Development of nanomaterial chemosensors for toxic metal ions sensing

Heavy metal ions are harmful to aquatic life and humans owing to their high toxicity and non‐biodegradability, so their removal from wastewater is an important task. Therefore, this work focuses on designing suitable, simple and economical nanosensors to detect and remove these metal ions with high selectivity and sensitivity. Based on this idea, different types of mesoporous materials such as hexagonal SBA‐15, cubic SBA‐16 and spherical MCM‐41, their chloro‐functionalized derivatives, as well as 4‐(4‐nitro‐phenylazo)‐naphthalen‐1‐ol (NPAN) azo dye have been synthesized, with the aim of designing some optical nanosensors for metal ions sensing applications. The mentioned azo dye has been anchored into the chloro‐functionalized mesoporous materials. The designed nanosensors were characterized using scanning and transmission electron microscopy as well as Fourier transform infrared and UV–visible spectral analysis, nitrogen adsorption–desorption isotherms, low‐angle X‐ray diffraction and thermogravimetric analyses. Their optical sensing to various toxic metal ions such as Cd (II), Hg (II), Mn (II), Fe (II), Zn (II) and Pb (II) at different values of pH (1.1, 4.9, 7 and 12) was investigated. The optimization of experimental conditions, including the effect of pH and metal ion concentration, was examined. The experimental results showed that the solution pH had a major impact on metal ion detection. The optical nanosensors respond well to the tested metal ions, as reflected by the enhancement in both absorption and emission spectra upon adding different concentrations of the metal salts and were fully reversible on adding ethylene diamine tetra acetic acid or citric acid to the formed complexes. High values of the binding constants for the designed nanosensors were observed at pHs 7 and 12, confirming the strong chelation of different metals to the nanosensor at these pHs. Also, high binding constants and sensitivity were observed for NPAN‐MCM‐41 as a nanosensor to detect the different metal ions. From the obtained results, we succeeded in transforming the harmful azo dye into an environmentally friendly form via designing of the optical nanosensors used to detect toxic metal ions in wastewater with high sensitivity.     

An eco-friendly multi-analyte high-performance thin layer chromatographic densitometric determination of amoxicillin,metronidazole, and famotidine in their ternary mixtures and simulated gastric juice: A promising protocol for eradicating Helicobacter pylori

Gastrointestinal tract disorders constitute a heavy burden to healthcare providers. To eradicate Helicobacter pylori infection, different triple therapy protocols have been proposed. Among which are combinations of proton pump inhibitors (e.g., omeprazole), histamine-2 receptor antagonists (e.g., famotidine), along with antibiotics (e.g., amoxicillin). In this work, a sensitive and accurate high-performance thin-layer chromatographic method was developed for the simultaneous determination of amoxicillin, metronidazole, and famotidine in bulk powder and laboratory-prepared combined-tablet mixtures. Complete separation of the cited compounds was achieved using pre-coated silica gel plates with a mixture of methanol:chloroform:toluene:water:glacial acetic acid (5:2:1.5:0.5:0.1 v/v/v/v/v) as the mobile phase. The method was fully validated as per the international conference of harmonization guidelines. Good linearity, a correlation coefficient of 0.9991, was obtained in the concentration ranges 0.1–1.6 μg/band (amoxicillin), 0.1–0.9 μg/band (metronidazole), and 0.1–0.9 μg/band (famotidine). Since the method allowed the determination of the three compounds in combined tablets with a high degree of selectivity, accuracy, precision, with cost-effectiveness, it could be used for regular quality control. Moreover, the applicability of the proposed method was extended to the determination of the ternary mixture in simulated gastric juice. Method greenness was assessed using different green metrics.     

Production of Terretonin N and Butyrolactone I by Thermophilic Aspergillus terreus TM8 Promoted Apoptosis and Cell Death in Human Prostate and Ovarian Cancer Cells

The anticancer activity of terretonin N (1) and butyrolactone I (2), obtained from the thermophilic fungus Aspergillus terreus TM8, was intensively studied against prostate adenocarcinoma (PC-3) and ovary adenocarcinoma (SKOV3) human cell lines. According to this study, both compounds showed potent cytotoxicity towards ovarian adenocarcinoma cells (SKOV3) with IC₅₀ 1.2 and 0.6 μg/mL, respectively. With respect to metastatic prostate cells (PC-3), the two compounds 1 and 2 showed a significantly promising cytotoxicity effect with IC₅₀ of 7.4 and 4.5 μg/mL, respectively. The tested fungal metabolites showed higher rates of early and late apoptosis with little or no necrotic apoptotic pathway in all treated prostate adenocarcinoma (PC-3) and ovary adenocarcinoma (SKOV3) human cell lines, respectively. The results reported in this study confirmed the promising biological properties of terretonin N (1) and butyrolactone I (2) as anticancer agents via the induction of cellular apoptosis. However, further studies are needed to elucidate the molecular mechanism by which cellular apoptosis is induced in cancer cells.     

Chemical Processes Involving 18-Crown-6-Ether in Activated Noncovalent Complexes with Protonated Peptides

These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes.     

Chemistry of Phosphorus Ylides. Part 37. The Reaction of Phosphonium Ylides with Indoles and Naphthofurans. Synthesis of Phosphanylidenes,Pyrans, Cyclobutenes,and Pyridazine as Antitumor Agents

The reaction of the stabilized phosphonium ylides 2a , 2b with indolinones 1a , 1b and naphthofuranone 13 afforded the corresponding propylidene and ethylidene derivatives 4a , 4b , 4c , 4d and 14a , 14b . On the other hand, the active phosphacumulenes 5a , 5b react with compounds 4a , 4b , 4c , 4d by [4 + 2]‐cycloaddition to give the stable phosphanylidene indole pyranones 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h . Although compounds 14a , 14b afforded the naphthofuropyrans 16a , 16b , 16c , 16d and triphenylphosphane. Moreover, the phosphallene ylide 7 react with compounds 4a , 4b , 4c , 4d and 14a , 14b to give phosphanylidenecyclobuteneindoline 9a , 9b , 9c , 9d and naphthalenones 18a , 18b , respectively. In addition, the naphthofuropyridazine 21 was obtained from the reaction of the hydrazone 19 and the phosphacumulene 5a . The antitumor activity of some of the new compounds was evaluated, in vitro, against colon and hepatocellular carcinoma cell lines. They showed values closed to that recorded by the reference drug Doxorubicin.     

Comparative study between two fabricated potentiometric sensors to enhance selectivity towards ferrous ions

Electroanalytical methods are highly selective for measuring electrical quantities including the charge, potential and current with their relation to chemical parameters. They are widely applied in various fields such as biochemical analysis, industrial quality control and environmental monitoring. They have many advantages over other techniques in that they are not time consuming and are specific for certain oxidation states of certain elements which give these techniques high selectivity and sensitivity features. This paper is based on two parts: the first part describes the fabrication of screen‐printed electrodes (SPEs) modified with methyl red as electroactive material, while second part describes the preparation and characterization of Fe(II)–methyl red complex using various spectroscopic tools, the complex being used for the construction of carbon paste electrodes (CPEs). The two proposed electrodes were successfully applied for the determination of Fe(II) in water and pharmaceutical (pharovit) samples. The electrodes under investigation show potentiometric response for Fe(II) in the concentration range 8.0 × 10^?7–1.0 × 10^?2 and 5.0 × 10^?7–1.0 × 10^?2 M at 25°C for SPE and CPE, respectively, and the electrode response is independent of pH in the range 1.5–7.0. These sensors show Nernstian slopes of 29.1 ± 0.2 and 29.7 ± 0.16 mV decade^?1 with detection limit values of 8.0 × 10^?7 and 5.0 × 10^?7 M for SPE and CPE, respectively. These electrodes show fast response time of 6 and 4 s and exhibit a lifetime of 100 and 30 days for SPE and CPE, respectively. The mechanism of chemical reaction between modifier and Fe(II) on the SPE surface was studied using infrared spectra, scanning electron microscopy and energy‐dispersive X‐ray analysis. The proposed potentiometric method was validated according to the IUPAC recommendations. The results obtained using the proposed sensors were comparable with those obtained with inductively coupled plasma analysis.     

Theoretical and experimental investigations of complexation with BF3.Et2O effects on electronic structures,energies and photophysical properties of Anil and tetraphenyl (hydroxyl) imidazol

The novel compounds (E)‐2‐(((4‐hydroxyphenyl)imino)methyl)phenol, Tetraphenyl (hydroxyl) imidazole and their corresponding Boron difluoride complexes were synthesized and characterized by spectroscopic techniques. Density functional theory calculations at B3LYP‐D3/6–311++G (d, p) level of theory were performed for the geometric parameters. The MEP surface studies were used to understand the behavior of molecules in terms of charge transfer and to determine how these molecules interact. We used the GIAO and the B3LYP‐D3 with a 6–311++ G (d, p) basis set to simulate the (¹H‐NMR and ¹⁹F‐NMR) and the IR spectra, respectively. The corresponding calculated results are in good agreement with the experimental data. The stability of the molecule arising from hyperconjugation interaction and charge delocalization were analyzed using NBO analysis. FMOs revealed the occurrence of charge transfer within the molecule. The complexation using BF₃.Et₂O was also found to have remarkable effects on the electrochemical properties of the studied molecules, where (b) and (d) present lower chemical stability, higher reactivity and higher polarizability than (a) and (c), respectively. Moreover, the energy gap of (a) and (c) decreased after complexation using BF₃.Et₂O, indicating the reliability of the electrochemical evaluation of LUMO and HOMO energy levels. These values are the factors explaining the possible charge transfer interaction within the molecule. The absorption and emission spectra of the model compound were also simulated and compared to experimental observations in the DMF solvent. The results of DFT calculations supported the structural and spectroscopic data and confirmed the structure modification of frontier molecular orbitals for BF₂ complexes as well as tunable potentials and energy levels.     

Reactions of tertiary propargyl alcohols with sodium halides under oxidative conditions

The study of the reactions of tertiary propargyl alcohols with sodium halides under oxidative conditions is presented. With sodium iodide, α-iodoenones were formed, however, with sodium bromide or chloride the α-haloenones were only formed in low yields under anhydrous conditions. Conversely, upon addition of water to the reaction mixtures, α,α-dibromoketones and α,α-dichloroketones were formed in good yields, but α,α-diiodoketones were not observed.     

Densitometric Kinetic Stability Studies of Some Plant Extracts Using Different Regression Methods

JPC – Journal of Planar Chromatography – Modern TLC -     

Thermal properties of mercury(II) and palladium(II) purine and pyrimidine complexes

Six solid Pd(II) and Hg(II) complexes of some purines and pyrimidines have been prepared and characterized by elemental analyses, IR, UV–Vis spectra, magnetic measurements, and thermal analyses. The data suggest tetrahedral and square planar geometries for mercury and palladium complexes, respectively. The thermal behavior of the complexes has been studied applying TG, DTA, and DSC techniques, and the thermodynamic parameters and mechanisms of the decompositions were evaluated. The ?S* values of the decomposition steps of the metal complexes indicated that the activated fragments have more ordered structure than the undecomposed complexes, and/or the decomposition reactions are slow. The thermal processes proceeded in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing small molecules such as H₂O, HCl or C=O. The palladium adenine complex is ended with the metal as a final product. However, the thermal reactions of the other five palladium and mercury pyrimidines complexes are ended with metal bonded to O, N, or S of the pyrimidine ring.