In this study, we report on novel optical chemosensors containing benzothiazole moeity, namely, 2‐(6‐chloro‐benzothiazol‐2‐yl azo)‐4‐methyl‐phenol (CBAMP) and 1‐(6‐chloro‐benzothiazol‐2‐yl azo)‐naphthalen‐2‐ol (CBAN), which were synthesized and characterized by Fourier transform infrared spectroscopy (FT‐IR), 1H‐NMR, 13C‐NMR, and mass spectrometry. The solvatochromic behavior was explored in different solvents of various polarities to explore the active fluorescent tautomer, and the photophysical parameters have been measured. The naked eyes, as well as ultraviolet–visible (UV–Vis) and fluorescence spectroscopy, were used to study the colorimetric and optical sensing properties of CBAMP and CBAN toward various metal ions and anions. These chemosensors have a strong detecting ability, with excellent sensitivity and selectivity for certain of the metal ions investigated, as well as CO32− and CN− over other anions. The Benesi–Hildebrand and Job's plots were used to determine the binding constants and stoichiometry of the formed metal ions–sensor complexes, respectively. Co2+ and Cu2+ ions have lower detection limits in CBAMP and CBAN than other metal ions (6.4 × 10−7 and 8.4 × 10−7 M, respectively). Furthermore, fluorescent imaging investigations for Co2+ and Cu2+ ions in living cells reveal CBAMP and CBAN's promise for biological chemosensing.
The kinetics for the exchange of Li', K', R b', and Cs' for Na' as the exchangeable cation on bentonite and montmorillonite K10 and KSF have been studied using conductimetric stoppedflow. Dilute aqueous suspensions of the clays, of particle sizes of a few micrometers, were used, so that diffusion was fast and the rate-determining step was the substitution of one cation by another on the lattice surface. The kinetics were treated in terms of relaxation from equilibrium. Relaxation times ranged from 100 to 250 ms, and forward rate constants from 30 to 500 M-' s-l. The reactions had very low activation enthalpies (7-25 kJ rno1-l) and were only slow enough to be studied by the stopped-flow technique because of the large negative entropies of activation (-120 to -170 J K -' mol-I). 0 1993 John Wiley & Sons, Inc.
Herein, we synthesized three novel benzothiazole azo dyes, including 4-chloro-2-(4-methyl-benzothiazol-2-ylazo)-phenol (CMBTAP), 1-(6-chloro-benzothiazol-2-ylazo)-naphthalen-2-ol (CBAN), and 2-(6-chloro-benzothiazol-2-ylazo)-4-methyl-phenol (CBAMP), and investigated their corrosion inhibition effect on carbon steel. The dyes were characterized by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance (NMR), 13C NMR, and mass spectroscopy. Weight loss, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements were performed to investigate the corrosion inhibition effect of the dyes on carbon steel in a 1.0 M HCl solution. The synergistic effects of the dyes with potassium iodide (KI) were also investigated. The inhibition efficiency (IE%) was enhanced by increasing the dose of the dyes (1 × 10–5 to 2 × 10–4 M) and decreased as the temperature increased from 25 to 45 °C. The addition of KI to a 1.0 M HCl solution containing the dyes improved the performance and efficiency as iodide ions promoted the formation of inhibition films on the surface of carbon steel. The dyes are mixed-type inhibitors, according to Tafel polarization. Scanning electron microscopy and energy dispersive X-ray analysis were used to evaluate the surface morphology of carbon steel sheets. Quantum theory calculations were utilized to evaluate the relationship between the dyes’ chemical structures and their inhibitory efficiency, which confirmed the experimental results. The calculations revealed that the dyes have low energy gap and Milliken and Fukui indices. Among all of the dyes, CMBTAP showed the highest adsorption energy. The corrosion IE was in the order CMBTAP > CBAMP > CBAN.
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.
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