Search Results (52)

Neurodegenerative diseases (NDDs), including Alzheimer’s disease (AD) and Parkinson’s disease (PD), are characterized by progressive neuronal dysfunction and loss and represent a significant global health challenge. Oxidative stress, neuroinflammation, and neurotransmitter dysregulation, particularly affecting acetylcholine (ACh) and monoamines, are key hallmarks of these conditions. The current therapeutic strategies targeting cholinergic and monoaminergic systems have some limitations, highlighting the need for novel approaches. Metallodrugs, especially ruthenium and platinum complexes, are gaining attention for their therapeutic use. Among metal complexes, gold(I) and silver(I) N-heterocyclic carbene (NHC) complexes exhibit several biological activities, but their application in NDDs, particularly as monoamine oxidase (MAO) inhibitors, remains largely unexplored. To advance the understanding of this field, we designed, synthesized, and evaluated the biological activity of a new series of Au(I) and Ag(I) complexes stabilized by NHC ligands and bearing a carboxylate salt of tert-butyloxycarbonyl (Boc)-N-protected proline as an anionic ligand. Through in silico and in vitro studies, we assessed their potential as acetylcholinesterase (AChE) and MAO inhibitors, as well as their antioxidant and anti-inflammatory properties, aiming to contribute to the development of potential novel therapeutic agents for NDD management. Full article

The concurrent preservation of structural integrity and improvement of electrical conductivity in FeP₂ anodes presents a persistent challenge. Herein, FeP₂ nanoparticles embedded within a 3D N-doped honeycomb-like carbon framework composite (FeP₂@NHC) are synthesized through a phosphorization process with a honeycomb-like Fe₃C@NHC as a precursor. The in situ incorporation of FeP₂ nanoparticles into the 3D carbon matrix effectively restrains the aggregation, pulverization, and stripping of material during cycling, and significantly enhances reaction kinetics and structural stability, achieving a superior electrochemical performance. Specifically, FeP₂@NHC electrodes demonstrate remarkable reversible capacity (1433.9 mA h g⁻¹ at 0.1 A g⁻¹), excellent rate-capability (399.9 mA h g⁻¹ at 10 A g⁻¹), and ultra-long cycle life (631.5 mA h g⁻¹ after 1000 cycles at 2 A g⁻¹). Moreover, XRD analysis reveals that iron-rich Fe₃C and Fe₃O₄ precursors can react with NaH₂PO₂ to form FeP₂ and FeP, respectively. This study offers a rational and practical strategy for designing other phosphorus-rich metal phosphide anode materials. Full article

Density functional theory (DFT) calculations were employed to study a series of complexes of general formula [Ru(salen)(X)(CO)]^0/−1 (X = Cl⁻, F⁻, SCN⁻, DMSO, Phosphabenzene, Phosphole, TPH, CN⁻, N₃⁻, NO₃⁻, CNH⁻, NHC, P(OH)₃, PF₃, PH₃). The effect of ligands X on the Ru-CO bond was quantified by the trans-philicity, Δσ¹³C NMR parameter. The potential of Δσ¹³C to be used as a probe of the CO photodissociation by Ru(II) transition metal complexes is established upon comparing it with other trans-effect parameters. An excellent linear correlation is found between the energy barrier for the Ru-CO photodissociation and the Δσ¹³C parameter, paving the way for studying photoCORMs with the ¹³C NMR method. The strongest trans-effect on the Ru-CO bond in the [Ru(salen)(X)(CO)]^0/−1 complexes are found when X = CNH⁻, NHC, and P(OH)₃, while the weakest for X = Cl⁻, NO₃⁻ and DMSO trans-axial ligands. The Ru-CO bonding properties were scrutinized using Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA) and Natural Orbital of Chemical Valence (NOCV) methods. The nature of the Ru-CO bond is composite, i.e., electrostatic, covalent and charge transfer. Both donation and backdonation between CO ligand and Ru metal centre equally stabilize the Ru(II) complexes. Ru-CO photodissociation proceeds via a ³MC triplet excited state, exhibiting a conical intersection with the T₁ ³MLCT excited state. Calculations show that these complexes show bands within visible while they are expected to be red emitters. Therefore, the [Ru(salen)(X)(CO)]^0/−1 complexes under study could potentially be used for dual action, photoCORMs and theranostics compounds. Full article

The addition reactions of water, alcohols, and primary and secondary amines to the 10-acetonitrilium derivative of nido-carborane were studied. Hydrolysis of 10-MeC≡N-7,8-C₂B₉H₁₁ results in iminol 10-MeC(OH)=HN-7,8-C₂B₉H₁₁, which, on treatment with a base, gives amide [10-MeC(=O)HN-7,8-C₂B₉H₁₁]⁻. The reactions of 10-MeC≡N-7,8-C₂B₉H₁₁ with alcohols lead to imidates 10-ROC(Me)=HN-7,8-C₂B₉H₁₁ (R = Me, Et) as mixtures of E- and Z-isomers. In the solid state, 10-MeOC(Me)=HN-7,8-C₂B₉H₁₁ adopts E-configuration. The reactions of 10-MeC≡N-7,8-C₂B₉H₁₁ with primary amines result in amidines 10-RNHC(Me)=HN-7,8-C₂B₉H₁₁ (R = Me, Et) as mixtures of E- and Z-isomers. In the solid state 10-EtNHC(Me)=HN-7,8-C₂B₉H₁₁ was found to have the Z-configuration, which is stabilized by intramolecular N-H⋯H-B interactions between the NH group originating from the primary amine and the BH group of the carborane cage. These interactions are rather strong (3.7 kcal/mol) and are likely to persist in solution. The reactions of 10-MeC≡N-7,8-C₂B₉H₁₁ with secondary acyclic (Me₂NH, Et₂NH) and cyclic (piperidine, morpholine) amines result in amidines 10-R₂NC(Me)=HN-7,8-C₂B₉H₁₁ (R = Me, Et; R₂ = N(CH₂)₅, N(CH₂CH₂)₂O) as single isomers, which, according to single crystal X-ray diffraction data, have the E-configuration. Full article

A number of N-heterocyclic carbene–silver compounds (NHCs)AgX were tested in the direct carboxylation of terminal alkynes using carbon dioxide as the C1 carbon feedstock. The reactions proceed at a pressure of 1 atm of CO₂ at room temperature, in the presence of Cs₂CO₃, and using silver–NHC complexes as catalysts. Thus, phenylacetylene and several alkynes are converted to the corresponding propiolic acids in good to high conversions. The activity of the catalysts is strongly influenced by the substituents on the NHC backbone and the nature of the counterion. Specifically, the most active compound exhibits iodide as the counterion and is stabilized by a benzimidazole derivative. After 24 h of reaction, a quantitative conversion is obtained utilizing DMF as the solvent and phenylacetylene as the substrate. Full article

This study investigates the antibacterial N-heterocyclic carbene (NHC)–silver complexes using the SwissADME platform, a web-based tool developed by the Swiss Institute of Bioinformatics (SIB). NHCs, particularly their silver complexes, have gained significant interest in medicinal chemistry for their potential as antibacterial and anticancer agents. The effectiveness of these complexes is closely linked to their structure, including factors like lipophilicity, which enhance their ability to penetrate bacterial cells and sustain the release of active silver ions. SwissADME provides computational estimates of pharmacokinetic properties, including absorption, distribution, metabolism, and excretion (ADME) characteristics, as well as drug-likeness and toxicity assessments. By evaluating parameters like molecular weight, topological polar surface area, lipophilicity (LogP), and water solubility, SwissADME offers insights into the drug-like potential of compounds. This study is inspired by a comprehensive review of antibacterial NHC–silver complexes published from 2006 to 2023, which identified superior structures with notable biological activity. The primary aim is to determine whether these active complexes exhibit distinct SwissADME parameters compared to others, providing a deeper understanding of the factors that influence their biological efficacy and aiding in the identification of promising drug candidates. Finally, experimental stabilities of exemplary complexes were confronted with absolute LUMO values derived from DFT calculations. Full article

Introduction: N-heterocyclic carbenes (NHCs) are considered important preferred auxiliary ligands for transition metals due to their strong σ-donor and weak π-acceptor properties and ease of structural modification in catalyst design. The functionalization of NHC by adding different substituent groups is an effective strategy for designing complexes with desired electronic and steric properties. NHC–Pd complexes are of particular importance due to their resistance to air, moisture and heat and their strong stability under catalytic and biological conditions. It is known that NHC–Pd complexes show excellent performance in the Suzuki–Miyaura cross-coupling reaction. The traditional Suzuki–Miyaura reaction involves the cross-coupling reaction of alkyl and arylboronic acids with aryl halides. This reaction has some advantages over other C-C coupling reactions. The use of water as a suitable and reliable solvent in the reaction, the fact that the reaction products are generally poorly soluble in water and can be easily separated from the reaction mixture, the use of non-toxic chemicals, the moderation of reaction conditions, and good functional group compatibility make it useful and worth studying. There are many examples of studies on the application of NHC–Pd complexes in the Suzuki–Miyaura reaction in aqueous media, and the highly effective catalytic activities and versatility of these reactions have been proven. Methods: In this study, a series of benzimidazole-based Pd–NHC complexes were synthesized. The synthesized complexes were characterized by spectroscopic methods. All complexes were tested as catalysts in the Suzuki–Miyaura cross-coupling reaction. Results: According to the obtained results, the synthesized benzimidazole-based Pd–NHC complexes were found to have high catalytic activity in the Suzuki–Miyaura cross-coupling reaction. Conclusions: The synthesized NHC-Pd complexes can be used as potential catalysts due to their high catalytic activity. It is thought that these catalysts can be used in different biochemical studies in the future. Full article

To regulate the energy flow in orchard ecosystems and maintain the environment, weeding has become a necessary measure for fruit farmers, and the use of automated mowers can help reduce labor costs and improve the economic efficiency of orchards. However, due to the complexity of the geographic and spatial environment of the orchard, in particular, the loose and undulating road surface, the interference of satellite signals by large trees, etc., which decreases the positioning accuracy and stability of the positioning system of the mower, and the high cost of the sensor also affect the popularization of intelligent mowers for these applications. To address the above problems, this paper constructs a positioning system through a low-cost global navigation satellite system (GNSS), inertial measurement unit (IMU), and odometry, and utilizes the Kalman filter algorithm based on the error state for a combined GNSS/IMU positioning so that the inertial navigation system can maintain a more accurate positioning when the GNSS signals are poor. Considering the side-slip and error accumulation problems of the odometry of the traction mower, the combined GNSS/IMU positioning information is used to optimize the odometry model and improve the navigation and positioning accuracy. To reduce the measurement error of the IMU and the problem of error accumulation, this paper utilizes the nonholonomic constraint (NHC) of a lawn mower to suppress the dispersion of IMU measurement errors and constructs periodic and nonperiodic zero-velocity updating (ZUPT) strategies in combination with the travel paths of lawn mower navigation operations in the region to update the IMU data to improve the positioning accuracy and stability of the positioning system. The experiments show that the average error of the constructed positioning system is controlled within 0.15 m, the maximum error is maintained at approximately 0.3 m, and the positioning system constructed by using low-cost sensors can achieve a positioning accuracy similar to that of the differential global navigation satellite system (DGNSS), which is beneficial for the promotion and application of intelligent mowers in orchards. Full article

N-heterocyclic carbene (NHC) silver(I) and gold(I) complexes have found different applications in various research fields, as in medicinal chemistry for their antiproliferative, anticancer, and antibacterial activity, and in chemistry as innovative and effective catalysts. The possibility of modulating the physicochemical properties, by acting on their ligands and substituents, makes them versatile tools for the development of novel metal-based compounds, mostly as anticancer compounds. As it is known, chemotherapy is commonly adopted for the clinical treatment of different cancers, even though its efficacy is hampered by several factors. Thus, the development of more effective and less toxic drugs is still an urgent need. Herein, we reported the synthesis and characterization of new silver(I) and gold(I) complexes stabilized by caffeine-derived NHC ligands, together with their biological and catalytic activities. Our data highlight the interesting properties of this series as effective catalysts in A³-coupling and hydroamination reactions and as promising anticancer, anti-inflammatory, and antioxidant agents. The ability of these complexes in regulating different pathological aspects, and often co-promoting causes, of cancer makes them ideal leads to be further structurally functionalized and investigated. Full article

The organoplatinum chemistry of the ligands 2-C₅H₄N-CH₂-NH-C₆H₃-2-OH-5-X (L1, X = H; L3, X = NO₂) and 2-C₅H₄N-CH=N-C₆H₃-2-OH-5-X (L2, X = H; L4, X = NO₂), which contain an appended phenol substituent, is described. Comparisons are made between the ligands with amine or imine groups (L1, L3 vs. L2, L4) and ligands with X = H or NO₂ (L1, L2 vs. L3, L4), and major differences are observed. Thus, on reaction with the cycloneophylplatinum(II) complex [{Pt(CH₂CMe₂C₆H₄)(μ-SMe₂)}₂], ligands L1, L2 and L4 give the corresponding platinum(II) complexes [Pt(CH₂CMe₂C₆H₄)(κ²-N,N′-L)], containing a Pt··HO hydrogen bond, whereas L3 gives a mixture of isomeric platinum(IV) hydride complexes [PtH(CH₂CMe₂C₆H₄)(κ³-N,N′,O-L3-H)], which are formed by oxidative addition of the phenol O-H bond and which react further with oxygen to give [Pt(OH)(CH₂CMe₂C₆H₄)(κ³-N,N′,O-L3-H)]. The differences in reactivity are proposed to be due to the greater acidity of the nitro-substituted phenol groups in L3 and L4 and to the greater ability of the deprotonated amine ligand L3 over L4 to stabilize platinum(IV) by adopting the fac-κ³-N,N′,O-L3-H coordination mode. Full article

Vinyl-addition polynorbornenes are of great interest as versatile templates for the targeted design of polymer materials with desired properties. These polymers possess rigid and saturated backbones, which provide them with high thermal and chemical stability as well as high glass transition temperatures. Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare. Herein, we report the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups on Pd-catalysts bearing N-heterocyclic carbene ligands ((NHC)Pd-systems). Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH₂ groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers, while single- and three-component (NHC)Pd-systems were applied as catalysts. In vinyl-addition polymerization, the reactivity of the investigated monomers varied substantially. The relative reactivity of these monomers was assessed in copolymerization experiments, which showed that the closer the bromine is to the norbornene double-bond, the lower the monomer’s reactivity. The most reactive monomer was the norbornene derivative with the largest substituent (with the longest linker). Tuning the catalyst’s nature and the conditions of polymerization, we succeeded in synthesizing high-molecular-weight homopolymers from norbornenes with bromoalkyl groups (M_n up to 1.4 × 10⁶). The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization. Full article

Volatile, reactive, and thermally stable organometallic copper and silver complexes are of significant interest as precursors for the metalorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) of ultra-thin metallic films. Well-established Cu^I and Ag^I precursors are commonly stabilized by halogens, phosphorous, silicon, and oxygen, potentially leading to the incorporation of these elements as impurities in the thin films. These precursors are typically stabilized by a neutral and anionic ligand. Recent advancements were established by the stabilization of these complexes using N-heterocyclic carbenes (NHCs) as neutral ligands. To further enhance the reactivity, in this study the anionic ligand is sequentially changed from β-diketonates to β-ketoiminates and β-diketiminates, yielding two new Cu^I and two new Ag^I NHC-stabilized complexes in the general form of [M(NHC) (R)] (M = Cu, Ag; R = β-ketoiminate, β-diketiminate). The synthesized complexes were comparatively analyzed in solid, dissolved, and gaseous states. Furthermore, the thermal properties were investigated to assess their potential application in MOCVD or ALD. Among the newly synthesized complexes, the β-diketiminate-based [Cu(tBuNHC) (NacNacMe)] was identified to be the most suitable candidate as a precursor for Cu thin film deposition. The resulting halogen-, oxygen-, and silicon-free Cu^I and Ag^I precursors for MOCVD and ALD applications are established for the first time and set a new baseline for coinage metal precursors. Full article

Molnupiravir is an antiviral drug against viral RNA polymerase activity approved by the FDA for the treatment of COVID-19, which is metabolized to β-D-N4-hydroxycytidine (NHC) in human blood plasma. A novel method was developed and validated for quantifying NHC in human plasma within the analytical range of 10–10,000 ng/mL using high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS) to support pharmacokinetics studies. For sample preparation, the method of protein precipitation by acetonitrile was used, with promethazine as an internal standard. Chromatographic separation was carried out on a Shim-pack GWS C18 (150 mm × 4.6 mm, 5 μm) column in a gradient elution mode. A 0.1% formic acid solution in water with 0.08% ammonia solution (eluent A, v/v) and 0.1% formic acid solution in methanol with 0.08% ammonia solution mixed with acetonitrile in a 4:1 ratio (eluent B, v/v) were used as a mobile phase. Electrospray ionization (ESI) was used as an ionization source. The developed method was validated in accordance with the Eurasian Economic Union (EAEU) rules, based on the European Medicines Agency (EMA) and Food and Drug Administration (FDA) guidelines for the following parameters and used within the analytical part of the clinical study of molnupiravir drugs: selectivity, suitability of standard sample, matrix effect, calibration curve, accuracy, precision, recovery, lower limit of quantification (LLOQ), carryover, and stability. Full article

Herein, we present a comparative study on the chemistry and biological activity of N-heterocyclic carbene (NHC)Pt(II)/Au(I) complexes. Accordingly, representative compounds of the cis/trans- [PtL₂X₂] (X = Cl (5, 6) or I (7, 8)), [PtL₃Cl]⁺ (9), [AuLX] (X = Cl (10) or I (11)), and [AuL₂]⁺ (12) type, where L is 1,3-diethylbenzimidazol-2-ylidene, were synthesized and characterized in detail to elucidate the role of the metal center on their physicochemical and biological properties. The stability of the complexes in the presence of cell culture medium and their reactivity toward relevant biomolecules were investigated by RP-HPLC. In addition, their effects on plasmid DNA and in vitro cytotoxicity in ovarian cancer cells and non-malignant fibroblasts were evaluated. Cationic [AuL₂]⁺ and [PtL₃X]⁺ species displayed the highest cytotoxicity and stability in cell culture medium in the series. They exhibited IC₅₀ values lower than the established metallodrugs cisplatin and auranofin in both wild-type and cisplatin-resistant ovarian cancer cells, being able to circumvent cisplatin resistance. Finally, Pt(II)–NHC complexes form 5′-guanosine monophosphate adducts under physiologically relevant conditions and interact with plasmid DNA in contrast to their Au(I) analogs, corroborating their distinct modes of action. Full article