Research

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25 pages, 8133 KiB

Open AccessArticle

Complexation of Cyclodextrins with Benzoic Acid in Water-Organic Solvents: A Solvation-Thermodynamic Approach

by Tatyana R. Usacheva, Vitaly A. Volynkin, Viktor T. Panyushkin, Dmitry A. Lindt, Thi Lan Pham, Thi Thu Ha Nguyen, Thi My Hanh Le, Diana A. Alister, Dzhovidon N. Kabirov, Natalya N. Kuranova, George A. Gamov, Roman A. Kushnir, Marco Biondi, Concetta Giancola and Valentin A. Sharnin

Molecules 2021, 26(15), 4408; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26154408 - 21 Jul 2021

Cited by 11 | Viewed by 2746

Abstract

The aim of this research is to obtain new data about the complexation between β-cyclodextrin (β-CD) and benzoic acid (BA) as a model reaction of the complex formation of hydrophobic molecules with cyclodextrins (CDs) in various media. This research may help developing cyclodextrin-based [...] Read more.

The aim of this research is to obtain new data about the complexation between β-cyclodextrin (β-CD) and benzoic acid (BA) as a model reaction of the complex formation of hydrophobic molecules with cyclodextrins (CDs) in various media. This research may help developing cyclodextrin-based pharmaceutical formulations through the choice of the appropriate solvent mixture that may be employed in the industrial application aiming to control the reactions/processes in liquid phase. In this paper, NMR results for the molecular complex formation between BA and β-CD ([BA⊂β-CD]) in D₂O-DMSO-d₆ and in D₂O-EtOH have shown that the stability of the complex in the H₂O-DMSO-d₆ varies within the experimental error, while decreases in H₂O-EtOH. Changes in the Gibbs energy of BA resolvation in water and water–dimethylsulfoxide mixtures have been obtained and have been used in the analysis of the reagent solvation contributions into the Gibbs energy changes of the [BA⊂β-CD] molecular complex formation. Quantum chemical calculations of the interaction energy between β-CD and BA as well as the structure of the [BA⊂β-CD] complex and the energy of β-CD and BA interaction in vacuum and in the medium of water, methanol and dimethylsulfoxide solvents are carried out. The stability of [BA⊂β-CD] complex in H₂O-EtOH and H₂O-DMSO solvents, obtained by different methods, are compared. The thermodynamic parameters of the [BA⊂β-CD] molecular complexation as well as the reagent solvation contributions in H₂O-EtOH and H₂O-DMSO mixtures were analyzed by the solvation-thermodynamic approach. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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11 pages, 3308 KiB

Open AccessArticle

Photocatalytic Activity of Fibrous Ti/Ce Oxides Obtained by Hydrothermal Impregnation of Short Flax Fibers

by Mikhail F. Butman, Nataliya E. Kochkina, Nikolay L. Ovchinnikov and Karl W. Krämer

Molecules 2021, 26(11), 3399; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26113399 - 03 Jun 2021

Cited by 3 | Viewed by 1378

Abstract

Fibrous Ti/Ce oxide photocatalysts were prepared for the first time by a biomimetic solution process using short flax fibers (flax straw processing waste) as a biotemplate. Titanium polyhydroxy complex solutions with 3% and 5% cerium were used as precursors. Flax fibers were impregnated [...] Read more.

Fibrous Ti/Ce oxide photocatalysts were prepared for the first time by a biomimetic solution process using short flax fibers (flax straw processing waste) as a biotemplate. Titanium polyhydroxy complex solutions with 3% and 5% cerium were used as precursors. Flax fibers were impregnated in an autoclave under hydrothermal conditions. Ti/Ce oxides were obtained from the biotemplate by annealing at 600 °C. The photocatalytic activity of the Ti/Ce oxides was studied by the adsorption and decomposition of the dye rhodamine B under UV irradiation. The photocatalytic decomposition of the dye was 50% and 75% faster for Ti/Ce oxides with 3% and 5% Ce, respectively, than for the analogous undoped fibrous TiO₂. The morphologies, textures, and structures of the photocatalysts were studied by scanning electron microscopy, low temperature N₂ adsorption/desorption, UV-Vis spectroscopy, and X-ray and XPS analytical methods. It was shown that the introduction of Ce into the precursor solution increased the surface irregularity of the Ti/Ce oxide crystallites compared to pure TiO₂. This effect scaled with the Ce concentration. Ce improved the UV light absorption of the material. The Ti/Ce oxides contained Ce⁴⁺/Ce³⁺ pairs that played an important role in redox processes and intensified the photocatalytic activity. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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19 pages, 3307 KiB

Open AccessArticle

Molecular Structure, Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine

by Yuriy A. Zhabanov, Alexey V. Eroshin, Igor V. Ryzhov, Ilya A. Kuzmin, Daniil N. Finogenov and Pavel A. Stuzhin

Molecules 2021, 26(10), 2945; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26102945 - 15 May 2021

Cited by 7 | Viewed by 1750

Abstract

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz [...] Read more.

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H₂TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D_2h and D_4h symmetry was obtained for H₂TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state ¹A_1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H₂TTDPz and NiTTDPz were studied experimentally and simulated theoretically. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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15 pages, 2841 KiB

Open AccessArticle

DFT Study of Molecular and Electronic Structure of Y, La and Lu Complexes with Porphyrazine and Tetrakis(1,2,5-thiadiazole)porphyrazine

by Yuriy A. Zhabanov, Igor V. Ryzhov, Ilya A. Kuzmin, Alexey V. Eroshin and Pavel A. Stuzhin

Molecules 2021, 26(1), 113; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26010113 - 29 Dec 2020

Cited by 12 | Viewed by 2468

Abstract

Electronic and geometric structures of Y, La and Lu complexes with porphyrazine (Pz) and tetrakis(1,2,5-thiadiazole)porphyrazine (TTDPz) were investigated by density functional theory (DFT) calculations and compared. The nature of the bonds between metal atoms and nitrogen atoms has been described using the analysis [...] Read more.

Electronic and geometric structures of Y, La and Lu complexes with porphyrazine (Pz) and tetrakis(1,2,5-thiadiazole)porphyrazine (TTDPz) were investigated by density functional theory (DFT) calculations and compared. The nature of the bonds between metal atoms and nitrogen atoms has been described using the analysis of the electron density distribution in the frame of Bader’s quantum theory of atoms in molecule (QTAIM). Simulation and interpretation of electronic spectra were performed with use of time-dependent density functional theory (TDDFT) calculations. Description of calculated IR spectra was carried out based on the analysis of the distribution of the potential energy of normal vibrations by natural vibrational coordinates. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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22 pages, 5950 KiB

Open AccessArticle

The Effect of Intramolecular Hydrogen Bond Type on the Gas-Phase Deprotonation of ortho-Substituted Benzenesulfonic Acids. A Density Functional Theory Study

by Nina I. Giricheva, Sergey N. Ivanov, Anastasiya V. Ignatova, Mikhail S. Fedorov and Georgiy V. Girichev

Molecules 2020, 25(24), 5806; https://doi.org/10.3390/molecules25245806 - 09 Dec 2020

Cited by 5 | Viewed by 2764

Abstract

Structural factors have been identified that determine the gas-phase acidity of ortho-substituted benzenesulfonic acid, 2-XC₆H₄–SO₃H, (X = –SO₃H, –COOH, –NO₂, –SO₂F, –C≡N, –NH₂, –CH₃, –OCH₃ [...] Read more.

Structural factors have been identified that determine the gas-phase acidity of ortho-substituted benzenesulfonic acid, 2-XC₆H₄–SO₃H, (X = –SO₃H, –COOH, –NO₂, –SO₂F, –C≡N, –NH₂, –CH₃, –OCH₃, –N(CH₃)₂, –OH). The DFT/B3LYP/cc-pVTZ method was used to perform conformational analysis and study the structural features of the molecular and deprotonated forms of these compounds. It has been shown that many of the conformers may contain anintramolecular hydrogen bond (IHB) between the sulfonic group and the substituent, and the sulfonic group can be an IHB donor or an acceptor. The Gibbs energies of gas-phase deprotonation Δ_rG⁰₂₉₈ (kJ mol^–1) were calculated for all compounds. It has been set that in ortho-substituted benzenesulfonic acids, the formation of various types of IHB is possible, having a significant effect on the Δ_rG⁰₂₉₈ values of gas-phase deprotonation. If the –SO₃H group is the IHB donor, then an ion without an IHB is formed upon deprotonation, and the deprotonation energy increases. If this group is an IHB acceptor, then a significant decrease in Δ_rG⁰₂₉₈ of gas-phase deprotonation is observed due to an increase in IHB strength and the A⁻ anion additional stabilization. A proton donor ability comparative characteristic of the –SO₃H group in the studied ortho-substituted benzenesulfonic acids is given, and the Δ_rG⁰₂₉₈ energies are compared with the corresponding values of ortho-substituted benzoic acids. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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21 pages, 9900 KiB

Open AccessArticle

Quantum Chemical Study Aimed at Modeling Efficient Aza-BODIPY NIR Dyes: Molecular and Electronic Structure, Absorption, and Emission Spectra

by Alexander E. Pogonin, Artyom Y. Shagurin, Maria A. Savenkova, Felix Yu. Telegin, Yuriy S. Marfin and Arthur S. Vashurin

Molecules 2020, 25(22), 5361; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25225361 - 17 Nov 2020

Cited by 8 | Viewed by 2766

Abstract

A comprehensive study of the molecular structure of aza-BODIPY and its derivatives, obtained by introduction of one or more substituents, was carried out. We considered the changes in the characteristics of the electronic and geometric structure of the unsubstituted aza-BODIPY introducing the following [...] Read more.

A comprehensive study of the molecular structure of aza-BODIPY and its derivatives, obtained by introduction of one or more substituents, was carried out. We considered the changes in the characteristics of the electronic and geometric structure of the unsubstituted aza-BODIPY introducing the following substituents into the dipyrrin core; phenyl, 2-thiophenyl, 2-furanyl, 3-pyridinyl, 4-pyridinyl, 2-pyridinyl, and ethyl groups. The ground-state geometries of the unsubstituted Aza-BODIPY and 27 derivatives were computed at the PBE/6-31G(d) and CAM-B3LYP/6-31+G(d,p) levels of theory. The time-dependent density-functional theory (TDDFT) together with FC vibronic couplings was used to investigate their absorption and emission spectra. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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17 pages, 3889 KiB

Open AccessArticle

DDAO Controlled Synthesis of Organo-Modified Silica Nanoparticles with Encapsulated Fluorescent Boron Dipyrrins and Study of Their Uptake by Cancerous Cells

by Aleksandr A. Goncharenko, Ilya A. Tarasyuk, Yuriy S. Marfin, Kirill V. Grzhegorzhevskii, Albert R. Muslimov, Andrey B. Bondarenko, Maxim D. Lebedev, Ilya A. Kuz’min, Artur S. Vashurin, Kirill V. Lepik, Alexander S. Timin and Evgeniy V. Rumyantsev

Molecules 2020, 25(17), 3802; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25173802 - 21 Aug 2020

Cited by 10 | Viewed by 2889

Abstract

The design of cargo carriers with high biocompatibility, unique morphological characteristics, and capability of strong bonding of fluorescent dye is highly important for the development of a platform for smart imaging and diagnostics. In this paper, BODIPY-doped silica nanoparticles were prepared through a [...] Read more.

The design of cargo carriers with high biocompatibility, unique morphological characteristics, and capability of strong bonding of fluorescent dye is highly important for the development of a platform for smart imaging and diagnostics. In this paper, BODIPY-doped silica nanoparticles were prepared through a “one-pot” soft-template method using a sol-gel process. Several sol-gel precursors have been used in sol-gel synthesis in the presence of soft-template to obtain the silica-based materials with the most appropriate morphological features for the immobilization of BODIPY molecules. Obtained silica particles have been shown to be non-cytotoxic and can be effectively internalized into the cervical cancer cell line (HeLa). The described method of synthesis allows us to obtain silica-based carriers with an immobilized fluorescent dye that provide the possibility for real-time imaging and detection of these carriers. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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Review

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24 pages, 4877 KiB

Open AccessReview

The Application of Porphyrins and Their Analogues for Inactivation of Viruses

by Natalya Sh. Lebedeva, Yury A. Gubarev, Mikhail O. Koifman and Oskar I. Koifman

Molecules 2020, 25(19), 4368; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25194368 - 23 Sep 2020

Cited by 40 | Viewed by 4445

Abstract

The problem of treating viral infections is extremely relevant due to both the emergence of new viral diseases and to the low effectiveness of existing approaches to the treatment of known viral infections. This review focuses on the application of porphyrin, chlorin, and [...] Read more.

The problem of treating viral infections is extremely relevant due to both the emergence of new viral diseases and to the low effectiveness of existing approaches to the treatment of known viral infections. This review focuses on the application of porphyrin, chlorin, and phthalocyanine series for combating viral infections by chemical and photochemical inactivation methods. The purpose of this review paper is to summarize the main approaches developed to date in the chemical and photodynamic inactivation of human and animal viruses using porphyrins and their analogues and to analyze and discuss the information on viral targets and antiviral activity of porphyrins, chlorins, of their conjugates with organic/inorganic compounds obtained in the last 10–15 years in order to identify the most promising areas. Full article

(This article belongs to the Special Issue Innovative University of Chemistry and Technology: A Modern Scientific Image-Celebrating the 90th Anniversary of the Ivanovo State University of Chemistry and Technology)

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