to bands detected on their IR or Raman spectra. This set was augmented with a set of 10 auxiliary, sulfur(II)-containing molecules, for which only "pure" vibrations involving S-containing motifs were assigned. This led to the set of more than 600 individual vibrations. Five factors attributed to these motifs were optimized. Scaling factors attributed to the characteristic types of internal coordinates including the second-row atoms and chlorine, which are applicable to the present molecules were preset. Their values, optimized for Baker's training set of molecules [J. Phys. Chem. A 102 (1998) 1412-1424] for all basis sets considered in this work, were also found, extending thus the applicability of the multi-parameter scaling methods. New scaling factors exhibit low statistical uncertainties. Reasonable agreement between experimental and SQM- or ESFF-scaled frequencies was obtained even for the 6-31G* basis set (RMS<12cm(-1)); extension of the basis set by adding polarization function on hydrogen atoms and/or diffuse functions provides significant improvement of the results, for which the RMS values are often (well) below 10 cm(-1). In addition, SQM scaling factors were found to occasionally exhibit large deviations from unity, which is to be contrasted with ESFF scaling factors.