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Chemical Sensors of Inorganic Cations and Anions

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A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (30 September 2023) | Viewed by 12324

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Special Issue Editors

Dr. George Gamov

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Guest Editor

Department of General Chemical Technology, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia
Interests: schiff bases; hydrazones; pyridoxal 5’-phosphate; complexation; stability constant calculation; sensors

Prof. Dr. Elena Antina

E-Mail Website
Guest Editor

Laboratory of Physical Chemistry of Solutions of Macrocyclic Compounds, Institute of Solution Chemistry, Russian Academy of Sciences, 153045 Ivanovo, Russia
Interests: dipyrromethene; photoinduced electron transfer; sensors; fluorescence; bodipy

Special Issue Information

Dear Colleagues,

The progress of industry development and new challenges related to the increasing anthropogenic load, which include pollution of water, air and soil by different inorganic cations and anions, determine the importance of the development of new analytical techniques. The timely detection of inorganic ionic species may be crucial in preventing disruption to technological processes or the contamination of water bodies, thus neglecting the potential harm to human health and the economy. Therefore, this issue aims to discuss and analyze the efforts of researchers to create sensors for detecting the different inorganic cations and anions in an environment. The set of experimental techniques suitable for this aim includes, but is not limited to, spectrophotometry, IR spectroscopy, fluorescent spectroscopy, potentiometric or other electrochemical methods, kinetic analysis, etc. Authors are encouraged to submit papers that contain inexpensive solutions that can easily be implemented in practice. Critical reviews of the different techniques developed to date are also welcome.

Dr. George Gamov
Prof. Dr. Elena Antina
Guest Editors

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Keywords

cation detection
anion detection
optical probes
electrochemical probes

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Published Papers (6 papers)

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Research

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13 pages, 8483 KiB

Open AccessArticle

A Multifunctional Fluorescent Probe Based on 1,8-Naphthalimide for the Detection of Co²⁺, F⁻, and CN⁻

by Ping Li, Xian-Xian Ji, Ming-Yao Xu, Yu-Long Liu and Liu Yang

Inorganics 2023, 11(7), 265; https://doi.org/10.3390/inorganics11070265 - 22 Jun 2023

Cited by 2 | Viewed by 1553

Abstract

Cations and anions are indispensable resources for the development of nature and modern industry and agriculture, and exploring more efficient technology to monitor them is urgently needed. A multifunctional fluorescent probe based on 1,8-naphthalimide, N-(2-thiophenhydrazide)acetyl-4-morpholine-1,8-naphthalimide (TMN), was successfully designed and synthesized for the detection of Co²⁺, F⁻, and CN⁻, with N-carboxymethyl-4-morpholine-1,8-naphthalimide and thiophene-2-carbohydrazide as starting materials. TMN displayed superior stability in MeCN with an “on–off” mode towards Co²⁺, F⁻, and CN⁻ by the naked eye. The linear response ranges of TMN were 0–3 and 4–19 μM with a detection limit of 0.21 μM for detecting Co²⁺, 0–5 and 5–22 μM with a detection limit of 0.36 μM for F⁻, and 0–10 and 10–25 μM with a detection limit of 0.49 μM for CN⁻. TMN could also recognize Co²⁺, F⁻, and CN⁻ in real samples. Finally, the possible sensing mechanisms of TMN for detecting Co²⁺, F⁻, and CN⁻ were deeply investigated. These results implied that TMN could be a potential chemosensor for monitoring metal cations and anions sensitively and selectively and could be used in real sample detection. Full article

(This article belongs to the Special Issue Chemical Sensors of Inorganic Cations and Anions)

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13 pages, 2711 KiB

Open AccessArticle

Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers

by Vladislava V. Matveevskaya, Dmitry I. Pavlov, Alexey A. Ryadun, Vladimir P. Fedin and Andrei S. Potapov

Inorganics 2023, 11(7), 264; https://doi.org/10.3390/inorganics11070264 - 22 Jun 2023

Cited by 9 | Viewed by 1615

Abstract

Supramolecular 3D Zn(II) coordination polymer {[Zn(bim)(bdc)]⋅0.8DMF⋅0.4EtOH⋅0.1H₂O }_n (Zn-MOF), constructed from Zn²⁺ ions, bis(imidazol-1-yl)methane (bim) and terephthalate (bdc²⁻) anions, was synthesized and structurally characterized. Zn-MOF crystallizes in the tetragonal crystal system, space group P4₂/n. Each Zn(II) ion coordinates two neutral bim molecules in a bridging bidentate coordination mode via nitrogen atoms at position 3 of the imidazole rings and two bdc²⁻ anions, with monodentate coordination of the carboxylate group for one of them and bidentate coordination for another. Zn(II) cations are in a distorted square pyramidal ZnN₂O₃ coordination environment. Metal cations are alternately linked by the bim and bdc²⁻ ligands, forming a two-dimensional layered structure along the crystallographic plane ab. As a result of layer interpenetration, a supramolecular 3D network is formed. Zn-MOF demonstrated blue (aquamarine) emission with a maximum at 430 nm upon excitation at 325 nm. The luminescence lifetime of 6 ns is characteristic for ligand-centered fluorescence. The luminescent sensing properties of Zn-MOF in ethanol suspension toward inorganic cations and anions were evaluated and an emission quenching response was observed for Fe³⁺ and chromate/dichromate ions. Photoinduced electron transfer from Zn-MOF to Fe³⁺ was elucidated as a possible quenching mechanism on the basis of DFT calculations. Full article

(This article belongs to the Special Issue Chemical Sensors of Inorganic Cations and Anions)

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10 pages, 1163 KiB

Open AccessArticle

Thermodynamics of Ag(I) Complex Formations with 2-Mercaptoimidazole in Water−Dimethyl Sulfoxide Solvents

by Surayo Bobosaidzoda, Anjuman Sodatdinova, Khazon Akimbekova, Diana Alister, Evgeniy Molchanov, Yuriy Marfin, Tatyana Usacheva and Safarmamad Safarmamadzoda

Inorganics 2023, 11(5), 199; https://doi.org/10.3390/inorganics11050199 - 3 May 2023

Cited by 3 | Viewed by 1477

Abstract

The stability of coordination compounds of metal ions with ligands is of fundamental importance for elaborating upon practical sensors for the detection and quantification of metal ions in environmental samples. In this work, the stability constants of silver(I) complexes with 2-mercaptoimidazole (2MI) in a mixed water–dimethyl sulfoxide (DMSO) solvent were determined at 298.15 K and 308.15 K. It was found that with increasing temperature, the stability of the complexes decreases. The dependence of lgβ₁ on the water−DMSO solvent compositions has its minimum at a concentration of dimethyl sulfoxide of 0.1 mol. fr. To explain the effect of the solvent, the solvation characteristics of the reagents were analyzed. In this regard, the 2MI Gibbs energy of transfer from water to aqueous dimethyl sulfoxide solvents was determined, and the influence of the aqueous DMSO solvent on the thermodynamics of 2MI protonation was analyzed. The stabilization of the silver ion and 2MI during the transition from water to a water–DMSO solvent makes a negative contribution to the change in the Gibbs energy of complexation, while the solvation of a complex particle promotes the complex formation. As a result, the Gibbs energy transfer values are slightly increased. The results of these thermodynamic studies could be useful for the development of sensor materials based on mercaptoimidazoles. Full article

(This article belongs to the Special Issue Chemical Sensors of Inorganic Cations and Anions)

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13 pages, 3014 KiB

Open AccessArticle

Complexes of Ni^II, Co^II, Zn^II, and Cu^II with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations

by Mohamed Ali Ahmed, Maksim A. Zhernakov, Edward M. Gilyazetdinov, Mikhail S. Bukharov, Daut R. Islamov, Konstantin S. Usachev, Alexander E. Klimovitskii, Nikita Yu. Serov, Vladimir A. Burilov and Valery G. Shtyrlin

Inorganics 2023, 11(4), 167; https://doi.org/10.3390/inorganics11040167 - 16 Apr 2023

Cited by 9 | Viewed by 2164

Abstract

Four new Ni^II, Co^II, Zn^II, and Cu^II complexes with the promising anti-tuberculosis drug (E/Z)-N′-((5-Hydroxy-3,4-bis(hydroxymethyl)-6-methylpyridin-2-yl)methylene)-isonicotino-hydrazide (LH) were synthesized and characterized by structural methods: single-crystal X-ray diffraction, vibrational spectroscopy, and mass spectrometry. The Ni^II, Co^II, and Zn^II metal ions form only amorphous phases with various morphologies according to mass spectrometry and IR spectroscopy. The Cu^II forms a crystalline 1D coordination polymer with the relative formula

{[Cu L Cl] \cdot 0.5 H_{2} O}_{\infty}^{1}

. Even though the LH ligand in the crystalline state includes a mixture of E-/Z-isomers, only the tautomeric iminol E-/Z-form is coordinated by Cu^II in the crystal. The copper(II) complex crystallizes in the monoclinic P2₁/n space group with the corresponding cell parameters a = 16.3539(11) Å, b = 12.2647(6) Å, and c = 17.4916(10) Å; α = 90°, β = 108.431(7)°, and γ = 90°. DFT calculations showed that the Z-isomer of the LH ligand in solution has the lowest formation energy due to intramolecular hydrogen bonds. According to the quantum chemical calculations, the coordination environment of the Cu^II atom during the transfer of the molecule into the solution remains the same as in the crystal, except for the polymeric bond, namely, distorted trigonal bipyramidal. Some of the complexes investigated can be used as effective sensors in biosystems. Full article

(This article belongs to the Special Issue Chemical Sensors of Inorganic Cations and Anions)

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16 pages, 8667 KiB

Open AccessArticle

Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal

by Vladimir Burmistrov, Viktor Aleksandriiskii, Igor Novikov, Alena Batrakova, Dmitry Belykh, Olga Startseva and Oskar I. Koifman

Inorganics 2023, 11(1), 24; https://doi.org/10.3390/inorganics11010024 - 2 Jan 2023

Cited by 4 | Viewed by 1868

Abstract

The experimental and theoretical study of the influence of metal complexing on geometry, aromaticity, chirality, and the ability to twist the nematic phase by complexes based on modified natural chlorin e6 was carried out. The geometry optimization of the chlorin e6 13(N)-methylamide-15,17-dimethyl ester (MADMECl) and its Zn, Cu, and Ni complexes by DFT (CAM-B3LYP/6–31 G(d,p) functional) method was performed. Based on these calculations, the acoplanarity degree of the macrocyclic ligand and the distortion energy of its dianion were estimated, which allowed the arrangement of the MADMECl complexes in the series Ni > Cu > Zn. Aromaticity was evaluated using the NICS criterion (nuclear independent chemical shift). An increase in the degree of aromaticity of the macrocycle upon complex formation was established. At the same time, the aromaticity of the inner conjugation contour corresponds to the same series as the acoplanarity, while the outer π-delocalization is characterized by the reverse sequence. An experimental evaluation of the electron circular dichroism of the Soret and the Q-bands, as well as the g-factor of dissymmetry, was carried out. The growth of these parameters with an increase in the degree of acoplanarity and aromaticity of the internal conjugation contour was determined. The induction of helical phases in mixtures of nematic liquid crystals (LCs) based on cyanobiphenyls and MADMECl macrocyclic metal complexes was studied by polarization microscopy, and the clearance temperatures and helix pitch of the mesophases were measured. A strong effect of the metal on the phase transition temperature and helical twisting power was established. Full article

(This article belongs to the Special Issue Chemical Sensors of Inorganic Cations and Anions)

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Review

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20 pages, 2277 KiB

Open AccessReview

Prediction of Sensor Ability Based on Chemical Formula: Possible Approaches and Pitfalls

by Daniil N. Yarullin, Maksim N. Zavalishin, George A. Gamov, Michail M. Lukanov, Alexander A. Ksenofontov, Natalia A. Bumagina and Elena V. Antina

Inorganics 2023, 11(4), 158; https://doi.org/10.3390/inorganics11040158 - 6 Apr 2023

Cited by 9 | Viewed by 2852

Abstract

This review presents an analysis of different algorithms for predicting the sensory ability of organic compounds towards metal ions based on their chemical formula. A database of chemosensors containing information on various classes of suitable compounds, including dipyrromethenes, BODIPY, Schiff bases, hydrazones, fluorescein, rhodamine, phenanthroline, coumarin, naphthalimide derivatives, and others (a total of 965 molecules) has been compiled. Additionally, a freely available software has been developed for predicting the sensing ability of chemical compounds, which can be accessed through a Telegram bot. This tool aims to assist researchers in their search for new chemosensors. Full article

(This article belongs to the Special Issue Chemical Sensors of Inorganic Cations and Anions)

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