Development of In-Needle SPME Devices for Microextraction Applied to the Quantification of Pesticides in Agricultural Water.

The chemical industry explosion in the 20th century has led to increased environmental pollution, affecting fauna, flora, and waterways. These substances alter water's taste, color, and smell, making it unfit for consumption or toxic. Agricultural water networks face threats from pollution before and after treatment. Some chemical contaminants, like pesticides, are embedded in natural biogeochemical cycles. In this study, we developed a simple and low-cost procedure for the fabrication of needles coated with polydimethylsiloxane (PDMS) as an efficient sorbent for the microextraction of organic pollutant traces from water. The prepared needles were used as an alternative for commercial solid-phase micro-extraction (SPME) devices in analytical chemistry. The PDMS polymeric phase was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The PDMS-coated needles were used for extraction of thirteen pesticides by direct-immersion solid-phase microextraction (DI-SPME) from contaminated waters, followed by determination with gas chromatography-mass spectrometry (GC-MS). The developed analytical method showed limits of detection (LODs) between 0.3 and 2.5 ng mL-1 and RSDs in the range of 0.8-12.2%. The homemade needles were applied for the extraction of pesticides in surface and ground aqueous samples collected from an agricultural area. Several target pesticides were identified and quantified in the investigated water samples.

Synthesis, optical properties, DNA, ß-cyclodextrin interaction, hydrogen isotope sensor and computational study of new enantiopure isoxazolidine derivative (ISoXD).

A novel isoxazolidine derivative (ISoXD) dye was successfully synthesized and comprehensively characterized. In this study, we conducted a thorough examination of its various properties, including optical characteristics, interactions with DNA and ß-cyclodextrin (ß-CD), molecular docking, molecular dynamic simulation, and density functional theory (DFT) calculations. Our investigation encompassed a systematic analysis of the absorption and emission spectra of ISoXD in diverse solvents. The observed variations in the spectroscopic data were attributed to the specific solvent's capacity to engage in hydrogen bonding interactions. Remarkably, the most pronounced intensities were observed in glycol, which can establish many hydrogen bonds with ISoXD. Furthermore, our study revealed a significant distinction in the fluorescence behavior of ISoXD when subjected to different solvents, particularly between CHCl3 and CDCl3. Moreover, we explored the fluorescence intensity of the ISoXD complex in the presence of various metals, both in ethanol and water. The ISoXD complex exhibited a substantial increase of fluorescence upon interaction with different metal ions. The utilization of DFT calculations allowed us to propose an intramolecular charge transfer (ICT) mechanism as a plausible explanation for this quenching phenomenon. The interaction of ISoXD with DNA and ß-CD was studied using absorption spectra. The binding constant (K) and the standard Gibbs free energy change (ΔGo) for the interaction between DNA and ß-CD with ISoXD were determined. In docking study, ISoXD exhibited significant docking scores (-6.511) and MM-GBSA binding free energies (-66.27 kcal/mol) within the PARP-1 binding cavity. Its binding pattern closely resembles to the co-crystal ligand veliparib, and during a 100ns MD simulation, ISoXD displayed strong stability and formed robust hydrogen bonds with key amino acids. These findings suggest ISoXD's potential as a PARP-1 inhibitor for further investigation in therapeutic development.

In Silico Design, Synthesis, and Evaluation of Novel Enantiopure Isoxazolidines as Promising Dual Inhibitors of α-Amylase and α-Glucosidase.

Isoxazolidine derivatives were designed, synthesized, and characterized using different spectroscopic techniques and elemental analysis and then evaluated for their ability to inhibit both α-amylase and α-glucosidase enzymes to treat diabetes. All synthesized derivatives demonstrated a varying range of activity, with IC50 values ranging from 53.03 ± 0.106 to 232.8 ± 0.517 µM (α-amylase) and from 94.33 ± 0.282 to 258.7 ± 0.521 µM (α-glucosidase), revealing their high potency compared to the reference drug, acarbose (IC50 = 296.6 ± 0.825 µM and 780.4 ± 0.346 µM), respectively. Specifically, in vitro results revealed that compound 5d achieved the most inhibitory activity with IC50 values of 5.59-fold and 8.27-fold, respectively, toward both enzymes, followed by 5b. Kinetic studies revealed that compound 5d inhibits both enzymes in a competitive mode. Based on the structure-activity relationship (SAR) study, it was concluded that various substitution patterns of the substituent(s) influenced the inhibitory activities of both enzymes. The server pkCSM was used to predict the pharmacokinetics and drug-likeness properties for 5d, which afforded good oral bioavailability. Additionally, compound 5d was subjected to molecular docking to gain insights into its binding mode interactions with the target enzymes. Moreover, via molecular dynamics (MD) simulation analysis, it maintained stability throughout 100 ns. This suggests that 5d possesses the potential to simultaneously target both enzymes effectively, making it advantageous for the development of antidiabetic medications.

Study of Modified Magnesium Phosphate Cement for Fluoride Removal.

In this study, we used a novel composite material based on magnesium phosphate cement (MPC) to explore the retention of fluoride from used water. Dead-burned magnesium oxide (MgO), ammonium dihydrogen phosphate (NH4H2PO4), and a few retarders were used to create this particular substance. Several studies have corroborated the performance of using aluminum in the capture of fluoride. From this perspective, we attempted to reinforce our matrix with different quantities of aluminum, which increased the resistance of the composite in water. The optimal conditions that were obtained were evaluated and scrutinized using a range of techniques, including scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transforms infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET). The adsorbents demonstrated a powerful ability to remove fluoride from contaminated water and the defluoridation capacity was evaluated at 4.84 mg/g. Equilibrium modeling was carried out, and the experimental data were expressed in accordance with the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms.

Synthesis and Characterization of New Composite Materials Based on Magnesium Phosphate Cement for Fluoride Retention.

In this research work, new composite materials based on magnesium phosphate cement (MPC) were developed to evaluate the retention of fluorine from wastewater. This material was prepared with dead burned magnesia oxide (MgO), ammonium dihydrogen phosphate (NH4H2PO4), and some retarding agents. We chose to synthesize with hydrogen peroxide instead of water; alumina and zeolite were also added to the cement. The obtained optimal conditions were studied and analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), BET, and thermogravimetric analysis (TGA). The adsorbents showed a strong ability to remove fluoride from contaminated water, and the best defluoridation capacity was evaluated as 2.21 mg/g for the H2O2 cement. Equilibrium modeling was performed, and the experimental data were presented according to the isotherms of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich.

In Situ Electrodeposition of Pb and Ag Applied on Fluorine Doped Tin Oxide Substrates: Comparative Experimental and Theoretical Study.

A comparison between lead and silver electrodeposition onto fluorine-doped tin oxide (FTO) electrodes from nitrate solution was investigated in this work. Chronoamperometry has been used as an in situ technique to track the dynamics of the electrodeposition during advanced nucleation phases. The experimental results are correlated with a theoretical evaluation. It has shown that they have a strong correlation with each other. After that, the obtained deposits are characterized and compared as well by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), and impedance spectroscopy. The data reflects the effect of the material under investigation on current density, deposition density, and dielectric properties. Additionally, the electrodeposition approach (a two-in-one technique) can be followed in order to make well-controlled thin films that can be used for various purposes in addition to recovering heavy metals from wastewater.

Microstructure and Magnetic Properties of Nanocrystalline Fe60-xCo25Ni15Six Alloy Elaborated by High-Energy Mechanical Milling.

In the present work, the effect of Si addition on the magnetic properties of Fe60-xCo25Ni15Six (x = 0, 5, 10, 20, and 30 at%) alloys prepared by mechanical alloying was analyzed by X-ray diffraction and magnetic vibrating sample magnetometry and SQUID. The crystallographic parameters of the bcc-solid solutions were calculated by Rietveld refinement of the X-ray diffraction patterns with Maud software. Scanning electron microscopy (SEM) was used to determine the morphology of the powdered alloys as a function of milling time. It was found that the Si addition has an important role in the increase of structural hardening and brittleness of the particles (favoring the more pronounced refinement of crystallites). The resulting nanostructure is highlighted in accordance with the concept of the structure of defects. Magnetic properties were related to the metalloid addition, formed phases, and chemical compositions. All processed samples showed a soft ferromagnetic behavior (Hc ≤ 100 Oe). The inhomogeneous evolution of the magnetization saturation as a function of milling time is explained by the magnetostriction effective anisotropy and stress induced during mechanical alloying.

Chemosensing Properties of Coumarin Derivatives: Promising Agents with Diverse Pharmacological Properties, Docking and DFT Investigation.

In this work, a three-component reaction of 3-acetyl-4-hydroxycoumarine, malononitrile, or cyanoacetate in the presence of ammonium acetate was used to form coumarin derivatives. The chemical structures of new compounds were identified by 1H, 13C NMR and an elemental analysis. These compounds were examined in vitro for their antimicrobial activity against a panel of bacterial strains. In addition, these compounds were investigated for antioxidant activities by superoxideradical, DPPH (2,2-Diphenyl-1-picrylhydrazyl), and hydroxyl radical scavenging assays, in which most of them displayed significant antioxidant activities. Furthermore, these compounds were evaluated for anti-inflammatory activity by indirect hemolytic and lipoxygenase inhibition assays and revealed good activity. In addition, screening of the selected compounds 2-4 against colon carcinoma cell lines (HCT-116) and hepatocellular carcinoma cell lines (HepG-2) showed that that 2-amino-4-hydroxy-6-(4-hydroxy-2-oxo-2H-chromen-3-yl)nicotinonitrile 4 exhibited good cytotoxic activity against standard Vinblastine, while the other compounds exhibited moderate cytotoxic activity. Docking simulation showed that2-amino-4-hydroxy-6-(4-hydroxy-2-oxo-2H-chromen-3-yl)nicotinonitrile 4 is an effective inhibitor of the tumor protein HCT-116. A large fluorescence enhancement in a highly acidic medium was observed, and large fluorescence quenching by the addition of traces of Cu2+ and Ni2+ was also remarked.

Exploration of the Mechanism of the Dimerization of Hydroxymethylsilanetriol Using Electronic Structure Methods.

Hydroxymethylsilanetriol undergoes condensation reactions to form new structures with an organic part in the formed bridges. As a first step to explore the formation of these bridges, we studied the corresponding mechanisms using simple models and theoretical methods. Three mechanisms were studied for the formation of dimers of hydroxymethylsilanetriol with bridges: Si-O-C-Si, Si-O-Si, and Si-C-O-C-Si. Energies are calculated using M06/6-311+G(d,p) single-point calculations on B3LYP-optimized geometries in solution and including B3LYP thermodynamic corrections. The first mechanism for the formation of the Si-O-C-Si bridge consists of one step. The second mechanism for the formation of the Si-O-Si bridge consists of two steps. The barrier for the last mechanism for the formation of the Si-C-O-C-Si bridge is too high and cannot occur at room temperature. The energy barriers are 31.8, 27.6, and 65.9 kcal mol-1 for the first, second, and third mechanisms, respectively. When adding one explicit water molecule, these energies are 25.9, 22.9, and 80.3 kcal mol-1, respectively. The first and second mechanisms can occur at room temperature, which is in agreement with the experimental results.

Distribution and ecological risk of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in surface sediments from the Bizerte lagoon, Tunisia.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in 18 surface sediment samples collected from Bizerte lagoon, Tunisia. The total concentrations of ten PCBs (∑PCBs) and of four OCPs (∑OCPs) in the sediments from this area ranged from 0.8 to 14.6 ng g(-1) dw (average value, 3.9 ng g(-1) dw) and from 1.1 to 14.0 ng g(-1) dw (average value, 3.3 ng g(-1) dw), respectively. Among the OCPs, the range of concentrations of dichlorodiphenyltrichloroethane and its metabolites (DDTs) and hexachlorobenzene (HCB) were 0.3-11.5 ng g(-1) dw (1.9 ng g(-1) dw) and 0.6-2.5 ng g(-1) dw (1.4 ng g(-1) dw), respectively. Compositional analyses of the POPs indicated that PCB 153, 138 and 180 were the predominant congeners accounting for 60 % of the total PCBs. In addition, p,p'-DDT was found to be the dominant DDTs, demonstrating recent inputs in the environment. Compared with some other regions of the world, the Bizerte lagoon exhibited low levels of PCBs and moderate levels of HCB and DDTs. The high ratios ΣPCBs/ΣDDTs indicated predominant industrial versus agricultural activities in this area. According to the established guidelines for sediment quality, the risk of adverse biological effects from such levels of OCPs and PCBs, as recorded at most of the study sites, was insignificant. However, the higher concentrations in stations S1 and S3 could cause biological damage.

Concentrations of organochlorine pesticides and polychlorinated biphenyls in human serum and their relation with age, gender, and BMI for the general population of Bizerte, Tunisia.

Human serum samples (n = 113) from Bizerte, northern Tunisia, collected between 2011 and 2012 were analyzed for 8 organochlorine pesticides (OCPs) including p,p'-dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers, dieldrin, and heptachlor and 12 polychlorinated biphenyls (PCBs) congeners. Concentrations of these residues in serum were determined by gas chromatography with electron capture detector and total cholesterol (CHOL) and triglycerides (TG) levels were evaluated by enzymatic colorimetric method. HCB, p,p'-DDE, PCB-138, PCB-153, and PCB-180, were the most abundant organochlorine compounds (OCs) detected in >95 % of the study subjects. The mean levels of p,p'-DDE and HCB in serum were 168.8 and 49.1 ng g(-1) lipid, respectively. The sum PCBs concentrations ranged from 37.5 to 284.6 ng g(-1) lipid in the samples, with mean and median value of 136.1 and 123.2 ng g(-1) lipid, respectively. The PCB profile consisted of persistent congeners, such as PCB-138, PCB-153, and PCB-180 which contributed for approximately 82.7 % to the ∑PCBs. Statistical analysis showed that most OCs correlated significantly with age, considering all samples together or with gender differentiation. The present study shows that the levels of p,p'-DDE and ∑DDTs were significantly higher in females than in males (p < 0.05), while PCBs levels were significantly higher in male (p < 0.05) than in females. No statistically significant association was found between body mass index and concentration of any organochlorine pesticide or PCB congeners 153, 138, 180, or ∑PCBs.

Concentration of polychlorinated biphenyls and organochlorine pesticides in mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax) from Bizerte Lagoon (Northern Tunisia).

Concentrations of polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were determined in two fish species, mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax), collected from Bizerte Lagoon and the Mediterranean Sea. In all samples, PCBs were found in higher concentrations than OCPs. The highest concentrations of OCPs and PCBs were found in sea bass, and in Bizerte Lagoon. Concentrations of DDTs and PCBs detected in this study were generally comparable or slightly higher than those found in studies from other Mediterranean and non-Mediterranean regions subject to a high anthropogenic impact. ∑PCBs, ∑HCHs and HCB levels were negatively correlated with lipid content, while no such correlation was seen for ∑DDTs. A significant correlation between levels and length and between levels and weight existed only for ∑PCBs. The daily intake of PCBs and OCPs ingested by people living in Bizerte through the studied fish species was estimated and compared with those observed in other areas.

Polybrominated diphenyl ethers and their methoxylated analogs in mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax) from Bizerte Lagoon, Tunisia.

Concentrations of ten polybrominated diphenyl ethers (PBDEs) and eight methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax) collected from the Bizerte Lagoon and the Mediterranean Sea were investigated. To the best of our knowledge, this is the first report of these compounds in marine fishes from Tunisia. The PBDE mean concentrations in fish from Bizerte Lagoon were 45.3 and 96.2 ng g(-1) lw respectively in mullet and sea bass, while the concentrations of these compounds in mullet and sea bass from Mediterranean Sea were 7.80 and 27.9 ng g(-1) lw respectively. MeO-PBDE concentrations in mullet and sea bass from Bizerte Lagoon ranged from 6.46 to 286 ng g(-1) lw and from 49.4 to 798 ng g(-1) lw respectively, while the concentrations of these compounds in mullet and sea bass from Mediterranean Sea ranged from 190 to 401 ng g(-1) lw and from 353 to 578 ng g(-1) lw respectively. The total PBDEs and total MeO-PBDEs concentration in fish from Bizerte Lagoon were similar or slightly lower than those reported for other species from other locations around the world.