Magnetic particle spray mass spectrometry for the determination of beta-blockers in plasma samples.

Magnetic particle spray mass spectrometry (MPS-MS), an innovative ambient ionization technique proposed by our research group, was employed to determine beta-blockers in human plasma samples. A dispersive solid phase extraction of atenolol, metoprolol, labetalol, propranolol, nadolol, and pindolol was carried out using magnetic molecularly imprinted polymer (M-MIP) particles that were attached to the tip of a metal probe, which was placed in the mass spectrometer inlet. A solvent (1% formic acid in methanol) was dispensed on the particles, and the Taylor cone was formed around them (in high voltage). The analytes were desorbed/ionized and determined by a triple quadrupole mass spectrometer. M-MIP was synthesized with oxprenolol as a pseudo-template, demonstrating good selectivity to beta-blockers compared with no-analog molecules, with an adsorption process occurring in monolayers, according to isotherm studies. Kinetic experiments indicated chemisorption as the predominant M-MIP/analyte interaction. The analytical curves were linear (R2 > 0.98), and the limit of quantification was 3 µg L-1 for all the analytes. Limits of detection ranged from 0.64 to 2.41 µg L-1. Precisions (relative standard deviation) and accuracies (relative error) ranged from 3.95 to 21.20% and -17.05 to 18.93%, respectively. MPS-MS proved to be a simple, sensitive, and advantageous technique compared with conventional approaches. The analyses were fast, requiring no chromatographic separation and without ionic suppression. The method is aligned with green chemistry principles, requiring minimal sample, solvent, and sorbent amounts. MPS-MS successfully integrates sample preparation and ambient ionization mass spectrometry and holds great potential for application with other sorbents, samples, and analytes.

N-compounds speciation analysis in environmental samples using ultrasound-assisted solid-liquid extraction and non-chromatographic techniques.

A fast, efficient, and non-chromatographic method was presented in this study for nitrite, nitrate, and p-nitrophenol (N-compounds) extraction and speciation analysis of environmental samples. By applying ultrasound-assisted solid-liquid extraction (USLE), analytes were efficiently extracted from water, soil, or sediment collected in areas of environmental disaster. These analytes were selectively converted to NO(g) through UV photolysis (NO3-), H2O2/UV photocatalysis (PNP), and direct conversion (NO2-). Following conversion, NO(g) was separated from the liquid phase and determined by high-resolution continuum source molecular absorption spectrometry (HR-CS MAS). The LODs obtained were 0.097 ± 0.004 mg L-1 for nitrite, 0.119 ± 0.004 mg L-1 for nitrate, and 0.090 ± 0.006 mg L-1 for p-nitrophenol. On applying this speciation method to environmental samples, concentrations were found to be up to 0.99 ± 0.03 mg L-1 (NO2-), 49.80 ± 2.5 mg L-1 (NO3-), and 0.10 ± 0.02 mg L-1 (PNP). Finally, addition/recovery study of real water, soil, and sediment samples showed 101 ± 2% recovery for NO2-, 100 ± 1% for NO3-, and 96 ± 5% for PNP.

UV photochemical hydride generation using ZnO nanoparticles for arsenic speciation in waters, sediments, and soils samples.

The environmental disasters that occurred due to the leakage of mining waste in Mariana-MG (2015) and Brumadinho-MG (2019), located in Brazil, attracted the attention of the scientific community. This designated efforts to investigate the environmental consequences of toxic waste in the affected ecosystem. Therefore, a simple, easily executed and accessible method was presented for arsenic speciation [As(III), As(V), and DMA]. Using an atomic absorption spectrometer coupled to the hydride generation system, the heterogeneous photocatalysis was applied in the reduction of As(V) and DMA to As(III). After the optimization, a calibration curve was constructed, with LODs equivalent to 3.20 µg L-1 As(III), 3.86 µg L-1 As(V), and 6.68 µg L-1 DMA. When applying the method for quantification in environmental samples, a concentration of up to 103.1 ± 9.4 µg L-1 As(V) was determined for surface water samples. The soil samples, 84.1 ± 3.6 µg L-1 As(III) and 112.4 ± 9.9 µg L-1 As(V) were quantified, proving the contamination of the ecosystems impacted by the environmental disasters. We proceeded the study through an addition/recovery method with samples of water, soil, and sediments (collected from impacted environments). Recovery values were equivalent to 99.0% for As(III), 93.8% for As(V), and 99.2% for DMA. Graphical abstract Photocatalytic reduction mechanism of As(V) and DMA to As(III) by heterogeneous photocatalysis.

Effects of ZnWO4 nanoparticles on growth, photosynthesis, and biochemical parameters of the green microalga Raphidocelis subcapitata.

Nanoparticles have applications in many sectors in the society. ZnWO4 nanoparticles (ZnWO4-NPs) have potential in the fabrication of sensors, lasers, and batteries, and in environmental remediation. Thus, these NPs may reach aquatic ecosystems. However, we still do not know their effects on aquatic biota and, to our knowledge, this is the first study that evaluates the toxicity of ZnWO4-NPs in a eukaryotic organism. We evaluated the toxicity of ZnWO4-NPs on the green microalga Raphidocelis subcapitata for 96 h, in terms of growth, cell parameters, photosynthesis, and biochemical analysis. Results show that most of Zn was presented in its particulate form, with low amounts of Zn2+, resulting in toxicity at higher levels. The growth was affected from 8.4 mg L-1, with 96h-IC50 of 23.34 mg L-1. The chlorophyll a (Chl a) content increased at 30.2 mg L-1, while the fluorescence of Chl a (FL3-H) decreased at 15.2 mg L-1. We observed increased ROS levels at 44.4 mg L-1. Regarding photosynthesis, the NPs affected the oxygen evolving complex (OEC) and the efficiency of the photosystem II at 22.9 mg L-1. At 44.4 mg L-1 the qP decreased, indicating closure of reaction centers, probably affecting carbon assimilation, which explains the decay of carbohydrates. There was a decrease of qN (non-regulated energy dissipation, not used in photosynthesis), NPQ (regulated energy dissipation) and Y(NPQ) (regulated energy dissipation via heat), indicating damage to the photoprotection system; and an increase in Y(NO), which is the non-regulated energy dissipation via heat and fluorescence. The results showed that ZnWO4-NPs can affect the growth and physiological and biochemical parameters of the chlorophycean R. subcapitata. Microalgae are the base of aquatic food chains, the toxicity of emerging contaminants on microalgae can affect entire ecosystems. Therefore, our study can provide some help for better protection of aquatic ecosystems.

CuO nanoparticles decorated on hydroxyapatite/ferrite magnetic support: photocatalysis, cytotoxicity, and antimicrobial response.

Photocatalysts supported in magnetic nanocomposites for application in environmental remediation processes have been evaluated for removing contaminants due to easy recovery and low toxicity to the ecosystem. In this work, copper oxide (CuO) nanoparticles with photocatalytic properties were decorated on magnetic support constituted by hydroxyapatite (HAP) and ferrite to achieve efficiency in contaminated water remediation under visible light irradiation. First, nanomaterials were obtained by precipitation route, allowing fast and straightforward synthesis. Then, CuO nanoparticles with 6 nm diameter were efficiently decorated on magnetic support (25 nm), showing a high ability to absorb visible light irradiation (bandgap) to promote electronic transition and charge separation. Under visible irradiation, CuO promotes the H2O2 reduction in the conduction band (BC) to form hydroxyl radicals (•OH), which are responsible for rhodamine B (RhB) dye degradation (> 90% in 60 min). Magnetic hysteresis assays confirmed the magnetic properties of HAP/ferrite support, which enabled the recovery and reuse of the magnetic photocatalyst efficiently up to 3 cycles. Due to low Cu2+ leaching after the photocatalytic application stage, cytotoxicity assay for the Allium cepa seeds did not exhibit abnormal cells other than those commonly found. Furthermore, the CuO-decorated nanoparticles showed bactericidal activity against S. aureus (Gram-positive) and E. coli (Gram-negative) microorganisms, being more significant for the first one. Thus, the developed nanocomposite of CuO nanoparticles decorated on the magnetic support surface showed to be a complete system for water remediation, acting in contaminant degradation under visible light irradiation and bactericidal control with environmentally friendly characteristics.Graphical abstract CuO nanoparticles decorated on hydroxyapatite/ferrite magnetic support acting as a photocatalytic and bactericidal system.

Potential of Nb2O5 nanofibers in photocatalytic degradation of organic pollutants.

Various photocatalytic nanomaterials for environmental remediation have been promoted due to the pollution caused by different organic pollutants. In this study, Nb2O5 nanofibers were obtained by electrospinning technique, presenting controlled crystallinity and high specific surface area to improve the photoactivity response. The structural characterization indicated Nb2O5 nanofibers with orthorhombic phase formation. The photoluminescence measurements showed different energy levels contributing to the electronic transition events. The nanofibers with a bandgap up to 3.6 eV were applied to photocatalysis of dyes (rhodamine B (RhB) or methylene blue (MB)) and fluoxetine (FLX), listed as an emergent pollutant. In the optimized condition (pH = 9), the RhB and MB photocatalysis was 59% and 93% more efficient than photolysis due to ζ = - 50 mV ± 5 for EtOH_550 sample increased interaction with MB (cationic) compared to RhB unprotonated (pKa = 3.7). Therefore, FLX (pKa = 10.7) was selected due to protonated form at pH = 9 and showed 68% ± 1 adsorption in 30 min for EtOH_550. The FLX photocatalytic degradation under UV light irradiation was up to 17% higher than the photolytic degradation. The formation of hydroxyl radicals in the photocatalytic system (EtOH_550) was proven by the Coumarine probe assay, corroborating with the greater amount of α-[2-(methylamino)ethyl]benzylalcohol (MAEB), a by-product obtained after FLX oxidation. Additionally, the material achieved specific catalytic activity for the different organic compounds (RhB, MB, or FLX). Therefore, Nb2O5 nanofibers were efficient for degrading three different pollutants under UV light, proving a viable alternative for environmental remediation.

Nb2O5 nanoparticles decorated with magnetic ferrites for wastewater photocatalytic remediation.

Nanotechnology has been studied on environmental remediation processes to foster greater photocatalysts efficiency and reuse in wastewater. This study investigated the photocatalytic efficiency and viability of niobium pentoxide (Nb2O5) nanoparticles decorated with magnetic ferrite (cobalt ferrite (CoFe2O4) or magnesium ferrite (MgFe2O4)) for atrazine photodegradation. Thus, the decorated Nb2O5 was synthesized by the polymeric precursor method, forming nanoparticles with sizes ranging from 25 to 50 nm. Nanocomposite elementary analyses showed a homogeneous distribution of elements on all particles surface. Efficient magnetic saturation was observed for pure CoFe2O4 (53 emu g-1) and MgFe2O4 (19 emu g-1) nanoparticles, promoting the magnetic removal of Nb2O5:CoFe2O4 and Nb2O5:MgFe2O4 nanocomposites. Photocatalytic assays showed 88% efficiency for atrazine photodegradation with all nanomaterials, which represented a 21% increase compared to photolysis in the 1st cycle. The magnetic nanocomposites when applied to a 5th cycle maintained the atrazine photodegradation activity. In this way, magnetic Nb2O5-based nanocomposites decorated with ferrite nanoparticles showed an efficient photocatalytic response, in addition to posterior magnetic removal from the aqueous medium. Therefore, the evaluated magnetic Nb2O5 nanocomposites may be an alternative to enhance the wastewater removal process and foster the reuse in advanced oxidative processes.