-
Molecules (Basel, Switzerland) Nov 2022The present review summarizes the work carried out mostly in the last decade on iridium and ruthenium complexes bearing various perylene ligands, of particular interest... (Review)
Review
The present review summarizes the work carried out mostly in the last decade on iridium and ruthenium complexes bearing various perylene ligands, of particular interest for bioimaging, photodynamic therapy, and solar energy conversion. In these complexes, the absorption spectra and the electrochemical properties are those of the perylene subunit plus those of the metal moiety. In contrast, the emissions are completely changed with respect to perylenes considered alone. Thus, fully organic perylenes are characterized by a strong fluorescence in the visible region, lifetimes of a few nanoseconds, and luminescence quantum yields approaching 100%, whereas perylene Ir and Ru complexes usually do not emit; however, in few cases, weak phosphorescent emissions, with lifetimes in the range of microseconds and relatively low quantum yields, are reported. This is due to a strong interaction between the perylene core and the heavy metal center, taking place after the excitation. Nevertheless, an important advantage deriving from the presence of the heavy metal center is represented by the ability to generate large amounts of singlet oxygen, which plays a key role in photodynamic therapy.
Topics: Iridium; Ruthenium; Perylene; Ligands; Luminescence
PubMed: 36432028
DOI: 10.3390/molecules27227928 -
Molecules (Basel, Switzerland) Feb 2017The organic chemistry of ruthenium has been one of the most vigorously growing research areas over the past decades. Considerable effort has been extended towards the...
The organic chemistry of ruthenium has been one of the most vigorously growing research areas over the past decades. Considerable effort has been extended towards the design and application of a broad series of ruthenium complexes, which culminated with the development by Ryoji Noyori (2001 Nobel Prize for Chemistry) of chiral ruthenium catalysts for stereoselective hydrogenation reactions [1], and the discovery by Robert H. Grubbs (2005 Nobel Prize for Chemistry) of well-defined ruthenium- benzylidene catalysts for olefin metathesis [2] [...].
Topics: Animals; Chemistry, Pharmaceutical; Drug Delivery Systems; Drug Design; Humans; Ruthenium
PubMed: 28208737
DOI: 10.3390/molecules22020255 -
Chemical Reviews Apr 2021Ruthenium-catalyzed cycloadditions to form five-, six-, and seven-membered rings are summarized, including applications in natural product total synthesis. Content is... (Review)
Review
Ruthenium-catalyzed cycloadditions to form five-, six-, and seven-membered rings are summarized, including applications in natural product total synthesis. Content is organized by ring size and reaction type. Coverage is limited to processes that involve formation of at least one C-C bond. Processes that are stoichiometric in ruthenium or exploit ruthenium as a Lewis acid (without intervention of organometallic intermediates), ring formations that occur through dehydrogenative condensation-reduction, σ-bond activation-initiated annulations that do not result in net reduction of bond multiplicity, and photochemically promoted ruthenium-catalyzed cycloadditions are not covered.
Topics: Catalysis; Cyclization; Heterocyclic Compounds; Organometallic Compounds; Oxidation-Reduction; Photochemical Processes; Polycyclic Compounds; Ruthenium; Stereoisomerism
PubMed: 33576620
DOI: 10.1021/acs.chemrev.0c01133 -
Angewandte Chemie (International Ed. in... Nov 2022The versatility of olefin metathesis is evident from its successful applications ranging from natural product synthesis to the valorization of renewable feedstocks. On... (Review)
Review
The versatility of olefin metathesis is evident from its successful applications ranging from natural product synthesis to the valorization of renewable feedstocks. On the other side, flow chemistry has recently gained particular interest among the synthetic community, offering valuable alternatives to classic batch chemistry and paving the way to the development of new transformations. The application of continuous-flow methods to olefin metathesis represents one of the most promising evolutions in the field at the interface of industrially relevant synthesis and reactor engineering, significantly improving some of the typical problems such as undesired self-reactions and ethylene-mediated catalyst deactivation. This Minireview aims to provide a brief survey covering the major aspects of those techniques which we hope may be of interest for the chemical community as well as those interested in catalysis, continuous processing, enabling technologies and reactor design.
Topics: Alkenes; Ruthenium; Catalysis; Biological Products
PubMed: 36111496
DOI: 10.1002/anie.202209564 -
International Journal of Molecular... Apr 2022(1) Background: Ruthenium and osmium complexes attract increasing interest as next generation anticancer drugs. Focusing on structure-activity-relationships of this...
(1) Background: Ruthenium and osmium complexes attract increasing interest as next generation anticancer drugs. Focusing on structure-activity-relationships of this class of compounds, we report on 17 different ruthenium(II) complexes and four promising osmium(II) analogues with cinnamic acid derivatives as O,S bidentate ligands. The aim of this study was to determine the anticancer activity and the ability to evade platin resistance mechanisms for these compounds. (2) Methods: Structural characterizations and stability determinations have been carried out with standard techniques, including NMR spectroscopy and X-ray crystallography. All complexes and single ligands have been tested for cytotoxic activity on two ovarian cancer cell lines (A2780, SKOV3) and their cisplatin-resistant isogenic cell cultures, a lung carcinoma cell line (A549) as well as selected compounds on three non-cancerous cell cultures in vitro. FACS analyses and histone γH2AX staining were carried out for cell cycle distribution and cell death or DNA damage analyses, respectively. (3) Results: IC50 values show promising results, specifically a high cancer selective cytotoxicity and evasion of resistance mechanisms for Ru(II) and Os(II) compounds. Histone γH2AX foci and FACS experiments validated the high cytotoxicity but revealed diminished DNA damage-inducing activity and an absence of cell cycle disturbance thus pointing to another mode of action. (4) Conclusion: Ru(II) and Os(II) compounds with O,S-bidentate ligands show high cytotoxicity without strong effects on DNA damage and cell cycle, and this seems to be the basis to circumvent resistance mechanisms and for the high cancer cell specificity.
Topics: Antineoplastic Agents; Carcinoma; Cell Line, Tumor; Cisplatin; Coordination Complexes; Drug Resistance, Neoplasm; Female; Histones; Humans; Ligands; Molecular Structure; Organometallic Compounds; Osmium; Ovarian Neoplasms; Ruthenium
PubMed: 35563367
DOI: 10.3390/ijms23094976 -
Molecules (Basel, Switzerland) Dec 2023Novel full-sandwich (-Cp)-Ru-paraphenylene complexes with the general formula [(-Cp)Ru(-L)](PF) where n = 1-3 and L = biphenyl, -terphenyl and -quaterphenyl, were...
Synthesis and Characterization of Ruthenium-Paraphenylene-Cyclopentadienyl Full-Sandwich Complexes: Cytotoxic Activity against A549 Lung Cancer Cell Line and DNA Binding Properties.
Novel full-sandwich (-Cp)-Ru-paraphenylene complexes with the general formula [(-Cp)Ru(-L)](PF) where n = 1-3 and L = biphenyl, -terphenyl and -quaterphenyl, were synthesized and characterized by means of spectroscopic and analytical techniques. The structures of the complexes [(-Cp)Ru(-biphenyl)](PF) (), [(-Cp)Ru(-terphenyl)](PF) () and [(-Cp)Ru(-terphenyl)](PF) () was determined by X-ray single crystal methods. The interaction of the complexes [(-Cp)Ru(-quaterphenyl)]Cl, ()Cl, and [(-Cp)Ru(-quaterphenyl)]Cl, ()Cl, with the DNA duplex d(5'-CGCGAATTCGCG-3') was studied using NMR techniques. The results showed that both complexes interacted non-specifically with both the minor and major grooves of the helix. Specifically, ()Cl exhibited partial binding through intercalation between the T7 and T8 bases of the sequence without disrupting the C-G and A-T hydrogen bonds. Fluorometric determination of the complexes' binding constants revealed a significant influence of the number of connected phenyl rings in the paraphenylene ligand (L) on the binding affinity of their complexes with the d(5'-CGCGAATTCGCG-3'). The complexes ()Cl and ()Cl were found to be highly cytotoxic against the A549 lung cancer cell line, with complex () being more effective than () (IC for ()Cl: 17.45 ± 2.1 μΜ, IC for ()Cl: 65.83 ± 1.8 μΜ) and with a selectivity index (SI) (SI for ()Cl: 1.1 and SI for ()Cl: 4.8).
Topics: Humans; Lung Neoplasms; Ruthenium; A549 Cells; Antineoplastic Agents; Organic Chemicals; Biphenyl Compounds
PubMed: 38202599
DOI: 10.3390/molecules29010017 -
Chemistry (Weinheim An Der Bergstrasse,... Apr 2022Tumor associated macrophages (TAMs) suppress the cancer immune response and are a key target for immunotherapy. The effects of ruthenium and rhodium complexes on TAMs...
Tumor associated macrophages (TAMs) suppress the cancer immune response and are a key target for immunotherapy. The effects of ruthenium and rhodium complexes on TAMs have not been well characterized. To address this gap in the field, a panel of 22 dirhodium and ruthenium complexes were screened against three subtypes of macrophages, triple-negative breast cancer and normal breast tissue cells. Experiments were carried out in 2D and biomimetic 3D co-culture experiments with and without irradiation with blue light. Leads were identified with cell-type-specific toxicity toward macrophage subtypes, cancer cells, or both. Experiments with 3D spheroids revealed complexes that sensitized the tumor models to the chemotherapeutic doxorubicin. Cell surface exposure of calreticulin, a known facilitator of immunogenic cell death (ICD), was increased upon treatment, along with a concomitant reduction in the M2-subtype classifier arginase. Our findings lay a strong foundation for the future development of ruthenium- and rhodium-based chemotherapies targeting TAMs.
Topics: Cell Line, Tumor; Humans; Immunotherapy; Rhodium; Ruthenium; Triple Negative Breast Neoplasms; Tumor-Associated Macrophages
PubMed: 35235227
DOI: 10.1002/chem.202104430 -
Topics in Current Chemistry (Cham) Jun 2022Luminescence chemosensors are one of the most useful tools for the determination and imaging of small biomolecules and ions in situ in real time. Based on the unique... (Review)
Review
Luminescence chemosensors are one of the most useful tools for the determination and imaging of small biomolecules and ions in situ in real time. Based on the unique photo-physical/-chemical properties of ruthenium(II) (Ru(II)) complexes, the development of Ru(II) complex-based chemosensors has attracted increasing attention in recent years, and thus many Ru(II) complexes have been designed and synthesized for the detection of ions and small biomolecules in biological and environmental samples. In this work, we summarize the research advances in the development of Ru(II) complex-based chemosensors for the determination of ions and small biomolecules, including anions, metal ions, reactive biomolecules and amino acids, with a particular focus on binding/reaction-based chemosensors for the investigation of intracellular analytes' evolution through luminescence analysis and imaging. The advances, challenges and future research directions in the development of Ru(II) complex-based chemosensors are also discussed.
Topics: Ions; Luminescence; Ruthenium
PubMed: 35695976
DOI: 10.1007/s41061-022-00392-8 -
Molecules (Basel, Switzerland) Jan 2020The Pictet-Spengler reaction (P-S) is one of the most direct, efficient, and variable synthetic method for the construction of privileged pharmacophores such as... (Review)
Review
The Pictet-Spengler reaction (P-S) is one of the most direct, efficient, and variable synthetic method for the construction of privileged pharmacophores such as tetrahydro-isoquinolines (THIQs), tetrahydro-β-carbolines (THBCs), and polyheterocyclic frameworks. In the (five-year period) following its centenary birthday, the P-S reaction did not exit the stage but it came up again on limelight with new features. This review focuses on the interesting results achieved in this period (2011-2015), analyzing the versatility of this reaction. Classic P-S was reported in the total synthesis of complex alkaloids, in combination with chiral catalysts as well as for the generation of libraries of compounds in medicinal chemistry. The P-S has been used also in tandem reactions, with the sequences including ring closing metathesis, isomerization, Michael addition, and Gold- or Brønsted acid-catalyzed -acyliminium cyclization. Moreover, the combination of P-S reaction with Ugi multicomponent reaction has been exploited for the construction of highly complex polycyclic architectures in few steps and high yields. The P-S reaction has also been successfully employed in solid-phase synthesis, affording products with different structures, including peptidomimetics, synthetic heterocycles, and natural compounds. Finally, the enzymatic version of P-S has been reported for biosynthesis, biotransformations, and bioconjugations.
Topics: Alkaloids; Biological Products; Cyclization; Models, Molecular; Ruthenium
PubMed: 31963860
DOI: 10.3390/molecules25020414 -
Brazilian Journal of Microbiology :... Mar 2022The present study aims to evaluate the antimicrobial property of Casiopeinas® copper- and ruthenium-based compounds against Aggregatibacter actinomycetemcomitans...
OBJECTIVES
The present study aims to evaluate the antimicrobial property of Casiopeinas® copper- and ruthenium-based compounds against Aggregatibacter actinomycetemcomitans serotype b (ATCC® 43,718™), as well as the cytotoxicity on an osteoblasts cell line of both compounds.
MATERIAL AND METHODS
The antibacterial effect of the copper-based compounds (CasII-gly, CasIII-ia) and the ruthenium-based compound (RuN-6) at four different concentrations was evaluated as the inhibition ratio of the bacterial growth after 48 h under anaerobic conditions, and the cell viability was measured through resazurin assay.
RESULTS
The copper- and ruthenium-based compounds used for this assay were (CasII-gly, CasIII-ia, and RuN-6), showing inhibitory activity between 39 and 62% compared to the antibiotic employed as control 66%. Cell viability was established between 61 and 96%.
CONCLUSIONS
Casiopeinas® and ruthenium showed dose and time dependent, inhibitory activity on A. actinomycetemcomitans, and low toxicity on cells (osteoblast) underexposure. The compound CasII-gly showed the best antimicrobial effect, and it could be considered a possible antimicrobial agent in periodontal therapy.
Topics: Aggregatibacter actinomycetemcomitans; Cell Survival; Copper; Osteoblasts; Ruthenium; Ruthenium Compounds
PubMed: 34741282
DOI: 10.1007/s42770-021-00648-3