Search Results (14)

Zinc oxide nanoparticles (NPs) are used in a wide range of consumer products and in biomedical applications, resulting in an increased production of these materials with potential for exposure, thus causing human health concerns. Although there are many reports on the size-related toxicity of ZnO NPs, the toxicity of different nanoforms of this chemical, toxicity mechanisms, and potency determinants need clarification to support health risk characterization. A set of well-characterized ZnO nanoforms (e.g., uncoated ca. 30, 45, and 53 nm; coated with silicon oil, stearic acid, and (3-aminopropyl) triethoxysilane) were screened for in vitro cytotoxicity in two cell types, human lung epithelial cells (A549), and mouse monocyte/macrophage (J774) cells. ZnO (bulk) and ZnCl₂ served as reference particles. Cytotoxicity was examined 24 h post-exposure by measuring CTB (viability), ATP (energy metabolism), and %LDH released (membrane integrity). Cellular oxidative stress (GSH-GSSG) and secreted proteins (targeted multiplex assay) were analyzed. Zinc oxide nanoform type-, dose-, and cell type-specific cytotoxic responses were seen, along with cellular oxidative stress. Cell-secreted protein profiles suggested ZnO NP exposure-related perturbations in signaling pathways relevant to inflammation/cell injury and corresponding biological processes, namely reactive oxygen species generation and apoptosis/necrosis, for some nanoforms, consistent with cellular oxidative stress and ATP status. The size, surface area, agglomeration state and metal contents of these ZnO nanoforms appeared to be physicochemical determinants of particle potencies. These findings warrant further research on high-content “OMICs” to validate and resolve toxicity pathways related to exposure to nanoforms to advance health risk-assessment efforts and to inform on safer materials. Full article

Oxidation potential (OP), reflecting the redox activities of particle matter (PM), is considered an optimal measure to explain the biological effects of PM exposure. However, the size resolution of the relationship between OP and chemical composition in PM, especially how the relationship changes after respiratory exposure, has not been well investigated. In this study, size-resolved indoor PM₁₀ samples were collected from a waste recycling plant from November to December 2021 using an Anderson eight-stage cascade impactor. OP, measured by a dithiothreitol (DTT) assay (defined as OP^DTT), and elements, determined by inductively coupled plasma–mass spectrometry (ICP-MS) in size-resolved PM, were determined to check their relationships and the related human exposure risk. The results indicated that compared with PM_0.4 and PM_0.4–2.1, PM_2.1–10 contributed the most to total OP^DTT and its bound elements contributed the most to potential health risks, both before and after respiratory exposure. The association between OP^DTT and the elements varied with PM size. Pearson correlation analysis showed that the PM_0.4- and PM_0.4–2.1-bound elements were moderate-to-strongly positively correlated with OP_v^DTT (r: 0.60–0.90). No significant correlation or dose–response relationship was found in PM_2.1–10. After respiratory exposure, several PM_0.4- and PM_0.4–2.1-bound elements had a moderate-to-strongly positive correlation with deposition fluxes of OP (defined as OP^Flux) (0.69–0.90). A generalized linear model analysis showed that the interquartile range (IQR) increase in the PM-bound elements (ng h⁻¹) was associated with a 41.7–58.1% increase in OP^Flux. Our study is a special case that enriches the knowledge of the association between OP^DTT and the chemical composition of PM of different sizes, especially after respiratory exposure, but the generalizability of the findings to other settings or types of PM may be limited. The associations among OP^DTT, other chemical compositions of PM, and human exposure risk merit further research. Full article

Metal–organic frameworks (MOFs) are hybrid materials that are being explored as active electrode materials in energy storage devices, such as rechargeable batteries and supercapacitors (SCs), due to their high surface area, controllable chemical composition, and periodic ordering. However, the facile and controlled synthesis of a pure MOF phase without impurities or without going through a complicated purification process (that also reduces the yield) are challenges that must be resolved for their potential industrial applications. Moreover, various oxide formations of the Ni during Ni-MOF synthesis also represent an issue that affects the purity and performance. To resolve these issues, we report the controlled synthesis of nickel-based metal–organic frameworks (NiMOFs) by optimizing different growth parameters during hydrothermal synthesis and by utilizing nickel chloride as metal salt and H₂bdt as the organic ligand, in a ratio of 1:1 at 150 °C. Furthermore, the synthesis was optimized by introducing a magnetic stirring stage, and the reaction temperature varied across 100, 150, and 200 °C to achieve the optimized growth of the NiMOFs crystal. The rarely used H₂bdt ligand for Ni-MOF synthesis and the introduction of the ultrasonication stage before putting it in the furnace led to the formation of a pure phase without impurities and oxide formation. The synthesized materials were further characterized by powder X-ray diffraction (XRD) technique, scanning electron microscopy (SEM), and UV–vis spectroscopy. The SEM images exhibited the formation of nano NiMOFs having a rectangular prism shape. The average size was 126.25 nm, 176.0 nm, and 268.4 nm for the samples (1:1)s synthesized at 100 °C, 150 °C, and 200 °C, respectively. The electrochemical performances were examined in a three-electrode configuration, in a wide potential window from −0.4 V to 0.55 V, and an electrolyte concentration of 2M KOH was maintained for each measurement. The charge–discharge galvanostatic measurement results in specific capacitances of 606.62 F/g, 307.33 F/g, and 287.42 F/g at a current density of 1 A/g for the synthesized materials at 100 °C, 150 °C, and 200 °C, respectively. Full article

Magnetic nanoparticles (MNPs) are interesting for their potential employment in biomedical and environmental technologies. Although they have been characterized by many techniques, there are some issues that need to be solved. For instance, it is not yet possible to finely characterize their size distribution or to detect their local magnetic properties. In this work, commercial MNPs were employed, which were made of iron oxide cores with a mean diameter of 8 nm embedded in a matrix of dextran to form skeins with a mean diameter of 20 nm. These MNPs have been dispersed in keratin, a natural protein extracted from wool. Thin films have been realized by spin coating water solutions with various MNP concentrations. Analysis was conducted using a set of techniques, namely Atomic Force Microscopy, Environmental Scanning Electron Microscopy, a Physical Property Measurement System–Vibrating Sample Magnetometer, and the spatially resolved Magneto-Optic Kerr Effect (NanoMOKE). These MNPs show superparamagnetic properties, although a wide distribution of blocking temperature values indicates that the cores are not isolated and interact with others. NanoMOKE not only allows us to map the magnetic behavior of MNP clusters, but also to detect the presence of isolated MNPs dispersed in the keratin matrix. Full article

Respiratory diseases have been proven to be directly related to air pollutants. Xuanwei, located in South China, has been known to have the highest mortality rate for lung cancer in China because of the air pollutants emitted through local coal combustion. However, the mechanism of lung cancer induced by air pollutants is not clear. Based on the fact that a large number of iron-bearing mineral particles was found in Xuanwei coal combustion particles, the iron-containing particles were hypothesized to play important roles in the pathogenesis of the high incidence rate of lung cancer in this area. In this study, raw coal samples were collected from a coal mine in the Xuanwei area. Size-resolved particles emitted from the raw coal samples were collected using an Anderson high-volume sampler. Mineralogical characterization and an assessment of the oxidative potential of the iron-containing particles were conducted using cutting-edge technologies, and the biological activity of the particles were evaluated via DTT assay. Our data showed that the iron-containing minerals accounted for more than 10% of the measured particles emitted from Xuanwei coal combustion samples. The content analysis of ·OH generated from Xuanwei coal combustion particles showed that ·OH content was dependent on the size of particles in the surrogated lung fluid. The concentration of ·OH increased as the particle size decreased. The DTT assay data further demonstrated that when the mass concentration of dissolved irons increased, the oxidation potential of the particles increased. The highest proportion of divalent iron in the total dissolved iron was found in the submicron particles in low pH solution(pH = 1), which indicated that the oxidative potential induced by submicron particles was stronger than that induced by coarse particles and fine particles. Armed with the above data, the toxicological mechanism of the iron-containing mineral particles can be investigated further. Full article

In this paper, individual particle analysis by automated scanning electron microscopy (SEM) coupled with energy-dispersive X-ray (EDX) was used to assess the size-resolved information of composition, size distribution, complex refractive index, and mixing state of mineral dust aerosol particles collected using different passive and active samplers. In the study, over 120,000 particles from 53 samples were analyzed. Results show that dust particles are the dominating mineral particle type during this campaign, comprising different classes of silicates, Si-rich (quartz-like), Ca-rich (calcite-like), CaMg-rich (dolomite-like), and CaS-rich (gypsum-like). The results also show that there is no significant difference in composition between suspended and deposited dust particles. By using the particle composition, the size-resolved complex refractive index of dust particles was calculated. The real part of the refractive index varied between 1.71 and 1.53 for wavelengths in the range of 370 to 950 nm. The imaginary part of the refractive index, determined mostly by iron oxide, varied between $3.28\times {10}^{-4}$ and $7.11\times {10}^{-5}$ for wavelengths ranging from 250 nm to 1640 nm. In addition, the refractive index values showed a slight decrease with increasing particle size. We also analyzed the potential for buffering of the acid mobilization of iron by other dust compounds. For particles which contain both iron (Fe) and (unprocessed) calcium (Ca), acids that are able to dissolve insoluble Fe particles can react with the Ca particles before reacting with Fe, but eventually, with longer processing time, the Fe particles could be processed. By analyzing the ratio of sulfate mass to the total aerosol mass of individual particles, the mixing state of sulfate particles to the total dust particles was investigated. The analysis showed that the finer dust particles were associated with higher content of sulfate, while the coarse dust particles correspond to lower sulfate contents, revealing that only fine mode sulfate is more internally mixed with mineral dust aerosol particles. Full article

Size and zeta potential are critical physicochemical properties of nanoparticles (NPs), influencing their biological activity and safety profile. These are essential for further industrial upscale and clinical success. However, the characterization of polydisperse, non-spherical NPs is a challenge for traditional characterization techniques (ex., dynamic light scattering (DLS)). In this paper, superparamagnetic iron oxide nanoparticles (SPIONs) were coated with polyvinyl alcohol (PVAL) exhibiting different terminal groups at their surface, either hydroxyl (OH), carboxyl (COOH) or amino (NH₂) end groups. Size, zeta potential and concentration were characterized by orthogonal methods, namely, batch DLS, nanoparticle tracking analysis (NTA), tunable resistive pulse sensing (TRPS), transmission electron microscopy (TEM), asymmetric flow field flow fractionation (AF4) coupled to multi-angle light scattering (MALS), UV–Visible and online DLS. Finally, coated SPIONs were incubated with albumin, and size changes were monitored by AF4-MALS-UV-DLS. NTA showed the biggest mean sizes, even though DLS PVAL-COOH SPION graphs presented aggregates in the micrometer range. TRPS detected more NPs in suspension than NTA. Finally, AF4-MALS-UV-DLS could successfully resolve the different sizes of the coated SPION suspensions. The results highlight the importance of combining techniques with different principles for NPs characterization. The advantages and limitations of each method are discussed here. Full article

A simple, one-step and facile method has been introduced to prepare fluorescent and electrochemically active carbon nanoparticles with single-size distribution and good long-term stability by electrochemical exfoliation of polyacrylonitrile-based carbon fibers in an alkaline solution-phase condition. The preparation condition was systematically optimized by studying the effect of temperature and electrolytes. It has been found that an electrochemical exfoliation reaction carried out at an applied potential of 2 V vs. Ag/AgCl in a phosphate-ion-containing alkaline solution at a temperature of 40 °C is an ideal condition for the preparation of 14 ± 4 nm-sized carbon nanoparticles. Unlike the literature protocols, there are no filtration and membrane dialysis-based off-line sample pretreatments adopted in this work. The as-prepared carbon nanoparticles were characterized by fluorescence, Raman spectrum, transmission electron microscope, and X-ray photoelectron spectroscopic characterization methods. It was found that the carbon–oxygen functional group rich in graphene–oxide quantum dots (GOQDs) such as carbon nanoparticles were formed in this work. A preliminary study relating to simultaneous electrochemical oxidation and the sensing of uric acid and ascorbic acid with well-resolved peaks was demonstrated as a model system to extend the new carbon material for electroanalytical applications. Furthermore, in situ synthesis of 2 nm-sized gold nanoparticles stabilized by GOQDs was presented. The carbon nanoparticles prepared by the direct method in this work have shown good stability over 6 months when stored at room temperature. The electrochemical exfoliation reaction has been found to be highly reproducible and suitable for bulk synthesis of luminescence-effective carbon nanoparticles to facilitate fundamental studies and practical applications. Full article

The human skin is exposed to various environmental factors including solar radiation and ambient air pollutants. Although, due to its physical and biological properties, the skin efficiently protects the body against the harm of environmental factors, their excessive levels and possible synergistic action may lead to harmful effects. Among particulate matter present in ambient air pollutants, PM_2.5 is of particular importance for it can penetrate both disrupted and intact skin, causing adverse effects to skin tissue. Although certain components of PM_2.5 can exhibit photochemical activity, only a limited amount of data regarding the interaction of PM_2.5 with light and its effect on skin tissue are available. This study focused on light-induced toxicity in cultured human keratinocytes, which was mediated by PM_2.5 obtained in different seasons. Dynamic Light Scattering (DLS) and Atomic Force Microscopy (AFM) were employed to determine sizes of the particles. The ability of PM_2.5 to photogenerate free radicals and singlet oxygen was studied using EPR spin-trapping and time-resolved singlet oxygen phosphorescence, respectively. Solar simulator with selected filters was used as light source for cell treatment to model environmental lightning conditions. Cytotoxicity of photoexcited PM_2.5 was analyzed using MTT assay, PI staining and flow cytometry, and the apoptotic pathway was further examined using Caspase-3/7 assay and RT-PCR. Iodometric assay and JC-10 assay were used to investigate damage to cell lipids and mitochondria. Light-excited PM_2.5 were found to generate free radicals and singlet oxygen in season-dependent manner. HaCaT cells containing PM_2.5 and irradiated with UV-Vis exhibited oxidative stress features–increased peroxidation of intracellular lipids, decrease of mitochondrial membrane potential, enhanced expression of oxidative stress related genes and apoptotic cell death. The data indicate that sunlight can significantly increase PM_2.5-mediated toxicity in skin cells. Full article

The durability of catalysts in fuel cells is a longstanding issue that needs to be resolved. Catalyst stability of the fuel cell has always been a problem, studies are underway to address them. Herein, to address this issue, we synthesize a hybrid structure consisting of SP carbon (SP) as the graphitic carbon and TiO₂ as the metal oxide using a microwave method for use as a support for Pt nanoparticles. Anatase TiO₂ and Pt nanoparticles with sizes of ~5 and 3.5 ± 1.4 nm, respectively, are uniformly dispersed on a modified graphitic SP carbon support (Pt-TiO₂-SP). This supported Pt catalyst exhibits significantly improves durability in the oxygen reduction reaction (ORR). Furthermore, the Pt-TiO₂-SP carbon hybrid catalyst manifests superior electrocatalytic stability and higher onset potential in ORR than those exhibited by Pt-SP carbon without TiO₂. Pt-TiO₂-SP exhibits an activity loss of less than 68 mV after 5000 electrochemical cycles, whereas an activity loss of ~100 mV is observed for Pt-SP carbon in a stability test. These results suggest that the strong metal–support interaction in TiO₂-supported Pt catalyst significantly enhances the activity of Pt nanocatalyst. Full article

Autism spectrum disorder (ASD) is a common neurodevelopmental disorder affecting 2% of children in the United States. Biochemical abnormalities associated with ASD include impaired methylation and sulphation capacities along with low glutathione (GSH) redox capacity. Potential treatments for these abnormalities include cobalamin (B12). This systematic review collates the studies using B12 as a treatment in ASD. A total of 17 studies were identified; 4 were double-blind, placebo-controlled studies (2 examined B12 injections alone and 2 used B12 in an oral multivitamin); 1 was a prospective controlled study; 6 were prospective, uncontrolled studies, and 6 were retrospective (case series and reports). Most studies (83%) used oral or injected methylcobalamin (mB12), while the remaining studies did not specify the type of B12 used. Studies using subcutaneous mB12 injections (including 2 placebo-controlled studies) used a 64.5–75 µg/kg/dose. One study reported anemia in 2 ASD children with injected cyanocobalamin that resolved with switching to injected mB12. Two studies reported improvements in markers of mitochondrial metabolism. A meta-analysis of methylation metabolites demonstrated decreased S-adenosylhomocysteine (SAH), and increased methionine, S-adenosylmethionine (SAM), SAM/SAH ratio, and homocysteine (with small effect sizes) with mB12. Meta-analysis of the transsulfuration and redox metabolism metabolites demonstrated significant improvements with mB12 in oxidized glutathione (GSSG), cysteine, total glutathione (GSH), and total GSH/GSSG redox ratio with medium to large effect sizes. Improvements in methylation capacity and GSH redox ratio were significantly associated with clinical improvements (with a mean moderate effect size of 0.59) in core and associated ASD symptoms, including expressive communication, personal and domestic daily living skills, and interpersonal, play-leisure, and coping social skills, suggesting these biomarkers may predict response to B12. Other clinical improvements observed with B12 included sleep, gastrointestinal symptoms, hyperactivity, tantrums, nonverbal intellectual quotient, vision, eye contact, echolalia, stereotypy, anemia, and nocturnal enuresis. Adverse events identified by meta-analysis included hyperactivity (11.9%), irritability (3.4%), trouble sleeping (7.6%), aggression (1.8%), and worsening behaviors (7.7%) but were generally few, mild, not serious, and not significantly different compared to placebo. In one study, 78% of parents desired to continue mB12 injections after the study conclusion. Preliminary clinical evidence suggests that B12, particularly subcutaneously injected mB12, improves metabolic abnormalities in ASD along with clinical symptoms. Further large multicenter placebo-controlled studies are needed to confirm these data. B12 is a promising treatment for ASD. Full article

The ability of mixtures of 1.2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and the amphiphilic diblock copolymers poly (ethylene oxide)-block-poly(ε-caprolactone) (PEO-b-PCL) to stabilize uni-lamellar nano-vesicles is reported. Small angle neutron scattering (SANS) is used to define their size distribution and bilayer structure and resolve the copresence of aggregates and clusters in solution. The vesicles have a broad size distribution which is compatible with bilayer membranes of relatively low bending stiffness. Their mean diameter increases moderately with temperature and their number density and mass is higher in the case of the diblock copolymer with the larger hydrophobic block. Bayesian analysis is performed in order to justify the use of the particular SANS fitting model and confirm the reliability of the extracted parameters. This study shows that amphiphilic block copolymers can be effectively used to prepare mixed lipid-block copolymer vesicles with controlled lamellarity and a significant potential as nanocarriers for drug delivery. Full article

A primary concern of commercial mined oil sands operations is the extent to which one can minimize the content of water and solids contaminants in the solvent-diluted bitumen products resulting from the bitumen production processes. During bitumen production, particles of about 2 µm or less may be responsible for the stabilization of water-in-bitumen emulsions that form during aqueous extraction of bitumen and purification of bitumen froth subsequently during the froth treatment processes, thus leading to the presence of those contaminants in solvent-diluted bitumen products. In this study, we separate and analyze sub-2 µm clay solids isolated from typical bitumen froth fed to a froth treatment plant at a commercial mined oil sands operation. Analytical transmission electron microscopy (TEM) with spatially-resolved energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) demonstrate key differences in morphology and composition between sub-2 µm clay aggregates with two distinct wettability characteristics: hydrophilic vs. biwettable particle surfaces. In particular, clay platelets with <200 nm lateral dimensions and thicknesses of a few atomic layers, which are intermixed within coarser sub-2 µm clay aggregates, are found to confer clear differences in morphological characteristics and wettability behaviors to the sub-2 µm clay aggregates. The <200 nm clay platelets found within sub-2 µm biwettable clays tend to arrange themselves with random orientations, whereas <200 nm clay platelets within sub-2 µm hydrophilic clays typically form well-ordered face-to-face stacks. Moreover, in biwettable sub-2 µm clay aggregates, <200 nm clay platelets often cover the surfaces of ~1–2 µm sized mineral particles, whereas similarly sized mineral particles in hydrophilic sub-2 µm clay aggregates, in contrast, generally have exposed surfaces without clay platelet coverage. These biwettable vs. hydrophilic behaviors are attributed to a difference in the surface characteristics of the <200 nm clay platelets caused by toluene-unextractable organic carbon coatings. Nanometer-scale carbon mapping reveals an inhomogeneous toluene-unextractable organic carbon coating on the surfaces of <200 nm platelets in biwettable clays. In contrast, hydrophilic clays have a significantly lower amount of toluene-unextractable organic carbon, which tends to be concentrated at steps or near metal oxide nanoparticles on clay particle surfaces. Mixing surface-active organic species, such as asphaltene, resin, or carboxylic organic acids of various types with inorganic solids can lead to a dramatically enhanced emulsion stability. Consequently, understanding the origin and characteristics of sub-2 µm clay solids in bitumen froth is important to (i) clarify their potential role in the formation of stable water-in-oil emulsions during bitumen production and (ii) improve froth treatment process performance to further reduce contaminant solids in solvent-diluted bitumen products. We discuss the implications of our results from these two perspectives. Full article

Size-segregated aerosol measurements were carried out at an urban and at an industrial site. Soluble and insoluble fractions of elements and inorganic ions were determined. Oxidative potential (OP) was assessed on the soluble fraction of Particulate Matter (PM) by ascorbic acid (AA), dichlorofluorescein (DCFH) and dithiothreitol (DTT) assays. Size resolved elemental, ion and OP doses in the head (H), tracheobronchial (TB) and alveolar (Al) regions were estimated using the Multiple-Path Particle Dosimetry (MPPD) model. The total aerosol respiratory doses due to brake and soil resuspension emissions were higher at the urban than at the industrial site. On the contrary, the doses of anthropic combustion tracers were generally higher at the industrial site. In general, the insoluble fraction was more abundantly distributed in the coarse than in the fine mode and vice versa for the soluble fraction. Consequently, for the latter, the percent of the total respiratory dose deposited in TB and Al regions increased. Oxidative potential assay (OP^AA) doses were distributed in the coarse region; therefore, their major contribution was in the H region. The contribution in the TB and Al regions increased for OP^DTT and OP^DCFH. Full article