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Inorganics
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10th Anniversary of Inorganics: Bioinorganic Chemistry
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10th Anniversary of Inorganics: Bioinorganic Chemistry

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

Deadline for manuscript submissions: closed (31 October 2023) | Viewed by 15112

Special Issue Editors

Prof. Dr. Vladimir Arion

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Guest Editor
Institute of Inorganic Chemistry, University of Vienna, Währinger Str. 42, 1090 Vienna, Austria
Interests: coordination and bioinorganic chemistry, more specifically development of metal-based anticancer drugs based on isomeric indoloquinolines, indolobenzazepines, indolobenzazocines and indolobenzazonines, as well as on thiosemicarbazones; ruthenium-nitrosyl complexes with heterocyclic azoles as NO-releasing molecules and potential aniticancer drugs; bis-(thio)semicarbazide macrocyclic complexes as catalysts in alkane oxidation; transition metal complexes with noninnocent open-chain ligands
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Dinorah Gambino

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Guest Editor
Área Química Inorgánica, Facultad de Química, Universidad de la República, Montevideo, Uruguay
Interests: vanadium chemistry and biological inorganic chemistry; metal-based drugs; bioorganometallic chemistry; medicinal inorganic chemistry
Special Issues, Collections and Topics in MDPI journals
Dr. Célia S. Bonnet

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Guest Editor
Centre de Biophysique Moléculaire, CNRS UPR 4301, Université d’Orléans, Rue Charles Sadron, CEDEX 2, 45071 Orléans, France
Interests: contrast agents for MRI; molecular imaging; paramagnetic complexes; lanthanide coordination chemistry; responsive contrast agents; CEST agents; thermodynamic stability and kinetic inertness of complexes; multimodal and theranostic contrast agents
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Lubov Snegur

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Guest Editor
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Interests: ferrocene; cobaltocene; synthesis; enantiomers; chiral resolution; inclusion complexes; antiproliferative effects; hippocampus
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

On the occasion of the 10th anniversary of our journal, we are excited to introduce the Special Issue “10th Anniversary of Inorganics: Bioinorganic Chemistry”. This Special Issue aims to collect original research articles or comprehensive review papers focused on recent advances in the following topics: the structures, functions and mechanisms of metalloenzymes; modern methods to determine their structure; the synthesis and characterization of transition metal complexes as model systems mimicking the structure, spectroscopic properties and function of biomolecules; theoretical simulations; the role of metal ions in biology and medicine; interaction of metal ions and small molecules containing them with biological molecules; metal-based drugs and their mechanisms of action, etc. Moreover, in order to be more visible and have a greater impact, we encourage submissions on this topic from a wide range of authors, and you are welcome to invite relevant authors to participate.

We look forward to receiving your valued contributions on this exciting occasion.

Prof. Dr. Vladimir Arion
Prof. Dr. Dinorah Gambino
Dr. Célia S. Bonnet
Prof. Dr. Lubov Snegur
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2200 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • metalloenzymes
  • vanadium chemistry
  • metal-based drugs
  • iron–sulfur cluster
  • antiproliferative effects
  • molecular imaging
  • contrast agents for MRI
  • paramagnetic complexes
  • NO-releasing molecules
  • artificial photosystem and energy conversion
  • bioinspired&biomimetic inorganic systems
  • metal ions in biology and medicine
  • biological inorganic chemistry
  • bioorganometallic chemistry
  • medicinal inorganic chemistry
  • nanotechnology in bioinorganic chemistry

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Published Papers (6 papers)

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Research

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16 pages, 3567 KiB  
Article
Heteroleptic Copper(II) Complexes Containing an Anthraquinone and a Phenanthroline as Synthetic Nucleases and Potential Anticancer Agents
by Ívina P. de Souza, Júlia R. L. Silva, Amanda O. Costa, Jennifer T. J. Freitas, Renata Diniz, Rodrigo B. Fazzi, Ana M. da Costa Ferreira and Elene C. Pereira-Maia
Inorganics 2023, 11(11), 445; https://doi.org/10.3390/inorganics11110445 - 19 Nov 2023
Viewed by 1932
Abstract
Two ternary copper(II) complexes with an anthraquinone and a N,N-heterocyclic donor, [Cu(dmp)(L)(H2O)](ClO4) (1), [Cu(bpy)(L)(dmso)](ClO4) (2), in which dmp = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, and HL = 1-hydroxyanthracene-9,10-dione were synthesized and fully characterized by [...] Read more.
Two ternary copper(II) complexes with an anthraquinone and a N,N-heterocyclic donor, [Cu(dmp)(L)(H2O)](ClO4) (1), [Cu(bpy)(L)(dmso)](ClO4) (2), in which dmp = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, and HL = 1-hydroxyanthracene-9,10-dione were synthesized and fully characterized by conductivity, elemental, and spectral analyses (FTIR and UV-Vis; EPR and ESI-MS). The structure of 1 reveals that Cu(II) is bound to two oxygens of L, two nitrogens of dmp, and a molecule of water in the fifth position. In complex 2.1, Cu(II) is also pentacoordinated with an O-bonded dmso in the axial position. The presence of the heteroleptic complexes in solution was evidenced by ESI-MS, EPR in dmso solution and UV-Vis spectrophotometry. All complexes bind to CT-DNA with affinity constants of approximately 104. Complex 2 can nick plasmid DNA but no cleavage was performed by complex 1. The investigation of DNA interactions by spectrofluorimetry using ethidium bromide (EB) showed that it was displaced from DNA sites by the addition of the complexes. The complexes inhibited the growth of chronic myelogenous leukemia and human squamous carcinoma cells with low IC50 values, complex 1 being the most effective. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Bioinorganic Chemistry)
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17 pages, 2526 KiB  
Article
Synthesis, Characterization, and Biological Properties of the Copper(II) Complexes with Novel Ligand: N-[4-({2-[1-(pyridin-2-yl)ethylidene]hydrazinecarbothioyl}amino)phenyl]acetamide
by Roman Rusnac, Olga Garbuz, Yurii Chumakov, Victor Tsapkov, Christelle Hureau, Dorin Istrati and Aurelian Gulea
Inorganics 2023, 11(10), 408; https://doi.org/10.3390/inorganics11100408 - 16 Oct 2023
Cited by 3 | Viewed by 2288
Abstract
For the first time, a thiosemicarbazone-type ligand containing a paracetamol structural unit was synthesized. Five new coordination compounds based on copper(II) salts: [Cu(L)CH3COO] (1), [{Cu(L)Cl}2]·H2O (2), [Cu(L)H2O·DMF]NO3 (3), [...] Read more.
For the first time, a thiosemicarbazone-type ligand containing a paracetamol structural unit was synthesized. Five new coordination compounds based on copper(II) salts: [Cu(L)CH3COO] (1), [{Cu(L)Cl}2]·H2O (2), [Cu(L)H2O·DMF]NO3 (3), [Cu(L)Br] (4), [Cu(L)H2O]ClO4 (5), were obtained, where HL is N-[4-({2-[1-(pyridin-2-yl)ethylidene]hydrazinecarbothioyl}amino)phenyl]acetamide. The new HL was characterized by NMR, FTIR, spectroscopy, and X-ray crystallography. All copper(II) coordination compounds were characterized by elemental analysis, FTIR, EPR spectroscopy, and molar electrical conductivity. Furthermore, single crystal X-ray diffraction analysis elucidated the structures of thiosemicarbazone HL as well as complexes 1–3. All compounds were tested for antimicrobial, antifungal, and antioxidant activities, and their toxicity to Daphnia magna was studied. Biological evaluation has revealed that most of the synthesized compounds demonstrate promising antibacterial, antifungal, and antioxidant activities. In many cases, their antibacterial/antifungal activity is comparable to that of certain drugs used in medicine for these purposes, and in some cases, even surpasses them. HL and complexes 2–5 exhibit antioxidant activity that surpasses that of Trolox. Furthermore, HL and complex 2 display virtually no toxicity to D. magna. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Bioinorganic Chemistry)
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14 pages, 2400 KiB  
Article
Synthesis, Structure and Antimicrobial Activity of New Co(II) Complex with bis-Morpholino/Benzoimidazole-s-Triazine Ligand
by Saied M. Soliman, Eman M. Fathalla, Mona M. Sharaf, Ayman El-Faham, Assem Barakat, Matti Haukka, Alexandra M. Z. Slawin, John Derek Woollins and Morsy A. M. Abu-Youssef
Inorganics 2023, 11(7), 278; https://doi.org/10.3390/inorganics11070278 - 29 Jun 2023
Cited by 3 | Viewed by 1592
Abstract
A new Co(II) perchlorate complex of the bis-morpholino/benzoimidazole-s-triazine ligand, 4,4′-(6-(1H-benzo[d]imidazol-1-yl)-1,3,5-triazine-2,4-diyl)dimorpholine (BMBIT), was synthesized and characterized. The structure of the new Co(II) complex was approved to be [Co(BMBIT)2(H2O)4](ClO4)2 [...] Read more.
A new Co(II) perchlorate complex of the bis-morpholino/benzoimidazole-s-triazine ligand, 4,4′-(6-(1H-benzo[d]imidazol-1-yl)-1,3,5-triazine-2,4-diyl)dimorpholine (BMBIT), was synthesized and characterized. The structure of the new Co(II) complex was approved to be [Co(BMBIT)2(H2O)4](ClO4)2*H2O using single-crystal X-ray diffraction. The Co(II) complex was found crystallized in the monoclinic crystal system and P21/c space group. The unit cell parameters are a = 22.21971(11) Å, b = 8.86743(4) Å, c = 24.38673(12) Å and β = 113.4401(6)°. This heteroleptic complex has distorted octahedral coordination geometry with two monodenatate BMBIT ligand units via the benzoimidazole N-atom and four water molecules as monodentate ligands. The hydration water and perchlorate ions participated significantly in the supramolecular structure of the [Co(BMBIT)2(H2O)4](ClO4)2*H2O complex. Analysis of dnorm map and a fingerprint plot indicated the importance of O···H, N···H, C···H, C···O, C···N and H···H contacts. Their percentages are 27.5, 7.9, 14.0, 0.9, 2.8 and 43.5%, respectively. The sensitivity of some harmful microbes towards the studied compounds was investigated. The Co(II) complex has good antifungal activity compared to the free BMBIT which has no antifungal activity. The Co(II) complex has good activity against B. subtilis, S. aureus, P. vulgaris and E. coli while the free BMBIT ligand has limited activity only towards B. subtilis and P. vulgaris. Hence, the [Co(BMBIT)2(H2O)4](ClO4)2*H2O complex has broad spectrum antimicrobial action compared to the free BMBIT ligand. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Bioinorganic Chemistry)
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22 pages, 4989 KiB  
Article
Nitrosyl/Diphenylphosphine/Amino Acid–Ruthenium Complexes as Inhibitors of MDA-MB-231 Breast Cancer Cells
by Marília I. F. Barbosa, Rodrigo S. Corrêa, Adriana P. M. Guedes, Alex M. Graça, Francyelli M. Andrade, Celisnólia M. Leite, Elisângela P. Silveira-Lacerda, Javier Ellena, Henrique V. Reis, Antônio C. Doriguetto and Alzir A. Batista
Inorganics 2023, 11(7), 270; https://doi.org/10.3390/inorganics11070270 - 25 Jun 2023
Cited by 4 | Viewed by 2770
Abstract
Herein, we report on the synthesis and characterization of ruthenium compounds with the general formula [RuCl(AA-H)(NO)(dppb]PF6, where AA = glycine (1), L-alanine (2), L-phenylalanine (3) and L-valine (4), and dppb = 1,4-bis [...] Read more.
Herein, we report on the synthesis and characterization of ruthenium compounds with the general formula [RuCl(AA-H)(NO)(dppb]PF6, where AA = glycine (1), L-alanine (2), L-phenylalanine (3) and L-valine (4), and dppb = 1,4-bis(diphenylphosphine)butane. The complexes were characterized using elemental analysis, UV/Vis and infrared spectroscopies, 1H, 13C, 31P NMR techniques, and cyclic voltammetry. Furthermore, the structures of the compounds (1) and (3) were determined using single-crystal X-ray diffraction. In vitro evaluation of the Ru(II)/nitrosyl/amino acid complexes revealed their cytotoxic activities against triple-negative MDA-MB-231 breast cancer cells, and against the non-tumor murine fibroblast cells. All the compounds decreased the percentage of viable cells, inducing cell death by apoptosis. Additionally, the Ru(II) complexes inhibited the migration of MDA-MB-231 cells at concentrations lower than 35 µM, after 48 h of exposure. Thus, these complexes may be promising agents for the treatment of triple-negative MDA-MB-231 breast cancer. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Bioinorganic Chemistry)
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19 pages, 4858 KiB  
Article
Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study
by Miriama Šimunková, Zuzana Barbieriková, Milan Mazúr, Marian Valko, Suliman Y. Alomar, Saleh H. Alwasel and Michal Malček
Inorganics 2023, 11(5), 208; https://doi.org/10.3390/inorganics11050208 - 12 May 2023
Cited by 2 | Viewed by 2048
Abstract
In this work, attention is focused on the non-essential amino acid L-Tyrosine (TYR) hydroxylated to L-DOPA, which is the precursor to the neurotransmitters dopamine, noradrenaline (norepinephrine; NE) and adrenaline (epinephrine; EP) known as catecholamines and their interactions with redox-active Cu(II). Catecholamines have multiple [...] Read more.
In this work, attention is focused on the non-essential amino acid L-Tyrosine (TYR) hydroxylated to L-DOPA, which is the precursor to the neurotransmitters dopamine, noradrenaline (norepinephrine; NE) and adrenaline (epinephrine; EP) known as catecholamines and their interactions with redox-active Cu(II). Catecholamines have multiple functions in biological systems, including the regulation of the central nervous system, and free (unbound) redox metal ions are present in many diseases with disturbed metal homeostasis. The interaction between catecholamines and Cu(II) has been studied by means of Electron Paramagnetic Resonance spectroscopy (EPR), EPR spin trapping and UV-vis spectroscopy. The obtained spectroscopic results are supported by Density Functional Theory calculations. Only minor qualitative and quantitative changes in the UV-vis spectra of all the studied compounds have been observed following their interactions with Cu(II) ions. The low-temperature EPR spectra were more convincing and confirmed the interaction between Cu(II) ions and all the studied compounds, involving hydroxyl groups and amino nitrogens. The use of an ABTS assay revealed that the compounds under study possessed radical-scavenging activities against ABTS•+ in the order TYR < EP < DA < NE~L-DOPA. The neurotransmitters DA, NE and EP, following their interaction with Cu(II), exhibit the ability to (partially) reduce Cu(II) to Cu(I) species which was confirmed using the Cu(I) specific chelator neocuproine. EPR spin-trapping experiments revealed the suppressed formation of hydroxyl radicals (•OH) in a copper(II) catalyzed Fenton-like system in the presence of catecholamines. Only in the case of EP was autooxidation in a stock solution observed. Furthermore, the oxidation of EP is enhanced in the presence of Cu(II) ions. In conclusion, it has been confirmed that the oxidation of catecholamines in the presence of copper promotes the redox cycling process, resulting in the formation of ROS, which may, in turn, cause damage to neuronal systems. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Bioinorganic Chemistry)
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Review

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25 pages, 3711 KiB  
Review
Paramagnetic Nuclear Magnetic Resonance: The Toolkit
by Leonardo Querci, Letizia Fiorucci, Enrico Ravera and Mario Piccioli
Inorganics 2024, 12(1), 15; https://doi.org/10.3390/inorganics12010015 - 29 Dec 2023
Cited by 3 | Viewed by 3496
Abstract
Nuclear Magnetic Resonance (NMR) spectroscopy is the ideal tool to address the structure, reactivity and dynamics of both inorganic and biological substances. The knowledge of nuclear spin interaction and spin dynamics is increasingly consolidated, and this allows for tailoring pulse sequences. When dealing [...] Read more.
Nuclear Magnetic Resonance (NMR) spectroscopy is the ideal tool to address the structure, reactivity and dynamics of both inorganic and biological substances. The knowledge of nuclear spin interaction and spin dynamics is increasingly consolidated, and this allows for tailoring pulse sequences. When dealing with paramagnetic systems, several decades of research have led to the development of rule-of-the-thumb criteria for optimizing the experiments, allowing for the detection of nuclei that are in very close proximity to the metal center. In turn, the observation of these systems, coupled with the development of robust and accessible quantum chemical methods, is promising to provide a link between the spectra and the structural features through the interpretation of the electronic structure. In this review, we list the challenges encountered and propose solutions for dealing with paramagnetic systems with the greatest satisfaction. In our intentions, this is a practical toolkit for optimizing acquisition and processing parameters for routine experiments aimed at detecting signals influenced by the hyperfine interaction. The implications of paramagnetic shift and line broadening are examined. With this endeavor, we wish to encourage non-expert users to consider the application of paramagnetic NMR to their systems. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Bioinorganic Chemistry)
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