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.

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.

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.

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.

Optimization of the Composition of Mesoporous Polymer-Ceramic Nanocomposite Granules for Bone Regeneration.

Difficult-to-treat bone damage resulting from metabolic bone diseases, mechanical injuries, or tumor resection requires support in the form of biomaterials. The aim of this research was to optimize the concentration of individual components of polymer-ceramic nanocomposite granules (nanofilled polymer composites) for application in orthopedics and maxillofacial surgery to fill small bone defects and stimulate the regeneration process. Two types of granules were made using nanohydroxyapatite (nanoHA) and chitosan-based matrix (agarose/chitosan or curdlan/chitosan), which served as binder for ceramic nanopowder. Different concentrations of the components (nanoHA and curdlan), foaming agent (sodium bicarbonate-NaHCO3), and chitosan solvent (acetic acid-CH3COOH) were tested during the production process. Agarose and chitosan concentrations were fixed to be 5% w/v and 2% w/v, respectively, based on our previous research. Subsequently, the produced granules were subjected to cytotoxicity testing (indirect and direct contact methods), microhardness testing (Young's modulus evaluation), and microstructure analysis (porosity, specific surface area, and surface roughness) in order to identify the biomaterial with the most favorable properties. The results demonstrated only slight differences among the resultant granules with respect to their microstructural, mechanical, and biological properties. All variants of the biomaterials were non-toxic to a mouse preosteoblast cell line (MC3T3-E1), supported cell growth on their surface, had high porosity (46-51%), and showed relatively high specific surface area (25-33 m2/g) and Young's modulus values (2-10 GPa). Apart from biomaterials containing 8% w/v curdlan, all samples were predominantly characterized by mesoporosity. Nevertheless, materials with the greatest biomedical potential were obtained using 5% w/v agarose, 2% w/v chitosan, and 50% or 70% w/v nanoHA when the chitosan solvent/foaming agent ratio was equal to 2:2. In the case of the granules containing curdlan/chitosan matrix, the most optimal composition was as follows: 2% w/v chitosan, 4% w/v curdlan, and 30% w/v nanoHA. The obtained test results indicate that both manufactured types of granules are promising implantable biomaterials for filling small bone defects that can be used in maxillofacial surgery.

Influence of Waste Engine Oil Addition on the Properties of Zeolite-Foamed Asphalt.

The previous studies on asphalt mix and asphalt with waste engine oil addition indicate the possibility of using this type of waste material for the construction of road pavements. The research presented in this paper aimed at the preliminary assessment of possible waste engine oil (WEO) addition to the asphalts foamed with water-soaked zeolites. In this research, synthetic zeolite Na-P1 and natural clinoptilolite were used. In order to improve the foaming effect, the zeolites were soaked with water before dispensing to the asphalt, in the amount of 75% asphalt weight for Na-P1 and 25% for clinoptilolite. The tests were performed for one type of waste engine oil-5W40 and two type of binders: 20/30 and polymer modified 25/55-60. The asphalt parameters such as the dynamic viscosity, penetration and softening point were determined with the addition of WEO and zeolites in the concentration of 0%, 3%, 5%, 7% for both materials. It was found that the WEO addition lowers the viscosity and softening point of asphalt but increases penetration. The zeolite addition affected the change of these parameters to a minor extent or was statistically irrelevant. The chemical analysis of the asphalt samples with WEO addition performed with the X-ray Fluorescence method did not show a significant amount of heavy metals which would increase the probability of low-temperature cracking. The analysis of the results indicates the possibility of using zeolite-foamed asphalt technology with WEO addition.

Modification of Lightweight Aggregates' Microstructure by Used Motor Oil Addition.

An admixture of lightweight aggregate substrates (beidellitic clay containing 10 wt % of natural clinoptilolite or Na-P1 zeolite) with used motor oil (1 wt %-8 wt %) caused marked changes in the aggregates' microstructure, measured by a combination of mercury porosimetry (MIP), microtomography (MT), and scanning electron microscopy. Maximum porosity was produced at low (1%-2%) oil concentrations and it dropped at higher concentrations, opposite to the aggregates' bulk density. Average pore radii, measured by MIP, decreased with an increasing oil concentration, whereas larger (MT) pore sizes tended to increase. Fractal dimension, derived from MIP data, changed similarly to the MIP pore radius, while that derived from MT remained unaltered. Solid phase density, measured by helium pycnometry, initially dropped slightly and then increased with the amount of oil added, which was most probably connected to changes in the formation of extremely small closed pores that were not available for He atoms.