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Advanced Studies on Toxic Chemicals: Properties and Characteristics

A special issue of Toxics (ISSN 2305-6304). This special issue belongs to the section "Human Toxicology and Epidemiology".

Deadline for manuscript submissions: closed (28 February 2022) | Viewed by 29329

Special Issue Editor

Special Issue Information

Dear Colleagues,

Chemical industry has been and is still one of those most contributing to the development of the society. But alongside this positive development fact, an implicit risk must be placed: many chemical substances, both inorganic (heavy metals such as mercury, arsenic, cadmium and copper, among others, as well as compounds such as asbestos, among others) and organic (solvents such as chloroform, carbon tetrachloride or acetone; hydrocarbons, pesticides and psychoactive drugs, both natural and synthetic, among many others), have specific or general potential toxic hazards. The study of the toxic scope of these substances, which are present in our daily life in food, medicines, utensils, work, and others, provides us with very interesting information to prevent and recover from the dangerous organic unbalances that such substances can cause us.

This Special Issue of Toxics aims to deepen the study of toxic substances, their properties, and their mechanism of action. In addition, it also focuses on analyzing the effects of intoxications, including professionals, on the organisms of the living beings as a result of the accidental or provoked ingestion of any of these toxics.

Prof. Dr. Miguel A. Esteso
Guest Editor

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Toxics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • toxic chemicals
  • contaminants
  • poisonings
  • organic toxics
  • inorganic toxics
  • heavy metals
  • drugs
  • gases

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Published Papers (11 papers)

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Editorial

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3 pages, 197 KiB  
Editorial
Advanced Studies on Toxic Chemicals: Properties and Characteristics
by Miguel A. Esteso
Toxics 2022, 10(8), 475; https://doi.org/10.3390/toxics10080475 - 15 Aug 2022
Cited by 1 | Viewed by 1157
Abstract
Examining the toxic scope of substances used in daily life (referred to as Contaminants of Emerging Concern (CEC)) in food, medicines, utensils, work and other industries, provides us with interesting information that will help us to prevent and recover from the dangerous organic [...] Read more.
Examining the toxic scope of substances used in daily life (referred to as Contaminants of Emerging Concern (CEC)) in food, medicines, utensils, work and other industries, provides us with interesting information that will help us to prevent and recover from the dangerous organic unbalances that these substances can cause [...] Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)

Research

Jump to: Editorial, Other

11 pages, 2523 KiB  
Article
Recognition of Heavy Metals by Using Resorcin[4]arenes Soluble in Water
by Edilma Sanabria, Miguel A. Esteso and Edgar F. Vargas
Toxics 2022, 10(8), 461; https://doi.org/10.3390/toxics10080461 - 9 Aug 2022
Cited by 1 | Viewed by 1489
Abstract
The complexing properties of two water-soluble resorcin[4]arenes (tetrasodium 5,11,17,23-tetrakissulfonatemethylen 2,8,14,20-tetra(butyl)resorcin[4]arene, Na4BRA, and tetrasodium 5,11,17,23-tetrakissulfonatemethylen-2,8,14,20-tetra(2-(methylthio)ethyl)resorcin[4]arene, Na4SRA) with polluting heavy metals such as Cu2+, Pb2+, Cd2+ and Hg2+ were studied by conductivity, and the findings [...] Read more.
The complexing properties of two water-soluble resorcin[4]arenes (tetrasodium 5,11,17,23-tetrakissulfonatemethylen 2,8,14,20-tetra(butyl)resorcin[4]arene, Na4BRA, and tetrasodium 5,11,17,23-tetrakissulfonatemethylen-2,8,14,20-tetra(2-(methylthio)ethyl)resorcin[4]arene, Na4SRA) with polluting heavy metals such as Cu2+, Pb2+, Cd2+ and Hg2+ were studied by conductivity, and the findings were confirmed by using other techniques to try to apply this knowledge to removing them. The results indicate that Na4BRA is able to complex Cu2+ in a 1:1 ratio and Pb2+ in a 1:2 ratio, while Na4SRA complexes Hg2+ in a 1:1 ratio. On the contrary, no indications have been observed that either of the resorcin[4]arenes studied complexes the Cd2+ ions. The results suggest that the bonds established between the sulfur atoms located at the lower edge of the SRA4− and the solvent hydrogens could prevent the entry of the guest into the host cavity. However, in the case of Hg2+ ions, the entry is favoured by the interactions between the sulfur donor atoms present on the lower edge of Na4SRA and the Hg2+ ions. Therefore, it can be said that Na4BRA is selective for Cu2+ and Pb2+ ions and Na4SRA is selective for Hg2+ ions. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
Show Figures

Figure 1

Figure 1
<p>Resorcin[4]arene sulfonate structure (Na<sub>4</sub>RA).</p>
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<p>Resorcin[4]arenes sulfonated, whose complexing properties with Cu<sup>2+</sup>, Pb<sup>2+</sup>, Cd<sup>2+</sup> and Hg<sup>2+</sup> were evaluated. (<b>a</b>) Tetrasodium 5,11,17,23-tetrakissulfonate methylen-2,8,14,20-tetra(butyl)resorcin[4]arene (Na<sub>4</sub>BRA). (<b>b</b>) Tetrasodium 5,11,17,23-tetrakissulfonatemethylen-2,8,14,20-tetra(2-(methylthio) ethyl)resorcin[4]arene (Na<sub>4</sub>SRA).</p>
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<p>Specific conductivity <span class="html-italic">versus</span> the [Cu<sup>2+</sup>]/[Na<sub>4</sub>BRA] ratio. The solid blue lines (which are represented displaced parallel for better visualization) are shown as a visual aid to indicate the cut-off point that relates to the change in the slope of the specific conductivity with respect to the stoichiometry of the complex.</p>
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<p>Potentiometric titration of Cu<sup>2+</sup> with Na<sub>4</sub>BRA, using a copper selective electrode (Cu-ISE). The lines are shown as a visual aid to identify the 1:1 stoichiometry of the complex.</p>
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<p>Specific conductivity <span class="html-italic">versus</span> the [Pb<sup>2+</sup>]/[Na<sub>4</sub>BRA] ratio. The solid blue lines are shown as a visual aid to indicate the cut-off point that relates the change in slope of the specific conductivity with respect to the stoichiometry of the complex.</p>
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<p>Specific conductivity <span class="html-italic">versus</span> the [Hg<sup>2+</sup>]/[Na<sub>4</sub>BRA] and [Cd<sup>2+</sup>]/[Na<sub>4</sub>BRA] ratios. The solid blue lines are displayed as a visual aid to see that there is no appreciable change in the slope of the plot.</p>
Full article ">Figure 7
<p>Specific conductivity <span class="html-italic">versus</span> the [Hg<sup>2+</sup>]/[Na<sub>4</sub>SRA] ratio. The solid blue lines are shown as a visual aid to indicate the cut-off point that relates the change in slope of the specific conductivity with respect to the stoichiometry of the complex.</p>
Full article ">Figure 8
<p>Specific conductivity <span class="html-italic">versus</span> the [guest]/[Na<sub>4</sub>SRA] ratio; being the guest (Δ) Pb<sup>2+</sup>, (◊) Cd<sup>2+</sup>, (•) Cu<sup>2+</sup>. The solid blue lines are displayed as a visual aid to see that there is no appreciable change in the slope of the plots.</p>
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10 pages, 337 KiB  
Article
Complexation of 5-Fluorouracil with β-Cyclodextrin and Sodium Dodecyl Sulfate: A Useful Tool for Encapsulating and Removing This Polluting Drug
by Ana M. T. D. P. V. Cabral, Ana C. G. Fernandes, Neuza A. M. Joaquim, Francisco Veiga, Sara P. C. Sofio, Isabel Paiva, Miguel A. Esteso, M. Melia Rodrigo, Artur J. M. Valente and Ana C. F. Ribeiro
Toxics 2022, 10(6), 300; https://doi.org/10.3390/toxics10060300 - 1 Jun 2022
Cited by 2 | Viewed by 1708
Abstract
The formation of complexes of the drug 5-fluorouracil (5-FU) with β-cyclodextrin (β-CD) and sodium dodecyl sulphate (SDS) was studied through experimental measurements of the ternary mutual diffusion coefficients (D11, D22, D12, and D [...] Read more.
The formation of complexes of the drug 5-fluorouracil (5-FU) with β-cyclodextrin (β-CD) and sodium dodecyl sulphate (SDS) was studied through experimental measurements of the ternary mutual diffusion coefficients (D11, D22, D12, and D21) for the systems {5-FU (component 1) + β-CD (component 2) + water} and {5-FU (component 1) + SDS (component 2) + water} at 298.15 K and at concentrations up to 0.05 mol dm−3 by using the Taylor dispersion method, with the objective of removing this polluting drug from the residual systems in which it was present. The results found showed that a coupled diffusion of 5-FU occurred with both β-CD and SDS, as indicated by the nonzero values of the cross-diffusion coefficients, D12 and D21, as a consequence of the complex formation between 5-FU and the β-CD or SDS species. That is, 5-FU was solubilized (encapsulated) by both carriers, although to a greater extent with SDS (K = 20.0 (±0.5) mol−1 dm3) than with β-CD (K = 10.0 (±0.5) mol−1 dm3). Values of 0.107 and 0.190 were determined for the maximum fraction of 5-FU solubilized with β-CD and SDS (at concentrations above its CMC), respectively. This meant that SDS was more efficient at encapsulating and thus removing the 5-FU drug. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
10 pages, 2289 KiB  
Article
Photocatalytic Degradation of Dielectric Mineral Oil with PCBs Content Coupled with Algae Treatment
by Andrés F. Suárez, Carlos E. Camargo, Miguel A. Esteso and Carmen M. Romero
Toxics 2022, 10(5), 209; https://doi.org/10.3390/toxics10050209 - 22 Apr 2022
Cited by 3 | Viewed by 1902
Abstract
Insulating oil contaminated with polychlorinated biphenyls (PCBs) is an environmentally important pollutant. This research focused on the establishment of the optimum conditions under which photocatalytic oxidation can be used together with biotreatment using the Nostoc sp. microorganism to degrade PCBs present in used [...] Read more.
Insulating oil contaminated with polychlorinated biphenyls (PCBs) is an environmentally important pollutant. This research focused on the establishment of the optimum conditions under which photocatalytic oxidation can be used together with biotreatment using the Nostoc sp. microorganism to degrade PCBs present in used dielectric oils. Among the optimal conditions studied were PCB concentration, initial pH, and titanium dioxide (TiO2) concentration for the photocatalytic step, and PCB concentration and photoperiod for the biotreatment step. The results indicate that the optimal conditions necessary for photocatalytic degradation were a pH of 6.10, 113 mg/L TiO2, and 765 mg/L PCBs, achieving close to 90% removal. For the biotreatment step, the results showed that PCBs progressively inhibited the microbiological growth, with the lowest cellular growth observed in the medium with the highest PCB concentration. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Figure 1

Figure 1
<p>General molecular structure of PCBs.</p>
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<p>Schematic illustration for the photocatalytic treatment coupled to the biotreatment process of dielectric oils.</p>
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<p>Surface response for the TOC removal of the photocatalytic experiments.</p>
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<p>(<b>a</b>) TOC removal percentage vs. time for the optimal of the SRM; (<b>b</b>) van’t Hoff adjustment of PCB removal data.</p>
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<p>Chloride ion concentration surface response.</p>
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<p>Surface response for PCB removal.</p>
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12 pages, 2978 KiB  
Article
Removal of Toxic Metal Ions Using Poly(BuMA–co–EDMA) Modified with C-Tetra(nonyl)calix[4]resorcinarene
by Alver Castillo-Aguirre, Mauricio Maldonado and Miguel A. Esteso
Toxics 2022, 10(5), 204; https://doi.org/10.3390/toxics10050204 - 20 Apr 2022
Cited by 4 | Viewed by 1852
Abstract
A copolymer of poly(BuMA–co–EDMA) modified with C-tetra(nonyl)calix[4]resorcinarene was obtained via the impregnation method. The formation of the modified copolymer was confirmed and investigated using various techniques; in this way, the presence of calix[4]resorcinarene was confirmed by FT-IR spectroscopy and by [...] Read more.
A copolymer of poly(BuMA–co–EDMA) modified with C-tetra(nonyl)calix[4]resorcinarene was obtained via the impregnation method. The formation of the modified copolymer was confirmed and investigated using various techniques; in this way, the presence of calix[4]resorcinarene was confirmed by FT-IR spectroscopy and by high resolution transmission electron microscopy. The modified copolymer was used for the removal of highly toxic cations (Pb2+, Hg2+, and Cd2+) from aqueous solutions. To perform the removal, we used the batch sorption technique and the effects of time of contact, pH, and volume of sample on the effective sorption were determined. The best results were observed for Pb2+ extraction, which was comparatively more efficient. Adsorption–desorption experiments revealed that the modified copolymer could be used for several cycles without significant loss of adsorption capacity. Finally, the results showed that the modified copolymer application is highly efficient for the removal of lead ions from aqueous solutions. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Figure 1

Figure 1
<p>Characterization of the sorbents. FT-IR spectra, (<b>a</b>) copolymer (<b>2</b>) and (<b>c</b>) modified copolymer <b>(3</b>). Scanning electron micrographs at 2 μm, (<b>b</b>) copolymer (<b>2</b>)<b>,</b> and (<b>d</b>) modified copolymer <b>(3</b>).</p>
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<p>Calibration curves for Pb<sup>2+</sup>, Hg<sup>2+</sup> and Cd<sup>2+</sup> in the range from 0.1 to 20.0 mgL<sup>−1</sup>.</p>
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<p>Comparison of removal (%) using sorbents (<b>2</b>) and (<b>3</b>) for each heavy metal.</p>
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<p>Standardized Pareto charts of the experimental design of the screening using impregnated copolymer (<b>3</b>). (<b>a</b>) Pb<sup>2+</sup>, (<b>b</b>) Hg<sup>2+</sup>, (<b>c</b>) Cd<sup>2+</sup>.</p>
Full article ">Figure 4 Cont.
<p>Standardized Pareto charts of the experimental design of the screening using impregnated copolymer (<b>3</b>). (<b>a</b>) Pb<sup>2+</sup>, (<b>b</b>) Hg<sup>2+</sup>, (<b>c</b>) Cd<sup>2+</sup>.</p>
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<p>Response surfaces of the experimental optimization design.</p>
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<p>Response surfaces of the experimental optimization design.</p>
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<p>Synthesis of <span class="html-italic">C</span>-tetra(nonyl)calix[4]resorcinarene (<b>1</b>).</p>
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<p>Synthesis of poly(BuMA–<span class="html-italic">co</span>–EDMA) (<b>2</b>).</p>
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<p>Impregnation of copolymer (<b>2</b>) with calix[4]resorcinarene (<b>1</b>).</p>
Full article ">
13 pages, 2204 KiB  
Article
Classification of Various Marijuana Varieties by Raman Microscopy and Chemometrics
by Luis Ramos-Guerrero, Gemma Montalvo, Marzia Cosmi, Carmen García-Ruiz and Fernando E. Ortega-Ojeda
Toxics 2022, 10(3), 115; https://doi.org/10.3390/toxics10030115 - 28 Feb 2022
Cited by 12 | Viewed by 4007
Abstract
The Raman analysis of marijuana is challenging because of the sample’s easy photo-degradation caused by the laser intensity. In this study, optimization of collection parameters and laser focusing on marijuana trichome heads allowed collecting Raman spectra without damaging the samples. The Raman spectra [...] Read more.
The Raman analysis of marijuana is challenging because of the sample’s easy photo-degradation caused by the laser intensity. In this study, optimization of collection parameters and laser focusing on marijuana trichome heads allowed collecting Raman spectra without damaging the samples. The Raman spectra of Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), and cannabinol (CBN) standard cannabinoids were compared with Raman spectra of five different types of marijuana: four Sativa varieties (Amnesia Haze, Amnesia Hy-Pro, Original Amnesia, and Y Griega) and one Indica variety (Black Domina). The results verified the presence of several common spectral bands that are useful for marijuana characterization. Results were corroborated by the quantum chemical simulated Raman spectra of their acid-form (tetrahydrocannabinol acid (THCA), cannabidiol acid (CBDA)) and decarboxylated cannabinoids (THC, CBD, and CBN). A chemometrics-assisted method based on Raman microscopy and OPLS-DA offered good classification among the different marijuana varieties allowing identification of the most significant spectral bands. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Graphical abstract

Graphical abstract
Full article ">Figure 1
<p>Molecular structure of tetrahydrocannabinol acid (THCA) and cannabidiol acid (CBDA). In the presence of heat or light, they decompose to decarboxylate molecules: Δ<sup>9</sup>-tetrahydrocannabinol (THC) or cannabidiol (CBD). The cannabinol (CBN) is an indicator of the thermal decomposition of cannabinoids, through prolonged exposure to elevated temperatures.</p>
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<p>Optical microscope image of a trichome head used for collecting the spectra (<b>left</b>: 10× magnification, used for exploring the sample and finding representative trichomes; <b>right</b>: 50× magnification, used for collecting the spectra only from different spots on the selected trichomes).</p>
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<p>Experimental average Raman spectrum of marijuana and the main cannabinoids (THC, CBD, CBN) used as standards.</p>
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<p>Raman data set highlighting the similarities and differences among the average spectra of the Indica (Black Domina, in black) and Sativa varieties (Amnesia Haze, in red; Amnesia Hy-Pro, in gold, Original Amnesia, in blue; and Y Griega, in green).</p>
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<p>(<b>A</b>) 2D score scatter plot from the OPLS-DA model applied to the Indica (green) and Sativa (blue) marijuana Raman spectra. (<b>B</b>) Contribution plot for the Indica against Sativa marijuana samples. The variables (wavelengths) colored in orange contribute the most to make the Indica class different from the Sativa class.</p>
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<p>3D score scatter plot from the OPLS-DA model applied to the Sativa marijuana Raman spectra in order to differentiate the sample types. <a href="#app1-toxics-10-00115" class="html-app">Supplementary Figure S3</a> shows the individual 2D representations of these 3D planes.</p>
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13 pages, 973 KiB  
Article
Screening of a Novel Solvent for Optimum Extraction of Anionic Surfactants in Water
by Jung-Hwan Yoon, Yong Geon Shin, Hyuck Soo Kim, M. B. Kirkham and Jae E. Yang
Toxics 2022, 10(2), 80; https://doi.org/10.3390/toxics10020080 - 8 Feb 2022
Cited by 3 | Viewed by 2545
Abstract
Anionic surfactants (AS) are detrimental aquatic pollutants due to their well-characterized toxicity to aquatic organisms. The concentration of AS in aquatic environments is increasing because of their extensive use in many industries and households. The standard reference method for AS analysis is to [...] Read more.
Anionic surfactants (AS) are detrimental aquatic pollutants due to their well-characterized toxicity to aquatic organisms. The concentration of AS in aquatic environments is increasing because of their extensive use in many industries and households. The standard reference method for AS analysis is to determine a methylene blue active substance (MBAS) complex formed between AS and the methylene blue (MB) cation by using chloroform. However, chloroform has a low AS extraction efficiency and other limiting properties, such as a high density and volatility, which make the conventional AS analytical method time-consuming and labor-intensive. In an effort to replace the use of chloroform, this study was carried out to screen novel solvents for their ability to extract AS in water samples. Criteria were based on AS extraction efficiency, physicochemical properties, and the stability of the solvent under different environmental conditions. Organic solvents, such as methyl isobutyl ketone (MIBK), 1,2-dichloroethane (DCE), dichloromethane, benzene, and n-hexane, were assessed. In extraction of the anionic surfactant sodium dodecyl sulfate (SDS), the mixture of MIBK-DCE (3:1) proved to be an optimum solvent as an alternative to chloroform. It not only enhanced SDS extractability but also improved properties, such as having a lower volatility, a lower density than water, and a quicker phase separation. Among solvents screened, no one single solvent in SDS extraction could meet such criteria. The performance of the MIBK-DCE (3:1) mixture in SDS extraction was stable, irrespective of pH and ionic strength of the SDS solution, washing process, and presence of cations. Anionic interference from halogen and polyatomic and organic anions in SDS extraction by MIBK-DCE (3:1) existed only at an elevated concentration, which is not occurring in the natural aquatic environment. Results demonstrated that a MIBK-DCE (3:1) mixture solvent could be used in AS analysis for a wide range of aquatic samples and it could be the basis for the development of a new analytical method to replace conventional chloroform. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Graphical abstract

Graphical abstract
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<p>Comparison of washing and not washing on the extractability of sodium dodecyl sulfate (SDS) by (<b>a</b>) methyl isobutyl ketone (MIBK), (<b>b</b>) 1,2-dichloroethane (DCE), and (<b>c</b>) chloroform.</p>
Full article ">Figure 1 Cont.
<p>Comparison of washing and not washing on the extractability of sodium dodecyl sulfate (SDS) by (<b>a</b>) methyl isobutyl ketone (MIBK), (<b>b</b>) 1,2-dichloroethane (DCE), and (<b>c</b>) chloroform.</p>
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17 pages, 4623 KiB  
Article
Effect of Carbamazepine, Ibuprofen, Triclosan and Sulfamethoxazole on Anaerobic Bioreactor Performance: Combining Cell Damage, Ecotoxicity and Chemical Information
by Mabel Díaz-Cubilla, Pedro Letón, Carlos Luna-Vázquez, Marta Marrón-Romera and Karina Boltes
Toxics 2022, 10(1), 42; https://doi.org/10.3390/toxics10010042 - 17 Jan 2022
Cited by 8 | Viewed by 3380
Abstract
Pharmaceuticals and personal care products (PPCPs) are partially degraded in wastewater treatment plants (WWTPs), thereby leading to the formation of more toxic metabolites. Bacterial populations in bioreactors operated in WWTPs are sensitive to different toxics such as heavy metals and aromatic compounds, but [...] Read more.
Pharmaceuticals and personal care products (PPCPs) are partially degraded in wastewater treatment plants (WWTPs), thereby leading to the formation of more toxic metabolites. Bacterial populations in bioreactors operated in WWTPs are sensitive to different toxics such as heavy metals and aromatic compounds, but there is still little information on the effect that pharmaceuticals exert on their metabolism, especially under anaerobic conditions. This work evaluated the effect of selected pharmaceuticals that remain in solution and attached to biosolids on the metabolism of anaerobic biomass. Batch reactors operated in parallel under the pressure of four individual and mixed PPCPs (carbamazepine, ibuprofen, triclosan and sulfametoxazole) allowed us to obtain relevant information on anaerobic digestion performance, toxicological effects and alterations to key enzymes involved in the biodegradation process. Cell viability was quantitatively evaluated using an automatic analysis of confocal microscopy images, and showed that triclosan and mixed pollutants caused higher toxicity and cell death than the other individual compounds. Both individual pollutants and their mixture had a considerable impact on the anaerobic digestion process, favoring carbon dioxide production, lowering organic matter removal and methane production, which also produced microbial stress and irreversible cell damage. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Figure 1

Figure 1
<p>Organic matter removal (in black squared lines), biogas production (in red triangular and blue rhomboidal lines) and ecotoxicity (in green circled lines) in anaerobic reactors: (<b>A</b>) Control reactor without pollutants; (<b>B</b>) Reactor containing SFM; (<b>C</b>) Reactor containing CBM; (<b>D</b>) Reactor containing IBU; (<b>E</b>) Reactor containing TCS; (<b>F</b>) Reactor containing mixed pollutants.</p>
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<p>Removal of selected pollutants in aqueous media and their accumulation into the sludge of anaerobic reactors: (<b>A</b>) liquid fraction; (<b>B</b>) solid fraction (sludge). Filled bars correspond to individual contaminant in reactors; hatched bars correspond to mixture of pollutants in reactor.</p>
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<p>Profile of enzymatic activities of anaerobic biomass exposed to selected PPCPs: (<b>A</b>) GST activity; (<b>B</b>) CAT activity; (<b>C</b>) ROS generation; (<b>D</b>) Esterase activity.</p>
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<p>Principal component analysis (PCA) for anaerobic digesters. Squares represent the bioreactors containing PPCPs (SFM, TCS, IBU, CBM, MIX) and the reactor free of pollutants (CNT). Lines indicate the parameters measured, including chemical (TOC, CH<sub>4</sub>, CO<sub>2</sub>) and biochemical (EST, ROS, GST, CAT, nonviable cell fraction and Ecotox).</p>
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<p>Viable to non-viable cell proportion in anaerobic reactors in presence of PPCPs at different culture time.</p>
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<p>Experimental setup and sample treatment for chemical and biochemical analysis.</p>
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<p>General block diagram of image processing procedure.</p>
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17 pages, 2610 KiB  
Article
Respiratory Safety Evaluation in Mice and Inhibition of Adenoviral Amplification in Human Bronchial Endothelial Cells Using a Novel Type of Chlorine Dioxide Gas Reactor
by Hae-Sung Yang, Kyeong-Min Kim, Napissara Boonpraman, Sun-Mi Yoon, Jeong-Eun Seo, Min-Woo Park, Jong-Seok Moon, Su-Young Yoo and Sun-Shin Yi
Toxics 2022, 10(1), 38; https://doi.org/10.3390/toxics10010038 - 13 Jan 2022
Cited by 3 | Viewed by 3450
Abstract
Since the onset of the COVID-19 pandemic, there has been a growing demand for effective and safe disinfectants. A novel use of chlorine dioxide (ClO2) gas, which can satisfy such demand, has been reported. However, its efficacy and safety remain unclear. [...] Read more.
Since the onset of the COVID-19 pandemic, there has been a growing demand for effective and safe disinfectants. A novel use of chlorine dioxide (ClO2) gas, which can satisfy such demand, has been reported. However, its efficacy and safety remain unclear. For the safe use of this gas, the stable release of specific concentrations is a must. A new type of ClO2 generator called Dr.CLOTM has recently been introduced. This study aimed to investigate: (1) the effects of Dr.CLOTM on inhibiting adenoviral amplification on human bronchial epithelial (HBE) cells; and (2) the acute inhalation safety of using Dr.CLOTM in animal models. After infecting HBE cells with a recombinant adenovirus, the inhibitory power of Dr.CLOTM on the virus was expressed as IFU/mL in comparison with the control group. The safety of ClO2 gas was indirectly predicted using mice by measuring single-dose inhalation toxicity in specially designed chambers. Dr.CLOTM was found to evaporate in a very constant concentration range at 0–0.011 ppm/m3 for 42 days. In addition, 36–100% of adenoviral amplification was suppressed by Dr.CLOTM, depending on the conditions. The LC50 of ClO2 gas to mice was approximately 68 ppm for males and 141 ppm for females. Histopathological evaluation showed that the lungs of female mice were more resistant to the toxicity from higher ClO2 gas concentrations than those of male mice. Taken together, these results indicate that Dr.CLOTM can be used to provide a safe indoor environment due to its technology that maintains the stable concentration and release of ClO2 gas, which could suppress viral amplification and may prevent viral infections. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Graphical abstract

Graphical abstract
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<p>Safe duration and concentration of ClO<sub>2</sub> gas controlled by Dr.CLO<sup>TM</sup>. After activation of Dr.CLO<sup>TM</sup>, the maximum concentration of ClO<sub>2</sub> gas was 0.011 ppm/m<sup>3</sup>. It was confirmed that the concentration was stably maintained between 0.000 and 0.011 ppm/m<sup>3</sup> for 42 days after Dr.CLO<sup>TM</sup> activation. Error bars represent mean ± SD.</p>
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<p>Quantitative and qualitative inhibitory effect of treatment by Dr.CLO<sup>TM</sup> on adenoviral amplification. (<b>A</b>) The dissolved chlorine concentration in cell culture medium after activation of Dr.CLO<sup>TM</sup> for 24 h. (<b>B</b>) When human bronchial epithelial (HBE) cells were inoculated with multiple adenovirus doses (1× &amp; 2×) using the immunocytochemistry (ICC) method, infected positive cells showed purple reactions. Infected cells are marked with red dotted circles. (<b>C</b>) Results of positive cells not treated with Dr.CLO<sup>TM</sup> and the number of positive cells inhibited when treated with Dr.CLO<sup>TM</sup>. Dr.CLO<sup>TM</sup> showed inhibitory effects on both 1× and 2× viral infections. (<b>D</b>) Adenoviral titers (IFUs/mL) inoculated randomly at three different concentrations were significantly reduced by Dr.CLO<sup>TM</sup>. The black square box represents the enlarged cell shape. The error bars indicate mean ± SEM; *, <span class="html-italic">p &lt;</span> 0.05; **, <span class="html-italic">p &lt;</span> 0.005; ***, <span class="html-italic">p &lt;</span> 0.0005; ****, <span class="html-italic">p &lt;</span> 0.0001.</p>
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<p>Body weight changes during the experiment. (<b>A</b>) For male animals, high concentrations of ClO<sub>2</sub> gas (Chamber #1–Chamber #4) resulted in high mortality. However, mice in Chamber #5 and Chamber #6 recovered their body weight gradually from D4–5. (<b>B</b>) For female animals, all animals in Chamber #1 died after exposure to a concentration of 240 ppm or more. However, animals corresponding to the remaining concentrations were resistant to ClO<sub>2</sub> gas and survived compared to males. Error bars represent mean ± SEM.</p>
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<p>Lung tissue hematoxylin &amp; eosin (H&amp;E) and Masson’s trichrome (MT) staining results for each group. (<b>A</b>) Male histopathological staining images according to ClO<sub>2</sub> gas concentration. From Chamber #1 to Chamber #5, edema in alveolar cells increased fibrosis of interstitial tissue. Mucosal cohesion and thromboembolic infraction of the alveolar lumen are recognized. (<b>B</b>) Histopathological staining images of female mice by ClO<sub>2</sub> gas concentrations. From Chamber #1 to Chamber #5, edema in alveolar cells increased fibrosis of interstitial tissue. Findings of mucosal congestions and thromboembolic infarction in the alveolar lumen are similar to those in males. However, compared to males, alveolar lumen accounted for a higher proportion. Distraction of the alveolar wall was recognized. Black square boxes are enlarged parts of lesions. Control: non-treated group; Chamber #1: 240 ppm &lt; group; Chamber #2: 200~240 ppm group; Chamber #3: 150~200 ppm group; Chamber #4: 100~150 ppm group; Chamber #5: 50~100 ppm group; Chamber #6: 20~50 ppm group. H&amp;E = hematoxylin and eosin; MT = Masson’s trichrome. Scale bar = 100 μm.</p>
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<p>Graph showing the space of the alveolar sac lumen within the lung lobe. The area ratio of the space where gas exchange can occur per unit area is shown. (<b>A</b>) When comparing results in males, each concentration in Chamber #1–Chamber #5 shows a significant difference for ClO<sub>2</sub> gas compared to the non-treated group. (<b>B</b>) When comparing results in females, each concentration in Chamber #1–Chamber #4 resulted in a significant difference for ClO<sub>2</sub> gas compared to the non-treated group. **, <span class="html-italic">p</span> &lt; 0.005; ***, <span class="html-italic">p</span> &lt; 0.0005; ****, <span class="html-italic">p</span> &lt; 0.0001. Error bars represent mean ± SEM.</p>
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11 pages, 3258 KiB  
Article
The Research of Toxicity and Sensitization Potential of PEGylated Silver and Gold Nanomaterials
by Dong-Han Lee, Seo-Yoon Choi, Ki-Kyung Jung, Jun-Young Yang, Ja-young Jeong, Jae-Ho Oh, Sung-Hyun Kim and Jin-Hee Lee
Toxics 2021, 9(12), 355; https://doi.org/10.3390/toxics9120355 - 16 Dec 2021
Cited by 5 | Viewed by 2632
Abstract
Polyethylene glycol (PEG) is a polymer used for surface modification of important substances in the modern pharmaceutical industry and biopharmaceutical fields. Despite the many benefits of PEGylation, there is also the possibility that the application and exposure of the substance may cause adverse [...] Read more.
Polyethylene glycol (PEG) is a polymer used for surface modification of important substances in the modern pharmaceutical industry and biopharmaceutical fields. Despite the many benefits of PEGylation, there is also the possibility that the application and exposure of the substance may cause adverse effects in the body, such as an immune response. Therefore, we aimed to evaluate the sensitization responses that could be induced through the intercomparison of nanomaterials of the PEG-coated group with the original group. We selected gold/silver nanomaterials (NMs) for original group and PEGylated silver/gold NMs in this study. First, we measured the physicochemical properties of the four NMs, such as size and zeta potential under various conditions. Additionally, we performed the test of the NM’s sensitization potential using the KeratinoSens™ assay for in vitro test method and the LLNA: 5-bromo-2-deoxyuridine (BrdU)-FCM for in vivo test method. The results showed that PEGylated-NMs did not lead to skin sensitization according to OECD TG 442 (alternative test for skin sensitization). In addition, gold nanomaterial showed that cytotoxicity of PEGylated-AuNMs was lower than AuNMs. These results suggest the possibility that PEG coating does not induce an immune response in the skin tissue and can lower the cytotoxicity of nanomaterials. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Figure 1

Figure 1
<p>Induction of luciferase activity (orange line) and cell viability (black line) of the KeratinoSens™ assay. The cells were treated with the (<b>A</b>) silver nanomaterials (AgNMs), (<b>B</b>) gold nanomaterials (AuNMs), and PEGylated nanomaterials for (<b>C</b>) AgNMs, and (<b>D</b>) AuNMs. Data are expressed as the mean ± SEM (<span class="html-italic">n</span> = 6).</p>
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<p>Luciferase activity (orange line) and cell viability (black line) of positive control (trans-cinnamic aldehyde, CASRN. 14371-10-9) in KeratinoSens™ assay. Data are expressed as the mean ± SEM (<span class="html-italic">n</span> = 6). The positive control was tested in parallel (concentration: 4–64 µM).3.2. Bronchoalveolar lavage fluid analysis.</p>
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<p>Results of AgNMs skin sensitization potential in LLNA: BrdU-FCM. The assessment parameters were as follows: (<b>A</b>) Body weight (g), (<b>B</b>) Ear thickness (mm), (<b>C</b>) Ear weight (mg), (<b>D</b>) Lymph node weight (mg), (<b>E</b>) Lymph node cell (LNC) count (×10<sup>7</sup> cells), and (<b>F</b>) Stimulation Index (SI). Data are expressed as the mean ± SEM (<span class="html-italic">n</span> = 4). Each treatment group was compared with the vehicle control group to determine the statistical significance. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt;0.001.</p>
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<p>Results of PEG-AgNMs skin sensitization potential in LLNA: BrdU-FCM. The assessment parameters were as follows: (<b>A</b>) Body weight (g), (<b>B</b>) Ear thickness (mm), (<b>C</b>) Ear weight (mg), (<b>D</b>) Lymph node weight (mg), (<b>E</b>) Lymph node cell (LNC) count (×10<sup>7</sup> cells), and (<b>F</b>) Stimulation Index (SI). Data are expressed as the mean ± SEM (<span class="html-italic">n</span> = 4). Each treatment group was compared with the vehicle control group to determine the statistical significance. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt;0.001.</p>
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<p>Results of AuNMs skin sensitization potential in LLNA: BrdU-FCM. The assessment parameters were as follows: (<b>A</b>) Body weight (g), (<b>B</b>) Ear thickness (mm), (<b>C</b>) Ear weight (mg), (<b>D</b>) Lymph node weight (mg), (<b>E</b>) Lymph node cell (LNC) count (×10<sup>7</sup> cells), and (<b>F</b>) Stimulation Index (SI). Data are expressed as the mean ± SEM (<span class="html-italic">n</span> = 4). Each treatment group was compared with the vehicle control group to determine the statistical significance. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt;0.001.</p>
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<p>Results of PEG-AuNMs skin sensitization potential in LLNA: BrdU-FCM. The assessment parameters were as follows: (<b>A</b>) Body weight (g), (<b>B</b>) Ear thickness (mm), (<b>C</b>) Ear weight (mg), (<b>D</b>) Lymph node weight (mg), (<b>E</b>) Lymph node cell (LNC) count (×10<sup>7</sup> cells), and (<b>F</b>) Stimulation Index (SI). Data are expressed as the mean ± SEM (<span class="html-italic">n</span> = 4). Each treatment group was compared with the vehicle control group to determine the statistical significance. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, and *** <span class="html-italic">p</span> &lt;0.001.</p>
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10 pages, 2517 KiB  
Case Report
Identification of 2C-B in Hair by UHPLC-HRMS/MS. A Real Forensic Case
by José Manuel Matey, Adrián López-Fernández, Carmen García-Ruiz, Gemma Montalvo, Félix Zapata and María A. Martínez
Toxics 2021, 9(7), 170; https://doi.org/10.3390/toxics9070170 - 15 Jul 2021
Cited by 4 | Viewed by 4044
Abstract
The analysis of drugs of abuse in hair and other biological matrices of forensic interest requires great selectivity and sensitivity. This has been traditionally achieved through target analysis, using one or more analytical methods that include different preanalytical stages, and more complex procedures [...] Read more.
The analysis of drugs of abuse in hair and other biological matrices of forensic interest requires great selectivity and sensitivity. This has been traditionally achieved through target analysis, using one or more analytical methods that include different preanalytical stages, and more complex procedures followed by toxicological laboratories. There is no exception with 2C-series drugs, such as 2C-B, a new psychoactive substance (NPS), which use has emerged and significantly increased, year by year, in the last decades. Continuously new analytical methods are required to selectively detect and identify these new marketed substances at very low concentrations. In this case report, one former case of a polydrug consumer (charged of a crime against public health in Spain) was reanalyzed in hair matrix. In this reanalysis, 2C-B has been positively detected and identified using liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS/MS). The most selective analytical UHPLC-HRMS/MS method alongside a universal and simpler pretreatment methodology has opened up more possibilities for the detection of substances of different chemical structure and optimization of different HRMS/MS detection approaches allowing the identification of 2-CB in the hair of a real forensic case. Full article
(This article belongs to the Special Issue Advanced Studies on Toxic Chemicals: Properties and Characteristics)
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Figure 1
<p>Sample of hair analyzed. An aliquot of 6 cm of length was collected, prepared for toxicological analysis and analyzed afterwards.</p>
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<p>Detection of precursor ion of 2C-B analysis of accuracy mass &lt; 5 ppm, using the UHPLC-HRMS/MS technique, in mode of acquisition Target Screening, in a real hair forensic case sample (<b>A</b>) and with a certified reference material in hair (<b>B</b>) with a concentration of 10 pg/mg in the hair matrix (LOD).</p>
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<p>Identification of 2C-B by UHPLC-HRMS/MS by confirmation in the second approach in a real hair forensic case sample (<b>a</b>); and compared using the detection in a Certified Reference Material of 2C-B as the pure solution in methanol at 1.0 mg/L (<b>b</b>).</p>
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<p>Identification of the main fragments of 2C-B by UHPLC-HRMS/MS by confirmation using a second detection approach in the real hair forensic sample using the PRM mode.</p>
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