Search Results (261)

Under aqueous conditions, transition-metal catalysis offers an attractive platform for greener C–N bond formation by reducing reliance on hazardous organic solvents. Herein, we report a microwave-assisted palladium-catalyzed selective N-arylation of anilines with 2,3-dihalopyridines in water. Systematic optimization revealed that a catalyst system comprising PdCl₂(1,10-phenanthroline)₂ and (±)-BINAP in the presence of K₃PO₄ enables efficient coupling under microwave irradiation. Under the optimized conditions (PdCl₂(1,10-Phenanthroline)₂, 2 mol%; (±)-BINAP, 3 mol%; K₃PO₄, 3.5 equiv; H₂O, 2.5 mL; 150 °C; 30 min), the coupling of aniline with 2,3-dichloropyridine afforded the corresponding aminopyridine product in up to 91% isolated yield. The method was extended to various 2,3-dihalopyridines and substituted anilines, providing moderate to excellent yields with good regioselectivity. Mechanistically, the transformation is consistent with a Pd(0)/Pd(II) catalytic cycle involving oxidative addition, amido complex formation, and reductive elimination. Full article

Ionic liquid (IL) N-methyl-N′-1-(4-t-butylphenylphosphinyl)butylimidazolium bis(trifluoromethylsulphonyl) imide was used for the first time as an ion carrier in membrane systems to selectively transport Au(III), Pt(IV), and Pd(II) ions. Au(III), Pd(II), and Pt(IV) were transported from HCl solutions utilizing a polymer inclusion membrane (PIM) with cellulose triacetate as the support, o-nitrophenyl pentyl ether as the plasticizer, and ionic liquid as the mentioned ion carrier. The modifications of source and receiving aqueous phase compositions are examined. High selectivity for Au(III) using the ionic liquid in the membrane was achieved at elevated HCl concentrations (≥0.5 M). When a 0.010 M KI solution was used as the receiving phase and a membrane with the optimal composition was applied, the extraction of Au(III) ions reached a maximum recovery rate of 93%. Moreover, PIM studies showed that carrier molecules doped in the membrane creates complexes with the Au(III) ion with a molar ratio of 1:1. The extractability of Au(III) through PIMs exceeded that of other metal ions, with the selectivity of transported metal ions ranked as follows: Au(III) >> Pt(IV), Pd(II). The recovery factors for gold, platinum, and palladium ions after 6 h of transport were 94%, 8%, and 1%, respectively. Full article

Three novel metal complexes of the tridentate ligand 4-nitro-2-(quinolin-8-yliminomethyl)phenol (NQP) were synthesized and fully characterized using elemental analysis, TGA, magnetic susceptibility, FT-IR, NMR, and UV–Vis spectroscopy. Stoichiometric studies and characterization data proposed square-planar Pd(II), tetrahedral Zn(II), and octahedral Fe(III) geometries. Density functional theory calculations (B3LYP and B3LYP/6-311G(d,p) with LANL2DZ for metals) showed good agreement with experimental findings and revealed enhanced nonlinear optical properties, as evidenced by increased polarizability and hyperpolarizability values. Biological studies demonstrated significant antimicrobial activity, with the Pd–NQP complex exhibiting superior efficacy against bacterial and fungal strains compared to ofloxacin and fluconazole, following the order NQP < Zn < Fe < Pd. Cytotoxicity assays against Hep-G2, MCF-7, and HCT-116 cell lines revealed strong anticancer activity, particularly for the Pd(II) complex (IC₅₀ = 6.35–12.95 μ_g/μL), comparable to cisplatin. All complexes showed higher DPPH radical scavenging activity than ascorbic acid and strong DNA-binding affinity. Antimicrobial activity was further validated experimentally, while molecular docking studies elucidated favorable binding interactions with microbial proteins and cancer-related targets. Full article

The induction of chirality to obtain enantiopure products of high synthetic value is of great importance across various scientific fields, particularly in the medical area, as it has been demonstrated that the different enantiomers of drugs interact differently with biological receptors. In this context, asymmetric catalysis focuses on the design of catalysts that are easy to synthesize, capable of efficiently and enantioselectively forming C–C bonds, and suitable for reuse in multiple catalytic processes. This work describes the application of a Pd(II) complex coordinated with the R and S forms of proline in direct Aldol, Morita–Baylis–Hillman, and Heck coupling reactions. The catalytic system efficiently promoted the aldol reaction, achieving yields of 80–95%, excellent diastereoselectivities (1:69 syn/anti), and enantiomeric excesses greater than 99%. From a mechanistic perspective, the formation of a transition state is proposed in which a proline molecule generates an enamine that, upon coordination with the metal center, is stabilized through interaction with the intermediate’s double bond. Moreover, the study of the Morita–Baylis–Hillman and Heck coupling reactions highlights the versatility of this type of catalyst. Full article

Organometallic and metal–organic compounds are widely used in different fields of chemistry and allied disciplines, including bioinorganic and medicinal chemistry. Of particular interest is the development of novel potential anticancer agents based on palladium(II) complexes of the so-called pincer-type ligands, featuring a specific monoanionic tridentate framework. In this work, hybrid imine–thiocarbamate ligands are shown to readily undergo direct cyclopalladation in solution and under solvent-free conditions, in particular upon mechanochemical activation, yielding a series of Pd(II) pincer complexes. The latter exhibit promising cytotoxic activity against several solid and hematopoietic cancer cell lines. Full article

Background: Manual dexterity (MD) impairment is a frequent and disabling feature in patients with Parkinson’s disease (PD) and paranoid schizophrenia (PS), significantly affecting functional independence and activities of daily living. However, rehabilitation strategies specifically targeting fine motor control remain insufficiently integrated into routine physiotherapy (PT). Objective: This study investigated the effects of a structured, progressive PT program incorporating targeted MD training on upper limb function in patients with PD and PS. Methods: A prospective, exploratory, interventional study was conducted in 30 patients, allocated to either an experimental group (EG, n = 20) or a control group (CG, n = 10). Participants had PD (Hoehn and Yahr stages II–III) or chronic, clinically stable PS. MD was assessed using the Purdue Pegboard Test, Coin Rotation Task, and Kapandji opposition score. The EG completed a four-phase, 40-week dexterity-oriented rehabilitation program, while the CG received standard disease-specific PT. Between-group differences in change scores were analyzed using one-way ANOVA. Results: The EG showed significantly greater improvements than the CG in thumb opposition, psychomotor processing speed, and unilateral and bilateral fine motor performance (p < 0.001 for all), with large to very large effect sizes (η² = 0.45–0.76). No significant between-group differences were observed for complex sequential assembly tasks. Conclusions: Integrating targeted MD training into structured PT programs significantly improves fine motor performance in patients with PD and PS, supporting its inclusion in rehabilitation protocols for residential and outpatient care settings. Full article

Lanthanide coordination polymers have been developed at a fast rate during the past two decades due to their appealing applications in the modern field of materials science and emerging technologies like luminescence, magnetism, sensing, gas adsorption, and catalysis. The role of lanthanides in imparting specific properties to the coordination polymers has been fully documented in extensive studies carried out by numerous research groups. It has been shown that because lanthanide(III) ions possess a variable coordination number, they readily build two-dimensional and three-dimensional architectures with definite channels, permanent pores, and distinct surface areas. Due to their strong oxophilic propensity and hard Lewis acid character, lanthanides favor the construction of stable coordination polymers and MOF configurations by strongly binding the coordinating groups of the organic linkers. Associated with palladium complexes, the lanthanide ions provide synergistic effects with Lewis acid sites, beneficial to the catalytic activity. These attractive characteristics of lanthanides enabled them to be fruitfully applied in Pd-Ln coordination polymers with catalytic properties. This review covers an array of Pd-Ln coordination polymers applied as heterogeneous catalysts in Suzuki–Miyaura C(sp²)-C(sp²) cross-coupling reactions. The activity and chemoselectivity of Pd(II) ions and Pd nanoparticles associated in coordination polymers with different lanthanides from a selected array of rare earth elements (Eu, Sm, Eu, Gd, Pr, Nd, Ce, La, or Tb) is discussed. High yields (>99%) are attained under optimized reaction conditions. The specific role of lanthanides and organic ligands in creating sustainable and recyclable heterogeneous Pd catalysts is evidenced. Mechanistic aspects of the C(sp²)-C(sp²) cross-coupling reactions are considered. The synergistic interaction between lanthanides and palladium as well as with the organic ligands is highlighted. Full article

The growing demand for palladium (Pd) necessitates the development of sustainable and efficient recovery methods. This work presents a green, one-step synthesis of activated carbon (AC) from winemaking waste (grape seeds) via direct pyrolysis, eliminating the need for separate, energy-intensive activation. Remarkably, the AC synthesized at the lowest temperature of 400 °C exhibited the highest Pd(II) adsorption capacity (16.20 mg/g at 50 °C), performing comparably to many literature-reported ACs that underwent complex activation processes. Characterization revealed that this optimal material possessed a favorable point of zero charge (PZC 7.78) and the lowest ash content (4.66%). Higher pyrolysis temperatures (400–800 °C) progressively increased surface basicity (PZC up to 11.00) and carboxylic group content (reaching 0.565 mmol/g at 800 °C). A comprehensive life cycle assessment (LCA) demonstrated the significant environmental advantage of this method, showing a 74% lower total environmental impact and a 92% reduction in acidification potential compared to commercial coal-based AC. These results prove that highly effective Pd(II) recovery can be achieved through a simplified, direct pyrolysis process, offering a sustainable and practical approach for precious metal recycling from waste biomass. Full article

The automotive industry is undergoing a significant transition, where the development of Battery Electric Vehicles (BEV) and the increasing use of intelligent vehicle functions are transforming vehicles into advanced Cyber-Physical Systems. For heavy-duty OEMs, this transition challenges a Product Development (PD) heritage inherent in an ecosystem of established processes, IT systems, and organization structures. This study primarily comprises semi-structured interviews, conducted at a heavy-duty OEM, and a focused literature search. The study contributes by the following: (i) identifying key PD challenges in the ICE–BEV transition, (ii) outlining obstacles in adopting Model-Based Systems Engineering (MBSE) for managing architectural complexity, and (iii) synthesizing recommendations for architecture-driven collaboration. Interview findings, highlighted intertwined challenges such as fragmented architecture descriptions across physical and software domains, weak continuity between early-phase system context and detailed design, and collaboration constrained by inconsistent terminologies, strained communication channels, and manual reconciliation of architectural information through documents and disconnected tools. These factors hinder function-component traceability and concurrent development across domains. While MBSE is often recommended to address such issues, practical obstacles are noted, including trade-offs between modeling effort and fidelity, limited support for early spatial layout integration, difficulties in bridging physical and software architectures, and the limited integration of document-based practices preferred in early conceptual phases. Based on these insights, the study recommends architecture-driven collaboration anchored in a federated vehicle-architecture description, supported by a distributed systems-engineering function. A layered development approach combining document artifacts with progressively rigorous MBSE is advised for early-phase agility, later-stage traceability, and structured information flow. Full article

Iminophosphine ligands find extensive applications in homogeneous catalysis; however, their potential antitumor activity is currently being explored. Including biologically active moieties, such as aminoalcohols, could enhance this activity further. Therefore, we have synthesised a novel series of Pd(II) and Pt(II) iminophosphine complexes incorporating aminoalcohols as biologically active moieties to explore the potential of enhancing this activity. The series of Pd(II) complexes includes complexes 2a, 2f, and 2h, which were previously reported by our research group as catalysts in Suzuki–Miyaura cross-coupling reaction in aqueous media. Besides their complete characterisation, some structures have been unequivocally corroborated by single-crystal X-ray diffraction (SC-XRD). To evaluate the cytotoxic potential of the complexes, a preliminary in vitro study was conducted on different cancerous cell lines, including using COS-7 cells as a healthy cell line. Notably, complexes 2e, 2f, and 3b exhibited selectivity towards human chronic myelogenous leukaemia (K562), demonstrating IC₅₀ values of 7.73 ± 1.4 µM, 8.53 ± 1.9 µM, and 8.83 ± 1.5 µM, respectively. Remarkably, the selectivity of these complexes surpassed that of cisplatin. Furthermore, in silico analysis indicated a higher binding energy of these complexes to DNA when compared to cisplatin. Full article

Transition metal complexes bearing protic N-heterocyclic carbene (pNHC) ligands are promising precatalysts for organic reactions due to their capacity for unique hydrogen-bonding interactions. Herein, we report the synthesis and structural characterization of the first Pd(II) complex featuring a pNHC derived from 1,2,4-triazole—a heterocyclic system previously unexplored for the preparation of metal/pNHC complexes. The complex was synthesized via oxidative addition of 3-bromo-5-cyclohexyl-1-methyl-1H-1,2,4-triazole to Pd(PPh₃)₄ in the presence of NH₄BF₄. Its molecular structure was characterized by NMR spectroscopy and X-ray diffraction analysis. Full article

Hydrogen-bond-like M···H–C interactions in square-planar d⁸ metal complexes have recently gained attention as structure-directing elements and design motifs in asymmetric catalysis. In this study, we explore these weak interactions not as static features, but as key modulators of molecular motion. We synthesized four cis-[N,N′-pentamethylenebis(iminomethylazolato)]M(II) (M = Pt, Pd), including iminomethyl-2-imidazole, iminomethyl-5-imidazole, and iminomethylpyrrolato Pt(II) complexes and an iminomethylpyrrolato Pd(II) analog. All complexes display reversible flipping of the alkylene bridge across the coordination plane, with the M···H–C interaction alternately engaging from above or below. This dynamic motion was characterized by variable-temperature ¹H NMR spectroscopy, revealing activation parameters for the flipping process. X-ray crystallography confirmed geometries consistent with hydrogen-bond-like interactions, while NBO analysis based on DFT calculations provided insight into their electronic nature. Interestingly, although Pt and Pd display comparable M···H–C distances, solvent effects dominate the flipping kinetics over metal identity. These findings highlight the role of hydrogen-bond-like M···H–C interactions not only in structural stabilization, but also in regulating conformational dynamics. Full article

Catalytic transfer hydrogenation (CTH) and microwave-assisted organic synthesis (MAOS) have each advanced the sustainability of reduction chemistry; however, their combined application to conjugated enones remains largely unexplored. To the best of our knowledge, no unified protocol has been reported for the rapid, one-pot conversion of chalcones into saturated alcohols under microwave irradiation. Herein, we report a concise and green method that integrates MAOS with Pd/C-catalyzed CTH, employing inexpensive ammonium formate in ethanol. In contrast to state-of-the-art hydrogenations that require pressurized H₂ or costly metal complexes, our strategy (i) achieves complete conversion within 20 min at 60 °C, (ii) tolerates both electron-rich and electron-poor substrates, (iii) reduces nitro-substituted chalcones in a single step, and (iv) consumes < 0.005 kWh per reaction—an approximately 250-fold energy saving relative to conventional procedures. These results position microwave-driven CTH as a scalable alternative for synthesizing pharmacologically relevant saturated alcohol scaffolds from readily available chalcones. Full article

The renin-angiotensin system (RAS) has evolved from being considered solely a peripheral endocrine system for cardiovascular control to being recognized as a complex molecular network with important functions in the central nervous system (CNS) and peripheral nervous system (PNS). Here we examine the organization, mechanisms of action, and clinical implications of cerebral RAS in physiological conditions and in various neurological pathologies. The cerebral RAS operates autonomously, synthesizing its main components locally due to restrictions imposed by the blood–brain barrier. The key elements of the system are (pro)renin; (pro)renin receptor (PRR); angiotensinogen; angiotensin-converting enzyme types 1 and 2 (ACE1 and ACE2); angiotensin I (AngI), angiotensin II (AngII), angiotensin III (AngIII), angiotensin IV (AngIV), angiotensin A (AngA), and angiotensin 1-7 (Ang(1-7)) peptides; RAS-regulating aminopeptidases; and AT1 (AT1R), AT2 (AT2R), AT4 (AT4R/IRAP), and Mas (MasR) receptors. More recently, alamandine and its MrgD receptor have been included. They are distributed in specific brain regions such as the hypothalamus, hippocampus, cerebral cortex, and brainstem. The system is organized into two opposing axes: the classical axis (renin/ACE1/AngII/AT1R) with vasoconstrictive, proinflammatory, and prooxidative effects, and the alternative axes AngII/AT2R, AngIV/AT4R/IRAP, ACE2/Ang(1-7)/MasR and alamandine/MrgD receptor, with vasodilatory, anti-inflammatory, and neuroprotective properties. This functional duality allows us to understand its role in neurological physiopathology. RAS dysregulation is implicated in multiple neurodegenerative diseases, including Alzheimer’s disease (AD), Parkinson’s disease (PD), and neuropsychiatric disorders such as depression and anxiety. In brain aging, an imbalance toward hyperactivation of the renin/ACE1/AngII/AT1R axis is observed, contributing to cognitive impairment and neuroinflammation. Epidemiological studies and clinical trials have shown that pharmacological modulation of the RAS using ACE inhibitors (ACEIs) and AT1R antagonists (ARA-II) not only controls blood pressure but also offers neuroprotective benefits, reducing the incidence of cognitive decline and dementia. These effects are attributed to direct mechanisms on the CNS, including reduction of oxidative stress, decreased neuroinflammation, and improved cerebral blood flow. Full article