Alteration of Hordeum vulgare and Sinapis alba germination and early growth in response to airborne low-metallic automotive brake wear debris.

Road transportation significantly contributes to environmental pollution, both in terms of exhaust and non-exhaust (brake wear) emissions. As was proven, brake wear debris is released in a wide variety of sizes, shapes, and compositions. Although studies confirming the possible adverse health and environmental impact of brake wear debris were published, there is no standardized methodology for their toxicity testing, and most studies focus only on one type of brake pad and/or one test. The lack of methodology is also related to the very small amount of material released during the laboratory testing. For these reasons, this study deals with the mixture of airborne brake wear debris from several commonly used low-metallic brake pads collected following the dynamometer testing. The mixture was chosen for better simulation of the actual state in the environment and to collect a sufficient amount of particles for thorough characterization (SEM, XRPD, XRF, chromatography, and particle size distribution) and phytotoxicity testing. The particle size distribution measurement revealed a wide range of particle sizes from nanometers to hundreds of nanometers, elemental and phase analysis determined the standard elements and compounds used in the brake pad formulation. The Hordeum vulgare and Sinapis alba were chosen as representatives of monocotyledonous and dicotyledonous plants. The germination was not significantly affected by the suspension of brake wear debris; however, the root elongation was negatively influenced in both cases. Sinapis alba (IC50 = 23.13 g L-1) was more affected than Hordeum vulgare (IC50 was not found in the studied concentration range) the growth of which was even slightly stimulated in the lowest concentrations of brake wear debris. The plant biomass was also negatively affected in the case of Sinapis alba, where the IC50 values of wet and dry roots were determined to be 44.83 g L-1 and 86.86 g L-1, respectively.

Effective and reproducible biosynthesis of nanogold-composite catalyst for paracetamol oxidation.

Pharmaceutical products are some of the most serious emergent pollutants in the environment, especially nowadays of the COVID-19 pandemic. In this study, nanogold-composite was prepared, and its catalytic activity for paracetamol degradation was investigated. Moreover, for the first time, recycled waste diatomite earth (WDE) from beer filtration was used for reproducible gold nanoparticle (Au NPs) preparation. We studied Au NPs by various psychical-chemical and analytical methods. Transmission and scanning electron microscopy were used for nanogold-composite morphology, size and shape characterization. Total element concentrations were determined using inductively coupled plasma mass and X-ray fluorescence spectrometry. X-ray powder diffraction analysis was used for crystal structure characterization of samples. Fourier transform infrared spectrometer was used to study the chemical changes before and after Au NP formation. The results revealed that the WDE served as both a reducing and a stabilizing agent for crystalline spherical 30 nm Au NPs as well as acting as a direct support matrix. The kinetics of paracetamol degradation was studied by high-performance liquid chromatography with a photodiode array detector. The conversion of paracetamol was 62% and 67% after 72 h in the absence or presence of light irradiation, respectively, with 0.0126 h-1 and 0.0148 h-1 reaction rate constants. The presented study demonstrates the successful use of waste material from the food industry for nanogold-composite preparation and its application as a promising catalyst in paracetamol removal.

Magnetically Modified Biosorbent for Rapid Beryllium Elimination from the Aqueous Environment.

Although both beryllium and its compounds display high toxicity, little attention has been focused on the removal of beryllium from wastewaters. In this research, magnetically modified biochar obtained from poor-quality wheat with two distinct FexOy contents was studied as a sorbent for the elimination of beryllium from an aqueous solution. The determined elimination efficiency was higher than 80% in both prepared composites, and the presence of FexOy did not affect the sorption properties. The experimental qmax values were determined to be 1.44 mg/g for original biochar and biochar with lower content of iron and 1.45 mg/g for the biochar with higher iron content. The optimum pH values favorable for sorption were determined to be 6. After the sorption procedure, the sorbent was still magnetically active enough to be removed from the solution by a magnet. Using magnetically modified sorbents proved to be an easy to apply, low-cost, and effective technique.

Microstructure and Properties of Nanostructured Coating on Ti6Al4V.

Implant surface properties of Ti6Al4V alloy that is currently used as a biocompatible material because of a variety of unique properties can be improved by a self-organized TiO2 layer. The TiO2 nanotubes forming on the titanium-based materials is a relatively recent technology for the surface properties modification and represents pronounced potential in promoting cell adhesion, proliferation, and differentiation that facilitate an implant osseointegration. This work focuses on the influence of surface treatment quality and anodic oxidation parameters on the structure features and properties of TiO2 nanotube coatings. The nanotubes were formed on Ti6Al4V alloy substrates by simultaneous surface oxidation and controlled dissolving of an oxide film in the presence of fluorine ions. The anodization process on ground or polished samples was performed at experimental condition of 30 V for 1 h. The selected anodized samples were heat treated for 2 h at 500 °C under flowing argon. All samples were characterized by scanning electron microscopy, X-ray diffraction analysis, and Raman spectroscopy. The corrosion rate in physiological solution reached 0.0043, 0.0182, and 0.0998 mm per year for the samples in polished and not-anodized, as-anodized, and anodized-heat treated conditions, respectively.

Polyaniline as a Precursor of Multi-Layer Graphene: Microscopic and Microspectroscopic Study.

Aluminosilicate-based nanocomposites containing multi-layer graphene were prepared from polyaniline/montmorillonite intercalate in two different forms: tablets and thin layers. Starting materials, polyaniline/montmorillonite powder and polyaniline/montmorillonite layers deposited on quartz glass, were prepared by in situ polymerization of aniline in presence of montmorillonite particles. Powder was compacted into tablets using pressure 400 MPa. Samples were calcined at 1300 °C in argon atmosphere and multi-layer graphene was formed from polyaniline in both cases as confirmed by Raman microspectroscopy. Changes in morphology and surface conductivity of uncalcined and calcined samples were observed using atomic force microscopy and conductive atomic force microscopy. Also the differences between surface and internal volume of tablets were studied. Conductive atomic force microscopy revealed that the most conductive areas can be found solely on the edges of aluminosilicate particles formed from montmorillonite during calcination process. Detailed observation of multi-layer graphene in these areas was performed using transmission electron microscopy.

Detection of Micron and Submicron Particles in Human Bronchogenic Carcinomas.

Metal based particles were detected in pulmonary tumor tissue samples and reference lung tissue samples (lung tissue without carcinoma) by Raman microspectroscopy and scanning electron microscopy. Many of these particles were in the size below 1 µm. Using scanning electron microscopy, particles based on iron were found in the majority of samples. Siderite was determined as the form of the iron in several samples by Raman microspectroscopy. The hypothesis that significant statistical dependence exists between the presence of metals in the lung tissue and lung cancer incidence was not proved. However, statistical dependence between smoking and lung cancer incidence was determined as well as insignificant correlation between the presence of titanium based particles and lung cancer incidence. Titanium-based compounds were identified as TiO2 in the form of anatase and rutile. Both the reference and the carcinoma samples exhibited magnetic properties as confirmed by vibration magnetometry measurements.

Organovermiculite as Regenerable Nanostructured Adsorbent for Treatment of Heavily Polluted Waste Water from Coke Industry.

Organically modified vermiculites can be used as nanostructured adsorbents of organic compounds from waters or gaseous phases similarly as organically modified smectites or bentonites. There is a large amount of research data focused on adsorption properties of organoclays, however only a little information is about their post-sorption treatment. This work is focused on study of two possible ways of subsequent processing of organovermiculite after its use as sorbent for heavily polluted waste water. At first, the vermiculite modified with hexadecylpyridinium ions was used in batch static sorption against phenol ammonium water from the coke industry to get highly contaminated sorption material, especially containing organic hydrocarbons and their derivatives. The sorbent is known to have excellent sorption properties; however ecotoxicological characteristics of original material showed that sorbent had hazardous properties even before its utilization. For that reason, it was necessary to design a post-sorption treatment. Two possible methods of treatment were investigated, specifically solvent treatment (with dichloromethane) and thermal treatment (thermodesorption) at temperatures of 300 and 1100 °C, respectively. The treated materials were studied using infrared spectroscopy, X-ray diffraction and carbon phase analyses. The solvent treatment confirmed that it is possible to reuse modified vermiculite as adsorbent several times, although adsorption capacity after each extraction decreases. The thermal treatment at 300 °C was not sufficient to remove all organic compounds from the vermiculite structure; however at 1100 °C the only presence of magnesium silicate, magnesium aluminate and ferric oxide confirmed the formation of an inert material convenient for an environmentally harmless disposal of used adsorbent.

Stability of Calcium Deficient Hydroxyapatite/Clay Mineral Nanocomposite in Solutions with Different pH.

Hydroxyapatite is one of the building blocks of hard tissues of living organisms. Therefore stability of nanoparticles in experimental solutions of different pH similar to one in human body is important issue for precise tailoring of the synthesis of hydroxyapatite particles on clay mineral substrate. In this study, the stability (amount of CaII and PV released into the water) of calcium deficient hydroxyapatite/clay mineral nanocomposites was investigated. The calcium deficient hydroxyapatite/clay mineral nanocomposites with montmorillonite and two vermiculites (Brazil and Bulgaria) were compared with pure calcium deficient hydroxyapatite. The stability was investigated for 24 h where calcium deficient hydroxyapatite/clay mineral nanocomposites and pure calcium deficient hydroxyapatite were placed into the water solutions with different pH values (pH= 5, 7, and 9). The presence of CaII and PV ions at solutions were determined using atomic emission spectrometry. The calcium deficient hydroxyapatite/clay mineral nanocomposites after stability testing were characterized by X-ray powder diffraction and infrared spectroscopy with Fourier transformation.

Micronization of Ibuprofen Particles Using Supercritical Fluid Technology.

Most of drugs are only slightly soluble in the circulatory system of the human body. This reduces the efficiency of their use and that is why new ways how to increase their solubility are investigated. One way to improve the solubility of the drug is to reduce its particle size. Conventional techniques such as crushing or grinding usually do not guarantee a narrow particle size distribution, which is required for pharmaceuticals. Application of supercritical fluids, especially of supercritical CO2, seems to be convenient method for the preparation of pharmaceuticals submicron particles or nanoparticles. The method enables the preparation of particles in a narrow size distribution and at the same time it does not leave any unwanted residues of solvents or other chemicals. The aim of this work is the micronization of ibuprofen particles using the supercritical fluid and characterization of formed products. The micronization of the particles was done using commercially available device Spe-ed SFE-4 in rapid expansion of supercritical solution mode. The applied temperatures and pressures were 308.15 K and 313.15 K and 200, 250 and 300 bar. The prepared particles were characterized using methods of X-ray diffraction, infrared spectroscopy, particle size distribution, scanning electron microscopy and tests of dissolution and permeability. Mean particles size was reduced from 180 µm (original ibuprofen) to 2.8-7.3 µm of the processed samples. The dissolution test confirmed better solubility and the permeability of newly formed particles improved.

Stevensite-Rich Moroccan Clay Intercalated by Polypyrrole: Towards the Enhancement of Electrical Conductivity.

Regularly arranged chains strongly affect the electrical conductivity of conductive polymers (e.g., polypyrrole). One of the easiest ways to achieve this arrangement is the insertion of the polymer into the interlayer space of solid inorganic layered matrix, i.e., the intercalation process. Among various kinds of layered materials, the clay minerals, especially the smectite group, deserves particular attention. Negative charge of smectite layers helps the intercalation process resulting in higher conductivity of the polymer in clay/polymer intercalates. Characterization of stevensite-rich Moroccan clay and intercalation of electrically conductive polypyrrole into stevensite-rich Moroccan clay in order to obtain material with higher conductivity in comparison with pure polypyrrole were two main purposes of this work. Two forms of stevensite/polypyrrole nanocomposites were studied: powder and pressed tablets. X-ray fluorescence spectroscopy, X-ray diffraction analysis, atomic force microscopy, thermogravimetry, infrared spectroscopy, Raman microspectroscopy, and scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy were used to study the composition and structure of the nanocomposites. Measurement of electrical conductivity of polypyrrole in stevensite/polypyrrole nanocomposites revealed enhanced conductivity for all samples and also anisotropy in the conductivity of the samples pressed in the tablets.

Photoactive and Non-Hazardous Kaolinite/ZnO Nanocomposite: Characterization and Reproducibility of the Preparation Process.

Photoactive and non-hazardous kaolinite/ZnO nanocomposite with 50 wt.% of ZnO nanoparticles was prepared using simple and cheap hydrothermal method. The resulting solid phase was separated by decantation, and dried at 105 °C. Calcination of the nanocomposites at 600 °C led to the kaolinite-metakaolinite phase transformation, to further growth of ZnO crystallites, and to significant increase in photodegradation activity. Whereas, for the several applications, e.g., in brake industry, the larger amount of composites is needed, thus, the evaluation of the reproducibility of preparation process is one of the crucial parameter. Prepared nanocomposites were deeply characterized by using X-ray fluorescence spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and Rietveld quantitative phase analysis. Photodegradation activity was evaluated by the discoloration of Acid Orange 7 aqueous solution under UV irradiation. All used analytical techniques and methods confirm the reproducibility of the preparation process and as well that ZnO nanoparticles are anchored tightly on the clay surface which prevents the release to the environment.

Determination of Oxidative Potential Caused by Brake Wear Debris in Non-Cellular Systems.

Wear debris from automotive brake systems represents a major source of non-exhaust emissions from road traffic and its production increases with number of cars worldwide. However, impact of brake wear debris on the environment and organisms is still not clear. One of the most possible ways by which these particles may affect living organisms is oxidative stress. Production of reactive oxidative species may cause damage of basic cell components, lipids, proteins, etc. Aim of this study is to perform characterization of airborne and nonairborne fractions of brake wear debris generated during standard dynamometer tests and evaluation of its potential to induce oxidative stress via lipid peroxidation and carbonylation of proteins in non-cellular system. Elemental and phase composition were determined by scanning electron microscopy, Raman microspectroscopy, and X-ray powder diffraction analysis. Carbon in amorphous form and graphite, copper, and iron in form of oxides were identified as major components in both studied fractions. Characteristic size of studied wear particles was evaluated by dynamic light scattering. Both airborne and nonairborne samples showed ability to induce oxidative stress which results from determination of carbonylated proteins.

Nanogold Biosynthesis Mediated by Mixed Flower Pollen Grains.

Physical and chemical methods for nanoparticle synthesis are disadvantageous to less energy demanding and more efficient and environmentally friendly biological approaches. Thus, in this paper, we designed simple, bottom-up, in vitro, static experiment under laboratory conditions using suspension of mixed flower pollen grains for nanoparticle synthesis. Pollen grains provided template substrates for gold nanoparticles synthesis from dissolved Au(III). Transmission and scanning electron microscopy along with ultraviolet-visible spectra confirmed the gold nanoparticles formation. The biosynthesized/phytosynthesized gold nanoparticles had relative narrow size distribution (from 3 to 11 nm) with dominant spherical morphology with no aggregated forms. Thus, the gold nanoparticles in pollen dispersion provides excellent stability and dispersity.

Improvement of Glibenclamide Water Solubility by Nanoparticle Preparation.

Glibenclamide, a drug used for the treatment of type 2 diabetes, belongs to Class II of Biopharmaceutical Classification System. It is a highly permeable, but poorly water-soluble drug. Nanoparticles of glibenclamide were prepared by an emulsion solvent evaporation method using dichloromethane as a solvent of glibenclamide and 3% (w/w) aqueous solution of carboxymethyl dextran sodium salt as a stabilizer, which was found as optimal. A solubility test comparing the water solubility of glibenclamide bulk and nanoparticles confirmed the improved (2-fold higher) solubility of glibenclamide nanoparticles (0.045 µg/ml) compared with bulk (0.024 µg/ml).

Settled Dust from Urban and Suburban Roads in an Industrial City Area: Location and Seasonal Differences in Metal Content.

Settled road dust, present on all roads surfaces in a relatively high abundance, is a complex of particles-ranging from nanosized to microsized-from both natural and anthropogenic sources and may pose possible risk to the biosphere as well as influence the atmosphere because of the road dust resuspension. Geographical and seasonal differences in heavy metal content of the settled road dust were studied at two sites: urban site with a heavy traffic in the industrial city of Ostrava, Czech Republic and suburban site of Ostrava with a negligible traffic load in settlement Ludgerovice. Dust samples were collected monthly during the period from March to October 2015. Obtained dust samples were homogenized and subsequently analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy; the results were then assessed by multivariate statistical methods (Principal components analysis, Factorial analysis on mixed data). The difference in the content of Ba, Cr, Cu, Mn, Ni, Pb, Sb, Sn, V, and Zn was explainable mainly by the factor of the site only the content of Fe was significantly dependent on the month of sampling. The contents of the particular elements and the correlations found among them confirm the assumption that heavy metals detected in the road dust samples from the urban site most likely originated primarily from the traffic-and particularly from the non-combustion processes.

Biological response of an in vitro human 3D lung cell model exposed to brake wear debris varies based on brake pad formulation.

Wear particles from automotive friction brake pads of various sizes, morphology, and chemical composition are significant contributors towards particulate matter. Knowledge concerning the potential adverse effects following inhalation exposure to brake wear debris is limited. Our aim was, therefore, to generate brake wear particles released from commercial low-metallic and non-asbestos organic automotive brake pads used in mid-size passenger cars by a full-scale brake dynamometer with an environmental chamber simulating urban driving and to deduce their potential hazard in vitro. The collected fractions were analysed using scanning electron microscopy via energy-dispersive X-ray spectroscopy (SEM-EDS) and Raman microspectroscopy. The biological impact of the samples was investigated using a human 3D multicellular model consisting of human epithelial cells (A549) and human primary immune cells (macrophages and dendritic cells) mimicking the human epithelial tissue barrier. The viability, morphology, oxidative stress, and (pro-)inflammatory response of the cells were assessed following 24 h exposure to ~ 12, ~ 24, and ~ 48 µg/cm2 of non-airborne samples and to ~ 3.7 µg/cm2 of different brake wear size fractions (2-4, 1-2, and 0.25-1 µm) applying a pseudo-air-liquid interface approach. Brake wear debris with low-metallic formula does not induce any adverse biological effects to the in vitro lung multicellular model. Brake wear particles from non-asbestos organic formulated pads, however, induced increased (pro-)inflammatory mediator release from the same in vitro system. The latter finding can be attributed to the different particle compositions, specifically the presence of anatase.

Preparation of Hydrochlorothiazide Nanoparticles for Solubility Enhancement.

Nanoparticles can be considered as a useful tool for improving properties of poorly soluble active ingredients. Hydrochlorothiazide (Class IV of the Biopharmaceutical Classification System) was chosen as a model compound. Antisolvent precipitation-solvent evaporation and emulsion solvent evaporation methods were used for preparation of 18 samples containing hydrochlorothiazide nanoparticles. Water solutions of surfactants sodium dodecyl sulfate, Tween 80 and carboxymethyl dextran were used in mass concentrations of 1%, 3% and 5%. Acetone and dichloromethane were used as solvents of the model compound. The particle size of the prepared samples was measured by dynamic light scattering. The selected sample of hydrochlorothiazide nanoparticles stabilized with carboxymethyl dextran sodium salt with particle size 2.6 nm was characterized additionally by Fourier transform mid-infrared spectroscopy and scanning electron microscopy. It was found that the solubility of this sample was 6.5-fold higher than that of bulk hydrochlorothiazide.

Microstructure, Optical and Photocatalytic Properties of TiO2 Thin Films Prepared by Chelating-Agent Assisted Sol-Gel Method.

Single and multilayer TiO2 thin films coated on two types of soda-lime glass substrates (microscope slides and cylinders) were prepared by a chelating agent-assisted sol-gel method, using ethyl acetoacetate as a chelating agent, dip-coating and calcination at 500 °C for 2 h in air. Phase composition, microstructural, morphological and optical properties of thin films were comprehensively investigated by using XRF, advanced XRD analysis, Raman and UV-vis spectroscopy and AFM. It was found out that the thickness of thin films increases linearly with increasing number of deposited layers, indicating a good adhesion of the titania solution to a glass substrate as well as to a previously calcined layer. 1 layer film crystallized to anatase-TiO2(B) mixture with minor/negligible amount of nanosized brookite, 2-4 layers films crystallized to anatase-brookite-TiO2(B) mixture. In contrast to other multilayers films, 4 layers film was highly inhomogeneous. The different phase composition of thin films was clarified based on the crystallization via titanate/s and metastable monoclinic TiO2(B) as a consequence of several phenomena; the diffusion of Na⁺ ions from a soda-lime glass substrate, acidic conditions and repeated thermal treatment. The multilayer films were in average highly transparent (80-95%) in the visible light region with the sharp absorption edge in the UV light region. Additionally, the photocatalytic properties of selected multilayer films were compared in AO7 photodegradation. Photocatalytic experiments showed that thicker 4 layers film of tricrystalline anatase-brookite-TiO2(B) phase mixture was similarly active as thinner 3 layers film of similar phase composition, which may be a consequence of the inhomogeneity of the thicker film.

Automotive airborne brake wear debris nanoparticles and cytokinesis-block micronucleus assay in peripheral blood lymphocytes: A pilot study.

Motor vehicle exhaust and non-exhaust processes play a significant role in environmental pollution, as they are a source of the finest particulate matter. Emissions from non-exhaust processes include wear-products of brakes, tires, automotive hardware, road surface, and traffic signs, but still are paid little attention to. Automotive friction composites for brake pads are composite materials which may consist of potentially hazardous materials and there is a lack of information regarding the potential influence of the brake wear debris (BWD) on the environment, especially on human health. Thus, we focused our study on the genotoxicity of the airborne fraction of BWD using a brake pad model representing an average low-metallic formulation available in the EU market. BWD was generated in the laboratory by a full-scale brake dynamometer and characterized by Raman microspectroscopy, scanning electron microscopy, and transmission electron microscopy showing that it contains nano-sized crystalline metal-based particles. Genotoxicity tested in human lymphocytes in different testing conditions showed an increase in frequencies of micronucleated binucleated cells (MNBNCs) exposed for 48h to BWD nanoparticles (NPs) (with 10% of foetal calf serum in culture medium) compared with lymphocytes exposed to medium alone, statistically significant only at the concentration 3µg/cm(2) (p=0.032).

Nanostructured composite material graphite/TiO2 and its antibacterial activity under visible light irradiation.

The paper addresses laboratory preparation, characterization and in vitro evaluation of antibacterial activity of graphite/TiO2 nanocomposites. Composites graphite/TiO2 with various ratio of TiO2 nanoparticles (30wt.%, and 50wt.%) to graphite were prepared using a thermal hydrolysis of titanylsulfate in the presence of graphite particles, and subsequently dried at 80°C. X-ray powder diffraction, transmission electron microscopy and Raman microspectroscopy served as phase-analytical methods distinguishing anatase and rutile phases in the prepared composites. Scanning and transmission electron microscopy techniques were used for characterization of morphology of the prepared samples. A developed modification of the standard microdilution test was used for in vitro evaluation of daylight induced antibacterial activity, using four common human pathogenic bacterial strains (Staphylococcus aureus, Escherichia coli, Enterococcus faecalis and Pseudomonas aeruginosa). Antibacterial activity of the graphite/TiO2 nanocomposites could be based mainly on photocatalytic reaction with subsequent potential interaction of reactive oxygen species with bacterial cells. During the antibacterial activity experiments, the graphite/TiO2 nanocomposites exhibited antibacterial activity, where differences in the onset of activity and activity against bacterial strains were observed. The highest antibacterial activity evaluated as minimum inhibitory concentration was observed against P. aeruginosa after 180min of irradiation.