Search Results (41)

A detailed characterization of metal clusters bound at the surface of crystalline metal oxide supports is crucial for identifying their structure–property relationships relevant to practical applications. Theoretical investigations based on first-principles calculations have proven to be helpful in characterizing supported metal clusters. In this work, the adsorption of an Sn dimer on the regular and defective (100) surfaces of MgO crystal was studied by means of density functional theory (DFT) calculations. The investigated defects included ${\mathrm{F}}_{\mathrm{s}}^0$, ${\mathrm{F}}_{\mathrm{s}}^{+}$, and ${\mathrm{F}}_{\mathrm{s}}^{2+}$ oxygen vacancies on MgO(100). From the results of the calculations, it is clear that the adsorption of Sn₂ at the ${\mathrm{F}}_{\mathrm{s}}^0$ and ${\mathrm{F}}_{\mathrm{s}}^{+}$ centers is stronger than that occurring on the defect-free MgO(100) surface. While the triplet spin multiplicity of a free Sn dimer tends to be preserved upon its adsorption at the ${\mathrm{F}}_{\mathrm{s}}^{2+}$ center, spin quenching is favored for the dimer adsorbed at the regular O²⁻ and defective ${\mathrm{F}}_{\mathrm{s}}^0$ and ${\mathrm{F}}_{\mathrm{s}}^{+}$ centers. The topological analysis of the electron density for the adsorbed dimer was carried out within the quantum theory of atoms in molecules (QTAIM). The calculated values of QTAIM parameters for the Sn-Sn bond of the adsorbed dimer do not differ radically from the corresponding values for the dimer in the gas phase. Full article

The reasonable design of low-cost, high-activity single-atom catalysts (SACs) is crucial for achieving highly efficient electrochemical CO₂RR. In this study, we systematically explore, using density functional theory (DFT), the performance of transition metal (TM = Mn, Fe, Co, Ni, Cu, Zn)-doped defect-type hexagonal boron nitride (h-BN) SACs TM@B₋₁N (B vacancy) and TM@BN₋₁ (N vacancy) in both CO₂RR and the hydrogen evolution reaction (HER). Integrated crystal orbital Hamiltonian population (ICOHP) analysis reveals that these catalysts weaken the sp orbital hybridization of CO₂, which promotes the formation of radical-state intermediates and significantly reduces the energy barrier for the hydrogenation reaction. Therefore, these theoretical calculations indicate that the Mn, Fe, Co@B₋₁N, and Co@BN₋₁ systems demonstrate excellent CO₂ chemical adsorption properties. In the CO₂RR pathway, Mn@B₋₁N exhibits the lowest limiting potential (U_L = −0.524 V), and its higher d-band center (−0.334 eV), which aligns optimally with the adsorbate orbitals, highlights its excellent catalytic activity. Notably, Co@BN₋₁ exhibits the highest activity in HER, while U_L is −0.217 V. Furthermore, comparative analysis reveals that Mn@B₋₁N shows 16.4 times higher selectivity for CO₂RR than for HER. This study provides a theoretical framework for designing bifunctional SACs with selective reaction pathways. Mn@B₋₁N shows considerable potential for selective CO₂ conversion, while Co@BN₋₁ demonstrates promising prospects for efficient hydrogen production. Full article

With unique 4f electronic shells, rare earth metal-based catalysts have been attracting tremendous attention in electrocatalysis, including oxygen reduction reaction (ORR). In particular, atomically dispersed Ce/CeO₂-based catalysts have been explored extensively due to several unique features. This review article provides a comprehensive understanding of (i) the significance of the effect of Ce high-spin state on ORR activity enhancement on the Pt and non-pt electrocatalysts, (ii) the spatially confining and stabilizing effect of ceria on the generation of atomically dispersed transition metal-based catalysts, (iii) experimental and theoretical evidence of the effect of Ce³⁺ ↔ Ce⁴⁺ redox pain on radical scavenging, (iv) the effect of the Ce 4f electrons on the d-band center and electron transfer between Ce to the N-doped carbon and transition metal catalysts for enhanced ORR activity, and (v) the effect of Pt/CeO₂/carbon heterojunctions on the stability of the Pt/CeO₂/carbon electrocatalyst for ORR. Among several strategies of synthesizing Ce/CeO₂ electrocatalysts, the metal–organic framework (MOF)-derived catalysts are being perused extensively due to the tendency of Ce to readily coordinate with O- and N-containing ligands, which upon undergoing pyrolysis, results in the formation of high surface area, porous carbon networks with atomically dispersed metallic/clusters/nanoparticles of Ce active sites. This review paper provides an overview of recent advancements regarding Ce/CeO₂-based catalysts derived from the MOF precursor for ORR in fuel cells and metal–air battery applications and we conclude with insights into key issues and future development directions. Full article

Catalysts with anionic metal centers have recently been proposed to enhance the performance of various chemical processes. Here, we focus on the reactivity of ${\mathrm{Co}\left(\mathrm{CO}\right)}_4^{-}$ for the polymerization of aziridine and carbon monoxide to form polypeptoids, motivated by earlier experimental studies. We used multi-reference and density functional theory methods to investigate possible reaction mechanisms and provide insights into the role of the negatively charged cobalt center. Two different reaction paths were identified. In the first path, ${\mathrm{Co}}^{-}$ acts as a nucleophile, donating an electron pair to the reaction substrate, while in the second path, it performs a single electron transfer to the substrate, initiating radical polymerization. The difference in the activation barriers for the two key steps is small and falls within the accuracy of our calculations. As suggested in the literature, solvent effects can play a primary role in determining the outcomes of such reactions. Future investigations will involve different metals or ligands and will investigate the effects of these two reaction paths on other chemical transformations. Full article

As one of the most important concepts in organic chemistry, aromaticity has attracted considerable attention from both theoretical and experimental chemists. Limited by the traditional rules (Hückel’s rules and Baird’s rules), species can only achieve aromaticity in a single state (S₀ or T₁) in most cases. In 2018, our group first reported 16 electron osmapentalene that showed aromaticity in both the S₀ and T₁ states, which is defined as adaptive aromaticity. In recent years, although adaptive aromatic compounds have been expanded, the adaptive aromatics containing metal-centered radical has not been reported. Here, we carry out density functional theory calculations to explore the aromaticity of the corresponding radicals based on osmapentalyne and osmapentalenes in their S₀ states. It is found that the corresponding radicals of adaptive aromatic osmapentalene exhibit aromaticity regardless of the radicals formed by oxidation or reduction, supported by a series of aromaticity indices including ΔBL, NICS, AICD, EDDB, and ELF. In contrast, for the nonaromatic or antiaromatic compound in the T₁ state, only its cationic radical shows aromaticity. Furthermore, the spin density localization on the metal center is the key factor for the radicals to achieve aromaticity. Full article

It is known that the presence of redox-inactive metals in the active center of an enzyme has a significant effect on its activity. In this regard and for other reasons, the effect of redox-inactive metals on redox processes, such as electron transfer, oxygen and hydrogen atom transfer, as well as the breaking and formation of O–O bonds in reactions catalyzed by transition metals, has been widely studied. Many questions about the role of redox-inactive metals in the mechanisms of these reactions remain open. In this paper, the mechanism of catalysis by bi- and triple hetero-binuclear heteroligand complexes including Ni and redox-inactive alkali metals ((A) {Ni(acac)₂∙L²} and (B) {Ni(acac)₂∙L²∙PhOH} (L² = MSt (M = Li, Na, or K)) in the process of the selective oxidation of ethylbenzene by molecular oxygen into α-phenyl ethyl hydroperoxide is considered. The activity of A and B complexes towards O₂, ROOH, and RO₂^• radicals was studied. Based on kinetic data, we suggest that the high catalytic efficiency of B triple complexes in oxidation processes may be associated with the role of outer-sphere regulatory interactions, with the formation of stable supramolecular structures due to intermolecular H bonds. This assumption was confirmed using the AFM method. Prospects for studying catalysis by complexes ({Ni(acac)₂∙L²} and {Ni(acac)₂∙L²∙PhOH}) that are models of NiARD (Ni-Acyreductone dioxygenase) are discussed. Full article

Environmentally persistent free radicals (EPFRs) are a new class of pollutants that have been identified as potential environmental contaminants due to their persistence and ability to generate reactive oxygen species (ROS) that cause oxidative stress in living organisms. This study investigates the formation and behavior of EPFRs during the photodegradation of organic pollutants, emphasizing the role of metal ions, precursor concentration, and environmental conditions. Results show that light exposure significantly enhances pollutant degradation rates, EPFR yield, and formation speed, though it simultaneously shortens EPFR lifespan due to reactive oxygen species (ROS) generation. In dark conditions, EPFR formation is slower but results in more stable radicals. Metal ions play a pivotal role, with Cu(II) exhibiting the highest EPFR generation capacity due to its strong electron-accepting properties, surpassing Zn(II) and Na(I), highlighting that metal ions with greater oxidizing potential enhance EPFR formation. The precursor, as both reaction product and reactant, plays a dual role in EPFR formation. Individual compounds like anthracene (ANT) yield stable carbon-centered radicals, while mixtures of polycyclic aromatic hydrocarbons (PAHs) produce more complex radical spectra. The study of the influencing factors and transformation mechanisms of EPFR generation in soil can provide a more comprehensive understanding of the environmental behavior of new pollutants, provide a scientific basis for sustainable development, and be of great significance for the assessment and management of environmental risks and the protection of the ecological environment. Full article

Environmental persistent free radicals (EPFRs) are a type of environmental risk substances existing in atmospheric particulate matter, which pose a challenge to human survival and sustainable development. The current understanding is that the formation mechanism of EPFRs is generally related to metallic materials. However, this study analyzed the PM_2.5 generated from cellulose combustion and found that EPFRs could be generated even without the metallic materials. Therefore, this paper explores the emission characteristics of non-metal-induced EPFRs, aiming to reveal the influencing factors, distribution, and decay characteristics of non-metal-induced EPFRs generated from cellulose combustion. The results show that combustion conditions such as combustion temperature and oxygen concentration have a significant impact on the emission concentration of non-metal-induced EPFRs in PM_2.5 from cellulose combustion. The emission concentrations of non-metal-induced EPFRs in PM_2.5 are at the order of magnitude of 10¹⁴ spins/m³ and over 50% is distributed in the inextricable substances. Their g-factor are in the range from 2.0015 to 2.0022, indicating that these EPFRs are carbon-centered radicals. Furthermore, non-metal-induced EPFRs in PM_2.5 from cellulose combustion have a half-life of several years or even longer, which exhibit distinct characteristics different from metal-induced EPFRs. Full article

Current research on synthetic and naturally occurring phenolic compounds is centered around their prominent antioxidant properties. Since reactive oxygen (ROS) and nitrogen (RNS) species cause considerable damage to cellular components upon their overproduction, associated with the pathogenesis of degenerative, cardiovascular and oncological diseases, antioxidants may reduce the risk of developing such conditions. Because hydroxyl, amino and sulfhydryl groups present in their structure, antioxidants may function as hydrogen atom and electron donors, as well as metal-reducing and metal-chelating agents. We synthesized phenolic Schiff bases from 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde; ortho-, meta- and para-mercaptoanilines; and 2,2′- and 4,4′-disulfanediyldianilines. Their antioxidant properties were studied in a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging assay. Full article

Four ligands based on the 2-tert-butyl-4-X-6-{Bis[(6-methoxy-pyridin-2-ylmethyl)-amino]-methyl}-phenol unit are synthesized: X = CHO (HL^CHO), putrescine-pyrene (HL^pyr), putrescine (HL^amine), and 2-tert-butyl-4-putrescine-6-{Bis[(6-methoxy-pyridin-2-ylmethyl)-amino]-methyl}-phenol (H₂L^bis). Complexes 1, 2, 3, and 4 are formed upon chelation to copper(II). The crystal structure of complex 1 shows a square pyramidal copper center with a very weakly bound methoxypridine moiety in the apical position. The pKa of the phenol moiety is determined spectrophotometrically at 2.82–4.39. All the complexes show a metal-centered reduction in their CV at E_p^c,red = −0.45 to −0.5 V vs. SCE. The copper complexes are efficient nucleases towards the ϕX174 DNA plasmid in the presence of ascorbate. The corresponding IC₅₀ value reaches 7 μM for 2, with a nuclease activity that follows the trend: 2 > 3 > 1. Strand scission is promoted by the hydroxyl radical. The cytotoxicity is evaluated on bladder cancer cell lines sensitive (RT112) or resistant to cisplatin (RT112 CP). The IC₅₀ of the most active complexes (2 and 4) is 1.2 and 1.0 μM, respectively, for the RT112 CP line, which is much lower than cisplatin (23.8 μM). Full article

The synthesis of metal nanomaterials is a timely topic due to their widespread use in fields such as crop protection, the environment, medicine, and engineering. Green synthesis of nanoparticles, which uses plant extracts instead of industrial chemical agents to reduce metal ions, has been developed to decrease costs, reduce pollution, and improve environmental and human health safety. In this paper, silver nanoparticles (AgNPs) were synthesized from the flower extract of Jasminum nudiflorum. The green synthesized AgNPs were characterized by UV-Vis, FTIR, XRD, SEM, and other technologies. The antifungal activity of the prepared AgNPs against Alternaria longipes was tested using the plate method, the concentration dilution method, and other methods, and the antioxidant activity of the prepared AgNPs was evaluated by DPPH and hydroxyl free scavenging methods. The results showed that AgNPs synthesized from J. nudiflorum flower extract have a face-centered cubic structure (fcc), and the average grain size of the nanoparticles is 13 nm; they are also mainly spherical in shape. Additionally, the concentration of AgNPs (ranging from 16 to 128 μg/mL) significantly inhibited the mycelial growth of A. longipes in comparison to the control. The inhibitory rate gradually increased with increasing AgNP concentration, ranging from 70.64% to 79.60% at a concentration of 128 μg/mL. The minimum inhibitory concentration was observed at 32 μg/mL. AgNPs induced overaccumulation of MDA in A. longipes, resulting in cell membrane damage and nucleic acid leakage. Moreover, the AgNPs have significant antioxidant properties, which increase with increasing concentration. The clearance rate of DPPH was 25.46 ± 0.90% when the concentration of AgNPs was 8 μg/mL, and the clearance rate of the hydroxyl radical was 28.62 ± 0.59% when the concentration of AgNPs was 128 μg/mL. Thus, the flower extract from J. nudiflorum holds potential as an environmentally friendly and green alternative for the synthesis of AgNPs, which have antifungal and antioxidant potential. Full article

The present study reports the biomimetic synthesis of silver nanoparticles (AgNPs) using a simple, cost effective and eco-friendly method. In this method, the flavonoid extract of Perilla frutescens (PFFE) was used as a bioreduction agent for the reduction of metallic silver into nanosilver, called P. frutescens flavonoid extract silver nanoparticles (PFFE-AgNPs). The Ultraviolet–Visible (UV-Vis) spectrum showed a characteristic absorption peak at 440 nm that confirmed the synthesis of PFFE-AgNPs. A Fourier transform infrared spectroscopic (FTIR) analysis of the PFFE-AgNPs revealed that flavonoids are involved in the bioreduction and capping processes. X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns confirmed the face-centered cubic (FCC) crystal structure of PFFE-AgNPs. A transmission electron microscopic (TEM) analysis indicated that the synthesized PFFE-AgNPs are 20 to 70 nm in size with spherical morphology and without any aggregation. Dynamic light scattering (DLS) studies showed that the average hydrodynamic size was 44 nm. A polydispersity index (PDI) of 0.321 denotes the monodispersed nature of PFFE-AgNPs. Further, a highly negative surface charge or zeta potential value (−30 mV) indicates the repulsion, non-aggregation, and stability of PFFE-AgNPs. PFFE-AgNPs showed cytotoxic effects against cancer cell lines, including human colon carcinoma (COLO205) and mouse melanoma (B16F10), with IC₅₀ concentrations of 59.57 and 69.33 μg/mL, respectively. PFFE-AgNPs showed a significant inhibition of both Gram-positive (Listeria monocytogens and Enterococcus faecalis) and Gram-negative (Salmonella typhi and Acinetobacter baumannii) bacteria pathogens. PFFE-AgNPs exhibited in vitro antioxidant activity by quenching 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydrogen peroxide (H₂O₂) free radicals with IC₅₀ values of 72.81 and 92.48 µg/mL, respectively. In this study, we also explained the plausible mechanisms of the biosynthesis, anticancer, and antibacterial effects of PFFE-AgNPs. Overall, these findings suggest that PFFE-AgNPs have potential as a multi-functional nanomaterial for biomedical applications, particularly in cancer therapy and infection control. However, it is important to note that further research is needed to determine the safety and efficacy of these nanoparticles in vivo, as well as to explore their potential in other areas of medicine. Full article

Confined catalytic realms and synergistic catalysis sites were constructed using bimetallic active centers in two-dimensional metal-organic frameworks (MOFs) to achieve highly selective oxygenation of cycloalkanes and alkyl aromatics with oxygen towards partly oxygenated products. Every necessary characterization was carried out for all the two-dimensional MOFs. The selective oxygenation of cycloalkanes and alkyl aromatics with oxygen was accomplished with exceptional catalytic performance using two-dimensional MOF Co-TCPPNi as a catalyst. Employing Co-TCPPNi as a catalyst, both the conversion and selectivity were improved for all the hydrocarbons investigated. Less disordered autoxidation at mild conditions, inhibited free-radical diffusion by confined catalytic realms, and synergistic C–H bond oxygenation catalyzed by second metal center Ni employing oxygenation intermediate R–OOH as oxidant were the factors for the satisfying result of Co-TCPPNi as a catalyst. When homogeneous metalloporphyrin T(4-COOCH₃)PPCo was replaced by Co-TCPPNi, the conversion in cyclohexane oxygenation was enhanced from 4.4% to 5.6%, and the selectivity of partly oxygenated products increased from 85.4% to 92.9%. The synergistic catalytic mechanisms were studied using EPR research, and a catalysis model was obtained for the oxygenation of C–H bonds with O₂. This research offered a novel and essential reference for both the efficient and selective oxygenation of C–H bonds and other key chemical reactions involving free radicals. Full article

Although environmental and clean energy research has identified graphitic carbon nitride impregnated with reduced graphene oxide (rGO/g-C₃N₄) as a potential, efficient non-metallic photocatalyst, its efficacy against Contaminants of Emerging Concern (CECs) is relatively unknown. This study reports an optimized photocatalyst (response surface methodology, RSM) to remove the plasticizer and endocrine disruptor bisphenol A (BPA) from water. The synthetic procedure included sonication of prepared particles of g-C₃N₄ and graphite oxide (rGO), followed by reduction with hydrazine (24 h reflux), increasing specific surface areas, and improving synthesis reproducibility. In optimal conditions, the produced photocatalyst (50 mg L^–1) removed 90% of BPA (100 mL, 100 μg L⁻¹) in 90 min (30 min in the dark + 60 min irradiated) using a UV source (centered at 365 nm, 26 W) and exhibiting pseudo-first-order kinetics. For comparison purposes, under the same experimental conditions, pure g-C₃N₄ removed 50% of the BPA solution. Radical scavenging tests identified the superoxide radical as the main reactive oxygen species involved in the degradation. Two major degradation products were identified by mass spectrometry, both of them less ecotoxic than BPA to a variety of test organisms, according to in silico estimations (ECOSAR 2.0). Full article

Six heteroleptic Cu(II) carboxylates (1–6) were prepared by reacting 2-chlorophenyl acetic acid (L¹), 3-chlorophenyl acetic acid (L²), and substituted pyridine (2-cyanopyridine and 2-chlorocyanopyridine). The solid-state behavior of the complexes was described via vibrational spectroscopy (FT-IR), which revealed that the carboxylate moieties adopted different coordination modes around the Cu(II) center. A paddlewheel dinuclear structure with distorted square pyramidal geometry was elucidated from the crystal data for complexes 2 and 5 with substituted pyridine moieties at the axial positions. The presence of irreversible metal-centered oxidation reduction peaks confirms the electroactive nature of the complexes. A relatively higher binding affinity was observed for the interaction of SS-DNA with complexes 2–6 compared to L¹ and L². The findings of the DNA interaction study indicate an intercalative mode of interaction. The maximum inhibition against acetylcholinesterase enzyme was caused for complex 2 (IC₅₀ = 2 µg/mL) compared to the standard drug Glutamine (IC₅₀ = 2.10 µg/mL) while the maximum inhibition was found for butyrylcholinesterase enzyme by complex 4 (IC₅₀ = 3 µg/mL) compared to the standard drug Glutamine (IC₅₀ = 3.40 µg/mL). The findings of the enzymatic activity suggest that the under study compounds have potential for curing of Alzheimer’s disease. Similarly, complexes 2 and 4 possess the maximum inhibition as revealed from the free radical scavenging activity performed against DPPH and H₂O₂. Full article