Search Results (3,450)

The development of efficient and sustainable advanced oxidation processes (AOPs) for organic pollutant removal is of great significance for water purification. In this study, a CoFeNi-layered double hydroxide (CoFeNi-LDH) catalyst was synthesized and applied for the simultaneous activation of peroxymonosulfate (PMS) and ozone to degrade rhodamine B (RhB) in aqueous solution. The CoFeNi-LDH/PMS/ozone system achieved a remarkable RhB removal efficiency of 95.2 ± 1.2% within 8 min under neutral pH conditions. Systematic parametric studies revealed that synergistic interactions among CoFeNi-LDH, PMS, and ozone contributed to the generation of reactive oxygen species (ROS), primarily sulfate radicals (SO₄^•−) and singlet oxygen (¹O₂), as confirmed by EPR and quenching experiments. Density functional theory (DFT) calculations demonstrated that ozone enhanced PMS adsorption and activation at CoFeNi catalytic sites. The catalyst exhibited robust magnetic recyclability and structural stability after repeated use. This work highlights a synergistic catalytic strategy for PMS/ozone activation, offering an effective and environmentally friendly platform for dye wastewater remediation. Full article

Integration of renewable energy into modern power grids remains limited by intermittency and the need for reliable energy storage. Redox flow batteries (RFBs) are promising for large-scale energy storage, yet their widespread adoption is hindered by the high cost. In this study, we investigate isopropanol as a redox-active species with Pt-Cu alloy electrocatalysts for aqueous-organic RFBs. A series of Pt_xCu catalysts with varying Pt:Cu ratios were synthesized and studied for isopropanol electro-oxidation reaction (IPAOR) performance. Among them, PtCu demonstrated the best performance, achieving a low activation energy of 14.4 kJ/mol at 0.45 V vs. RHE and excellent stability at 1 M isopropanol (IPA) concentration. Kinetic analysis and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy revealed significantly reduced acetone accumulation on PtCu compared to pure Pt, indicating enhanced resistance to catalyst poisoning. Density functional theory (DFT) calculations further identified the first proton-coupled electron transfer (PCET) as the rate-determining step (RDS) with C-H bond scission as the preferred pathway on PtCu. A proof-of-concept PtCu-catalyzed H-cell demonstrated stable cycling over 200 cycles, validating the feasibility of IPA as a low-cost, regenerable redox couple. These findings highlight PtCu-catalyzed IPA/acetone(ACE) chemistry as a promising platform for next-generation aqueous-organic RFBs. Full article

Effluents from the textile industry, particularly those containing synthetic azo dyes, poses a significant environmental threat, necessitating the development of more effective and sustainable pollutant removal methods. Traditional dye removal techniques often fall short in efficiency and environmental impact, prompting the exploration of enzymatic degradation as a promising alternative. This study focuses on chloroperoxidase, a natural biocatalyst recognized for its ability to oxidize synthetic dyes into less harmful products. By exploring the mechanistic distinction between chlorination and oxidative processes, we investigate the enzyme’s specific degradation pathways for azo dyes and the resulting by-products. Utilizing analytical techniques, including liquid chromatography/mass spectrometry (LC/MS), and density functional theory (DFT), we gain insights into the decolorization mechanism, revealing that the enzyme preferentially generates oxidative products through C–N bond cleavage as its initial degradation step. These findings underscore not only the unique mechanistic properties of chloroperoxidase but also its potential as a biocatalyst for industrial applications. This study advocates further research into the optimization of enzyme-based systems, highlighting their relevance in advancing greener chemical practices in the textile industry, thus contributing to more sustainable manufacturing processes. Full article

Hydrogen energy is viewed as a promising green energy source because of its high energy density, abundant availability, and clean combustion results. Hydrogen storage is the critical link in a hydrogen economy. Using first-principles density functional theory calculations, this work explored the role of B and N in modulating the binding properties of transition metal-modified graphene. The hydrogen storage performance of Sc-, Ti-, and V-modified B-doped graphene was evaluated. Boron doping induces an electron-deficient state, enhancing interactions between transition metals and graphene. Sc, Ti, and V preferentially adsorbed at the carbon ring’s hollow site in B-doped graphene, with their binding energies being 1.87, 1.74, and 1.69 eV higher than those in pure graphene, respectively. These systems can stably adsorb up to 5, 4, and 4 H₂ molecules, with average adsorption energies of −0.528, −0.645, and −0.620 eV/H₂, respectively. The hydrogen adsorption mechanism was dominated by orbital interactions and polarization effects. Among the systems studied, Sc-modified B-doped graphene exhibited superior hydrogen storage characteristics, making it a promising candidate for reversible applications. Full article

Aromaticity tuning of biaryl monophosphines can significantly impact their catalytic performance. Biaryl monophosphines constitute a crucial class of compounds due to their potential as ligand precursors in asymmetric Pd-catalyzed cross-coupling and some other catalytic reactions. In this study, we investigate the tuning of aromaticity within a series of selected biaryl monophosphine derivatives exhibiting diverse steric and electronic properties. XRD structures and Hirshfeld surface analyses were complemented by DFT calculations. Aromaticity indices, such as geometric HOMA, HOMER, and magnetic NICS, were evaluated and correlated with ligand properties. NICS(1)zz was the most sensitive to aromaticity changes. The results showed that among the ring-activating substituents, methoxy groups were more beneficial than hydroxy ones. The hydroxy groups not only modulated the aromaticity but also induced unfavorable conformational changes of the catalyst precursors through strong inter- and intramolecular hydrogen bonding. The spatial arrangement of the P atom adjacent to the aryl ring system confers catalytic advantages by promoting the assembly of coordination compounds (catalysts) in which Pd—C bond formation occurs, yielding C,P-chelated five-membered palladacyclic structures. The hydroxy substituents blocked access to the P atom, thereby hindering catalytic performance. The studies show that even subtle changes in the monophosphine biaryl scaffold, especially aromaticity tuning should be carefully evaluated during the rational design of new efficient catalysts. The studied compounds were evaluated for their biological activity against three Gram-positive and four Gram-negative bacteria as model microorganisms. The research was supplemented by in vitro cytotoxicity evaluation. Full article

This research prepared and characterised novel mixed coordination complexes derived from escitalopram with eugenol and curcumin to form (L₁) and (L₂), respectively. The complexes were prepared via Williamson ether synthesis and analysed by FTIR, UV–Vis, ¹H-NMR spectroscopy, elemental analysis, molar conductivity, and magnetic susceptibility. The results confirmed their octahedral geometries. Magnetic investigation reported high-spin configurations for Mn(II), Co(II), and Ni(II) complexes, whereas Cu(II) exhibited a distorted octahedral arrangement with characteristic d–d transitions. In addition, the calculation of Density functional theory (DFT) provided more insight into the detailed structural and electronic properties of the new ligand and its complexes. Antimicrobial compounds were evaluated against Escherichia coli, Staphylococcus aureus, and Candida albicans through the agar well diffusion method. The reported results revealed that Cobalt complexes showed antimicrobial activity followed by Copper (Cu), Nickel (Ni) and Manganese(Mn) complexes, respectively, due to an increase in Co-lipophilicity, which leads to improved diffusion through microbial cell membranes. The research findings confirmed that escitalopram-based mixed ligands coordinate with transition metals and could have significant biological applications. Full article

Bilayer transition metal dichalcogenides (TMDs) are promising materials for next-generation field-effect transistors (FETs) due to their atomically thin structure and favorable transport properties. In this study, we employ density functional theory (DFT) to compute the electronic band structures and phonon dispersions of bilayer WS₂, WSe₂, and MoS₂, and the electron-phonon scattering rates using the EPW (electron-phonon Wannier) method. Carrier transport is then investigated within a semiclassical full-band Monte Carlo framework, explicitly including intrinsic electron-phonon scattering, dielectric screening, scattering with hybrid plasmon–phonon interface excitations (IPPs), and scattering with ionized impurities. Freestanding bilayers exhibit the highest mobilities, with hole mobilities reaching 2300 cm²/V·s in WS₂ and 1300 cm²/V·s in WSe₂. Using hBN as the top gate dielectric preserves or slightly enhances mobility, whereas HfO₂ significantly reduces transport due to stronger IPP and remote phonon scattering. Device-level simulations of double-gate FETs indicate that series resistance strongly limits performance, with optimized WSe₂ pFETs achieving ON currents of 820 A/m, and a 10% enhancement when hBN replaces HfO₂. These results show the direct impact of first-principles electronic structure and scattering physics on device-level transport, underscoring the importance of material properties and the dielectric environment in bilayer TMDs. Full article

In this article, we present density functional theory (DFT) calculations for $Z{n}_{(1-x)}{M}_{x}O$, where M represents one of the following substitutional metallic impurities: Ga, Cd, Cu, Pd, Ag, In, or Sn. Our study is based on the wurtzite structure of pristine ZnO. We employ the Quantum Espresso package, using a fully unconstrained implementation of the generalized gradient approximation (GGA) with an additional U correction for exchange and correlation effects. We analyze the density of states, energy gaps, and absorption spectra for these doped systems, considering the limitations of a finite-size cell approximation. Rather than focusing on precise numerical values, we highlight the following two key aspects: the location of impurity-induced electronic states and the overall trends in optical properties across the eight systems, including pristine ZnO. Our results indicate that certain dopants introduce electronic levels within the band gap, which enhance optical absorption in the visible, near-infrared, and near-ultraviolet regions. For instance, Sn-doped ZnO shows a pronounced absorption peak at ∼2.5 eV, which is in the middle of the visible spectrum. In the case of Ag and Pd impurities, they lead to increased electromagnetic radiation absorption at the near ultra-violet spectrum. This represents a promising performance for efficient solar radiation absorption, both at the Earth’s surface and in outer space. Furthermore, Ga- and In-doped ZnO present bandgaps of ∼0.9 eV, promising an interesting performance in the near infrared region. These findings suggest potential applications in solar energy harvesting and selective sensors. Full article

Molecularly imprinted polymer (MIP) biosensors offer an attractive strategy for selective biomolecule detection, yet imprinting proteins with structural fidelity remains a major challenge. In this work, we present a rationally designed electrochemical biosensor for matrix metal-loproteinase-8 (MMP-8), a key salivary biomarker of periodontal disease. By integrating graphene oxide (GO) with electropolymerized poly(eriochrome black T, EBT) films on screen-printed carbon electrodes, the partially reduced GO interface enhanced electrical conductivity and facilitated the formation of well-defined poly(EBT) films with re-designed polymerization route, while template extraction generated artificial antibody-like sites capable of specific protein binding. The MIP-based electrodes were comprehensively validated through morphological, spectroscopic, and electrochemical analyses, demonstrating stable and selective recognition of MMP-8 against structurally similar interferents. Complementary density functional theory (DFT) modeling revealed energetically favorable interactions between the EBT monomer and catalytic residues of MMP-8, providing molecular-level insights into imprinting specificity. These experimental and computational findings highlight the importance of rational monomer selection and nanomaterial-assisted polymerization in achieving selective protein imprinting. This work presents a systematic approach that integrates electrochemical engineering, nanomaterial interfaces, and computational validation to address long-standing challenges in protein-based MIP biosensors. By bridging molecular design with practical sensing performance, this study advances the translational potential of MIP-based electrochemical biosensors for point-of-care applications. Full article

Background/Objectives: Lifitegrast is a recent therapeutic agent provoking scientific and regulatory interest due to its outstanding safety profile and high efficacy in the treatment of dry eye disease. Methods: Herein we employ NMR spectroscopy and mass spectrometry to investigate the weak spots of lifitegrast under standard to extreme stress conditions, resulting in the characterization of three known and nine new degradation products (of which DP7 presented the greatest structural challenge, but was eventually determined as C10 hydroxy derivative, warranting a revision of its previously suggested structure). Results: The first weak spot is identified as a N1–C40 amide bond, and its high susceptibility to hydrolysis is explained through computational DFT analysis. The second and third weak spots are elucidated through bond dissociation energy (BDE) calculations which highlighted the oxidative vulnerabilities of both the piperidine and benzofuran ring. Conclusions: Additionally, two degradation products, observed in initial, extended, and targeted oxidative forced degradation studies, were selected for in silico toxicity assessment and were predicted to have toxicity profiles comparable to or lower than lifitegrast. Full article

This work thoroughly investigated the compound 4-(2,5-Dimethoxyphenyl)-3,4-dihydrobenzo[g]chromene-2,5,10-trione (DMDCT) using molecular docking, quantum chemical analysis, and vibrational spectroscopy methodology. The medicinal chemistry group has been particularly interested in chromene and benzochromene derivatives due to their wide range of pharmacological actions, including anticancer, antibacterial, anti-inflammatory, antioxidant, antiviral, and neuroprotective capabilities. In this connection, DMDCT has been explored to evaluate its biological, electrical, and structural properties. DFT using the B3LYP functional and 6–31G basis was established to conduct theoretical computations with the Gaussian 09 program. The findings from these computations provide insight into the following topics: NBO interactions, optimal molecular geometry, Mulliken charge distribution, frontier molecular orbitals, and MEP. Second-order perturbation theory has been used to assess stabilization energies arising from donor–acceptor interactions. Furthermore, general features such as chemical hardness, softness, and electronegativity were studied. The results suggest that DMDCT has stable electronic configurations and biologically relevant active sites. This integrated experimental and theoretical study supports the potential of DMDCT as a practical scaffold for future therapeutic applications and contributes valuable information regarding its vibrational and electronic behavior. Full article

Sustainable aviation fuel (SAF) is a drop-in alternative to conventional jet fuels, designed to reduce greenhouse gas (GHG) emissions while requiring minimal infrastructure changes and certification under the American Society for Testing and Materials (ASTM) D7566 standard. This study assesses recently identified high-energy-density (HED) strained polycycloalkanes as SAF candidates. Strain energy (E_se) was calculated using density functional theory (DFT), while operational properties such as boiling point (BP) and flash point (FP) were predicted using support vector regression (SVR) models. The models demonstrated strong predictive performance (R² > 0.96) with mean absolute errors of 6.92 K for BP and 9.58 K for FP, with robustness sensitivity analysis. It is found that approximately 65% of these studied polycycloalkanes fall within the Jet A fuel property boundaries. The polycycloalkanes (C₉–C₁₅) with strain energies below approximately 60 kcal/mol achieve an balance between energy density and ignition safety, aligning with the specifications of Jet A. The majority of structures were dominated by five-membered rings, with a few three- or four-membered rings enhancing favorable trade-offs among BP, FP, and HED. This early pre-screening indicates that moderately strained polycycloalkanes are safe, energy-dense candidates for next-generation sustainable jet fuels and provide a framework for designing high-performance SAFs. Full article

With their considerable capacity and structurally favorable characteristics, layered transition metal oxides have become strong contenders for cathode use in sodium-ion batteries (SIBs). Nevertheless, their practical deployment is challenged by pronounced capacity loss, predominantly induced by unstable cathode–electrolyte interphase (CEI) at elevated voltages. In this study, difluoroethylene carbonate (DFEC) is introduced as a functional electrolyte additive to engineer a robust and uniform CEI. The fluorine-enriched CEI effectively suppresses parasitic reactions, mitigates continuous electrolyte decomposition, and facilitates stable Na⁺ transport. Consequently, Na/NaNi_1/3Fe_1/3Mn_1/3O₂ (Na/NFM) cells with 2 wt.% DFEC retain 78.36% of their initial capacity after 200 cycles at 1 C and 4.2 V, demonstrating excellent long-term stability. Density functional theory (DFT) calculations confirm the higher oxidative stability of DFEC compared to conventional solvents, further supporting its interfacial protection role. This work offers valuable insights into electrolyte additive design for high-voltage SIBs and provides a practical route to significantly improve long-term electrochemical performance. Full article

Curcumin (CUR) is the primary metabolite isolated from the Curcuma longa L. rhizome. Most synthetic and biological studies have focused mainly on the curcumin molecule due to its essential biological activity as an antioxidant, anti-cancer, and anti-Alzheimer’s disease agent. However, the natural extract of turmeric also contains two essential curcuminoids (demethoxycurcumin (DMC) and bisdemethoxycurcumin (BDMC)), which altogether comprise the so-called C-3 complex. They are present in commercial compositions for treating biliary or digestive ailments. The vegetal rhizome’s extraction typically leads to a mixture of the three main curcuminoids, CUR, DMC, and BDMC, in variable proportions, and each of these metabolites has reported specific synthetic routes. Herein, we have performed the synthesis and isolation of the three major curcuminoids using the method called scrambling of aldehydes followed by aldol di-condensation reactions. A density functional theory (DFT) approach supported the experimental results by inspecting the predicted energies for the aldol condensation. Thus, the di-condensation reaction is substantially favoured (ΔG° = −2685.9 kJ/mol) over the mono-condensation reaction (ΔG° = −1393.753 kJ/mol). Our approach allows us to mimic closely the proportions of these curcuminoids found in extracts from natural sources that follow the order CUR > DMC > BDMC, respectively. The proportion of aldehydes can be modified in the scrambling reaction with an adequate mixture of aldehydes to render the order DMC > CUR > BDMC. This is an advantageous way to increase the amount of the unsymmetric DMC metabolite. Full article

Highly Hazardous Pesticides (HHPs) pose severe risks to human health and the environment, making it essential to understand their molecular stability and degradation pathways. In this study, the Quantum Theory of Atoms in Molecules (QTAIM) was applied to four representative organophosphate pesticides, allowing the identification of electronically weak bonds as intrinsic sites of lability. These findings are consistent with reported hydrolytic, oxidative, enzymatic, and microbial degradation routes. Importantly, QTAIM descriptors proved largely insensitive to solvation, confirming their intrinsic character within the molecular electronic structure. To complement QTAIM, conceptual DFT (Density Functional Theory) reactivity indices were analyzed, revealing that solvent effects induce more noticeable variations in global and local descriptors than in topological parameters. In addition, a Topological Analysis of the Fukui Function (TAFF) was performed, which mapped nucleophilic, electrophilic, and radical susceptibilities directly onto QTAIM basins. The TAFF analysis confirmed that bonds identified as weak by QTAIM (notably P–O, P–S, and P–N linkages) also coincide with the most reactive sites, thereby reinforcing their mechanistic role in degradation pathways. This integrated framework highlights the robustness of QTAIM, the sensitivity of global and local reactivity descriptors to solvation revealed by conceptual DFT, and the complementary insights provided by TAFF, contributing to risk assessment, remediation strategies, and the rational design of safer pesticides. Full article