Search Results (897)

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies. Full article

Van der Waals (vdW) heterostructures, typically composed of two-dimensional (2D) atomic layers, have attracted significant attention over the past few decades. Their performance is closely dependent on their composition and interlayer interactions. In this study, we constructed four types of 2D hexagonal BP monolayer (h-BP)/borophosphene vdW heterostructures with different stacking orders: (i) B-B stacking, (ii) P-P stacking, (iii) moire-I, and (iv) moire-II. Their structural stability and their electronic and optical properties were explored by using first-principles calculations. The results show that h-BP/borophosphene heterostructures can maintain their configurations with good structural stability and minimal lattice mismatch. All vdW heterostructures exhibit semiconducting characteristics, and their band gaps are highly dependent on interlayer stacking orders. Due to the regular atomic arrangement and enhanced interlayer dipole interactions, the B-B stacking bilayer opens a relatively large band gap of 0.157 eV, while the moire-II bilayer exhibits a very small band gap of 0.045 eV because of its irregular atom arrangements. By calculating the complex dielectric function, optical absorption spectra of B-B and P-P stacking bilayers were discussed. This study suggests that h-BP/borophosphene heterostructures have desirable optical properties, broadening the potential applications of the constituent monolayers. 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

Vanillin photoinduced deprotonation was evaluated and analyzed. Vibronic states and transitions were computationally investigated. Optimizations and vertical electron transitions in the gas phase and with the continuum solvation model were computed using the time-dependent density functional theory. Static absorption and emission (photostatic optical) spectra were statistically averaged over the excited instantaneous molecular conformers fluctuating on quantum–classical molecular dynamic trajectories. Photostatic optical spectra were generated using the hybrid quantum–classical molecular dynamics for explicit solvent models. Conical intersection searching and nonadiabatic molecular dynamics simulations defined potential energy surface propagations, intersections, dissipations, and dissociations. The procedure included mixed-reference spin–flip excitations for both procedures and trajectory surface hopping for photodynamics. Insignificant structural deformations vs. hydroxyl bond cleavage followed by deprotonation were demonstrated starting from different initial structural conditions, which included optimized, transition state, and several other important fluctuating configurations in various environments. Vanillin electronic structure changes were illustrated and analyzed at the key points on conical intersection and nonadiabatic molecular dynamics trajectories by investigating molecular orbital symmetry and electron density difference. The hydroxyl group decomposed on transition to a σ-molecular orbital localized on the elongated O–H bond. 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

Herein, electrospun nanofibers composed of polyaniline (PANI), polyethylene oxide (PEO), and Luffa cylindrica (LC) cellulose, reinforced with titanium dioxide (TiO₂) nanoparticles, were synthesized via electrospinning to investigate the effect of TiO₂ nanoparticles on PANI/PEO/LC nanocomposites and the effect of conductivity on nanofiber morphology. Cellulose extracted from luffa was added to the PANI/PEO copolymer solution, and two different ratios of TiO₂ were mixed into the PANI/PEO/LC biocomposite. The morphological, vibrational, and thermal characteristics of biocomposites were systematically investigated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). As anticipated, the presence of TiO₂ enhanced the electrical conductivity of biocomposites, while the addition of Luffa cellulose further improved the conductivity of the cellulose-based nanofibers. FTIR analysis confirmed chemical interactions between Luffa cellulose and PANI/PEO matrix, as evidenced by the broadening of the hydroxyl (OH) absorption band at 3500–3200 cm⁻¹. Additionally, the emergence of characteristic peaks within the 400–1000 cm⁻¹ range in the PANI/PEO/LC/TiO₂ spectra signified Ti–O–Ti and Ti–O–C vibrations, confirming the incorporation of TiO₂ into the biocomposite. SEM images of the biocomposites reveal that the thickness of nanofibers decreases by adding Luffa to PANI/PEO nanofibers because of the nanofibers branching. In addition, when blending TiO₂ nanoparticles with the PANI/PEO/LC biocomposite, this increment continued and obtained thinner and smother nanofibers. Furthermore, the incorporation of cellulose slightly improved the crystallinity of the nanofibers, while TiO₂ contributed to the enhanced crystallinity of the biocomposite according to the XRD and DCS results. Similarly, the TGA results supported the DSC results regarding the increasing thermal stability of the biocomposite nanofibers with TiO₂ nanoparticles. These findings demonstrate the potential of PANI/PEO/LC/TiO₂ nanofibers for advanced applications requiring conductive and structurally optimized biomaterials, e.g., for use in humidity or volatile organic compound (VOC) sensors, especially where flexibility and environmental sustainability are required. Full article

We present a simple method for customizing the optical characteristics of gold-core, silver-shell (Au@Ag) nanoparticles through controlled morphosynthesis via a seed-mediated chemical reduction approach. By systematically adjusting the concentration of cetyltrimethylammonium chloride (CTAC), we obtained precise control over both the thickness of the Ag shell and the particle shape, transitioning from spherical nanoparticles to distinctly defined nanocubes. Bright field and high-angle annular dark-field scanning transmission electron microscopy (BF-STEM and HAADF-STEM), and energy-dispersive X-ray spectroscopy (EDS) were employed to validate the structural and compositional changes. To link morphology with optical behavior, we utilized the Mie and Maxwell–Garnett theoretical models to simulate the dielectric response of the core–shell nanostructures, showing trends that align with experimental UV-visible absorption spectra. This research presents an easy and adjustable method for modifying the plasmonic properties of Ag@Au nanoparticles by varying their shape and shell, offering opportunities for advanced applications in sensing, photonics, and nanophotonics. Full article

We studied the adsorption thermodynamics and mechanism behind the binding of nitric oxide (NO) in the interior surfaces and structural fragments of the high metal center density microporous Metal-Organic Framework (MOF) CPO-27-Cu, by gas sorption, at a series of temperatures. For the purpose of comparison, we also measured the corresponding CO₂ adsorption isotherms, and as a result, the isosteric heats of adsorption for the two studied adsorptives were derived, being in the range of 12–15 kJ/mol for NO at loadings up to 0.5 NO molecules per formula unit (f.u.) of the bare compound (C₄O₃HCu), and 23–25 kJ/mol CO₂ in the range 0–1 CO₂ per f.u. Microscopically, the mode of NO binding near the square pyramid Cu(II) centers was directly accessed with the use of in situ NO gas adsorption X-ray Absorption Spectroscopy (XAS). Additionally, during the vacuum/temperature activation of the material and consequent NO adsorption, the electronic state of the Cu-species was monitored by observing the corresponding X-ray Near Edge Spectra (XANES). Contrary to the previously anticipated chemisorption mechanism for NO binding at Cu(II) species, we found that at slightly elevated temperatures, under ambient, but also cryogenic conditions, only relatively weak physisorption takes place, with no evidence for a particular adsorption preference to the coordinatively unsaturated Cu-centers of the material. Full article

Zinc oxide (ZnO) is a wide bandgap semiconductor of great scientific and technological interest due to its high exciton binding energy and outstanding structural and optical properties, making it an ideal material for applications in optoelectronics, sensors, and photocatalysis. This study presents the rapid synthesis of highly crystalline ZnO nanostructures using two alternative routes: (1) direct thermal decomposition of zinc acetate and (2) a physical-green route assisted by Mangifera indica extract. Both routes were subjected to identical calcination thermal conditions (400 °C for 2 h), allowing for an objective comparison of their effects on structural, vibrational, morphological, and optical characteristics. X-ray diffraction analyses confirmed the formation of a pure hexagonal wurtzite phase in both samples, highlighting a higher crystallinity index (91.6%) and a larger crystallite size (35 nm) in the sample synthesized using the physical-green route. Raman and FTIR spectra supported these findings, revealing greater structural order. Electron microscopy showed significant morphological differences, and UV-Vis analysis showed a red shift in the absorption peak, associated with a decrease in the optical bandgap (from 3.34 eV to 2.97 eV). These results demonstrate that the physical-green route promotes significant improvements in the structural and functional properties of ZnO, without requiring changes in processing temperature or the use of additional chemicals. Full article

LiTaO₃ crystals doped with Cr³⁺ and Nd³⁺ ions are promising for developing active nonlinear laser media. In this work, the defect structure of LiTaO₃ crystals, including those doped with Cr³⁺ and Nd³⁺, is examined. X-ray patterns of all six investigated LiTaO₃:Cr:Nd crystals are identical and correspond to a highly perfect structure. Using optical microscopy, the presence of defects of various shapes, microinhomogeneities, and lacunae was revealed. The optical absorption and Raman scattering spectra of a series of nonlinear, optical, double-doped LiTaO₃:Cr³⁺:Nd³⁺ (0.06 ≤ [Cr³⁺] ≤ 0.2; 0.2 ≤ [Nd³⁺] ≤ 0.45 wt%) crystals showed that at concentrations of doping Cr³⁺ ions less than 0.09 wt% and Nd³⁺ ions less than 0.25 wt%, the crystal structure is characterized by a low level of defects, and the optical transmission spectra characterized by narrow lines corresponding to electron transitions in Nd³⁺ ions. In this case, for the radiative transition in the cation sublattice, the existence of three nonequivalent neodymium centers is observed, and for the radiative transition, two nonequivalent centers are observed. IR absorption spectroscopy in the OH⁻-stretching vibration range revealed two main spectral regions: 3463–3465 cm⁻¹, associated with stoichiometry changes, and 3486–3490 cm⁻¹, linked to complex defects such as (V^-_Li)-OH and (Ta⁴⁺_Li)-OH. A distinct low-intensity line at ~3504 cm⁻¹ was observed only in doped crystals, attributed to (Nd²⁺_Li)-OH defects that significantly distort the oxygen-octahedral clusters due to the larger ionic radius of Nd³⁺ compared to Ta⁵⁺. In contrast, Cr-related defects cause only minor distortions. The Klauer method indicated that the highest concentration of OH⁻-groups occurs in the LiTaO₃:Cr³⁺ (0.09 wt%):Nd³⁺ (0.25 wt%) crystal, where multiple complex defects are present. Full article

Developing functional perovskites is important for advancing solar energy conversion technologies. This study investigates the effects of dopants on the structural, optical, electronic, and solar conversion performances of Ba₂M_0.4Bi_1.6O₆ double perovskites. X-ray diffraction (XRD) and Rietveld refinement confirm crystallization in the I2/m space group (M = La, Ce, Pr, Pb), and Fm$\overline{3}$m and I2/m space groups (M = Y). The B1-O-B2 structure modulates to highly ordered (M = La, Y), partially ordered (M = Pr), or disordered (M = Ce, Pb). UV-vis spectra show strong light absorption, with Tauc plots estimating ~1.57 eV (M = La) and ~1.73 eV (M = Pr) optical band gaps. Under AM 1.5G illumination, the M = La photoelectrode generates photocurrents of 1 mA cm⁻² at 0.3 V_RHE, surpassing M = Ce and Pb (1 μm, 4-times spin-coating). Increasing its thickness to 7.7 μm (4-times dip-coating) further enhances the photocurrents to 2.3 mA cm⁻² at 0.2 V_RHE, outperforming all counterparts due to improved stability. Fine-tuning crystal and electronic structures via strategic B-site doping provides a new route for engineering Ba₂Bi₂O₆-based double perovskites for broad solar energy conversion applications. Full article

Eugenol-based azo dyes illustrate how bio-sourced compounds like eugenol can be transformed through synthetic processes into functional and colorful compounds. The main purpose of the present work was to develop new responsive colorimetric sensors for metal cations based on eugenol-derived azo compounds. The incorporation of the azo group into the eugenol framework allows for strong electronic interactions with metal cations, leading to distinct color changes observable to the naked eye. These azo-eugenol dyes exhibit shifts in their UV-Vis absorption spectra upon complexation with metal cations such as copper (Cu²⁺) and lead (Pb²⁺), making them effective sensors for environmental and analytical applications. The eugenol-based azo dyes were subjected to photophysical studies to understand selectivity, response time, and stability in relation to metal cations, which will be a starting point for the monitoring of toxic metal contaminants in aqueous environments. Full article

In this paper, we experimentally investigated the excitation of spoof surface plasmon polaritons (SSPPs) supported by a 1D subwavelength grating with a rectangular profile in the terahertz (THz) frequency range. Using the attenuated total reflection technique and the THz radiation of the Novosibirsk free electron laser, we carried out detailed studies of both angular and gap spectra at several wavelengths. A shallow grating supporting a fundamental mode was fabricated by means of multibeam X-ray lithography and used as a test sample. The results indicated that we achieved 1-THz tunability of resonance in the frequency range from 1.51 to 2.54 THz on a single grating, which cannot be obtained with active tunable metamaterials. The Q factors of the resonances in the angular spectra were within the range of 19.4–37.6, while the resonances of the gap spectra had a Q factor lying within the 1.17–2.03 range. The gap adjustment capability of the setup shown in the work has great potential in modulation of the absorption efficiency, whereas the angular tuning and recording data from each point of the grating will enable real-time monitoring of changes in the surrounding medium. All of this is highly important for enhanced terahertz real-time absorption spectroscopy and imaging. Full article

Background: Nedaplatin is a platinum-based anticancer drug that combines the benefits of Cisplatin and Carboplatin, retaining Cisplatin’s anticancer activity while reducing toxicity similar to Carboplatin. After hydrolysis, Nedaplatin targets purines in DNA and forms cross-links that induce cell death via apoptosis. However, it is important to consider how the presence of other chemical compounds with structural similarities to Adenine or Guanine, such as aromatic, purine, or pyrimidine compounds containing a nitrogen atom with a free electron pair, might influence its activity at the cellular level. Alkaloids with structures similar to DNA nucleobases are common, and their influence on Nedaplatin’s activity requires investigation. Methods: In this study, the interactions between Nedaplatin (including its hydrolyzed forms, such as [Pt(NH₃)₂(H₂O)₂]²⁺ and [Pt(NH₃)₂(H₂O)(OH)]⁺) and nucleobases (Adenine and Guanine) and purine alkaloids (Caffeine, Theobromine and Theophylline) were thoroughly investigated using theoretical (density functional theory, DFT) and experimental (UV-Vis spectroscopy) methods. DFT calculations were performed at the B3LYP/6-31G(d,p)/LANL2DZ and MN15/def2-TZVP levels, with structure optimization and harmonic analysis in the gas phase and aqueous solution (modeled using IEF-PCM). UV-Vis spectroscopy was used to verify theoretical findings by examining changes in absorption spectra. Results: Both theoretical and experimental studies confirmed that Nedaplatin forms complexes with both nucleobases and purine alkaloids. Nedaplatin was found to exhibit a higher affinity for nucleobases than for purine alkaloids. Furthermore, this affinity was dependent on the computational method used and on the hydrolyzed form of Nedaplatin. Theoretical calculations showed the formation of stable complexes through bonding with nitrogen atoms in the ligand molecules, which was confirmed by changes in UV-Vis spectra, indicating adduct formation. Conclusions: The results indicate that Nedaplatin readily forms complexes with both nucleobases and purine alkaloids, showing a stronger affinity for nucleobases. This finding highlights the potential importance of Nedaplatin’s interactions with other compounds present in the body, which may influence its effectiveness and mechanism of action in cancer therapy. These studies provide new insights into the molecular mechanisms of Nedaplatin’s action and may contribute to a better understanding of its pharmacological interactions. However, research requires confirmation not only in in vivo studies but also in clinical trials. Full article

Lithium (Li)-rich continental brines found in the Lithium Triangle region in South America are a natural resource of paramount importance. In the present research, the analytical performance of laser-induced breakdown spectroscopy (LIBS) technology was assessed for the quantitative analysis of Li in natural brines aimed at enhancing the efficient exploration of salt flats (called salars). Brine samples were collected from different salars located in the Puna plateau (Northwest Argentina) and analyzed by LIBS in the form of solid pressed pellets. Broadband emission spectra (180–900 nm) were recorded and spectrally analyzed by specially designed computational algorithms. The laser-induced plasmas were characterized by calculating the electron density and the temperature. The Li elemental concentrations in the brines were determined through univariate calibration with the Li I emission line at 670.77 nm by using a suitable set of standards with Li concentrations up to 1300 $\mathsf{\mu }$g/g. The calculated limit of detection was LoD = 0.2 ± 0.1 $\mathsf{\mu }$g/g. The Li content in the brines determined with LIBS showed a good agreement (normalized standard deviation: σ_N = 25%) with the concentrations measured with atomic absorption spectroscopy. The results demonstrated the feasibility of the LIBS technique for the quantitative analysis of Li in natural brines, thus contributing to advancing the exploration of Li-rich resources. Full article