Search Results (428)

Polylactic acid (PLA) is a biopolymer made from starch that is both sustainable and low-cost. But its chemical inertness limits its application in the removal of heavy metals from aqueous environments. This study addresses the limitations by functionalizing PLA with N-hydroxysuccinimide (NHS) and N-sulfosuccinimide (S-NHS). It is hypothesized that introducing the sulfonate group using S-NHS increases the electron-donating capabilities of PLA, optimizing its adsorption capabilities for heavy metals. Density Functional Theory (DFT) calculations of energy, optimization, frequencies and NBOs in Gaussian 16 (M05-2X/LanL2DZ) and Multiwfn 4.0 were used for the electronic properties of the pristine and functionalized polymer and their interactions with a simplified system of hexahydrated ions of nickel (Ni²⁺), arsenic (As³⁺), and lead (Pb²⁺) cations were analyzed. The results indicated that PLA-S-NHS has an energy gap (Egap) of 3.31 eV, being lower than that of PLA (5.51 eV) and PLA-NHS (4.42 eV), signaling an increase in its adsorption capabilities. Its total dipole moment (TDM) reached 196.16 Debye. The metal–polymer complexes exhibit high TDMs, such as 1104.78 Debye with Pb in PLA-S-NHS, confirming greater interactions. The NBO analysis shows that S-NHS functionalization strengthens the donor–acceptor interactions with the sulfonate group oxygens acting as a primary donor, enhancing the adsorption of heavy metals; this is shown by the adsorption energies (Eads), confirming that functionalization with S-NHS enhances the interaction with metal ions, with negative Eads values observed for all complexes, especially for Pb²⁺, indicating thermodynamically favorable adsorption. The functionalization with S-NHS optimizes the electronic properties of PLA for heavy-metal adsorption, thereby validating the hypothesis and providing a molecular basis for the rational design of advanced bioadsorbents. These results indicate the potential application of these functionalized PLA polymers, especially as membranes, for the selective extraction of heavy metals from aqueous solutions. Full article

This work provides an integrated experimental and computational evaluation of the cationic surfactant Quaternium-22 (Q-22) as a potentially eco-compatible corrosion inhibitor for carbon steel (CS) in 1 M hydrochloric acid. Gravimetric analysis and electrochemical techniques, including electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP), were employed over a temperature range of 20–50 °C. Q-22 exhibited mixed-type inhibition behavior, with efficiency rising to 97% at an optimal concentration of 277 μmol L⁻¹. Performance was concentration-dependent but diminished with increasing temperature, indicating partial inhibitor desorption at elevated temperatures. Thermodynamic evaluation confirmed a spontaneous adsorption process consistent with the Langmuir isotherm, involving a combined physisorption and chemisorption mechanism. Surface characterization via scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle (CA) measurement, and X-ray photoelectron spectroscopy (XPS) confirmed the formation of a coherent, hydrophobic inhibitor layer that substantially reduced surface roughness and corrosion damage. Theoretical investigations using density functional theory (DFT), natural bond orbital (NBO) analysis, and molecular dynamics (MD) simulations revealed strong adsorption energies and favorable electronic properties consistent with the inhibitor’s high experimental efficacy. Overall, the results demonstrate that Q-22 is a highly effective, eco-compatible corrosion inhibitor for CS in acidic environments, operating through a stable adsorptive film-forming mechanism. Full article

We report a straightforward and versatile synthetic route to pyridinium-fused 1,3-selenazoles via the electrophilic cyclization of 2-pyridylselenyl chloride with alkynes. The reaction proceeds efficiently under mild conditions with representative terminal and internal alkynes. While the cyclization exhibits high regioselectivity favoring the 3-substituted isomer for most substrates, reactions with 2-pyridyl- and 2-quinolylacetylenes yield regioisomeric mixtures. DFT calculations rationalize this divergence, revealing a competition between kinetic and thermodynamic control; the 3-isomer is kinetically favored, while the 2-isomer is thermodynamically stabilized by an ancillary chalcogen bond between the selenium atom and the pyridine nitrogen of the alkyne substituent. Molecular structures were confirmed by single-crystal X-ray diffraction, and the non-covalent interactions governing supramolecular assembly in the solid state were rigorously analyzed using MEP surfaces, the QTAIM, and NBO analysis. Antifungal evaluation identified several compounds with notable activity against phytopathogenic fungi, highlighting the potential of this novel heterocyclic scaffold in agrochemical applications. Full article

The utilization and chemical transformation of carbon dioxide remains a pressing problem in modern chemistry. Numerous experimental and theoretical studies have focused on the interaction of CO₂ with amines. In this work, quantum chemical density functional theory (DFT) calculations of equilibrium geometries, energies, electronic and vibrational characteristics of CO₂-sensitive mono-, di-, tris-hydroxyamidines and their associates were carried out by the B3LYP/6-31G(d, p) method. The harmonic vibrational frequencies were scaled and compared with the experimental FTIR spectra for supporting wavenumber assignments. Natural bond orbital (NBO) analysis of the atomic charges and charge delocalization was employed to investigate the nature of hydrogen bonding in hydroxyamidine associates. We also used the intrinsically polarizable continuum model (IEFPCM), and the DFT-D3 method was applied to account for dispersion effects during associate formation. Using the 6-311+G(2d, p) basis set for tris-hydroxyamidine, and its adducts, a comparative analysis of the experimental and calculated ¹H NMR spectra was performed. Here, we considered non-trivial sites of carbon dioxide absorption and hydroxyamidine protonation, which, to our knowledge, have hardly been considered by other authors. Present DFT results agree rather well with the experimental data and support new insight into the formation of the PIL structure. Full article

Phenothiazine is a heteroaromatic molecule capable of various noncovalent interactions, including halogen bonding and π-stacked association. Despite its broad use in functional materials and pharmaceutical ingredients, a systematic comparison of these interaction modes has been lacking. Here, we report a combined experimental and computational study of intermolecular interactions of phenothiazine with a prototypical halogen-bond (HaB) donor (tetrabromomethane), planar π-electron acceptors (tetracyanopyrazine and tetrafluoro-p-benzoquinone), and multifunctional species capable of both interaction types (iodo- and bromo-3,5-dinitrobenzenes). X-ray structural analysis revealed that CBr₄ forms exclusively C–Br···π halogen bonds with the aromatic rings of phenothiazine, whereas all π-acceptors yield alternating donor–acceptor stacks characterized by multiple short contacts indicative of multicenter interactions. Notably, co-crystals of iodo- and bromodinitrobenzenes with phenothiazine display only π-stacked architectures. Density-functional calculations showed that isolated HaB complexes involving N, S, or π sites of phenothiazine possess comparable binding energies (≈−3 kcal mol⁻¹), whereas π-stacked complexes are substantially stronger (≈−9–12 kcal mol⁻¹). QTAIM, NCI, NBO, and energy-decomposition analyses indicated that while amounts of charge transfer in halogen-bonded and π-stacked complexes are comparable, the enhanced stability of the latter originates primarily from a large dispersion contribution. These results rationalize the solid-state preference for π-stacking over halogen bonding in systems where both motifs are accessible and clarify the hierarchy and physical origin of noncovalent interactions involving phenothiazine, providing guidance for the design of supramolecular assemblies and functional materials based on this versatile electron donor. Full article

The accelerated discovery of high-performance lead-free piezoelectric ceramics is hindered by the vast compositional space and the limited interpretability of conventional machine learning (ML) models. Here, we propose a physics-informed and interpretable ML framework with integrated uncertainty quantification to predict and understand the piezoelectric coefficient d₃₃ of (K_0.5Na_0.5) NbO₃ (KNN)-based ceramics. A curated dataset of 1113 experimental samples is used to construct 65 descriptors by decoupling A-site and B-site ionic contributions. Pearson correlation analysis reduces these to an optimized 11-dimensional feature set for training deep neural networks, Wide & Deep networks, and residual networks. A Bayesian neural network further provides predictive uncertainty, which quantitatively reflects the confidence of machine-learning-based d₃₃ predictions rather than experimental measurement uncertainty. To achieve physical interpretability, SHapley Additive exPlanations (SHAP) are combined with the Sure Independence Screening and Sparsifying Operator (SISSO) to derive a compact analytical descriptor revealing that sintering temperature, B-site electronic anisotropy, and A-site ionic displacement jointly govern d₃₃. The proposed framework achieves high accuracy (R² ≈ 0.81) while offering transparent design rules for next-generation lead-free piezoelectrics. Full article

Oxygen nanobubble (NBO₂) water is reportedly a promising therapeutic and radiosensitizing agent against solid cancers. However, the significance of nanobubble size in inflammation-associated colorectal carcinogenesis in vivo remains elusive. We investigated whether small NBO₂ water exerts stronger preventive effects against colitis and colorectal carcinogenesis in an azoxymethane/dextran sulfate sodium–induced mouse model of colitis-associated cancer. Differences in particle size between the small and large NBO₂ water samples were confirmed by atomic force microscopy. The mice received drinking water containing either small or large sized NBO₂ throughout the experiment. Small NBO₂ water significantly reduced disease activity index scores, histopathological colitis scores, colonic shortening, CD68-positive inflammatory macrophage density, and tumor numbers. However, body weight, water intake, food intake, and spleen weight were unaffected. Immunohistochemistry revealed that small NBO₂ water reduced the percentage of Ki-67-positive tumor cells and the proportions of hypoxia-inducible factor-1α–positive epithelial and stromal cells, whereas no significant differences were observed in CD8- or forkhead box P3-positive cells. We conclude that nanometer-sized oxygen bubbles prevent inflammation-associated colorectal carcinogenesis, and that particle size is a critical determinant of biological effects. Small amounts of NBO₂ water may help control colitis and tumor development by alleviating hypoxia in the tumor microenvironment. Full article

Investigating aluminum nitride (AlN) clusters is essential for understanding the properties of bulk AlN materials. The incorporation of hydrogen into AlN clusters represents an effective strategy for structural modification and for tuning their physicochemical properties. In this work, we conducted density functional theory (DFT) calculations on the dynamically stable global-minimum (GM) structure of Al₆N₆H₈. Compared to the precursor Al₆N₆ cluster, the incorporation of eight hydrogen atoms achieves coordination saturation of all aluminum and nitrogen atoms, inducing a structural transformation from a hexagonal prism with D_3d symmetry to a cuboid structure with D_2h symmetry. The HOMO–LUMO gap of the Al₆N₆H₈ cluster is increased by 1.85 eV compared to that of Al₆N₆, indicating a remarkable enhancement in stability. Chemical bonding and natural bond orbital (NBO) charge analyses reveal that the Al–N, Al–H, and N–H bonds are predominantly covalent single bonds, with a degree of ionicity arising from electronegativity differences. The hydrogen atoms bonded to Al and N can be substituted with a series of other atoms or functional groups, thereby further tuning the structures and properties of the clusters. To facilitate future experimental characterization, the infrared spectrum of Al₆N₆H₈ was calculated, which shows an overall blue shift in the Al–N bond’s bending and stretching vibrations compared to those in the Al₆N₆ cluster. Full article

Precise control over nanostructure evolution is critical for optimizing the electrochemical performance of pseudocapacitive materials. In this work, Nb₂O₅ nanostructures were synthesized via a time-engineered hydrothermal route by systematically varying the reaction duration (6, 12, and 18 h) to elucidate its influence on structural development, charge storage kinetics, and supercapacitor performance. Structural and surface analyses confirm the formation of phase-pure monoclinic Nb₂O₅ with a stable Nb⁵⁺ oxidation state. Morphological investigations reveal that a 12 h reaction time produces hierarchically organized Nb₂O₅ architectures composed of nanograin-assembled spherical aggregates with interconnected porosity, providing optimized ion diffusion pathways and enhanced electroactive surface exposure. Electrochemical evaluation demonstrates that the NbO-12 electrode delivers superior pseudocapacitive behavior dominated by diffusion-controlled Nb⁵⁺/Nb⁴⁺ redox reactions, exhibiting high areal capacitance (5.504 F cm⁻² at 8 mA cm⁻²), fast ion diffusion kinetics, low internal resistance, and excellent cycling stability with 85.73% capacitance retention over 12,000 cycles. Furthermore, an asymmetric pouch-type supercapacitor assembled using NbO-12 as the positive electrode and activated carbon as the negative electrode operates stably over a wide voltage window of 1.5 V, delivering an energy density of 0.101 mWh cm⁻² with outstanding durability. This study establishes hydrothermal reaction-time engineering as an effective strategy for tailoring Nb₂O₅ nanostructures and provides valuable insights for the rational design of high-performance pseudocapacitive electrodes for advanced energy storage systems. Full article

Lead-free transparent ferroelectric ceramics with integrated opto-electro-mechanical functionalities are pivotal for next-generation multifunctional devices. In this study, K_0.48Na_0.52NbO₃-xLa₂O₃ (KNN-xLa, x = 0.005 − 0.04) ceramics were fabricated via a conventional solid-state route to investigate the La³⁺-induced multiscale structural evolution and its modulation of optical and electrical properties. La³⁺ substitution drives a critical structural transition from an anisotropic orthorhombic phase (Amm2) to a high-symmetry pseudocubic-like tetragonal phase (P4mm) for x ≥ 0.025, characterized by minimal lattice distortion (c/a = 1.0052). This enhanced structural isotropy, coupled with submicron grain refinement (<1 μm) driven by ${\mathrm{V}}_{\mathrm{A}}^{\prime }$-mediated solute drag, effectively suppresses light scattering. Consequently, a high-transparency plateau (T₇₈₀ ≈ 53–58%, T₁₇₀₀ ≈ 70–72%) is achieved for 0.025 ≤ x ≤ 0.035. Simultaneously, the system undergoes a crossover from normal ferroelectric (FE) to relaxor (RF) state, governed by an FE–RF boundary at x = 0.015. While x = 0.005 exhibits robust piezoelectricity (d₃₃ ≈ 92 pC/N), the x = 0.015 composition facilitates a transitional polar state with large strain (0.179%) and high polarization (P_m ≈ 33.3 μC/cm², P_r ≈ 15.8 μC/cm²). Piezoresponse force microscopy (PFM) confirms the domain evolution from lamellar macro-domains to speckle-like polar nanoregions (PNRs), elucidating the intrinsic trade-off between optical transparency and piezoelectricity. This work underscores La³⁺ as a potent structural modifier for tailoring phase boundaries and defect chemistry, providing a cost-effective framework for developing high-performance transparent electromechanical materials. Full article

This computational study investigates the thermal decomposition of 1,2,4-triazol-3(2H)-ones and their thione analogues using Density Functional Theory (DFT). The reaction proceeds via a concerted, six-membered cyclic transition state, primarily driven by the breaking of the N–N bond. A key finding is that the accuracy of the calculated activation energies (Ea) strongly depends on the choice of DFT functional. For sulfur-containing systems (thiones), the hybrid functional APFD (with 25% Hartree–Fock exchange) provides the most reliable results, effectively describing their higher polarizability. In contrast, for oxygen-containing systems (triazolones), the dispersion-corrected functional B97D-GD3BJ (with 0% Hartree–Fock exchange) delivers superior accuracy by better modeling electrostatic and dispersion interactions. The -CH₂CH₂CN group at the N-2 position acts not only as a protecting group but also stabilizes the transition state through non-covalent interactions. Electron-withdrawing substituents slightly increase the E_a, while electron-donating groups decrease it. Sulfur analogues consistently show significantly lower activation energies (by ~40 kJ/mol) than their oxygen counterparts, explaining their experimentally observed faster decomposition. This work establishes a dual-methodology computational framework for accurately predicting the kinetics of these reactions, providing valuable insights for the regioselective synthesis of biologically relevant triazole derivatives via controlled pyrolysis. Full article

The polar oxide Lithium Niobate Tantalate is probed using time-resolved luminescence spectroscopy with the goal of revealing an initial structural insight into the solid solution by analyzing the spectral properties and dynamics of radiatively decaying self-localization phenomena. A blue-green luminescence band can be induced by ultraviolet nanosecond laser pulses with a temperature-dependent intensity and spectral width, pointing to the radiative decay of optically generated self-trapped excitons as its origin, i.e., electron–hole pairs with strong coupling to either the NbO₆- or TaO₆-octahedra. The luminescence decay takes place in the microsecond time range and deviates significantly from a single exponential behavior, so the determined lifetime constants of up to ≈70 μs and stretching factors (1/3–1/5) are validated in more detail using alternative evaluation methods. We discuss our findings, considering the interplay of radiative and non-radiative decay channels, the transition from self-trapped to free excitons, and the presence of a structural disorder of the oxygen octahedra in the solid solutions. Overall, our results suggest self-trapped excitons as local probes for an initial structural elucidation and provide essential information about further experimental and theoretical studies on the atomic structure of Lithium Niobate Tantalate, but also for improving the crystal quality in the framework of applications in photonics and quantum optics. Full article

Photoactivatable nitric oxide donors (photoNORMs) are promising agents for controlled NO release and real-time optical tracking in biomedical theranostics. Here, we report a comprehensive density functional theory (DFT) and time-dependent DFT (TDDFT) study on a series of hybrid ruthenium–gold nanocluster systems of the general formula [(L)Ru(NO)(SH)@Au₂₀], where L = salen, bpb, porphyrin, or phthalocyanine. Structural and bonding analyses reveal that the Ru–NO bond maintains a formal {RuNO}⁶ configuration with pronounced Ru → π*(NO) backbonding, leading to partial reduction of the NO ligand and an elongated N–O bond. Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA), and Extended Transition State–Natural Orbitals for Chemical Valence (ETS–NOCV) analyses confirm that Ru–NO bonding is dominated by charge-transfer and polarization components, while Ru–S and Au–S linkages exhibit a delocalized, donor–acceptor character coupling the molecular chromophore with the metallic cluster. TDDFT results reproduce visible–near-infrared (NIR) absorption features arising from mixed metal-to-ligand and cluster-mediated charge-transfer transitions. The calculated zero–zero transition and reorganization energies predict NIR-II emission (1.8–3.8 μm), a region of high biomedical transparency, making these systems ideal candidates for luminescence-based NO sensing and therapy. This study establishes fundamental design principles for next-generation Ru-based photoNORMs integrated with plasmonic gold nanoclusters, highlighting their potential as multifunctional, optically trackable theranostic platforms. Full article

Acetaminophen (APAP) is a widely used pharmaceutical increasingly detected as a contaminant in aquatic environments due to its persistent nature and incomplete removal by conventional wastewater treatment. This study investigates the adsorption performance and mechanisms of commercial activated carbon (M) and its hydrothermally modified form (MH) for APAP removal. Characterization via elemental analysis, X-ray photoelectron spectroscopy (XPS), and N₂ adsorption isotherms revealed that hydrothermal treatment reduced oxygen content and enhanced micro- and mesopore volumes, resulting in a more homogeneous and carbon-rich surface. Batch adsorption experiments conducted under varying pH (5–7) and temperature (30–40 °C) conditions showed that MH achieved up to 94.3% APAP removal, outperforming the untreated carbon by more than 15%. Kinetic modeling indicated that adsorption followed a pseudo-second-order mechanism (R² > 0.99), and isotherm data fitted best to the Langmuir model for MH and the Freundlich model for M, reflecting their differing surface properties. Adsorption was enhanced at lower pH and higher temperatures, consistent with an endothermic and pH-dependent mechanism. Complementary density functional theory (DFT) simulations confirmed that π–π stacking is the dominant interaction between APAP and the carbon surface. The most favorable configuration involved coplanar stacking with non-oxidized graphene (ΔG = −33 kJ/mol), while oxidized graphene models exhibited weaker interactions. Natural Bond Orbital (NBO) analysis further supported the prevalence of π–π interactions over dipole interactions. These findings suggest that surface deoxygenation and improved pore architecture achieved via hydrothermal treatment significantly enhance APAP adsorption, offering a scalable strategy for pharmaceutical pollutant removal in water treatment applications. Full article

The Ti6Al4V alloy is considered the most beneficial of the titanium alloys for use in biomedical applications. However, it corrodes when exposed to various biocompatible fluids. This investigation aims to evaluate the corrosion inhibition performance of the Ti6Al4V in a saline solution (SS) using thiocolchicoside (TCC) drug as an environmentally acceptable corrosion inhibitor. The corrosion assessments were conducted using potentiodynamic polarization curves (PPCs), open-circuit potential (OCP), and electrochemical impedance spectroscopy (EIS) methodologies, supplemented by scanning electron microscopy (SEM), energy-dispersive X-ray (EDS) analysis, atomic force microscopy (AFM), and contact angle (CA) measurements. The outcomes indicated that the inhibitory efficacy improved with higher TCC concentrations (achieving 92.40% at 200 mg/L of TCC) and diminished with an increase in solution temperature. TCC’s physical adsorption onto the surface of the Ti6A14V, which adheres to the Langmuir adsorption isotherm, explains its mitigating power. The TCC acts as a mixed-type inhibitor. The adsorption and inhibitory impact of TCC were examined at various temperatures using PPC and EIS. When TCC is present, the corrosion’s apparent activation energy is higher (35.79 kJ mol⁻¹) than when it is absent (14.46 kJ mol⁻¹). In addition, the correlation between the structural properties of thiocolchicoside (TCC) and its corrosion inhibition performance was systematically analyzed. Density Functional Theory (DFT) calculations were utilized to characterize the adsorption mechanism, supported by Natural Bond Orbital (NBO) analysis and Molecular Dynamics (MD) simulations. The combined computational and electrochemical findings confirm that TCC provides effective and enhanced corrosion protection for the Ti6Al4V alloy in a saline environment. These characteristics provide compelling evidence for the suitability of these pharmaceutical compounds as promising corrosion inhibitors. Full article