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Keywords = ruthenium(II)–gold(I)

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23 pages, 4574 KB  
Article
A Heterobimetallic Au(I)–Ru(II) Complex Bridged by dppb: Synthesis, Structural and Solution Characterization, BSA Interaction and In Vivo Toxicity Evaluation in Wistar Rats
by Adnan Zahirović, Sunčica Roca, Muhamed Fočak, Selma Fetahović, Višnja Muzika, Damir Suljević, Anela Topčagić, Maja Mitrašinović-Brulić, Irnesa Osmanković, Debbie C. Crans and Aleksandar Višnjevac
Inorganics 2025, 13(10), 323; https://doi.org/10.3390/inorganics13100323 - 29 Sep 2025
Abstract
A novel heterobimetallic ruthenium(II)–gold(I) complex featuring a bridging bis(diphenylphosphino)butane (dppb) ligand was prepared and fully characterized. Single-crystal X-ray diffraction revealed a piano-stool geometry around Ru(II) with η6-cymene, two chlorido ligands, and one phosphorus atom from dppb, while the Au(I) center adopts [...] Read more.
A novel heterobimetallic ruthenium(II)–gold(I) complex featuring a bridging bis(diphenylphosphino)butane (dppb) ligand was prepared and fully characterized. Single-crystal X-ray diffraction revealed a piano-stool geometry around Ru(II) with η6-cymene, two chlorido ligands, and one phosphorus atom from dppb, while the Au(I) center adopts a linear P–Au–Cl coordination. Structural integrity in the solution was confirmed by 1D and 2D NMR spectroscopy, while solution behavior was further monitored by variable solvent 31P NMR and UV/Vis spectroscopy, indicating that the organometallic Ru–arene core remains intact, whereas the chlorido ligands coordinated to Ru exhibit partial lability. Complementary characterization included elemental analysis, FTIR, and UV/Vis spectroscopy. Spectrofluorimetric and FRET analyses showed that Au(dppb), Ru(dppb), and the heterobimetallic AuRu complex bind to BSA with apparent constants of 1.41 × 105, 5.12 × 102, and 2.66 × 104 M−1, respectively, following a static quenching mechanism. In vivo biological evaluation in Wistar rats revealed no significant hepatotoxicity or nephrotoxicity, with only mild and reversible histological alterations and preserved hepatocyte nuclear morphology. Hematological analysis indicated a statistically significant reduction in leukocyte populations, suggesting immunomodulatory potential, while elevated serum glucose levels point to possible endocrine or metabolic activity. These findings highlight compound structural stability and intriguing bioactivity profile, making it a promising platform for further organometallic drug development and testing. Full article
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45 pages, 11103 KB  
Review
Anticancer Activity of Metallodrugs and Metallizing Host Defense Peptides—Current Developments in Structure-Activity Relationship
by Celia María Curieses Andrés, José Manuel Pérez de la Lastra, Elena Bustamante Munguira, Celia Andrés Juan and Eduardo Pérez-Lebeña
Int. J. Mol. Sci. 2024, 25(13), 7314; https://doi.org/10.3390/ijms25137314 - 3 Jul 2024
Cited by 13 | Viewed by 2951
Abstract
This article provides an overview of the development, structure and activity of various metal complexes with anti-cancer activity. Chemical researchers continue to work on the development and synthesis of new molecules that could act as anti-tumor drugs to achieve more favorable therapies. It [...] Read more.
This article provides an overview of the development, structure and activity of various metal complexes with anti-cancer activity. Chemical researchers continue to work on the development and synthesis of new molecules that could act as anti-tumor drugs to achieve more favorable therapies. It is therefore important to have information about the various chemotherapeutic substances and their mode of action. This review focuses on metallodrugs that contain a metal as a key structural fragment, with cisplatin paving the way for their chemotherapeutic application. The text also looks at ruthenium complexes, including the therapeutic applications of phosphorescent ruthenium(II) complexes, emphasizing their dual role in therapy and diagnostics. In addition, the antitumor activities of titanium and gold derivatives, their side effects, and ongoing research to improve their efficacy and reduce adverse effects are discussed. Metallization of host defense peptides (HDPs) with various metal ions is also highlighted as a strategy that significantly enhances their anticancer activity by broadening their mechanisms of action. Full article
(This article belongs to the Section Bioactives and Nutraceuticals)
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17 pages, 4951 KB  
Article
An Unprecedented Metal Distribution in Silica Nanoparticles Determined by Single-Particle Inductively Coupled Plasma Mass Spectrometry
by Juan Han, Xu Wu, Julia Xiaojun Zhao and David T. Pierce
Nanomaterials 2024, 14(7), 637; https://doi.org/10.3390/nano14070637 - 6 Apr 2024
Cited by 1 | Viewed by 1673
Abstract
Metal-containing nanoparticles are now common in applications ranging from catalysts to biomarkers. However, little research has focused on per-particle metal content in multicomponent nanoparticles. In this work, we used single-particle inductively coupled plasma mass spectrometry (ICP-MS) to determine the per-particle metal content of [...] Read more.
Metal-containing nanoparticles are now common in applications ranging from catalysts to biomarkers. However, little research has focused on per-particle metal content in multicomponent nanoparticles. In this work, we used single-particle inductively coupled plasma mass spectrometry (ICP-MS) to determine the per-particle metal content of silica nanoparticles doped with tris(2,2′-bipyridyl)ruthenium(II). Monodispersed silica nanoparticles with varied Ru doping levels were prepared using a water-in-oil microemulsion method. These nanoparticles were characterized using common bulk-sample methods such as absorbance spectroscopy and conventional ICP-MS, and also with single-particle ICP-MS. The results showed that averaged concentrations of metal dopant measured per-particle by single-particle ICP-MS were consistent with the bulk-sample methods over a wide range of dopant levels. However, the per-particle amount of metal varied greatly and did not adhere to the usual Gaussian distribution encountered with one-component nanoparticles, such as gold or silver. Instead, the amount of metal dopant per silica particle showed an unexpected geometric distribution regardless of the prepared doping levels. The results indicate that an unusual metal dispersal mechanism is taking place during the microemulsion synthesis, and they challenge a common assumption that doped silica nanoparticles have the same metal content as the average measured by bulk-sample methods. Full article
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32 pages, 10134 KB  
Review
Complexes of Ruthenium(II) as Promising Dual-Active Agents against Cancer and Viral Infections
by Assunta D’Amato, Annaluisa Mariconda, Domenico Iacopetta, Jessica Ceramella, Alessia Catalano, Maria Stefania Sinicropi and Pasquale Longo
Pharmaceuticals 2023, 16(12), 1729; https://doi.org/10.3390/ph16121729 - 15 Dec 2023
Cited by 22 | Viewed by 5449
Abstract
Poor responses to medical care and the failure of pharmacological treatment for many high-frequency diseases, such as cancer and viral infections, have been widely documented. In this context, numerous metal-based substances, including cisplatin, auranofin, various gold metallodrugs, and ruthenium complexes, are under study [...] Read more.
Poor responses to medical care and the failure of pharmacological treatment for many high-frequency diseases, such as cancer and viral infections, have been widely documented. In this context, numerous metal-based substances, including cisplatin, auranofin, various gold metallodrugs, and ruthenium complexes, are under study as possible anticancer and antiviral agents. The two Ru(III) and Ru(II) complexes, namely, BOLD-100 and RAPTA-C, are presently being studied in a clinical trial and preclinical studies evaluation, respectively, as anticancer agents. Interestingly, BOLD-100 has also recently demonstrated antiviral activity against SARS-CoV-2, which is the virus responsible for the COVID-19 pandemic. Over the last years, much effort has been dedicated to discovering new dual anticancer–antiviral agents. Ru-based complexes could be very suitable in this respect. Thus, this review focuses on the most recent studies regarding newly synthesized Ru(II) complexes for use as anticancer and/or antiviral agents. Full article
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22 pages, 5871 KB  
Article
Phosphine Functionalized CpC Ligands and Their Metal Complexes
by Florian Nährig, Yu Sun and Werner R. Thiel
Chemistry 2023, 5(2), 912-933; https://doi.org/10.3390/chemistry5020062 - 18 Apr 2023
Viewed by 2545
Abstract
Simple nucleophilic aliphatic substitution gives access to mono- and diphosphine ligands with a CpC group in the backbone. The monophosphine ligand coordinates to gold(I) via the phosphine site, to thallium(I) via the cyclopentadienyl site and to ruthenium(II) via a combination of both, [...] Read more.
Simple nucleophilic aliphatic substitution gives access to mono- and diphosphine ligands with a CpC group in the backbone. The monophosphine ligand coordinates to gold(I) via the phosphine site, to thallium(I) via the cyclopentadienyl site and to ruthenium(II) via a combination of both, resulting in an ansa-type structure. Coordination with the cyclopentadiene site is not possible for the diphosphine ligand. In this case, monodentate coordination to gold(I) and bidentate coordination to the [PdCl(μ2-Cl)]2, the [Rh(CO)(μ2-Cl)]2, and the Rh(CO)Cl fragment is observed, showing the variability in coordination modes possible for the long-chain diphosphine ligand. Ligands and complexes were characterized by means of NMR and IR spectroscopy, elemental analysis and X-ray structure analysis. Full article
(This article belongs to the Special Issue Commemorating 150 Years of Justus von Liebig’s Legacy)
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20 pages, 13869 KB  
Review
Gold (III) Derivatives in Colon Cancer Treatment
by Agata Gurba, Przemysław Taciak, Mariusz Sacharczuk, Izabela Młynarczuk-Biały, Magdalena Bujalska-Zadrożny and Jakub Fichna
Int. J. Mol. Sci. 2022, 23(2), 724; https://doi.org/10.3390/ijms23020724 - 10 Jan 2022
Cited by 33 | Viewed by 4663
Abstract
Cancer is one of the leading causes of morbidity and mortality worldwide. Colorectal cancer (CRC) is the third most frequently diagnosed cancer in men and the second in women. Standard patterns of antitumor therapy, including cisplatin, are ineffective due to their lack of [...] Read more.
Cancer is one of the leading causes of morbidity and mortality worldwide. Colorectal cancer (CRC) is the third most frequently diagnosed cancer in men and the second in women. Standard patterns of antitumor therapy, including cisplatin, are ineffective due to their lack of specificity for tumor cells, development of drug resistance, and severe side effects. For this reason, new methods and strategies for CRC treatment are urgently needed. Current research includes novel platinum (Pt)- and other metal-based drugs such as gold (Au), silver (Ag), iridium (Ir), or ruthenium (Ru). Au(III) compounds are promising drug candidates for CRC treatment due to their structural similarity to Pt(II). Their advantage is their relatively good solubility in water, but their disadvantage is an unsatisfactory stability under physiological conditions. Due to these limitations, work is still underway to improve the formula of Au(III) complexes by combining with various types of ligands capable of stabilizing the Au(III) cation and preventing its reduction under physiological conditions. This review summarizes the achievements in the field of stable Au(III) complexes with potential cytotoxic activity restricted to cancer cells. Moreover, it has been shown that not nucleic acids but various protein structures such as thioredoxin reductase (TrxR) mediate the antitumor effects of Au derivatives. The state of the art of the in vivo studies so far conducted is also described. Full article
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17 pages, 31063 KB  
Article
Facile N9-Alkylation of Xanthine Derivatives and Their Use as Precursors for N-Heterocyclic Carbene Complexes
by Moloud Mokfi, Jörg Rust, Christian W. Lehmann and Fabian Mohr
Molecules 2021, 26(12), 3705; https://doi.org/10.3390/molecules26123705 - 17 Jun 2021
Cited by 6 | Viewed by 3227
Abstract
The xanthine-derivatives 1,3,7-trimethylxanthine, 1,3-dimethyl-7-benzylxanthine and 1,3-dimethyl-7-(4-chlorobenzyl)xanthine are readily ethylated at N9 using the cheap alkylating agents ethyl tosylate or diethyl sulfate. The resulting xanthinium tosylate or ethyl sulfate salts can be converted into the corresponding PF6 and chloride salts. The reaction [...] Read more.
The xanthine-derivatives 1,3,7-trimethylxanthine, 1,3-dimethyl-7-benzylxanthine and 1,3-dimethyl-7-(4-chlorobenzyl)xanthine are readily ethylated at N9 using the cheap alkylating agents ethyl tosylate or diethyl sulfate. The resulting xanthinium tosylate or ethyl sulfate salts can be converted into the corresponding PF6 and chloride salts. The reaction of these xanthinium salts with silver(I) oxide results in the formation of different silver(I) carbene-complexes. In the presence of ammonia, ammine complexes [Ag(NHC)(NH3)]PF6 are formed, whilst with Et2NH, the bis(carbene) salts [Ag(NHC)2]PF6 were isolated. Using the xanthinium chloride salts neutral silver(I) carbenes [Ag(NHC)Cl] were prepared. These silver complexes were used in a variety of transmetallation reactions to give the corresponding gold(I), ruthenium(II) as well as rhodium(I) and rhodium(III) complexes. The compounds were characterized by various spectroscopic methods as well as X-ray diffraction. Full article
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14 pages, 10491 KB  
Article
Additive Manufacture of Three Dimensional Nanocomposite Based Objects through Multiphoton Fabrication
by Yaan Liu, Qin Hu, Fan Zhang, Christopher Tuck, Derek Irvine, Richard Hague, Yinfeng He, Marco Simonelli, Graham A. Rance, Emily F. Smith and Ricky D. Wildman
Polymers 2016, 8(9), 325; https://doi.org/10.3390/polym8090325 - 1 Sep 2016
Cited by 21 | Viewed by 10427
Abstract
Three-dimensional structures prepared from a gold-polymer composite formulation have been fabricated using multiphoton lithography. In this process, gold nanoparticles were simultaneously formed through photoreduction whilst polymerisation of two possible monomers was promoted. The monomers, trimethylopropane triacrylate (TMPTA) and pentaerythritol triacrylate (PETA) were mixed [...] Read more.
Three-dimensional structures prepared from a gold-polymer composite formulation have been fabricated using multiphoton lithography. In this process, gold nanoparticles were simultaneously formed through photoreduction whilst polymerisation of two possible monomers was promoted. The monomers, trimethylopropane triacrylate (TMPTA) and pentaerythritol triacrylate (PETA) were mixed with a gold salt, but it was found that the addition of a ruthenium(II) complex enhanced both the geometrical uniformity and integrity of the polymerised/reduced material, enabling the first production of 3D gold-polymer structures by single step multiphoton lithography. Full article
(This article belongs to the Special Issue Three-Dimensional Structures: Fabrication and Application)
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18 pages, 2169 KB  
Article
Application on Gold Nanoparticles-Dotted 4-Nitrophenylazo Graphene in a Label-Free Impedimetric Deoxynivalenol Immunosensor
by Christopher Edozie Sunday, Milua Masikini, Lindsay Wilson, Candice Rassie, Tesfaye Waryo, Pricilla G. L. Baker and Emmanuel I. Iwuoha
Sensors 2015, 15(2), 3854-3871; https://doi.org/10.3390/s150203854 - 6 Feb 2015
Cited by 39 | Viewed by 8253
Abstract
In this paper, we report a new concept to construct a label-free electrochemical inhibition-based immunosensor for the detection of the mycotoxin deoxynivalenol (DON) in cereal samples. The electrochemical impedance spectroscopy of tris(bipyridine) ruthenium (II) chloride was used as a marker enhanced with gold [...] Read more.
In this paper, we report a new concept to construct a label-free electrochemical inhibition-based immunosensor for the detection of the mycotoxin deoxynivalenol (DON) in cereal samples. The electrochemical impedance spectroscopy of tris(bipyridine) ruthenium (II) chloride was used as a marker enhanced with gold nanoparticles-dotted 4-nitrophenylazo functionalized graphene (AuNp/G/PhNO2) nanocatalyst mediated in Nafion on a glassy carbon electrode. Under the optimized conditions, the formation of immunocomplexes inhibited electron flow and increased the charge transfer resistance of the sensing interface linearly. The change in impedance was proportional to DON concentrations in the range of 6–30 ng/mL with a sensitivity and detection limit of 32.14 ΩL/ng and 0.3 µg/mL, respectively, which compares favorably with the ELISA result. The proposed sensor had a stability of 80.3%, good precision and selectivity in DON standard solution containing different interfering agents, indicating promising application prospect for this strategy in designing impedimetric, electrochemiluminescent, voltammetric or amperometric sensors. Full article
(This article belongs to the Special Issue Immunosensors 2014)
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