The most significant factor in the design of high-performance nonlinear optical (NLO) materials is electronic symmetry, which directly influences hyperpolarizability and second harmonic generation (SH Show more
The most significant factor in the design of high-performance nonlinear optical (NLO) materials is electronic symmetry, which directly influences hyperpolarizability and second harmonic generation (SHG) response. This work presents two isostructural one-dimensional coordination complexes, {[Co2(CMP)2(BIPY)2(H2O)6]·11H2O}n (I) and {[Ni2(CMP)2(BIPY)2(H2O)6]·11H2O}n (II), (CMP = Cytidine Monophosphate, BIPY = 4,4'-bipyridine), crystallized in the noncentrosymmetric (NCS) P21 space group. The cobalt-based complex (I) establishes an NCS environment due to its pronounced octahedral distortion and lower electronic symmetry, coupled with intrachain hydrogen bonding and π-π stacking, resulting in enhanced hyperpolarizability and a robust second-harmonic generation response. Conversely, the nickel-based complex (II) demonstrates comparatively weaker NLO characteristics attributable to its higher symmetry. Experimental and theoretical findings have established that the superior NLO performance of complex (I) is intrinsically linked to its low symmetry, narrow band gap, and significant intermolecular interactions. This research demonstrates that disrupting electronic symmetry can significantly amplify the nonlinear optical response through supramolecular architecture in coordination polymers. Show less
Hybrid phosphines with anionic hard donor functions can be used to create an adaptable ligand environment for soft late transition metals. Herein, we show that the change of coordination of a Show more
Hybrid phosphines with anionic hard donor functions can be used to create an adaptable ligand environment for soft late transition metals. Herein, we show that the change of coordination of a diphosphine–phosphinic acid (P3OOH) in response to acid–base interactions or hydrogen bonding results in structural transformations of a disilver complex [Ag2(P3OO)2] (1) to give solvated and protonated derivatives [Ag2(P3OOH)2]2+ (2) and [Ag3(P3OO)3H]+ (3), accompanied by the alteration of the quantum yield of the solid-state photoluminescence from 0.06 up to 0.69. The related diphosphine–phosphide oxide complexes [M2(P3O)2] (M = Ag, Au) are oxidized to phosphinate compounds 2 and non-luminescent [Au2(P3OO)2H]+ (5) in the presence of triflic acid. Alternatively, [Au2(P3O)2] readily accommodates an additional gold(I) ion to yield a trinuclear cluster [Au3(P3O)2]+ (6), which is brightly sky-blue phosphorescent in the crystalline state (Φem = 0.76). The phosphide oxide group −PO in 6 is stable towards oxidation under acidic conditions in solution but undergoes protonation that results in two orders of magnitude (>170-fold) increase of the emission intensity. Complex 6 acts as a guest in the crystalline matrix of 5 due to their structural similarity and affords solid solutions with bright luminescence at a doping content of 1–2%.
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[Ru(bpy) 3 ] 2+ has long served as the archetypal coordination complex for probing inorganic photophysics and photochemistry. Its intense visible MLCT absorption, quantitative intersystem crossing, a Show more
[Ru(bpy) 3 ] 2+ has long served as the archetypal coordination complex for probing inorganic photophysics and photochemistry. Its intense visible MLCT absorption, quantitative intersystem crossing, and microsecond 3 MLCT lifetime established it as a benchmark photosensitizer across energy conversion, sensing, and catalysis. This review complements a recent historical perspective on [Ru(bpy) 3 ] 2+ by providing a contemporary view of its use as a versatile platform for advanced photochemical design. We first discuss updated views of its excited-state landscape, including refined descriptions of metal-centered states, minimum-energy crossing points, and photodissociation pathways, as well as the profound influence of counterions and microenvironments on excited-state energetics, stability, and reactivity. We then survey emerging applications, multiphoton solvated electron generation, mechanochemical ball-mill photoredox catalysis, and spin-forbidden red-light excitation. Next, we examine polynuclear complexes and dyads derived from the [Ru(bpy) 3 ] 2+ scaffold, emphasizing delocalized and antidissipative 3 MLCT states, long-lived charge separation, and integration into biohybrid or supramolecular architectures. Finally, we outline "real-life" applications in industrial photoredox chemistry, electrochemiluminescence immunoassays, oxygen sensing, and photodynamic therapy, and we position [Ru(bpy) 3 ] 2+ alongside emerging photosensitizers based on earth-abundant metals. Rather than being superseded, [Ru(bpy) 3 ] 2+ now functions as both a robust technological workhorse and an indispensable reference for next-generation photocatalyst design. Show less
While various metal complexes demonstrate immunogenic cell death (ICD)-inducing properties, there is a lack of studies comparing ICD properties in structurally similar complexes with different Show more
While various metal complexes demonstrate immunogenic cell death (ICD)-inducing properties, there is a lack of studies comparing ICD properties in structurally similar complexes with different metal centers. In this study, we synthesized four structurally similar Rh(I) and Ir(I) complexes with redox-active 1,2-bis(arylimino)acenaphthene (Ar-bian) ligands and assessed their anticancer and ICD-inducing properties. Analysis of damage-associated molecular patterns (DAMPs), ROS localization and dying cell populations highlighted the distinct roles of the metal center and the ligands. Specifically, only Rh(I) complexes induced the release of the three essential DAMPs and high levels of late apoptotic cells, while the Ir(I) complexes failed to trigger crucial “eat-me” signals. This work offers valuable insights into structure–activity relationships in metal complexes in the context of ICD.
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Iron complexes of tetradentate macrocyclic ligands containing N-heterocyclic carbene (NHC) donors have been referred to as organometallic heme analogues, but they usually lack the redox noninno Show more
Iron complexes of tetradentate macrocyclic ligands containing N-heterocyclic carbene (NHC) donors have been referred to as organometallic heme analogues, but they usually lack the redox noninnocence under oxidizing conditions that is characteristic of porphyrins. Here we report a novel NHC/N-donor hybrid macrocyclic ligand containing two trans NHC moieties, a pyridine and a redox active carbazolide fragment. Its FeII, FeIII and formal FeIV complexes have been isolated and comprehensively characterized, where UV/vis and 57Fe Mössbauer spectroscopies, SQUID magnetometry and density functional theory (DFT) calculations reveal that the latter are best described as FeIII systems antiferromagnetically coupled to a carbazolide-based organic π-radical. Two different redox series are obtained depending on the axial ligands: nitriles such as MeCN give low-spin (LS) configurations of the metal ion, while in case of weakly coordinating solvents and triflate anions the iron adopts an intermediate-spin (IS) configuration; MeCN binding constants have been determined. As in other heme analogues with NHC-based macrocycles, the strong equatorial σ-donor character raises the energy of the Fe(dx2-y2) orbital, making high-spin (HS) iron species inaccessible. The combined features of equatorial ligand redox noninnocence, restriction to LS/IS surfaces and tunability via the axial coligands makes this a promising platform for bioinspired reactivity such as the generation of reactive Fe/Ox intermediates. Show less
Abstract Most clinically used chemotherapeutic agents act by inducing apoptosis. However, their clinical effectiveness is often limited by poor therapeutic efficacy and the rapid development of drug r Show more
Abstract Most clinically used chemotherapeutic agents act by inducing apoptosis. However, their clinical effectiveness is often limited by poor therapeutic efficacy and the rapid development of drug resistance. In contrast, oncosis, as an inflammatory form of cell death independent of adenosine triphosphate (ATP) and apoptotic pathways, exhibits unique advantages in overcoming tumor drug resistance and regulating anti‐tumor immune responses. Herein, we present the first iridium(III)‐based immunogenic oncosis inducers designed to concurrently induce oncosis and activate the cGAS–STING pathway, thereby bridging chemotherapy with immunotherapy. Through a bioisosteric design strategy, we identified benzoselenazole and benzothiazole derivatives as key pharmacophores for triggering oncosis. These iridium(III)‐based oncosis‐inducers rapidly disrupt mitochondrial architecture, induce oxidative stress, and promote Ca(II) release, which subsequently activate calpain and porimin to initiate oncosis in multidrug‐resistant cancer cells. Transcriptomic profiling further revealed their ability to regulate actin cytoskeleton organization, modulate ABC transporter activity, and affect glycolysis/gluconeogenesis. Notably, the metal complexes induce mitochondrial swelling and mt‐DNA damage, leading to robust activation of the cGAS–STING innate immune pathway and eliciting a strong anticancer immune response. Based on these multimodal mechanisms, the Ir(III)‐based immunogenic oncosis inducers were able to effectively kill drug‐resistant cancer cells and enhance the anticancer immune response in tumor mouse models. Show less
A molecular CoIII complex (1), supported by a 14-membered macrocyclic ligand, was developed. The oxygen reduction reaction (ORR) catalyzed by 1 was investigated under electroc Show more
A molecular CoIII complex (1), supported by a 14-membered macrocyclic ligand, was developed. The oxygen reduction reaction (ORR) catalyzed by 1 was investigated under electrochemical and spectrochemical conditions in acetonitrile, using trifluoroacetic acid (TFAH) as the proton source, and revealed selective catalytic 4e-/4H+ reduction in both cases. Kinetic analyses revealed a first-order dependence on the concentrations of both catalyst and O2, but no dependence on TFAH or decamethylferrocene (under chemical conditions). The catalytic rate constant was determined to be 3.6 × 103 M-1 s-1 under electrochemical and 90 M-1 s-1 under spectrochemical conditions. A reported Co(III) complex (2), featuring a bis-pyridine-dioxime ligand architecture, also catalyzed the 4e-/4H+ reduction of O2 but displayed first-order dependence on catalyst, TFAH, and O2. These results suggest that variations in the coordination environment around the Co center lead to distinct ORR mechanisms, despite identical product selectivity. Complex 1 exhibited an effective overpotential of 0.78 V, which is 240 mV lower than that of 2 (ηeff = 1.02 V), underscoring the role of ligand architecture in tuning the catalytic overpotential. Overall, this study underscores the pivotal role of ligand design in shaping ORR kinetics, mechanism, and efficiency, offering valuable insights for the development of ORR catalysts. Show less
ABSTRACT Understanding how metals coordinate to organic ligands is a precondition for the rational design of metal complexes and catalysts. Whereas certain types of ligands are capable of just one eas Show more
ABSTRACT Understanding how metals coordinate to organic ligands is a precondition for the rational design of metal complexes and catalysts. Whereas certain types of ligands are capable of just one easy‐to‐predict coordination modality, others may present tens and sometimes even hundreds of coordination options (mono‐, bi‐, or polydentate), and predicting the correct one may be a challenge even to seasoned chemists. The current paper describes a “hybrid” computational approach in which a Machine Learning, ML, algorithm learns to predict complex coordination patterns using knowledge‐based “rules” derived from the Cambridge Structural Database, CSD. This model is applicable to a broad scope of ligands (including hemilabile and haptic ones as well as those with denticity > 6) and different metals at different oxidation states. The algorithm's code is disclosed and can be readily deployed in RDKit via our RDMetallics python‐wrapper. It is also deployed as a publicly accessible web portal for demonstration and use. Show less
An integrated multimodal imaging workflow of cryogenic super-resolution fluorescence microscopy and soft X-ray tomography, Orbitrap secondary ion mass spectrometry, and inductively coupled plasma-mass Show more
An integrated multimodal imaging workflow of cryogenic super-resolution fluorescence microscopy and soft X-ray tomography, Orbitrap secondary ion mass spectrometry, and inductively coupled plasma-mass spectrometry has revealed the unexpected targeting of a half-sandwich cyclopentadienyl Rh(III) phenylazopyridine anticancer complex to cellular lipid membranes and lipid droplets. The complex accumulates in plasma membranes with a surprisingly intense switch-on luminescence in living cancer cells, drives remodeling of lipid droplet architecture, and penetrates deeply into lipid-rich tissue environments. DFT modeling shows strong supramolecular interactions between the complex and glycerophosphorylcholine lipids. Show less
Zinc is a crucial element in cellular processes, and its homeostasis has intricate relationships with the initiation, progression, and therapeutic intervention of cancer. Activation of the cyc Show more
Zinc is a crucial element in cellular processes, and its homeostasis has intricate relationships with the initiation, progression, and therapeutic intervention of cancer. Activation of the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway has been proven to be an effective strategy for cancer immunotherapy. Herein, we report four phosphorescent iridium complexes (Ir1–Ir4) with zinc chelating ligands. Among them, Ir1 can bind and image mitochondrial chelatable zinc ions via phosphorescence-lifetime responses, consequently modulating the expression of zinc-regulatory proteins. Furthermore, the in situ formed heteronuclear metal complex Ir1-Zn2 shows nuclease mimetic activities, capable of hydrolyzing mitochondrial DNA (mtDNA) to release mtDNA fragments for the activation of the cGAS-STING pathway. In conclusion, we designed a mitochondria-targeting phosphorescent Ir(III) complex with dual functions in dysregulation of zinc homeostasis and generation of nuclease in situ, which provides an innovative approach to stimulate the cGAS-STING pathway.
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Mitochondria are associated with cellular energy metabolism, proliferation, and mode of death. Damage to mitochondrial DNA (mtDNA) greatly affects mitochondrial function by interfering with energy pro Show more
Mitochondria are associated with cellular energy metabolism, proliferation, and mode of death. Damage to mitochondrial DNA (mtDNA) greatly affects mitochondrial function by interfering with energy production and the signaling pathway. Monofunctional trinuclear platinum complex MTPC demonstrates different actions on the mtDNA of cancerous and normal cells. It severely impairs the integrity and function of mitochondria in the human lung cancer A549 cells, such as dissipating mitochondrial membrane potential, decreasing the copy number of mtDNA, interfering in nucleoid proteins and polymerase gamma gene, reducing adenosine triphosphate (ATP), and inducing mitophagy, whereas it barely affects the mtDNA of the human kidney 2 (HK-2) cells. Moreover, MTPC promotes the release of mtDNA into the cytosol and stimulates the cyclic GMP-AMP synthase-stimulator of interferon genes (cGAS-STING) pathway, thus showing the potential to trigger antitumor immunity. MTPC displays significant cytotoxicity against A549 cells, while it exhibits weak toxicity toward HK-2 cells, therefore displaying great advantage to overcome the lingering nephrotoxicity of platinum anticancer drugs. Discrepant effects of a metal complex on mitochondria of different cells mean that targeting mitochondria has special significance in cancer therapy. Show less
Abstract Transition metal complexes have been widely utilized as cellular imaging tools. To impart organelle specificity, ligand architecture is usually modified to modulate properties like overall ch Show more
Abstract Transition metal complexes have been widely utilized as cellular imaging tools. To impart organelle specificity, ligand architecture is usually modified to modulate properties like overall charge and lipophilicity. In many such designs, the metal identity and its intrinsic properties are often ignored. To address this gap, in this study, we explored the effects of changing the metal center on the localization patterns of isostructural complexes. To this end, we employed the thiosemicarbazone Dp44mT to synthesize coumarin‐conjugated complexes of Au(III), Pt(II), and Pd(II). Although the metal centers in these compounds share a formal d 8 configuration, they differ in properties such as ionic radius, charge density, and ligand exchange rates, which can affect their subcellular localization patterns. In addition, we synthesized a second set of analogous complexes using BODIPY as the conjugating fluorophore to assess the influence of using a different dye on the cellular distribution. Confocal imaging revealed that the complexes exhibited distinct intracellular distributions. For instance, while the coumarin‐conjugated Pt(II) complex localized specifically in lysosomes, the corresponding lipophilic Pd(II) complex lacked this specificity and instead followed a diffusely cytosolic distribution. Similarly, the more lipophilic BODIPY conjugated complexes were non‐specific in their cellular distribution as well. Overall, the findings of this study highlight the interplay of metal identity and lipophilicity in determining the localization patterns of Dp44mT‐based metal complexes, offering fresh insights into the design of new metal‐based imaging tools. Show less
Conformer generation is crucial for computational chemistry tasks such as structure-based modeling and property prediction. Although reliable methods exist for organic molecules, coordination complexe Show more
Conformer generation is crucial for computational chemistry tasks such as structure-based modeling and property prediction. Although reliable methods exist for organic molecules, coordination complexes remain challenging due to their diverse coordination geometries, ligand types, and stereochemistry. Current tools often lack the flexibility and reliability required for these systems. Here, we introduce MetalloGen, a novel algorithm designed for the automated generation of 3D conformers of mononuclear coordination complexes. MetalloGen accepts either SMILES strings or molecular graph representations as input and enables the generation of reliable conformers, including those with multiple polyhapto ligands, which are typically inaccessible to conventional conformer generators. To rigorously assess MetalloGen's performance, we benchmarked it on three distinct data sets: a curated collection of experimentally determined structures from the Cambridge Structural Database, the MOR41 benchmark set encompassing a wide range of organometallic reactions and complex ligand environments, and three catalytic reactions. Across all test sets, MetalloGen consistently reproduced appropriate geometries with high fidelity and demonstrated robust stereochemical control, even for challenging cases involving multiple polyhapto ligands. The versatility and reliability of MetalloGen make it a valuable tool for more accurate and efficient computational investigations in inorganic and organometallic chemistry. Show less
Copper(II), manganese(II), and mercury(II) complexes of 4-amino-5-(2-(1-pyridine-2-yl)ethylidene)hydrazinyl)-4H-1,2,4-triazole-3-thiol (H2TAP) were synthesized and characterized using CHN analysis, FT Show more
Copper(II), manganese(II), and mercury(II) complexes of 4-amino-5-(2-(1-pyridine-2-yl)ethylidene)hydrazinyl)-4H-1,2,4-triazole-3-thiol (H2TAP) were synthesized and characterized using CHN analysis, FT-IR, 1H-NMR, 13C-NMR, UV–Vis, ESR, MS, PXRD, magnetic moment measurements, molar conductance, and TG/DTA. DFT calculations indicate octahedral geometries and the neutral bidentate or tridentate chelating behavior of the ligand. Cyclic voltammetry revealed the complexes’ redox properties, and Job’s method elucidated stoichiometric compositions in solution. Biochemical assays demonstrated antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Candida albicans. The MnII complex exhibited potent antitumor activity against HepG-2 cells. Antioxidant and DNA binding studies showed promising results, with docking investigations indicating strong interactions between the ligand/complexes and target proteins (PDB: 1YWN) and DNA (PDB: 8EC1), suggesting therapeutic potential. Show less
AbstractPhotoactivatable metal complexes offer the prospect of novel drugs with low side effects and new mechanisms of action to combat resistance to current therapy. We highlight recent progress in t Show more
AbstractPhotoactivatable metal complexes offer the prospect of novel drugs with low side effects and new mechanisms of action to combat resistance to current therapy. We highlight recent progress in the design of platinum, ruthenium, iridium, gold and other transition metal complexes, especially for applications as anticancer and anti‐infective agents. In particular, understanding excited state chemistry related to identification of the bioactive species (excited state metallomics/pharmacophores) is important. Photoactivatable metallodrugs are classified here as photocatalysts, photorelease agents and ligand‐activated agents. Their activation wavelengths, cellular mechanisms of action, experimental and theoretical metallomics of excited states and photoproducts are discussed to explore new strategies for the design and investigation of photoactivatable metallodrugs. These photoactivatable metallodrugs have potential in clinical applications of Photodynamic Therapy (PDT), Photoactivated Chemotherapy (PACT) and Photothermal Therapy (PTT). Show less
Three copper(II) complexes – [Cu2(bipy)2L4] (1), [Cu2(phen)2L4] (2) and [Cu2(dmphen)2L4]·2H2O (3) – were synthesized based on 5-methyltetrazole (HL) and 2,2′-bipyridine/1,10-phenanthroline der Show more
Three copper(II) complexes – [Cu2(bipy)2L4] (1), [Cu2(phen)2L4] (2) and [Cu2(dmphen)2L4]·2H2O (3) – were synthesized based on 5-methyltetrazole (HL) and 2,2′-bipyridine/1,10-phenanthroline derivatives. A crystallographic study revealed that complexes 1–3 have a binuclear structure with coordination polyhedron close to the square pyramid. Stability of the complexes in aqueous solution was studied by UV-Vis spectroscopy and conductometry. In vitro cytotoxicity study was carried out in 2D and 3D cell culture models and showed that complexes 2 and 3 possess cytotoxic activity against tumor cells (A549, Hep2, HepG2, MCF7) with LC50 values exceeding those of the medical drug cisplatin. At the same time, being less active, compound 1 has a selectivity index of 3.1 to hepatocellular carcinoma (HepG2 cell line) compared to non-tumor MRC5 cells. The Hoechst/Propidium iodide staining assay and ROS generation assay on Hep2 cells indicated that the cytotoxic effects of the complexes involved apoptosis induction without ROS accumulation.
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In the frame of our research aiming to develop efficient triplet-emitting materials, we are exploring the role of the second coordination sphere in enhancing the rigidity of structures and its control Show more
In the frame of our research aiming to develop efficient triplet-emitting materials, we are exploring the role of the second coordination sphere in enhancing the rigidity of structures and its controlling aspect over the extents of excited state distortions. We thus synthesised three N^C^N cyclometalated complexes [M(LBn)Cl] (M = Pt, Pd, and Ni), where the two ortho-positions of the pyridyl moieties in 1,3-di(2-pyridyl)-benzene are benzyl substituted (Bn) forming a tight binding pocket for the metal and the Cl− ancillary ligand. The molecular structures from single-crystal X-ray diffraction show a markedly distorted square planar M(II) coordination with τ4 values of around 0.4. UV-vis absorption spectra show long-wavelength bands in the range 350 to 5400 nm with the energies increasing along the series Ni < Pt < Pd. The Pt(II) complex emits in solution at 298 K (λmax = 544 nm) and displays aggregated emission within poly(methyl methacrylate) (PMMA) films at various concentrations at 298 K. The Pd(II) derivative exhibits a broad emission band at 77 K in a frozen glassy 2-MeTHF matrix, peaking at 530 nm. Very different from the Pt(II) and Pd(II) spectra, the Ni(II) sample showed a broad emission with λmax = 699 nm at 77 K, with a quantum yield of 20% and ms lifetime. TD-DFT calculated decomposition of the assumed emissive T1 state showed similar 3MLCT character of about 30% for all three complexes, but marked differences in LC character of about 38% for Pd and Pt and only 5% for Ni. In turn, for Ni the by far the highest MC character (42%) was calculated which strongly speaks against triplet photoluminescence from the Ni(II) complex. Show less
A fundamental biological mechanism, programmed cell death (PCD), is essential for tissue homeostasis, immunological control, and development. Its dysregulation is a characteristic of many dise Show more
A fundamental biological mechanism, programmed cell death (PCD), is essential for tissue homeostasis, immunological control, and development. Its dysregulation is a characteristic of many diseases in multicellular organisms, including cancer, where unchecked proliferation is made possible by evading cell death. Therefore, one of the main tenets of contemporary anticancer therapies is the restoration or induction of PCD in cancer cells. One potential, least invasive method among these is photodynamic treatment (PDT). PDT uses light-activatable photosensitisers, which cause cancer cells to explode with reactive oxygen species (ROS) when exposed to light. These ROS harm important biomolecules, throw off the cellular redox equilibrium, and cause cells to die. PDT-induced cell death was previously believed to be mostly caused by autophagy, necrosis, or apoptosis. Recent research, however, has shown that it can trigger a wider range of unconventional cell death pathways. ROS can cause ferroptosis by oxidising membrane lipids, fragmenting DNA, and lowering intracellular glutathione (GSH) levels. Similarly, necroptosis or pyroptosis can result from severe oxidative stress activating death receptor signalling. Sometimes, in response, cells use survival strategies like autophagy, which can also lead to cell death. This review explores these new, unconventional methods of cell death and how PDT can be used to take advantage of them. Next-generation photosensitisers based on iridium (Ir), ruthenium (Ru), and rhenium (Re) complexes are given special attention because they provide deep tissue penetration, improved photostability, and adjustable ROS production. Their incorporation into PDT has revolutionary potential for improving cancer treatment precision and conquering therapeutic resistance.
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Abstract Complex compounds [CuL(phen)(H2O)(NO3)]NO3 (1), [CuL(bipy)(NO3)2]·2EtOH (2), [CuL2(H2O)2 (NO3)2] (2a), [CuL(dmbipy)(NO3)2]·3EtOH (3), and [CuL2(NO3)2] (3a), where L is 3-(5-phenyl-2H-tetrazol Show more
Abstract Complex compounds [CuL(phen)(H2O)(NO3)]NO3 (1), [CuL(bipy)(NO3)2]·2EtOH (2), [CuL2(H2O)2 (NO3)2] (2a), [CuL(dmbipy)(NO3)2]·3EtOH (3), and [CuL2(NO3)2] (3a), where L is 3-(5-phenyl-2H-tetrazol-2-yl)pyridine, phen is 1,10-phenanthroline, bipy is 2,2′-bipyridine, and dmbipy is 4,4′-dimethyl-2,2′-bipyridine, are obtained and structurally characterized. It is shown that L behaves as the monodentate ligand being coordinated by the nitrogen atom of the pyridine ring. The coordination polyhedron made of copper atoms is a square pyramid in complexes 1 and 3, a distorted octahedron and a distorted square in complexes 2a and 3a respectively. Complex 1 is characterized by the elemental analysis, powder X-ray diffraction, and IR spectroscopy. Furthermore, its cytotoxic properties are studied on human larynx carcinoma (Hep2), breast adenocarcinoma (MCF7), and non-tumor human fibroblast (MRC5) cell lines. Complex 1 is shown to exhibit the pronounced cytotoxic action (LC50(Hep2) = 4.1±0.4 µM and LC50(MCF7) = 4.9±0.1 µM), however, does not exhibit selectivity against tumor cell lines (LC50(MRC5) = = 3.06 ±0.02 µM). Show less
The endoplasmic reticulum plays an important role in maintaining the protein homeostasis of cells as well as regulating Ca2+ storage. An increased load of unfolded proteins in the endoplasmic Show more
The endoplasmic reticulum plays an important role in maintaining the protein homeostasis of cells as well as regulating Ca2+ storage. An increased load of unfolded proteins in the endoplasmic reticulum due to alterations in the cell's metabolic pathway leads to the activation of the unfolded protein response, also known as ER stress. ER stress plays a major role in maintaining the growth and survival of various cancer cells, but persistent ER stress can also lead to cell death and hence can be a therapeutic pathway in the treatment of cancer. In this review, we focus on different types of small molecules that impair different ER stress sensors, the protein degradation machinery, and chaperone proteins. We also review the metal complexes and other miscellaneous compounds inducing ER stress through multiple mechanisms. Finally, we discuss the challenges in this emerging area of research and the potential direction of research to overcome them towards next-generation ER-targeted cancer therapy.
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AbstractG-quadruplex DNA secondary structures are formed in guanine-rich sequences and have been found to play an important role in regulating different biological processes. Indeed, guanine-rich sequ Show more
AbstractG-quadruplex DNA secondary structures are formed in guanine-rich sequences and have been found to play an important role in regulating different biological processes. Indeed, guanine-rich sequences with the potential to form G-quadruplexes are present in different regions in the human genome, such as telomeres and the promoter region of different genes, including oncogene promoters. Thus, the rational design of small molecules capable of interacting, stabilising or damaging with high specificity these secondary structures represents an important strategy for the development of potent anticancer drugs. In this review, we highlight the interaction between G-quadruplex structures and their ligands, specifically emphasising the role of metal complexes. We provide detailed structural insight into the binding modes of metal complex-G-quadruplex interaction by analysing 18 sets of coordinates from X-ray and NMR currently available in the Protein Data Bank (PDB), with a primary focus on X-ray structural data. Show less
Iridium(III) complexes nowadays became rising stars in various health-related applications. Thus, there is a necessity to assess cytotoxicity of the synthesized molecules against cancer/normal cell li Show more
Iridium(III) complexes nowadays became rising stars in various health-related applications. Thus, there is a necessity to assess cytotoxicity of the synthesized molecules against cancer/normal cell lines. In this report, we present a dataset of 2694 experimental cytotoxicity values of 803 iridium complexes against 127 different cell lines. We specify the experimental conditions and provide representation of the complexes molecules in machine-readable format. The dataset provides a starting point for exploration of new iridium-based cellular probes and opens new possibilities for predictions of toxicities and data-driven generation of new organometallic anticancer agents. Show less
As the most frequent and deadly type of cancer in women, breast cancer has a high propensity to spread to the brain, bones, lymph nodes, and lungs. The discovery of cisplatin marked the beginn Show more
As the most frequent and deadly type of cancer in women, breast cancer has a high propensity to spread to the brain, bones, lymph nodes, and lungs. The discovery of cisplatin marked the beginning of the development of anticancer metal-based medications, although the drug's severe side effects have limited its usage in clinical settings. The remarkable antimetastatic and anticancer activity of different ruthenium complexes such as NAMI-A, KP1019, KP1339, etc. reported in the 1980s has bolstered the discovery of ruthenium complexes with various types of ligands for anticancer applications. The review meticulously elucidates the cytotoxic and antimetastatic potential of reported ruthenium complexes against breast cancer cells. Notably, arene-based and cyclometalated ruthenium complexes emerge as standout candidates, showcasing remarkable potency with notably low IC50 values. These findings underscore the promising therapeutic avenues offered by ruthenium-based compounds, particularly in addressing the challenges posed by conventional treatments in refractory or aggressive breast cancer subtypes. Moreover, the review comprehensively integrates a spectrum of ruthenium complexes, spanning traditional metal complexes to nano-based formulations and light-activated variants, underscoring the versatility and adaptability of ruthenium chemistry in breast cancer therapy.
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Abstract The review is devoted to copper coordination compounds based on 2,2′-bipyridine / 1,10-phenanthroline and diverse N-, O-, S-donor ligands exhibiting cytotoxic properties. Therefore, they can Show more
Abstract The review is devoted to copper coordination compounds based on 2,2′-bipyridine / 1,10-phenanthroline and diverse N-, O-, S-donor ligands exhibiting cytotoxic properties. Therefore, they can be a starting platform for developing antitumor drugs. The review covers the structural aspects of the complexes, the features of their cytotoxic activity and its mechanism, as well as in vivo studies. Show less