Article
Pharmacology & Pharmacy
Simona Braccini, Giorgia Rizzi, Lorenzo Biancalana, Alessandro Pratesi, Stefano Zacchini, Guido Pampaloni, Federica Chiellini, Fabio Marchetti
Summary: A series of novel diiron complexes were synthesized and evaluated for their anticancer activity, showing potent cytotoxicity against cancer cell lines with remarkable selectivity and good performance in inhibiting cell proliferation. Additionally, these complexes were capable of inducing significant ROS production and had the potential to inhibit the enzyme thioredoxin reductase.
Article
Chemistry, Multidisciplinary
Simona Braccini, Giacomo Provinciali, Lorenzo Biancalana, Guido Pampaloni, Federica Chiellini, Fabio Marchetti
Summary: The study presents diiron complexes with anticancer activity, along with a synthetic procedure. The reaction of the compounds may lead to iron oxidation and active monoiron species. Additionally, neutral complexes exhibit moderate inhibition on ovarian cancer cell lines.
APPLIED SCIENCES-BASEL
(2021)
Article
Biochemistry & Molecular Biology
Beatrice Campanella, Simona Braccini, Giulio Bresciani, Michele De Franco, Valentina Gandin, Federica Chiellini, Alessandro Pratesi, Guido Pampaloni, Lorenzo Biancalana, Fabio Marchetti
Summary: Diiron vinyliminium complexes are promising organometallics with potential anticancer activity. The synthesis and evaluation of [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(R-3)C(R-4)CN(R-1)(R-2)}]CF3SO3 (2a-c, 4a-d) complexes were performed, including their solubility in D2O, Log P-ow, stability in D2O/Me2SO-d(6) mixture, and antiproliferative activity against ovarian cancer cell lines A2780 and A2780cisR, as well as the nontumoral cell line Balb/3T3 clone A31. The cytotoxicity data of 50 vinyliminium complexes were correlated with the structural properties, showing a positive correlation between octanol-water partition coefficient and relative antiproliferative activity on ovarian cancer cell lines. However, the effects of different substituents provided guidelines for the development of novel, more effective compounds. Three additional complexes (4p-r) were designed, synthesized, and biologically investigated, revealing their ability to inhibit thioredoxin reductase enzyme and induce cancer cell production of reactive oxygen species.
Article
Chemistry, Inorganic & Nuclear
Silvia Schoch, Simona Braccini, Lorenzo Biancalana, Alessandro Pratesi, Tiziana Funaioli, Stefano Zacchini, Guido Pampaloni, Federica Chiellini, Fabio Marchetti
Summary: In this study, a series of cationic triiron complexes resulting from the conjugation of ferrocenyl skeleton with a diiron bis-cyclopentadienyl core were synthesized and their cytotoxicity on cancer cell lines and non-tumoral cells was evaluated. The results showed that most of the cationic complexes exhibited low toxicity in cancer cells and non-tumoral cells.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Biochemistry & Molecular Biology
Giulio Bresciani, Stefano Zacchini, Guido Pampaloni, Marco Bortoluzzi, Fabio Marchetti
Summary: Diiron mu-aminocarbyne complexes can be synthesized by reacting sodium cyanate and tetrabutylammonium thiocyanate with pre-prepared diiron aminocarbyne complexes, yielding different substituted diiron cyanide complexes with yields of 67-81%, through substitution of the acetonitrile ligand. When reacted with potassium selenocyanate at reflux temperature, cyanide complexes can be obtained with yields of 45-67%. When reacted at room temperature in acetone, a small amount of potassium selenocyanate complexes can be obtained. All products were fully characterized and the chiral structure was determined by single crystal X-ray diffraction. DFT calculations shed light on the coordination mode and stability of the {NCSe-} fragment.
Article
Biochemistry & Molecular Biology
Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni, Stefano Zacchini, Gianluca Ciancaleoni, Fabio Marchetti
Summary: This study focused on the characterization of metal-nitrile bonding by synthesizing new nitrile compounds and related complexes, and exploring their properties using various techniques. The results revealed insights into the electron-donor power of the R substituents and the Fe-N bond energies, which were elucidated by DFT calculations on specific complexes.
Article
Chemistry, Inorganic & Nuclear
Chiara Saviozzi, Sara Stocchetti, Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni, Fabio Marchetti
Summary: The reactions between diiron aminocarbyne complexes and primary amines resulted in the replacement of the acetonitrile ligand and the formation of new diiron complexes. The diiron-oxazolidinone conjugate was also successfully prepared. However, the reactions with NHEt2 in the presence of Me3NO led to unstable products. The behavior of the diiron complexes in aqueous media was also studied.
Article
Biochemistry & Molecular Biology
Giulio Bresciani, Jakub Cervinka, Hana Kostrhunova, Lorenzo Biancalana, Marco Bortoluzzi, Guido Pampaloni, Vojtech Novohradsky, Viktor Brabec, Fabio Marchetti, Jana Kasparkova
Summary: This study reports the synthesis of novel diiron complexes with an indole-functionalized vinyliminium ligand and investigates their antiproliferative activity and mechanism of action. The complexes display selective cytostatic effects towards cancer cells, induce apoptosis, and interact with mitochondrial DNA and proteins, as well as exhibit reactive oxygen species (ROS)-scavenging properties and antioxidant activity. This study highlights the importance and therapeutic potential of these diiron complexes as anticancer agents.
CHEMICO-BIOLOGICAL INTERACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Matthew P. Sullivan, Monika Cziferszky, Iogann Tolbatov, Dianna Truong, Davide Mercadante, Nazzareno Re, Ronald Gust, David C. Goldstone, Christian G. Hartinger
Summary: Metal complexes exhibit different binding behaviors with proteins, with Ru and Rh complexes targeting surface l-histidine residues, while Os and Ir derivatives predominantly located in electronegative binding pockets after ligand exchange. Computational studies support the binding profiles and suggest the role of protein microenvironment in eliciting selectivity for specific binding sites on the protein.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Roberta Cargnelutti, Ricardo F. Schumacher, Andrei L. Belladona, Jean C. Kazmierczak
Summary: This review provides an overview of pyridyl-selenium compounds and their metal complexes in the fields of pharmacology, material science, and technology, covering coordination chemistry, synthetic methodologies, and structural characterization. Relevant direct applications in nanomaterial preparation, organic synthesis catalysis, photocatalytic hydrogen production, and oxygen activation are also discussed.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Q. Umar, Y. Huang, A. Nazeer, H. Yin, J. C. Zhang, M. Luo, X. G. Meng
Summary: Seven new metal coordination complexes were synthesized and their anticancer activities against human tumour cells were tested, with one complex showing the best activity. Analysis of the crystal structures and characteristic peaks indicated a correlation between the biological activity and the structure of the compounds.
Article
Biochemistry & Molecular Biology
Alice De Palo, Dijana Draca, Maria Grazia Murrali, Stefano Zacchini, Guido Pampaloni, Sanja Mijatovic, Danijela Maksimovic-Ivanic, Fabio Marchetti
Summary: Piano-stool iridium complexes based on the pentamethylcyclopentadienyl ligand have been extensively studied as potential anticancer drugs, with two complexes showing significant antiproliferative activity on multiple cancer cell lines. These complexes do not affect the viability of primary mouse peritoneal cells and exert their tumoricidal effects through a combination of effects on cellular proliferation, apoptosis, and senescence triggered by mitochondrial failure and reactive oxygen and nitrogen species production.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Inorganic & Nuclear
Carla Gotzmann, Olivier Blacque, Thomas Fox, Roger Alberto
Summary: The functionalization of highly oxidation and hydrolysis stable mono-cationic rhenium bis-arene complexes is of great interest, with structural features of Hoechst Dye serving as a model. The extended aromatic bis-arene unit with benzimidazole moieties resulted in complexes with deep orange color and multiple transition maxima in UV/Vis absorption spectra, with charge transfer natures analyzed through DFT calculations. Different transitions of the complexes, including intra-ligand, ligand-to-ligand, and metal-to-ligand charge transitions, were compared with corresponding free ligands.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Sofiia K. Emashova, Aleksei A. Titov, Alexander F. Smol'yakov, Andrey Yu Chernyadyev, Ivan A. Godovikov, Maria Godovikova, Pavel Dorovatovskii, Alexander A. Korlykov, Oleg A. Filippov, Elena S. Shubina
Summary: This study investigates the fluorescence properties of 3-trifluoromethyl-pyrazoles containing triphenylamine and carbazole groups, as well as their silver complexes, in both solution and solid state. The results show that the electronic coupling between triphenylamine substituent and pyrazole leads to fluorescence emission in solution, while the rigid structure of the N-ethyl carbazole substituent results in typical carbazole-centered fluorescence. Aggregation plays a major role in determining the emission properties in the solid state.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Multidisciplinary
Ming Luo, Dafa Chen, Qian Li, Haiping Xia
Summary: Aromatic compounds play important roles in synthetic chemistry, biomedicines, and materials science. Transition-metal-based metallaaromatics, as a special type of aromatic complex, have a transition metal in an aromatic framework. The properties and applications of metallaaromatics are constantly emerging.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Andreas C. Hans, Patrick M. Becker, Johanna Haussmann, Simon Suhr, Daniel M. Wanner, Vera Lederer, Felix Willig, Wolfgang Frey, Biprajit Sarkar, Johannes Kaestner, Rene Peters
Summary: This article discloses a catalyst type that enables highly efficient direct 1,4-additions. The catalyst is a zwitterionic entity, with acetate binding to negatively charged Cu-II and serving as a counterion for benzimidazolium. All three functionalities are involved in the catalytic activation. The productivity of maleimides increased by a factor greater than 300 compared to the literature (TONs up to 6700). High stereoselectivity and productivity were achieved for a wide range of other Michael acceptors as well. The polyfunctional catalyst, accessible in only 4 steps from N-Ph-benzimidazole with an overall yield of 96%, remained robust during catalysis, allowing for multiple reuse with nearly constant efficiency. Mechanistic studies, particularly using DFT, provided a detailed understanding of how the catalyst operates. The benzimidazolium unit stabilizes the coordinated enolate nucleophile and prevents the dissociation of acetate/acetic acid from the catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Jan Hormann, Olga Verbitsky, Xiaoyu Zhou, Beatrice Battistella, Margarete van der Meer, Biprajit Sarkar, Cunyuan Zhao, Nora Kulak
Summary: We synthesized and characterized Cu(ii) complexes CuL1-CuL6 with cyclen-based ligands. The ligands L-1-L-6 comprise different donor sets including S and O atoms. The substitution of N donor atoms with hard donor O atoms leads to efficient oxidative nucleases, but dissociation of the complex upon reduction. We are showing that the rational combination of O and S atoms next to two nitrogen donors within the macrocycle leads to the stabilization of both redox states, resulting in the highest oxidative DNA cleavage activity within this family of cyclen-based Cu(ii) complexes.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Giovanni Canil, Juan Gurruchaga-Pereda, Simona Braccini, Lorella Marchetti, Tiziana Funaioli, Fabio Marchetti, Alessandro Pratesi, Luca Salassa, Chiara Gabbiani
Summary: Photoactivatable Pt(IV) prodrugs have great potential as metal-based drugs due to their chemical inertness in oxidized form and selective targeting compared to Pt(II) compounds. A new Pt(IV) complex, soluble in water and unreactive until reduction, was synthesized. The complex exhibited rapid and efficient photoreduction with visible light, facilitated by a catalytic system based on flavin and NADH. The reactivity of the prodrug against biological targets was only observed after photoreduction to its Pt(II) analogue.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Alberto Gobbo, Xinyuan Ma, Gianluca Ciancaleoni, Stefano Zacchini, Lorenzo Biancalana, Massimo Guelfi, Guido Pampaloni, Steven P. Nolan, Fabio Marchetti
Summary: The potential of ruthenium(II) arene complexes in catalytic transfer hydrogenation has been widely investigated, but studies on homologous compounds with tris(1-pyrazolyl)methane (tpm) ligand are lacking. In this study, RuCl(kappa(3)-tpm)(PPh3)(2)]Cl reacted with various nitrogen ligands to form [RuCl(kappa(3)-tpm)(PPh3)(L)]Cl (L=NCMe, NCPh, imidazole) in nearly quantitative yields. These complexes were evaluated as catalytic precursors in the transfer hydrogenation of ketones, and complex 2 exhibited the highest activity.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Maite Noessler, Rene Jaeger, David Hunger, Marc Reimann, Tobias Bens, Nicolas I. Neuman, Arijit Singha Hazari, Martin Kaupp, Joris van Slageren, Biprajit Sarkar
Summary: Due to their ability to form stable molecular complexes, terpyridine ligands with tailor-made properties are of great interest in chemistry and material science. By synthesizing two terpyridine ligands with different fluorinated phenyl rings, we were able to prepare Co-II and Fe-II complexes and investigate their properties using various analytical techniques. Our findings revealed the structural characteristics, electrochemical behavior, and magnetic properties of these complexes, providing valuable insights into their applications and potential uses.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Simon Suhr, Nicolai Schroter, Merlin Kleoff, Nicolas Neuman, David Hunger, Robert Walter, Clemens Lucke, Felix Stein, Serhiy Demeshko, Hang Liu, Hans -Ulrich Reissig, Joris van Slageren, Biprajit Sarkar
Summary: Two homoleptic Fe(II) complexes with superbasic terpyridine derivatives as ligands were studied to investigate the relationship between spin state and electrochemical/spectroscopic behavior. Antiferromagnetic coupling between a ligand-centered radical and the high-spin metal center resulted in an anodic shift of the first reduction potential and a mixed valency species with a moderately intense intervalence-charge-transfer band. The different spin states also influenced the electrochemical reactivity, with the low-spin species acting as a precatalyst for electrocatalytic CO2 reduction and showing a Faradaic efficiency of 37% for CO formation, while the high-spin species only catalyzed proton reduction with a modest Faradaic efficiency of approximately 20%.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Luca Lenzi, Micaela Degli Esposti, Simona Braccini, Chiara Siracusa, Felice Quartinello, Georg M. Guebitz, Dario Puppi, Davide Morselli, Paola Fabbri
Summary: Valorization of glycerol and levulinic acid by a solvent-free and mild-condition reaction resulted in the production of a fully bio-based glycerol trilevulinate plasticizer (GT) that showed high efficiency in plasticizing different polymers. GT significantly reduced the glass-transition temperature and stiffness of both amorphous and semicrystalline polymers, as well as decreased their melting temperature and crystallinity degree. The enzymatic hydrolysis of GT into its initial constituents makes it environmentally safe and potentially applicable in the biomedical field, as indicated by the unharmful results in the IC50 tests.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Inorganic & Nuclear
Chiara Saviozzi, Sara Stocchetti, Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni, Fabio Marchetti
Summary: The reactions between diiron aminocarbyne complexes and primary amines resulted in the replacement of the acetonitrile ligand and the formation of new diiron complexes. The diiron-oxazolidinone conjugate was also successfully prepared. However, the reactions with NHEt2 in the presence of Me3NO led to unstable products. The behavior of the diiron complexes in aqueous media was also studied.
Article
Chemistry, Inorganic & Nuclear
Giulio Bresciani, Serena Boni, Tiziana Funaioli, Stefano Zacchini, Guido Pampaloni, Natalia Busto, Tarita Biver, Fabio Marchetti
Summary: We synthesized and evaluated the anticancer potential of two series of diruthenium biscyclopentadienyl carbonyl complexes. Novel dimetallacyclopentenone compounds (2-4) were obtained from the thermal reaction of [Ru2Cp2(CO)(μ-CO)(μ-η^1:η^3-C(Ph)C(Ph)C(O)}], 1, with alkynes HCCR [R = C5H4FeCp (Fc), 3-C6H4(Asp), 2-naphthyl; Cp = η(5)-C5H5, Asp = OC(O)-2-C6H4C(O)Me]. The resulting complexes showed cytotoxic activity against cancer cells, different interactions with nucleic acids, and production of ROS.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Giulio Bresciani, Jan Vanco, Tiziana Funaioli, Stefano Zacchini, Tomas Malina, Guido Pampaloni, Zdenek Dvorak, Zdenek Travnicek, Fabio Marchetti
Summary: Diruthenacyclopentenone complexes were synthesized and characterized. The complexes exhibited stronger cytotoxicity than cisplatin against various cancer cell lines, with the 17α-estradiol derived complex showing the highest activity. Further studies revealed that some complexes affected the cell cycle, apoptosis, oxidative stress, and autophagy.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Sara Benetti, Maria Dalla Pozza, Lorenzo Biancalana, Stefano Zacchini, Gilles Gasser, Fabio Marchetti
Summary: Novel diiron vinyliminium complexes were synthesized and characterized by various spectroscopic techniques. Their solubility in D2O, Log Pow coefficients, and stability in aqueous media were determined. The antiproliferative activity of these complexes on cancer cell lines was evaluated and their mechanism of action was investigated by assessing their influence on mitochondrial respiration.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Roberta Colaiezzi, Chiara Saviozzi, Nicola di Nicola, Stefano Zacchini, Guido Pampaloni, Marcello Crucianelli, Fabio Marchetti, Andrea Di Giuseppe, Lorenzo Biancalana
Summary: The reductive N-monomethylation of nitroarenes can be conveniently realized in one-pot using methanol as the reductant, methylating agent, and solvent. New ruthenium(II) arene complexes were developed as efficient catalytic precursors for the tandem reduction/N-methylation of aromatic nitrocompounds with methanol, starting from commercially available and inexpensive dioxime ligands.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Inorganic & Nuclear
Cristiana Cesari, Beatrice Berti, Marco Bortoluzzi, Cristina Femoni, Tiziana Funaioli, Federico Maria Vivaldi, Maria Carmela Iapalucci, Stefano Zacchini
Summary: Heterometallic Chini-type clusters [Pt6-xNix(CO)(12)](2-) (x = 0-6) with different Pt/Ni compositions were obtained by reacting [Pt-6(CO)(12)](2-) with Ni-clusters. The site preference of Pt and Ni within their metal cages has been computationally investigated.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Beatrice Campanella, Simona Braccini, Giulio Bresciani, Michele De Franco, Valentina Gandin, Federica Chiellini, Alessandro Pratesi, Guido Pampaloni, Lorenzo Biancalana, Fabio Marchetti
Summary: Diiron vinyliminium complexes are promising organometallics with potential anticancer activity. The synthesis and evaluation of [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(R-3)C(R-4)CN(R-1)(R-2)}]CF3SO3 (2a-c, 4a-d) complexes were performed, including their solubility in D2O, Log P-ow, stability in D2O/Me2SO-d(6) mixture, and antiproliferative activity against ovarian cancer cell lines A2780 and A2780cisR, as well as the nontumoral cell line Balb/3T3 clone A31. The cytotoxicity data of 50 vinyliminium complexes were correlated with the structural properties, showing a positive correlation between octanol-water partition coefficient and relative antiproliferative activity on ovarian cancer cell lines. However, the effects of different substituents provided guidelines for the development of novel, more effective compounds. Three additional complexes (4p-r) were designed, synthesized, and biologically investigated, revealing their ability to inhibit thioredoxin reductase enzyme and induce cancer cell production of reactive oxygen species.
