Search Results (168)

In this study, we report for the first time a brand-new protocol for the multigram-scale synthesis of 5-methyl-6-oxo-1,6-dihydropyridazine-3-carboxylic and 2,8-dimethylimidazo[1,2-b]pyridazine-6-carboxylic acids, without the utilization of metal-complex catalysts. The developed technology for the production of the aforementioned acids is of great importance for two reasons. Firstly, these acids serve as intermediates in the synthesis of risdiplam, the first small-molecule drug approved for the treatment of spinal muscular atrophy. Secondly, they themselves are valuable building blocks right from a broader medicinal chemistry perspective. The synthesis of risdiplam was carried out using a modified synthetic protocol, utilizing the acids indicated above as the key intermediates. The protocols presented in this study enable the production of target compounds with high purity and an acceptable yield. Full article

Coumarin and cytisine and their derivatives have significant biological activity. In addition, the electronic properties of coumarin derivatives are very sensitive to the molecular environment, which allows for their use as sensors for bioluminescent imaging. Due to the fact that cytisine exhibits high activity in binding to nicotinic acetylcholine receptors, a compound combining parts of cytisine and coumarin may have a broader spectrum of biological activity and also act as a photoactive element for promising use in optoelectronic devices. This article reports the synthesis of a crystalline cytisine–coumarin complex (IUPAC: N-(2-oxo-2H-chromene-3-carbonyl)cytisine), along with the results of both theoretical and experimental investigations of its structural and electronic properties. The structure of this new compound was established on the basis of X-ray diffraction and Fourier transform infrared spectroscopy data and was confirmed through density functional theory calculations using periodic crystal and single-molecule approaches. Interpretations of the IR absorption peaks and the atomic patterns of the vibrational modes are given. The electronic band structure and the contributions of individual atoms to the electronic density of states are analyzed. The structural and optical properties considered may be useful for quality control of the compound and for studying similar matrices. Full article

The sludge pyrolysis technology for biochar production delivers dual environmental benefits, addressing both sludge disposal challenges and enabling environmental remediation through the utilization of the resultant biochar. However, the complex multi-step procedures and low catalyst output in previous studies constrain the practical implementation of this technology. A facile sludge pyrolysis method was constructed to achieve the batch production of municipal sludge biochar (MSB) in this study. Compared to municipal sludge (MS), the resultant MSB showed a higher BET surface area, more well-developed pore channel architecture, and plentiful active sites for activating peroxymonosulfate (PMS). Under the optimized conditions (C_MSB = C_PMS = 0.2 g/L), 93.34% of Acid Red G (ARG, 20 mg/L) was degraded after 10 min, posing an excellent rate constant of 0.278 min⁻¹. Additionally, MSB demonstrated excellent broad pH adaptability, ion interference resistance, reusability, and recyclability for ARG elimination. It was primary Fe sites that excited PMS to generate ${\mathrm{O}}_2^{•-}$ and Fe-oxo species (Fe^IV=O) for ARG degradation. The reaction process exhibited minimal heavy metal leaching, indicating limited environmental risk. Therefore, the practical applicability of the sludge biochar production, coupled with its scalable manufacturing capacity and exceptional catalytic activity, collectively demonstrated that this study established a viable pyrolysis methodology for municipal sludge, offering critical insights for sludge disposal and resource reutilization. Full article

The interaction of cobalt(II) with first-generation quinolones oxolinic acid (Hoxo), flumequine (Hflmq), pipemidic acid (Hppa) and cinoxacin (Hcx) in the presence of the N,N′-donor heterocyclic ligands 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) afforded a series of novel cobalt complexes, namely [Co(bipy)₂(oxo)](PF₆)₂·H₂O (1), [Co(phen)₂(oxo)](PF₆)₂·0.5CH₃OH·0.5H₂O (2), [Co(bipy)₂(flmq)](PF₆)₂·0.5CH₃OH·0.5H₂O (3), [Co(bipy)₂(ppa)](PF₆)₂·CH₃OH·0.5H₂O (4), [Co(phen)₂(cx)](PF₆)₂·CH₃OH·0.5H₂O (5), and [Co(phen)₂(flmq)](PF₆)·0.5CH₃OH·H₂O (6). The characterization of the complexes involved physicochemical techniques, various spectroscopies and single-crystal X-ray crystallography. The affinity of complexes to calf-thymus (CT) DNA was monitored with various techniques, suggesting intercalation in-between the DNA-nucleobases as the most probable interaction mode, which may be combined with electrostatic interactions as a result of the cationic nature of the complexes. The affinity of the complexes for bovine and human serum albumin proteins was monitored, and the determined corresponding albumin-binding constants revealed a tight and reversible interaction. Full article

This study is dedicated to the design of multiple redox-active oligonuclear manganese complexes supported with a bis(tetradentate) ligand (TPDP = 1,3-bis(bis(2-pyridinylmethyl)amino)-2-propanol) for high-contrast electrochromism based on the reversible redox process between Mn(II) (colorless) and Mn(III) (dark brown). Pentanuclear Mn₅ complex 1 (colorless) was synthesized via a one-pot reaction of Mn²⁺ and TPDP, while tetranuclear Mn₄ complex 2 (brown) was obtained through aerial oxidation of complex 1. Mn₅ complex 1 features a central MnCl₆ unit connected to two Mn₂(μ-TPDP) fragments through μ₃-Cl⁻ and μ-Cl⁻, whereas Mn₄ complex 2 adopts a symmetric tetranuclear structure with two mixed-valence Mn₂^II,III(μ-TPDP)(μ-Cl) fragments that are further linked by μ-oxo. Electrochemical studies revealed multi-step reversible redox properties for both complexes, attributed to Mn^II/Mn^III processes with significant electronic coupling (ΔE_1/2 = 0.27–0.37 V) between Mn centers. Spectroelectrochemical analysis revealed dynamic optical modulation through the tunable d-d transition and ligand-to-metal charge transfer (LMCT) state through reversible multiple redox processes based on Mn(II) ⇆ Mn(III) interconversion. The fabricated electrochromic device (ECD) exhibited reversible and high optical contrast between the colored state (dark brown) and the bleaching state (colorless). The results highlight the potential of polynuclear manganese complexes as high-contrast electrochromic materials for next-generation smart windows and adaptive optical technologies. Full article

The aerobic catabolism of steroids in bacteria is highly conserved, and the mechanism of steroid degradation in mycobacteria has been extensively studied. However, the branching modification pathways of steroids in mycobacteria remain a mystery, including the likely roles of cytochromes P450. In this study, we unraveled the CYP105S17 converting androst-4-ene-3,17-dione (AD) to 17β-hydroxy-4-androstene-3,16-dione (16-oxo-TS), which was subsequently reduced to 16α,17β-dihydroxy-androst-4-ene-3-one (16α-OH-TS) under reductive conditions in Mycolicibacterium neoaurum. By applying this modification pathway, the genetically modified strains overexpressing CYP105S17 were able to produce 16α-OH-TS at titers 13.0 g/L with a conversion rate of 91.9% (supplemented with 20 g/L phytosterols as the substrate) through a two-stage biotransformation process. This is the first instance of utilizing the native P450 of Mycobacterium to produce 16-hydroxylated steroid intermediates at the 10 g scale. This work provides invaluable perspectives and guidance to researchers seeking to understand the complexities of steroid metabolism in bacteria, and also highlights the great potential of Mycobacterium as a production platform for hydroxylated steroid intermediates or pharmaceuticals. Full article

A new complex, tetrakis(1,10-phenanthroline)-bis(succinate)-(µ₂-oxo)-bis(iron(III)) nonahydrate, [Fe₂(Phen)₄(Succinate)₂(μ-O)](H₂O)₉, was synthesized using the slow evaporation method. This study provides a comprehensive characterization of this coordination compound, focusing on its structural, spectroscopic, and thermal properties, which are relevant for applications in catalysis, material science, and chemical engineering processes. Single-crystal X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared (FT-IR), ultraviolet-visible (UV-Vis) spectroscopy, and thermoanalytical analyses were employed to investigate the material properties. Intermolecular interactions were further explored through Hirshfeld surface analysis. XRD results revealed a monoclinic crystal system with the C2/c space group, lattice parameters: a = 12.7772(10) Å, b = 23.0786(15) Å, c = 18.9982(13) Å, β = 93.047(2)°, V = 5594.27(7) ų, and four formulas per unit cell (Z = 4). The crystal packing is stabilized by C–H⋯O, C–O⋯H, C–H⋯π, and π⋯π intermolecular interactions, as confirmed by vibrational spectroscopy. The heteroleptic coordination environment, combining weak- and strong-field ligands, results in a low-spin state with an estimated crystal field stabilization energy of −4.73 eV. Electronic properties indicate direct allowed transitions (γ = 2) with a maximum optical band gap of 2.66 eV, suggesting potential applications in optoelectronics and photochemical processes. Thermal analysis demonstrated good stability within the 25–136 °C range, with three main stages of thermal decomposition, highlighting its potential for use in high-temperature processes. These findings contribute to the understanding of Fe(III)-based complexes and their prospects in advanced material design, catalytic systems, and process optimization. Full article

Dinuclear di-µ-oxo complexes of Mn³⁺ and Mn⁴⁺ ions, and mononuclear complexes of Mn³⁺ ions with tetraazamacrocycles ([12]aneN₄, [14]aneN₄, [15]aneN₄) and C-substituted derivative (Me₆[14]aneN₄) as well as mononuclear complexes of Mn²⁺ ions with N-substituted derivatives ((N-Me)₂[14]aneN₄, (N-Me)₄[14]aneN₄, (N-Me)Me₂py [14]aneN₄) and with oxo₂[14]aneN₄ were studied. Based on spectroscopic (UV VIS and IR) and conductometric studies, the types of synthesised complexes (cis or trans isomers of mononuclear Mn³⁺ complexes, oxygen bridges and class II according to Robin and Day classification for dinuclear complexes) were determined. On the basis of voltammetric and spectroelectrochemical studies, trans-cis isomerisation at the level of Mn²⁺ ion complexes and cis-trans isomerisation at the level of Mn³⁺ ion complexes were demonstrated for complexes of ligands with free C positions. The N-substituted derivatives oxidise according to the EC mechanism, in which the follow-up reaction is a disproportionation reaction. The thermodynamic stabilisation of Mn³⁺ ions was determined by comparing the formal potentials (E_f⁰), the disproportionation constants (k₁) and the formation constants (β^III). The study showed the possibility of oxidation of mononuclear, pseudo-octahedral Mn³⁺ ion complexes to dinuclear complexes and the greatest stabilisation of Mn³⁺ ions, both in monomers and dimers of ligands with free N positions. Full article

We explore the structural and electronic properties of representative insulin-mimetic oxovanadium and zinc complexes as computed in vacuum, in water clusters and upon binding to PTEN and PTP1B phosphatases. Albeit diverse, the enzymes’ active sites represent evolutionary variant choices of the same type of biochemistry. Though different in respect to covalency and the orbital nature of bonding, theory predicts comparable ionic radii, bond lengths and square pyramidal coordination for the considered vanadyl and zinc systems when in an aqueous environment. Employing docking, DFT and quantum mechanics/molecular mechanics methods, we address possible polar interactions in the protein environments and compute infrared/Raman modes and optical electronic properties, which may be suitable for the structural analysis of the specific chemical moieties in binding studies. Accounting for how protein embedding may alter the electronic states of metal centres, we discuss artificial intelligence-assisted protein field engineering to assist biomedical and quantum information applications. Full article

Metallosurfactants combine the unique soft-matter properties of surfactants with magnetic functionalities of metal ions. The inclusion of iron-based species, in particular, can further boost the functionality of the material, owing to iron’s ability to adopt multiple oxidation states and form both high-spin and low-spin complexes. Motivated by this, a series of hybrid inorganic-organic dodecylpyridinium metallosurfactants with iron-containing counterions was developed. It was established that using either divalent or trivalent iron halides in a straightforward synthetic procedure yields C₁₂Py-metallosurfactants with distinct complex counterions: (C₁₂Py)₂[Fe₂X₆O] and (C₁₂Py)[FeX₄] (X = Cl or Br), respectively. A combination of techniques—including conductometry, dynamic and electrophoretic light scattering, single-crystal and thermogravimetric analysis, and magnetic measurements—provided in-depth insights into their solution and solid-state properties. The presence of different iron-based counterions significantly influences the crystal structure (interdigitated vs. non-interdigitated bilayers), magnetic properties (paramagnetic vs. nonmagnetic singlet ground state), and self-assembly (vesicles vs. micelles) of the dodecylpyridinium series. To our knowledge, this is the first report on the synthesis and characterization of hybrid organic-inorganic metallosurfactants containing the μ-oxo-hexahalo-diferrate anion. Full article

This study explores poly(methyl methacrylate) (PMMA)-based composites as potential alternatives to conventional TiO₂-based photocatalysts. Specifically, it examines PMMA composites enriched with oxo–titanium(IV) complexes, [Ti₈O₂(OⁱPr)₂₀(man)₄] (1), [Ti₄O(OⁱPr)₁₀(O₃C₁₄H₈)₂] (2), and [Ti₆O₄(OⁱPr)₂(O₃C₁₄H₈)₄(O₂CEt)₆] (3), alongside ruthenium(III) complexes, K[Ru(Hedta)Cl]∙2H₂O (4) and [Ru(pic)₃]·H₂O (5). We assessed the physicochemical, adsorption, and photocatalytic properties of these composites with structural analyses (Raman spectroscopy, X-ray absorption (XAS), and SEM-EDX), confirming the stability of complexes within the PMMA matrix. Composites containing titanium(IV) compounds demonstrated notably higher photocatalytic efficiency than those with ruthenium(III) complexes. Based on activity profiles, composites were categorized into three types: (i) UV-light active (complexes (1) and (2)), (ii) visible-light active (complexes (4) and (5)), and (iii) dual-range active (complex (3)). The results highlight the strong potential of titanium(IV)–PMMA composites for UV-driven photocatalysis. Moreover, their activity can be extended to the visible range after structural modifications. Ruthenium(III)–PMMA composites, in turn, showed superior performance under visible light. Overall, PMMA composites with titanium(IV) or ruthenium(III) complexes demonstrate promising photocatalytic properties for applications using both UV and visible light ranges. Full article

Hydrogenation and dehydrogenation reactions are fundamental in chemistry and essential for all living organisms. We employ density functional theory (DFT) to understand the reaction mechanism of the oxidative dehydrogenation (ODH) of the pyridyl-amine complex [Fe^IIIL³]³⁺ (L³, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanonane) to the mono-imine complex [Fe^IIL⁴]²⁺ (L⁴, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanon-1-ene) in the presence of dioxygen. The nitrogen radical [Fe^IIL³_N8•]²⁺, formed by deprotonation of [Fe^IIIL³]³⁺, plays a crucial role in the reaction mechanism derived from kinetic studies. O₂ acts as an oxidant and is converted to H₂O. Experiments with the deuterated ligand L³ reveal a primary C-H kinetic isotope effect, k^CH/k^CD = 2.30, suggesting C-H bond cleavage as the rate-determining step. The DFT calculations show that (i) ³O₂ abstracts a hydrogen atom from the α-pyridine aliphatic C-H moiety, introducing a double bond regio-selectively at the C₇N₈ position, via the hydrogen atom transfer (HAT) mechanism, (ii) O₂ does not coordinate to the iron center to generate a high-valent Fe oxo species observed in enzymes and biomimetic complexes, and (iii) the experimental activation parameters (ΔH^≠ = 20.38 kcal mol⁻¹, ΔS^≠ = −0.018 kcal mol⁻¹ K⁻¹) fall within in the range of values reported for HAT reactions and align well with the computational results for the activated complex [Fe^IIL³_N8•]²⁺···³O₂. Full article

The single-atom catalyst (SAC) activated persulfate process has emerged as a highly efficient technology for eliminating refractory organic compounds in aqueous environments. This review delves into the intricacies of utilizing SACs for the effective removal of various contaminants in water. The common supports and the preparation procedures of SACs are summarized at first. The synthesis methods of SACs (i.e., wet chemical method, one-pot hydrothermal method, and high-temperature pyrolysis method) are also described. Then, a comprehensive overview of the diverse reaction mechanisms in SAC-activated persulfate systems is presented, including a radical oxidation process via sulfate or hydroxyl radicals and superoxide radicals, or a nonradical process via single oxygen, surface active complex, and high-valent metal-oxo species oxidation. The impact of key factors such as peroxides concentration, SAC dosage, reaction pH, inorganic anions, organic matter, operando stability, and real water is also delved. The removal of various pollutants (i.e., azo dyes, phenolic compounds, pharmaceuticals, and bacteria) by this process is further summarized. Finally, the challenges and perspectives in the field of water treatment utilizing SACs are discussed. Full article

Thermal decomposition (pyrolysis) of coal bottom ash (collected after lignite combustion in coal-fired power plant TEKO-B, Republic of Serbia) was investigated, using the simultaneous TG-DTG techniques in an inert atmosphere, at various heating rates. By using the XRD technique, it was found that the sample (CBA-TB) contains a large amount of anorthite, muscovite, and silica, as well as periclase and hematite, but in a smaller amount. Using a model-free kinetic approach, the complex nature of the process was successfully resolved. Thermodynamic analysis showed that the sample is characterized by dissociation reactions, which are endothermic with positive activation entropy changes, where spontaneity is achieved at high reaction temperatures. The model-based method showed the existence of a complex reaction scheme that includes two consecutive reaction steps and one single-step reaction, described by a variety of reaction models as nucleation/growth phase boundary-controlled, the second/n-th order chemical, and autocatalytic mechanisms. It was established that an anorthite I1 phase breakdown reaction into the incongruent melting product (CaO·Al₂O₃·2SiO₂) represents the rate-controlling step. Autocatalytic behavior is reflected through chromium-incorporated SiO₂ catalyst reaction, which leads to the formation of chromium(II) oxo-species. These catalytic centers are important in ethylene polymerization for converting light olefin gases into hydrocarbons. Adiabatic T_D24 prediction simulations of the process were also carried out. Based on safety analysis through validated kinetic parameters, it was concluded that the tested sample exhibits high thermal stability. Applied thermal treatment was successful in promoting positive changes in the physicochemical characteristics of starting material, enabling beneficial end-use of final products and reduction of potential environmental risks. Full article