Search Results (802)

This study details how 3-(naphthalen-2-yl)-1-phenylprop-2-en-1-one (3NPEO) behaves in terms of photophysics when exposed to different solvents. The solvatochromic effect study reveals significant polarity shifts in the excited states of the 3NPEO compound, likely due to an intramolecular proton transfer mechanism. Measurements of dipole moments provide insight into their resonance structures in both ground and excited states. Electrochemical analysis revealed a reversible redox process, indicating a favorable charge transport potential. HOMO and LUMO energies of the compound were computed via oxidation and reduction potential standards. 3NPEO exhibits optimal one-photon and two-photon absorption characteristics, validating its suitability for visible wavelength laser applications in photonic devices. Furthermore, molecular docking and dynamics simulations demonstrated strong interactions between 3NPEO and the progesterone receptor enzyme, supported by structure–activity relationship (SAR) analyses. In vitro cytotoxicity assays on the MDAMB-231 breast cancer cell line showed moderate tumor cell inhibitory activity. Apoptosis studies confirmed the induction of both early and late apoptosis. These findings suggest that 3NPEO holds promise as a potential anticancer agent targeting the progesterone receptor in breast cancer cells. Overall, the findings highlight the substantial influence of solvent polarity on the photophysical properties and the design of more effective and stable therapeutic agents. Full article

Background: Melanoma metastasis, driven by tumor microenvironment (TME)-mediated crosstalk facilitated by extracellular vesicles (EVs), remains a major therapeutic challenge. A critical barrier to clinical translation is the overlap in protein cargo between tumor-derived and healthy cell EVs. Objective: To address this, we developed Scaffold-free Functional Deconvolution (SFD), a novel computational approach that leverages a comprehensive healthy cell EV protein database to deconvolute non-oncogenic background signals. Methods: Beginning with 1915 proteins (identified by MS/MS analysis on an Orbitrap Fusion Lumos Mass Spectrometer using the IonStar workflow) from melanoma EVs isolated using REIUS, SFD applies four sequential filters: exclusion of normal melanocyte EV proteins, prioritization of metastasis-linked entries (HCMDB), refinement via melanocyte-specific databases, and validation against TCGA survival data. Results: This workflow identified 21 high-confidence targets implicated in metabolic-associated acidification, immune modulation, and oncogenesis, and were analyzed for reduced disease-free and overall survival. SFD’s versatility was further demonstrated by surfaceome profiling, confirming enrichment of H7-B3 (CD276), ICAM1, and MIC-1 (GDF-15) in metastatic melanoma EV via Western blot and flow cytometry. Meta-analysis using Vesiclepedia and STRING categorized these targets into metabolic, immune, and oncogenic drivers, revealing a dense interaction network. Conclusions: Our results highlight SFD as a powerful tool for identifying clinically relevant biomarkers and therapeutic targets within melanoma EVs, with potential applications in drug development and personalized medicine. Full article

In this study, the impact of incorporating energetic substituents such as -NO₂, -NH₂, -NH₃, -N₂ (both with perchlorate anion), and -N₃ into 4,6-dinitrobenzimidazol-2-one on its detonation performance and stability was investigated. The DFT B3LYP/cc-pVTZ method was employed to evaluate key molecular properties: the HOMO–LUMO gap, cohesive energy, chemical hardness, and electronegativity. Based on these parameters, the resulting changes in chemical and thermal stability were assessed. The results achieved highlight the significant role of ionic bonding in enhancing both the stability and density of the compounds. Our results indicate that the benzimidazoles enriched by energetic groups possess energetic properties better than TNT, with some variants surpassing HMX. The analysis of the stability and sensitivity based on oxygen balance investigation suggests that by varying the incorporated substituents, it is possible to design both primary and secondary explosives from a common molecular scaffold. Full article

In the present study, two novel donor–acceptor (D–A) conjugated copolymers, PIDTBDI and PIDTTBDI, were successfully synthesized via Stille coupling polymerization. These alternating copolymers incorporate indacenodithiophene and indacenodithienothiophene as donor units, coupled with benzothiadiazole dicarboxylic imide as the electron-deficient acceptor unit. The influence of extended conjugation on the structural, optical, thermal, and electrochemical properties of the copolymers was systematically investigated and confirmed by density functional theory (DFT). XRD analysis confirmed that both polymers are amorphous. Thermogravimetric analysis revealed that both materials possess excellent thermal stability, with decomposition temperatures exceeding 270 °C. The theoretical and experimental values of the energy gap confirmed the thermal stability of the studied polymers. The molecular weight was determined to be 10,673 Da for PIDTBDI and 7149 Da for PIDTTBDI. Despite the variation in molecular weight, both copolymers exhibited comparable optical and electrochemical bandgaps of approximately 1.57 and 1.69 eV, respectively. Electrochemical measurements showed that PIDTBDI has a HOMO energy level of −5.30 eV and a LUMO level of −3.61 eV, while PIDTTBDI displays HOMO and LUMO levels of −5.28 eV and −3.59 eV, respectively. These results indicate that minor structural differences can considerably affect the electronic characteristics of the polymers, thus altering their overall efficacy in solar cell applications. Full article

In this study, three alternating donor–acceptor (D–A) type [12]cycloparaphenylene ([12]CPP) derivatives ([12]CPP 1a, 2a, and 3a) were designed through precise molecular engineering, and their multidimensional photophysical responses and chiroptical properties were systematically investigated. The effects of the alternating D–A architecture on electronic structure, excited-state dynamics, and optical behavior were elucidated through density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The results show that the alternating D–A design significantly reduced the HOMO–LUMO energy gap (e.g., 3.11 eV for [12]CPP 2a), enhanced charge transfer characteristics, and induced pronounced red-shifted absorption. The introduction of an imide-based acceptor ([12]CPP 2a) further strengthened the electron push-pull interaction, exhibiting superior performance in two-photon absorption, while the symmetrically multifunctionalized structure ([12]CPP 3a) predominantly exhibited localized excitation with the highest absorption intensity but lacked charge transfer features. Chiral analysis reveals that the alternating D–A architecture modulated the distribution of chiral signals, with [12]CPP 1a displaying a strong Cotton effect in the low-wavelength region. These findings not only provide a theoretical basis for the molecular design of functionalized CPP derivatives, but also lay a solid theoretical foundation for expanding their application potential in optoelectronic devices and chiral functional materials. Full article

Access to clean water is a pressing global concern and membrane technologies play a vital role in addressing this challenge. Thin-film composite membranes prepared via interfacial polymerization (IPol) using meta-phenylenediamine (MPD) and trimesoyl chloride (TMC) exhibit excellent separation performance, but face limitations such as fouling and low hydrophilicity. This study investigated the interaction between MPD and sulfonated zinc phthalocyanine, Zn(SO₂⁻)₄Pc, as a potential strategy for enhancing membrane properties. Using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT), we analyzed the optimized geometries, electronic structures, UV–Vis absorption spectra, FT-IR vibrational spectra, and molecular electrostatic potentials of MPD, Zn(SO₂⁻)₄Pc, and their complexes. The results show that MPD/Zn(SO₂⁻)₄Pc exhibits reduced HOMO-LUMO energy gaps and enhanced charge delocalization, particularly in aqueous environments, indicating improved stability and reactivity. Spectroscopic features confirmed strong interactions via hydrogen bonding and π–π stacking, suggesting that Zn(SO₂⁻)₄Pc can act as a co-monomer or additive during IPol to improve polyamide membrane functionality. A conformational analysis of MPD/Zn(SO₂⁻)₄Pc was conducted using density functional theory (DFT) to evaluate the impact of dihedral rotation on molecular stability. The 120° conformation was identified as the most stable, due to favorable π–π interactions and intramolecular hydrogen bonding. These findings offer computational evidence for the design of high-performance membranes with enhanced antifouling, selectivity, and structural integrity for sustainable water treatment applications. Full article

Tungsten and tungsten alloys are widely used in important industrial fields due to their high density, hardness, melting point, and corrosion resistance. However, machining often leaves processing marks on their surface, significantly affecting the surface quality of precision components in industrial applications. Electrolytic polishing offers high efficiency, low workpiece wear, and simple processing. In this study, an electrolytic polishing method is adopted and a novel trisodium phosphate–sodium hydroxide electrolytic polishing electrolyte is developed to study the effects of temperature, voltage, polishing time, and solution composition on the surface roughness of a tungsten–nickel–iron alloy. The optimal voltage, temperature, and polishing time are determined to be 15 V, 55 °C, and 35 s, respectively, when the concentrations of trisodium phosphate and sodium hydroxide are 100 g·L⁻¹ and 6 g·L⁻¹. In addition, glycerol is introduced into the electrolyte as an additive. The calculated LUMO value of glycerol is −5.90 eV and the HOMO value is 0.40 eV. Moreover, electron enrichment in the hydroxyl region of glycerol can form an adsorption layer on the surface of the tungsten alloy, inhibit the formation of micro-pits, balance ion diffusion, and thus promote the formation of a smooth surface. At 100 mL·L⁻¹ of glycerol, the roughness of the tungsten–nickel–iron alloy decreases significantly from 1.134 μm to 0.582 μm. The electrochemical polishing mechanism of the tungsten alloy in a trisodium phosphate electrolyte is further investigated and explained according to viscous film theory. This study demonstrates that the trisodium phosphate–sodium hydroxide–glycerol electrolyte is suitable for electropolishing tungsten–nickel–iron alloys. Overall, the results support the application of tungsten–nickel–iron alloy in the electronics, medical, and atomic energy industries. Full article

In this study, we synthesized novel donor–π–acceptor (D–π–A) functional dyes bearing a carbonyl-bridged bithiophene as a π-conjugated spacer and evaluated the absorption and fluorescence properties as well as the photostability. The developed dyes 1-CO–3-CO possess an N,N-diphenylaminophenyl electron donor unit and an electron acceptor unit such as a formyl group (1-CO), an (N,N-diethylthiobarbituryl)methylene moiety (2-CO), or a (3-dicyanomethylidene-1-indanon-2-yl)methylene moiety (3-CO). The absorption spectra of 1-CO–3-CO in dichloromethane at room temperature showed absorption maxima at 569 nm, 631 nm, and 667 nm, respectively, and the stronger acceptors in 2-CO and 3-CO led to enhancement of the ICT character. In addition, 2-CO and 3-CO had a second absorption band in the visible region, showing panchromatic absorption properties. Electrochemical analyses of the developed dyes revealed that the carbonyl bridging group in the π-spacer contributes to stabilization of the frontier orbitals such as the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively), in comparison with the referential dyes bearing a dibutylmethylene-bridged bithiophene spacer, 1-CBu₂–3-CBu₂. The HOMO/LUMO stabilization brought about high photostability in the doped poly(methyl methacrylate) film. Full article

Autonomous Underwater Vehicles (AUVs) are gradually becoming some of the most important equipment in deep-sea exploration. However, in the dynamic nature of the deep-sea environment, any unplanned fault of AUVs would cause serious accidents. Traditional fault diagnosis models are trained in static and fixed datasets, making them difficult to adopt in new and unknown deep-sea environments. To address these issues, this study explores incremental learning to enable AUVs to continuously adapt to new fault scenarios while preserving previously learned diagnostic knowledge, named the RM-MFKAN model. First, the approach begins by employing the Rainbow Memory (RM) framework to analyze data characteristics and temporal sequences, thereby delineating boundaries between old and new tasks. Second, the model evaluates data importance to select and store key samples encapsulating critical information from prior tasks. Third, the RM is combined with the enhanced KAN network, and the stored samples are then combined with new task training data and fed into a multi-branch feature fusion neural network. The proposed RM-MFKAN model was conducted on the “Haizhe” dataset, and the experimental results have demonstrated that the proposed model achieves superior performance in fault diagnosis for AUVs. Full article

Background/Objectives: This study aims to present a strategic approach to enhancing the photostability and antioxidative resilience of curcumin and capsaicin by integrating selected natural stabilizers within a nanoemulsion-based delivery system. Methods: Coffee extract (Coffea arabica Linn.), along with its active components and vitamin E-containing natural oils, was assessed in terms of improving the photostabilizing and antioxidative retention abilities of curcumin and capsaicin. An optimized ratio of the active mixture was then loaded into a nanoformulation. Results: The analysis of active contents with validated high-performance liquid chromatography (HPLC), ferric reducing antioxidant power (FRAP), and 2,2-diphenyl-1-picrylhydrazyl (DPPH) assays confirmed the stabilization enhancement after irradiation with UV and white light for 72,000–84,000 lux hours. The optimized combination of coffee extract with turmeric and chili mixtures loaded into the optimized nanoemulsion enhanced the half-lives (T_1/2) of curcumin and capsaicin by 416% and 390%, respectively. The interactions of curcumin and capsaicin with caffeine and chlorogenic acid were elucidated using computational calculations. Interaction energies (E_int), HOMO-LUMO energy gap (HLG) analysis, and global reactivity descriptors revealed hydrogen bonding interactions be-tween capsaicin and chlorogenic acid, as well as between curcumin and caffeine. Conclusions: By leveraging the synergistic antioxidative properties of coffee extract and vitamin E within a nanoemulsion matrix, this study overcomes the intrinsic stability limitations of curcumin and capsaicin, offering a robust platform for future pharmaceutical and nutraceutical applications. Full article

This study theoretically investigates the potential of a polyacrylamide copolymerized with amylose, a primary component of starch, to evaluate its efficiency in removing heavy metals from industrial wastewater. This material concept seeks to combine the high adsorption capacity of polyacrylamide with the low cost and biodegradability of starch, ultimately aiming to offer an economical, efficient, and sustainable alternative for wastewater treatment. To this end, a computational model based on density functional theory (DFT) was developed, utilizing the B3LYP functional with the 6-311++G(d,p) basis set, a widely recognized combination that strikes a balance between accuracy and computational cost. The interactions between an acrylamide-amylose (AM/Amy) polymer matrix, as well as the individual polymers (AM and Amy), and the metal ions Pb, Hg, and Cd in their hexahydrated form (M·6H₂O) were analyzed. This modeling approach, where M represents any of these metals, simulates a realistic aqueous environment around the metal ion. Molecular geometries were optimized, and key parameters such as total energy, dipole moment, frontier molecular orbital (HOMO-LUMO) energy levels, and Density of States (DOS) graphs were calculated to characterize the stability and electronic reactivity of the molecules. The results indicate that this proposed copolymer, through its favorable electronic properties, exhibits a high adsorption capacity for metal ions such as Pb and Cd, positioning it as a promising material for environmental applications. Full article

Molybdenum disulfide is more attractive and valuable at the molecular level due to its unique structure and exceptional properties. Here, new-type MoS₂-ring chains are constructed and theoretically investigated for relevant electronic properties influenced by the length of the chain and the bias. Different from traditional wires, our findings demonstrate that the conductance of such a new-type chain presents unusually non-exponential decay with the length of the chain, with a particularly anomalous length of seven rings, which shows stronger equilibrium conductance than a shorter four-ring chain. Multi-peaks of electron transmission and delocalized electronic states contribute such uniqueness. Mo atoms play a vital role in electron transport. Essentially, a narrower “HOMO-LUMO” (the two closest energy levels to the Fermi level of MoS₂-ring chain) gap compensates for the lower device density of states of new-type molybdenum disulfide-ring chains. The usual electronic structure of a seven-ring chain is derived from its slightly arched structure and mainly originates from interference, which is the resonance occurring between the electrodes. Noticeably, the bias could greatly enhance conductance, which could reach 1000 times more than the equilibrium conductance. At a certain bias, the conductance of a seven-ring chain even exceeds the shortest one- or two-ring chain. Furthermore, the threshold voltage (at which the maximum conductance appears) gradually decreases with the length of the chain and eventually remains at 0.7 V. The valuable negative differential resistance (NDR) effect could be found in such a molecular chain, which becomes more obvious as the length rises until the seven-ring chain reaches the peak. Our findings shed light on the relations between electronic properties and the length of a new-type molybdenum disulfide-ring chain, and provide support for such new-type chains in applications of innovative low-power and controllable electronics. Full article

The one-dimensional (1D) Sb(III)-based organic–inorganic hybrid perovskite (AImd)₂¹_∞[SbI₅] (AImd = 1-allylimidazolium) crystallizes in the orthorhombic, centrosymmetric space group Pnma. The structure consists of corner-sharing [SbI₆] octahedra forming 1D chains separated by allylimidazolium cations. Void analysis through Mercury CSD software confirmed a densely packed lattice with a calculated void volume of 1.1%. Integrated quantum theory of atoms in molecules (QTAIM) and non-covalent interactions index (NCI) analyses showed that C–H···I interactions between the cations and the ¹_∞[SbI₅]²⁻ network predominantly stabilize the supramolecular assembly followed by N–H···I hydrogen bonds. The calculated growth morphology (GM) model fits very well to the experimental morphology. UV–Vis diffuse reflectance spectroscopy allowed us to determine the optical band gap to 3.15 eV. Density functional theory (DFT) calculations employing the B3LYP, CAM-B3LYP, and PBE0 functionals were benchmarked against experimental data. CAM-B3LYP best reproduced Sb–I bond lengths, while PBE0 more accurately captured the HOMO–LUMO gap and the associated electronic descriptors. These results support the assignment of an inorganic-to-organic [Sb–I] → π* charge-transfer excitation, and clarify how structural dimensionality and cation identity shape the material’s optoelectronic properties. Full article

We report a computational investigation on the reachability of the molecular similarity index (MSI) approach for predicting the relative drug strength of methylcarbamate derivatives. Traditional MSI values have been obtained by calculating the overlap integral of total electron momentum densities between one molecule and another. Furthermore, we have proposed and tested orbital-specific MSI (OS-MSI) values, obtained by doing the same but with electron momentum densities of a selected molecular orbital (MO) such as the highest occupied MO (HOMO) and the lowest unoccupied MO (LUMO). In the calculations, a Boltzmann-weighted electron momentum density estimated by a theoretical probability distribution of rotamers was used, while the solvation effect was considered using the polarizable continuum model. It is shown that the traditional MSI values as well as the OS-MSI values for the HOMO do not have any correlation with experimental relative toxicity of the methylcarbamate derivatives. In contrast, it has been observed and found that the OS-MSI values for the LUMO exhibit a noticeable correlation with the experimental data. The reason behind this observation is discussed in relation to the drug reaction mechanism of the methylcarbamate derivatives. Full article

Contact electrification (CE), or triboelectrification, is an electron transfer phenomenon occurring at the interface between dissimilar materials due to differences in polarity, holding significant research value in tribology. The microscopic mechanisms of CE remain unclear due to the complex coupling of multiple physical processes. Recently, with the rise of triboelectric nanogenerator (TENG) technology, solid–liquid contact electrification has demonstrated vast application potential, sparking considerable interest in its underlying mechanisms. Emerging experimental evidence indicates that at water–polymer CE interfaces, the process involves not only traditional ion adsorption but also electron transfer. Halogen-containing functional groups in the solid material significantly enhance the CE effect. To elucidate the microscopic mechanism of water–polymer CE, this study employed first-principles density functional theory (DFT) calculations, simulating the interfacial electrification process using unit cell models of water contacting polymers. We systematically and quantitatively investigated the charge transfer characteristics at interfaces between water and three representative polymers with similar backbones but different halogen-functionalized (F, Cl) side chains: fluorinated ethylene propylene (FEP), polyvinyl chloride (PVC), and polytetrafluoroethylene (PTFE), focusing on evaluating halogen’s influence and mechanism on interfacial electron transfer. The results reveal that electron transfer is primarily governed by the energy levels of the polymer’s lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO). Halogen functional groups modulate the material’s electron-donating/accepting capabilities by altering these frontier orbital energy levels. Consequently, we propose that the critical strategy for polymer chemical modification resides in lowering the LUMO energy level of electron-accepting materials. This study provides a novel theoretical insight into the charge transfer mechanism at solid–liquid interfaces, offers guidance for designing high-performance TENG interfacial materials, and holds significant importance for both the fundamental theory and the development of advanced energy devices. Full article