Search Results (93)

Current tumor diagnostics rely on fluorodeoxyglucose (FDG)-PET imaging, but FDG’s short half-life and high cost limit its widespread use. Infrared (IR) probes are emerging as non-radioactive alternatives to conventional tracers for tissue section and other in vitro imaging applications. Because cells and tissues are relatively free of absorption peaks between 1800 and 2200 cm⁻¹, metal-carbonyl complexes, especially cyclopentadienylrhenium(I) tricarbonyl (Cp[Re(CO)₃]) derivatives, absorb strongly in this window and provide robust platforms for bioconjugation. Furthermore, Cp[Re(CO)₃] fragments can be introduced into organic substrates via an elegant three-component reaction that simultaneously forges the cyclopentadienyl-metal and cyclopentadienyl-substituent bonds. As a result, the functionalized half-sandwich complex is obtained in a single step without any special handling issues. We have therefore properly modified a glucose molecule with that complex and developed a novel glucoconjugated Cp[Re(CO)₃] probe that enables IR-based visualization of diseased cells at 2100 cm⁻¹, offering a non-invasive, non-radioactive histological tool and a promising basis for future medical imaging devices. Full article

The rhenium(I) tricarbonyl complex fac-[Re(CO)₃(5,6-epoxy-5,6-dihydro-1,10-phenanthroline)Br] (ReL) has previously demonstrated promising luminescent properties, enabling its direct application as a probe for walled cells such as Candida albicans and Salmonella enterica. In this new study, we present a significantly expanded and comprehensive characterization of ReL, incorporating a wide range of experimental and computational techniques not previously reported. These include variable-temperature ¹H and ¹³C NMR spectroscopy, CH-COSY, single-crystal X-ray diffraction, Hirshfeld surface analysis, DFT calculations, Fukui functions, non-covalent interaction (NCI) indices, and electrochemical profiling. Structural analysis confirmed a pseudo-octahedral geometry with the bromide ligand positioned cis to the epoxy group. NMR data revealed the coexistence of cis and trans isomers in solution, with the trans form being slightly more stable. DFT calculations and aromaticity descriptors indicated minimal electronic differences between isomers, supporting their unified treatment in subsequent analyses. Electrochemical studies revealed two oxidation and two reduction events, consistent with ECE and EEC mechanisms, including a Re(I) → Re(0) transition at −1.50 V vs. SCE. Theoretical redox potentials showed strong agreement with experimental data. Biological assays revealed a dose-dependent cytotoxic effect on HeLa cells, contrasting with previously reported low toxicity in microbial systems. These findings, combined with ReL’s luminescent and antimicrobial properties, underscore its multifunctional nature and highlight its potential as a bioactive and imaging agent for advanced therapeutic and microbiological applications. Full article

The number of structurally investigated cyclopentadienyl (Cp⁻) complexes of technetium is limited in contrast to the situation with its heavier homolog, rhenium. Although this could be attributed to the radioactivity of all isotopes of the radioelement, there are also clear chemical differences to analogous compounds of the other group seven elements, manganese and rhenium. Technetium Cp⁻ compounds are known with the metal in the oxidation states “+1” to “+7”, with a clear dominance of Tc(I) carbonyls and nitrosyls. Corresponding carbonyl complexes also play a significant role in the development of ^99mTc-based radiopharmaceuticals with the aromatic ring as an ideal position for the attachment of biomarkers. In this paper, the present status of the synthetic and structural chemistry of technetium with Cp⁻ ligands is discussed, together with recent developments in the corresponding ^99mTc labeling chemistry. Full article

The sorption, structural, and thermal properties of the interpolymer system based on polymethacrylic acid (PMAA) and poly-4-vinylpyridine (P4VP) were studied at different component ratios for the extraction of rhenium (ReO₄⁻) and molybdenum (${\mathrm{M}\mathrm{o}\mathrm{O}}_4^{2-}$) ions from model solutions. The results showed that sorption efficiency depends on both composition and contact time. Systems with molar ratios of 3:3 and 2:4 exhibited the highest activity, reaching more than 90% extraction for rhenium and up to 94% for molybdenum after 48 h. FTIR spectra indicated the involvement of carboxyl and pyridine groups in complex formation with the metal ions, as evidenced by band shifts and the appearance of new absorption features. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) demonstrated that modification of PMAA with P4VP enhances the thermal stability of the system, which is maintained even after desorption. The system with the optimal composition showed structural stability and the ability to regenerate without a notable decrease in sorption capacity. Sorption performance was preserved across a wide pH interval, with maximum values at pH 2–4, which makes the system suitable for hydrometallurgical applications. Comparison with literature data indicates agreement with current approaches to rare-metal recovery, while the PMAA–P4VP system is distinguished by improved stability and potential for further development. These findings provide a basis for the design of selective and environmentally safe processes for rhenium and molybdenum recovery, relevant to the conditions of the Republic of Kazakhstan, where technogenic solutions rich in these metals are available. Full article

Anthraquinones are molecules with numerous biological properties that can act as DNA intercalators and topoisomerase IIa inhibitors. In this work, the development of technetium-99m radiotracers was pursued via the technetium-tricarbonyl “2 + 1” mixed-ligand approach, fac-[^99mTc][Tc^I(CO)₃(NN′)(N)]⁺, with a (N,N′) bidentate chelator and a N co-ligand. In one approach, the ligands used were 2,2′-bipyridine (bpy) and N-functionalized-imidazole, where imidazole was conjugated to an anthraquinone moiety. In the other approach, 2-picolylamine and imidazole were used as the mixed-ligand system, where picolylamine was conjugated to an anthraquinone moiety. The synthesis of the ligands was achieved by reaction of 2-picolylamine with a suitably functionalized anthraquinone (Aqpa) or anthrapyrazole (Appa) and imidazole with a suitably functionalized anthraquinone (Aqim). The rhenium reference compounds, fac-[Re^I(CO)₃(bpy)(Aqim)]⁺ with bpy as a bidentate chelator and fac-[Re^I(CO)₃(Aqpa or Appa)(Im)]⁺, with imidazole (Im) as a co-ligand, were synthesized and characterized with spectroscopic methods. The radiotracer technetium-99m complexes fac-[^99mTc][Tc(CO)₃(bpy)(Aqim)]⁺ and fac-[^99mTc][Tc(CO)₃(Aqpa or Appa)(Im)]⁺ were prepared and characterized with standard methods. The purified radiotracers displayed high stability (≥90%) after incubation 24 h in 1 mM L-histidine or rat plasma. The tracers’ cell uptake was evaluated in vitro in CT-26 cells, and their pharmacokinetic properties and tumor uptake were evaluated in vivo in CT26-tumor-bearing mice. The “2 + 1” technetium-tricarbonyl approach leads to in vitro stable tracers, and this mixed-ligand system shows promise for further evaluation. Full article

A bidentate ligand concept based on β-carbolines functionalized with a 1,2,4-triazolyl-moiety was designed and realized, enabling the development of a series of neutral rhenium(I) complexes. This new class of anionic ligands, incorporating either an unsubstituted 9H-pyrido[3,4-b]indole core (L_nHo) or a 9-methyl-substitued variant (L_Me-nHo), was developed towards tailored photofunctionality. Structural modification via methyl substitution at the indole moiety was found to enhance overall phosphorescence efficiency. Comparative studies of two monodentate auxiliary units revealed that 1,3,5-triaza-7-phosphaadamantane (PTA) significantly reduces the photoluminescence efficiency compared to pyridine (Py). Solvent-dependent photoluminescence studies indicated that a lowered polarity leads to an increase in photoluminescence quantum yields (Φ_L). The complex Re(L_Me-nHo)Py emerged as the most efficient emitter, displaying a Φ_L of 44% in dichloromethane (DCM). Notably, all complexes exhibited efficient quenching of excited triplet states by diffusional collision with triplet dioxygen (³O₂), yielding good singlet dioxygen (¹O₂) photoproduction efficiencies (Φ_Δ) with a maximum of 45% observed for Re(L_nHo)Py. These results highlight the suitability of these complexes for applications requiring efficient phosphorescence and oxygen photosensitization, such as bioimaging, and photodynamic therapy or photooxidation catalysis, while underscoring the central role of the tailored β-carboline-based chromoluminophores in enabling precise tuneability of photophysical properties. Full article

This work reports the synthesis and characterization of a novel rhenium(I) complex incorporating a phosphorus–nitrogen (P,N) ligand. The compound crystallizes in a distorted octahedral geometry, as confirmed by single-crystal X-ray diffraction analysis. The complexes were evaluated as catalysts in the transfer hydrogenation of acetophenone using 2-propanol as the hydrogen source. Comparative studies with other rhenium(I) complexes bearing polypyridine ligands revealed high catalytic performance, achieving conversions between 68% and 99%. These results highlight the promising potential of P,N-ligand rhenium complexes in homogeneous transfer hydrogenation catalysis. The optimal reaction time was found to be 4 h for the complexes studied, with only the fac-[Re(CO)₃(PN)Cl] complex showing improved conversion upon extending the reaction time to 7 h, likely due to the donor effects provided by the P,N-ligand. Full article

Sulfonamides represent a versatile class of biologically active compounds, best known for their antibacterial activity, but increasingly investigated for their potential in oncology. Free sulfonamides themselves display cytotoxic properties; however, coordination with metal ions often enhances both selectivity and potency, while also introducing new mechanisms of action. Although numerous studies have reported sulfonamide–metal complexes with anticancer activity, a systematic overview linking biological properties to the central metal atom has been lacking. This review summarizes current research on sulfonamide complexes with transition metals and selected main-group elements, focusing on their pharmacological potential as anticancer agents. The compounds discussed include complexes of titanium, chromium, manganese, rhenium, ruthenium, osmium, iridium, palladium, platinum, copper, silver, gold, iron, cobalt, nickel, uranium, calcium, magnesium and bismuth. For each group, representative structures are presented along with cytotoxicity data against cancer cell lines, comparisons with reference drugs such as for example cisplatin, and where relevant, studies on carbonic anhydrase inhibition. The survey of available data demonstrates that many sulfonamide–metal complexes show cytotoxic activity comparable to or greater than existing chemotherapeutic agents, while in some cases exhibiting reduced toxicity toward non-cancerous cells. These findings highlight the promise of sulfonamide–metal complexes as a fertile area for anticancer drug development and provide a framework for future design strategies. This review covers the research on anti-cancer activity of sulfonamide complexes during the years 2007–2025. Full article

The thioether-functionalized 2-azabutadiene (ⁱPrS)₂C=C(H)-N=CPh₂ L1 ligates to Mn(CO)₅Br to form the five-membered chelate compound fac-MnBr(CO)₃[(ⁱPrS)₂C=C(H)-N=CPh₂] MnPropBr, whose crystal structure has been determined from X-ray diffraction data. In the crystal, different secondary intermolecular interactions, such as Br^…HC and π^…π, give rise to a supramolecular network. The electronic properties of the metal–ligand bonds in MnPropBr are similar to those of complex MnPhBr (with R = SPh instead of ⁱPrS); this also applies to a series of structurally analogous fac-ReX(CO)₃[(RS)₂C=C(H)-N=CPh₂] (X = Cl, Br and I; R = SⁱPr, SPh and S^tBu) rhenium complexes and are discussed on the basis of QT-AIM (Quantum Theory of Atoms in Molecules) calculations. New bond length/electron density relationships are proposed for the metal–halide bonds, including, for the first time, complexes of one given metal and all three corresponding halides. In order to obtain a set of coherent data, three manganese complexes that belong to the family fac-MnX(CO)₃[N∩N] (X = Cl, Br and I; N∩N is a chelating ligand with two coordinating N atoms) were included in this study. Full article

The use of radiosensitizers is a beneficial approach in cancer radiotherapy treatment. However, the enhancement of radiation effects on cancer cells by radiosensitizers involves several different mechanisms, reflecting the chemical nature of the radiosensitizer. G-quadruplex (G4) DNA ligands have emerged in recent years as a potential new class of radiosensitizers binding to specific DNA sequences. Recently, we have shown that the Re(I) tricarbonyl complex PDF-Pz-Re and its pyrazolyl-diamine chelator PDF-Pz, carrying a N-methylated pyridostatin (PDF) derivative, act as G4 binders of various G4-forming DNA and RNA sequences. As described in this contribution, these features prompted us to evaluate PDF-Pz-Re and PDF-Pz as radiosensitizers of prostate cancer PC3 cells submitted to concomitant treatment with Co-60 radiation. The compound RHPS4 was also tested, as this G4 ligand was previously shown to exhibit strong radiosensitizing properties in other cancer cell lines. The assessment of the resulting radiobiological effects, namely through clonogenic cell survival, DNA damage, and ROS production assays, showed that PDF-Pz-Re and PDF-Pz were able to radiosensitize PC3 cells despite being less active than RHPS4. Our results corroborate that G4 DNA ligands are a class of compounds with potential interest as radiosensitizers, deserving further studies to optimize their radiosensitization activity and elucidate the mechanisms of action. Full article

Antimicrobial resistance (AMR) poses a critical global health threat by rendering existing antibiotics ineffective against infections, leading to increased mortality, prolonged illnesses, and higher healthcare costs. Developing new antibiotics is essential to combat resistant pathogens, safeguard modern medical procedures, and prevent a return to a pre-antibiotic era where common infections become untreatable. We report a series of chiral tricarbonyl rhenium(I) complexes incorporating enantiopure pinene-substituted bipyridine ligands (L#) of the general formula fac-[Re(CO)₃L#X] and fac-[Re(CO)₃L#Py]⁺ (where X = Cl or Br and Py = pyridine). These complexes were isolated as mixtures of two diastereomers, characterized by standard techniques, and evaluated for cytotoxic activity against methicillin-resistant and methicillin-sensitive Staphylococcus aureus (MRSA and MSSA). The results revealed notable antibacterial efficacy (MIC = 1.6 μM), reflected in high therapeutic indices (Ti > 10). In contrast, analogous complexes bearing non-chiral 2,2′-bipyridine ligands exhibited no activity, underscoring the critical role of chirality in modulating biological interactions at the molecular level. These findings highlight the potential of chiral Re(I) complexes as promising scaffolds for the development of more potent and selective antibacterial agents. Full article

The use of metal-based complexes is currently taking centre stage in the field of nanomedicine for the treatment and control of various ailments. Rhenium(I) tricarbonyl complexes have frequently been evaluated in vitro for their anticancer activities, and a few have advanced to in vivo and clinical trials, owing to the distinct application characteristics of these complexes. Their inception in drug development is key. This study explores a detailed chronological overview of the medical applications of Re(I) tricarbonyl complexes over the past six years (2019–2024), focusing on their applications and clinical tests in the control and management of various ailments. An in-depth examination of their activities in anticancer treatments, Chagas disease, antifungal infections, antimalarial, and microbial infections was conducted, comparing the complexes to various standard antibiotics, conventional antimalarial drugs, antifungals, and standard anticancer agents. Full article

Due to their rare properties of solid-state luminescence enhancement (SLE), tricarbonylrhenium complexes are promising candidates for applications as photoluminescent materials. However, the effect of isomerism on optical properties is still not well known. The aim of this in-depth study is to explore the behavior of a 2-(1,2,3-triazol-1-yl)pyridine (tapy) complex and compare it with that of the isomers studied previously. Two derivatives that incorporate a mesoionic carbene ligand and represent an emerging class of molecules were also synthesized and compared with the corresponding isomers. The crystallographic data revealed that compounds in the solid state have little or no π–π interactions. The spectroscopic study was supported by DFT calculations. All the compounds were weakly phosphorescent in solution but exhibited a marked SLE effect. The Re-Tapy complex is an excellent solid-state emitter (PLQY = 0.62), well suited for applications related to aggregation-induced phosphorescence emission (AIPE). Its sensitivity to mechanical stimuli was unprecedented among the isomers considered to date. On the other hand, triazolylidene complexes are less emissive than their pyta_(1,2,3) counterparts. This study shows how the ligand isomerism influences the optical properties of tricarbonylrhenium(I) complexes. It indicates that selecting the right pattern is a key factor for the design of efficient photoluminescent materials. Full article

Rhenium metal is extensively utilized in the aerospace industry for the manufacturing of various superalloys due to its unique properties, and plays an indispensable role in the field of high technology. Rhenium resources are primarily associated with copper, molybdenum, and other metal ores. Ammonium perrhenate is predominantly derived from copper and molybdenum ore roasting flue gas scrubbers containing various impurities in the rhenium-containing contaminated acid. The complex composition of the contaminated acid renders the enrichment and purification of ammonium perrhenate more challenging, necessitating further research and development of the technology. This paper reviews the research progress in ammonium perrhenate enrichment and purification technology, encompassing chemical precipitation, adsorption, extraction, ion exchange, extraction chromatography, and recrystallization. It analyses the advantages and limitations of various methods, with the aim of providing a reference for future developments in ammonium perrhenate enrichment and purification technology. Furthermore, the paper presents a prospective view on the development of ammonium perrhenate enrichment and purification technology, focusing on the objective of obtaining more selective purification materials and more efficient purification techniques for ammonium perrhenate. Full article

This study investigates the extraction of rhenium using trialkylbenzyl ammonium chloride (TABAC) as an alternative to trialkylamine (TAA) for recovering rhenium from highly diluted solutions. Rhenium, present as ReO₄⁻ over a wide acidity range, was extracted via an anion exchange mechanism in single-stage experiments monitored by inductively coupled plasma mass spectrometry (ICP-MS). Key variables, including pH, acid concentration, and the concentrations of extractant and metal, were examined. The results demonstrated a high extraction efficiency exceeding 99% within a pH range of 2 to 7 and from solutions containing sulfuric or hydrochloric acid at concentrations of 0.1 to 3.0 M (mol/L). However, extraction from nitric acid solutions was less efficient, with less than 30% recovery. Performance for both TAA-kerosene and TABAC-kerosene followed the order H₂SO₄ > HCl > HNO₃. The optimal TABAC concentration was 10⁻² M (mol/L) in kerosene. TABAC also showed higher selectivity than TAA, with separation coefficients Re/Mo = 66.8 and Re/W = 55.8 in 0.1–1.0 M (mol/L) sulfuric acid. Based on equilibrium studies, the complexes formed during extraction were identified as [R₃R′NH]ReO₄. This approach may offer environmentally friendly and cost-effective benefits for large-scale industrial applications, enabling efficient recovery of valuable rhenium while reducing waste and environmental impact. Full article