Search Results (335)

Solid solutions of the metallocenes ferrocene (Cp₂Fe), nickelocene (Cp₂Ni), and cobaltocene (Cp₂Co) have been prepared by manually grinding the components together, or by co-crystallizing them from solution. In the solid solutions Cp₂Fe/Cp₂Ni and Cp₂Co/Cp₂Ni, the cyclopentadienyl (Cp) protons relax via dipolar electron–proton interactions, which represent the dominant relaxation mechanism. The ¹H T₁ relaxation times of the molecules Cp₂Ni and Cp₂Co, dissolved in CDCl₃, and in the solid solutions, show that the relaxation takes place intramolecularly. The relaxation of the protons is propagated exclusively via the unpaired electrons of the metal centers to which their Cp rings are coordinated, due to the large intermolecular distances that are greater than 3.91 Å. In contrast, the intramolecular distances between the electrons of the metal atoms and the protons of their coordinated Cp rings are merely 2.70 Å. Using these intramolecular distances and the ¹H T₁ relaxation times, the electron relaxation times T_1e have been determined as 17 × 10⁻¹³ s in CDCl₃ solutions and 45 × 10⁻¹³ s in the solid state for Cp₂Ni. The corresponding T_1e times for Cp₂Co are calculated as ca. 5 × 10⁻¹³ s and 20 × 10⁻¹³ s. Grinding Cp₂Fe and Cp₂Ni together leads to two different ¹H T₁ relaxation times for the protons of Cp₂Fe. The longer T₁ relaxation time indicates domains that consist mostly of Cp₂Fe molecules. The short T₁ times show a close contact of Cp₂Fe and Cp₂Ni molecules. An analysis of the short ¹H T₁ times reveals the presence of at least two to three short distances of 3.91 Å between Cp₂Fe and Cp₂Ni molecules. These results support the hypothesis that dry grinding of the metallocenes Cp₂Fe and Cp₂Ni in ratios that were changed in 10% increments from 90%/10% to 30%/70% leads to domains that mostly consist of Cp₂Fe molecules, and additionally to domains that contain a mixture of the components on the molecular level. Full article

Single crystals of the layered EuRECuTe₃ series with RE = Nd, Sm, Tb and Dy are obtained for the first time, completing the series of studies on quaternary tellurides synthesized using the halide flux method. These compounds crystallize in the orthorhombic space group Pnma (no. 62) with unit cell parameters ranging from a = 11.5634(7) Å, b = 4.3792(3) Å and c = 14.3781(9) Å for EuNdCuTe₃ to a = 11.2695(7) Å, b = 4.3178(3) Å and c = 14.3304(9) Å for EuDyCuTe₃. The influence of prismatic polyhedra [EuTe₆₊₁]⁷⁻ structural units on the stabilization of 3d framework composed by 2d layered fragments [RECuTe₃]²⁻, which have a key role in the interlayer interaction, is established. A comparative analysis of structural and magnetic properties dependence on the rare-earth element radius r_i(RE³⁺) in the EuRECuTe₃ series (RE = Sc, Y, Nd–Lu) is carried out. The structural contraction, including decrease in degree of tetrahedral polyhedra distortion, bond lengths shortening and unit cell volume shrinking with increasing r_i(RE³⁺), is established. It is shown that the structural alternation leads to transition from ferromagnetic to ferrimagnetic ordering. It was established that changes in the cationic sublattice have a more significant impact on structural transitions in the series of quaternary tellurides than changes in the anionic sublattice. The electronic structure and elastic and dynamic properties were estimated using ab initio calculations. The exfoliation energy for each compound is obtained by estimation of monolayer ground state energy as a result of structure relaxation. The symmetry and structural properties of monolayer EuRECuTe₃ (RE = Nd, Sm, Tb, Dy) compound are established and the orthorhombic symmetry is obtained with layer group pm2_1b. Full article

Magnetic resonance techniques are powerful, nondestructive, non-invasive tools with broad applications in radiation dosimetry. Electron paramagnetic resonance (EPR) enables direct quantification of dose-dependent radiation-induced paramagnetic defects, while nuclear magnetic resonance (NMR) reflects the influence of such defects through changes in line width and nuclear spin relaxation. To date, these methods have typically been applied independently. Their combined use to probe radiation damage in the same material offers new opportunities for comprehensive characterization and preferred dosimetry techniques. In this work, we apply both EPR and NMR to investigate radiation damage in lithium carbonate (Li₂CO₃). A detailed EPR analysis of γ-irradiated samples shows that the concentration of paramagnetic defects increases with dose, following two distinct linear regimes: 10–100 Gy and 100–1000 Gy. A gradual decay of the EPR signal was observed over 40 days, even under cold storage. In contrast, ⁷Li NMR spectra and spin–lattice relaxation times in Li₂CO₃ exhibit negligible sensitivity to radiation doses up to 1000 Gy, while ¹H NMR results remain inconclusive. Possible mechanisms underlying these contrasting behaviors are discussed. Full article

Background and objectives: Mental health issues such as anxiety and stress are prevalent in educational settings, highlighting the need for individualized, scalable interventions. Mind–body approaches are promising for distress management, and this study explored which body-based strategies students found effective. Methods: A cross-sectional study assessed mental health and the use of body-based coping strategies among 152 primarily female students, age 21–52, in the Educational Program for Psychomotor Therapy, a group familiar with such strategies. An electronic survey assessed well-being (WHO-5), stress (PSS-10), anxiety (HADS-A), and use of 13 mind–body practices (e.g., breathing, grounding, muscle relaxation). Participants were grouped by mental health risk and a logistic regression explored associations with coping strategy use. Results: High-frequency use of more body-based strategies predicted lower odds of being in the high-risk group (p = 0.039), while sporadic use of more strategies predicted high mental health risk (p = 0.022). Breathing and grounding were the most frequently used and helpful practices, with minimal barriers. High-risk students cited capability concerns and time as barriers, while all participants mentioned forgetting to use the practices. Conclusions: High-risk students use a broader range of practices sporadically, whereas low-risk students adopt selected strategies more consistently. Proper integration of practices through education and training may be crucial for enhancing their efficacy. Full article

In this study, supramolecular inclusion complexes composed of komecosanol (Ko), a lipophilic compound derived from rice bran, and α-cyclodextrin (αCD) were prepared using a solvent-free three-dimensional (3D) ball milling method. Their physicochemical properties were examined using various techniques. Powder X-ray diffraction analysis of the ground mixture at a Ko/αCD ratio of 1/8 revealed the disappearance of diffraction peaks characteristic of Ko and the emergence of new peaks, indicating the formation of a distinct crystalline phase. Moreover, differential scanning calorimetry analysis showed the disappearance of the endothermic peaks corresponding to Ko, indicating molecular-level interactions with αCD. Near-infrared spectroscopy results suggested the formation of hydrogen bonds between the C–H groups of Ko and the O–H groups of αCD. Solid-state ¹³C CP/MAS NMR and T₁ relaxation time measurements indicated the formation of a pseudopolyrotaxane structure, while scanning electron microscopy images confirmed distinct morphological changes consistent with complex formation. These findings demonstrate that 3D ball milling facilitates the formation of Ko/αCD inclusion complexes with a supramolecular architecture, providing a novel approach to improve the formulation and bioavailability of poorly water-soluble lipophilic compounds. Full article

Electrons trapped above the surface of helium provide a means to study many-body physics free from the randomness that comes from defects in other condensed-matter systems. Localizing an electron in an electrostatic quantum dot makes its energy spectrum discrete, with controlled level spacing. The lowest two states can act as charge qubit states. In this paper, we study how the coupling to the quantum field of capillary waves on helium—known as ripplons—affects electron dynamics. As we show, the coupling can be strong. This bounds the parameter range where electron-based charge qubits can be implemented. The constraint is different from the conventional relaxation time constraint. The electron–ripplon system in a dot is similar to a color center formed by an electron defect coupled to phonons in a solid. In contrast to solids, the coupling in the electron on helium system can be varied from strong to weak. This enables a qualitatively new approach to studying color center physics. We analyze the spectroscopy of the pertinent synthetic color centers in a broad range of the coupling strength. Full article

In the present study, novel conjugated lignin/chitosan nanoparticles (LCNPs) were synthesized by a first-time simple green methodology using interfacial co-assembly between both biopolymers. The physicochemical (ζ-potential, size, concentration of surface acidic/basic groups), structural (surface functional groups), and morphological characteristics of the blank and quercetin-encapsulated (Q-LCNPs) nanoparticles were analyzed by the Boehm method, Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The experimentally determined encapsulation capacity was satisfactory—95.75%. The in vitro quercetin release efficiency in acidic solution that simulated the gastric microenvironment was 21.9%, followed by 68.5% and 99.8% cumulative release efficiency in simulated intestinal media at pH 7.4 and 6.8, respectively. The satisfactory applicability of the Weibull and sigmoidal mathematical models towards the experimental in vitro release data was indicative of the remarkable roles of diffusion and relaxation mechanisms. Full article

This study systematically investigates the effects of trap concentration on self-heating and terahertz (THz) responses in GaN HEMTs using Sentaurus TCAD. Traps, inherently unavoidable in semiconductors, can be strategically introduced to engineer specific energy levels that establish competitive dynamics between the electron momentum relaxation time and the carrier lifetime. A simulation-based exploration of this mechanism provides significant scientific value for enhancing device performance through self-heating mitigation and THz response optimization. An AlGaN/GaN heterojunction HEMT model was established, with trap concentrations ranging from 0 to $5\times {10}^{17} {\mathrm{c}\mathrm{m}}^{-3}$. The analysis reveals that traps significantly enhance channel current (achieving 3× gain at $1\times 10^{17} {\mathrm{c}\mathrm{m}}^{-3}$) via new energy levels that prolong carrier lifetime. However, elevated trap concentrations (>$1\times {10}^{16} {\mathrm{c}\mathrm{m}}^{-3}$) exacerbate self-heating-induced current collapse, reducing the min-to-max current ratio to 0.9158. In THz response characterization, devices exhibit a distinct DC component (${\mathrm{U}}_{\mathrm{d}\mathrm{c}}$) under non-resonant detection ($\mathsf{\omega }\mathsf{\tau }\ll 1$). At a trap concentration of $1\times {10}^{15} {\mathrm{c}\mathrm{m}}^{-3}$, ${\mathrm{U}}_{\mathrm{d}\mathrm{c}}$ peaks at $0.12 \mathrm{V}$ when ${\mathrm{V}}_{\mathrm{g}}\mathrm{D}\mathrm{C}=-7.8 \mathrm{V}$. Compared to trap-free devices, a maximum response attenuation of 64.89% occurs at ${\mathrm{V}}_{\mathrm{g}}\mathrm{D}\mathrm{C}=-4.9 \mathrm{V}$. Furthermore, ${\mathrm{U}}_{\mathrm{d}\mathrm{c}}$ demonstrates non-monotonic behavior with concentration, showing local maxima at $4\times {10}^{15} {\mathrm{c}\mathrm{m}}^{-3}$ and $7\times {10}^{15} {\mathrm{c}\mathrm{m}}^{-3}$, attributed to plasma wave damping and temperature-gradient-induced electric field variations. This research establishes trap engineering guidelines for GaN HEMTs: a concentration of $4\times {10}^{15} {\mathrm{c}\mathrm{m}}^{-3}$ optimally enhances conductivity while minimizing adverse impacts on both self-heating and the THz response, making it particularly suitable for high-sensitivity terahertz detectors. Full article

Monolayer (ML) molybdenum disulfide (MoS₂) is a typical valleytronic material which has important applications in, for example, polarization optics and information technology. In this study, we examine the effect of continuous wave (CW) laser pumping on the basic optoelectronic properties of ML MoS₂ placed on a sapphire substrate, where the pump photon energy is larger than the bandgap of ML MoS₂. The pump laser source is provided by a compact semiconductor laser with a 445 nm wavelength. Through the measurement of THz time-domain spectroscopy, we obtain the complex optical conductivity for ML MoS₂, which are found to be fitted exceptionally well with the Drude–Smith formula. Therefore, we expect that the reduction in conductivity in ML MoS₂ is mainly due to the effect of electronic backscattering or localization in the presence of the substrate. Meanwhile, one can optically determine the key electronic parameters of ML MoS₂, such as the electron density n_e, the intra-band electronic relaxation time τ, and the photon-induced electronic localization factor c. The dependence of these parameters upon CW laser pump intensity is examined here at room temperature. We find that 445 nm CW laser pumping results in the larger n_e, shorter τ, and stronger c in ML MoS₂ indicating that laser excitation has a significant impact on the optoelectronic properties of ML MoS₂. The origin of the effects obtained is analyzed on the basis of solid-state optics. This study provides a unique and tractable technique for investigating photo-excited carriers in ML MoS₂. Full article

Polypropylene (PP), with its good physical, thermal, and mechanical properties and excellent processing capabilities, has become one of the most used synthetic polymers. It is known that the overall properties of semicrystalline polymers, including PP, are governed by morphology, which is influenced by the crystallization behavior of the polymer under specific conditions. The most important industrial PP remains the isotactic one, and it has been studied extensively for its polymorphic characteristics and crystallization behavior for over half a century. Due to its regular chain structure, isotactic polypropylene (iPP) belongs to the group of polymers with a high tendency for crystallization. The rapid quenching of molten iPP fails to produce a completely amorphous polymer but leads to an intermediate crystalline order. On the other hand, slow cooling yields a material with high crystalline content. The processing conditions that occur in practice and industry are between these two extremes and, in some cases, are even very close. Therefore, the study of limits in processability and the impact of extreme preparation conditions on morphology, structure, thermal, and mechanical properties fills a gap in the current understanding of how the processing conditions of iPP can be used to design the desired properties for specific applications and is in the focus of this research. The first set of samples (Q samples) was obtained by rapid quenching, while the second was prepared by very slow cooling from the melt to room temperature (SC samples). Testing of samples was performed by optical microscopy (OM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic dielectric spectroscopy (DDS), and mechanical measurements. Characterization revealed that slowly cooled samples exhibited a significantly higher degree of crystallinity and larger crystallites (χ ≥ 55% and L₍₁₁₀₎ ≈ 20 nm), compared to quenched samples (χ < 30%, L₍₁₁₀₎ ≤ 3 nm). Mechanical testing showed a drastic contrast: quenched samples exhibited elongation at break > 500%, while slowly cooled samples broke below 15%, reflecting their brittle behavior. For the first time, DDS is applied to investigate molecular mobility differences between processing-dependent structural forms, specifically the mesomorphic (smectic) and α-monoclinic forms. In slowly cooled samples, α relaxation exhibited both enhanced intensity and an upward temperature shift, indicating stronger structural constraints due to a much higher crystalline phase content and significantly larger crystallite size, respectively. These findings provide novel insights into the structure–property–processing relationship, which is crucial for industrial applications. Full article

Bis- and trisphosphines incorporating methylene and aryl spacers readily adsorb on the surface of porous activated carbon (AC). The adsorption can be performed in the absence of solvents, even when the phosphines have high melting points, or from solutions. The diverse phosphines Ph₂PCH₂PPh₂ (dppm), Ph₂P(CH₂)₂PPh₂ (dppe), Ph₂P(CH₂)₃PPh₂ (dppp), Ph₂P(p-C₆H₄)PPh₂ (dppbz), and (Ph₂PCH₂)₃CCH₃ (tdme) were adsorbed in submonolayers on AC. The adsorbed phosphines were studied by ³¹P MAS (magic angle spinning) NMR spectroscopy, and their mobilities on the surface were confirmed by determining the ³¹P T₁ relaxation times. All phosphine groups of each bis- and trisphosphine molecule are in contact with the surface, and the molecules exhibit translational mobility as one unit. All phosphines used here are air-stable. Once a submonolayer is created on the AC surface, oxygen from the air is co-adsorbed and transforms all phosphines quantitatively into phosphine oxides at room temperature. The oxidation proceeds in a consecutive manner with the oxidation of one phosphine group after another until the fully oxidized species are formed. Studies of the kinetics are based on integrating the signals in the solution ³¹P NMR spectra. High temperatures and low surface coverages increase the speed of the oxidation, while light and acid have no impact. The oxidation is fast and complete within one hour for 10% surface coverage at room temperature. In order to study the mechanism and slow down the oxidation, a higher surface coverage of 40% was applied. No unwanted P(V) side products or water adducts were observed. The clean phosphine oxides could be recovered in high yields by washing them off of the AC surface. The oxidation is based on radical activation of O₂ on the AC surface due to delocalized electrons on the AC surface. This is corroborated by the result that AIBN-derived radicals enable the air oxidation of PPh₃ in solution at 65 °C. When the air-stable complex (CO)₂Ni(PPh₃)₂ is applied to the AC surface and exposed to the air, OPPh₃ forms quantitatively. The new surface-assisted air oxidation of phosphines adsorbed on AC renders expensive and hazardous oxidizers obsolete and opens a synthetic pathway to the selective mono-oxidation of bis- and trisphosphines. Full article

This study provides new insight into the mechanisms governing solid state dewetting (SSD) in SiGe alloys and underscores the potential of this bottom-up technique for fabricating self-organized defect-free nanostructures for CMOS-compatible photonic and nanoimprint applications. In particular, we investigate the SSD of Si_1−xGe_x thin films grown by molecular beam epitaxy on silicon-on-insulator (SOI) substrates, focusing on and clarifying the interplay of dewetting dynamics, strain elastic relaxation, and SiGe/SOI interdiffusion. Samples were annealed at 820 °C, and their morphological and compositional evolution was tracked using atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Raman spectroscopy, considering different annealing time steps. A sequential process typical of the SiGe alloy has been identified, involving void nucleation, short finger formation, and ruptures of the fingers to form nanoislands. XRD and Raman data reveal strain relaxation and significant Si-Ge interdiffusion over time, with the Ge content decreasing from 29% to 20% due to mixing with the underlying SOI layer. EDX mapping confirms a Ge concentration gradient within the islands, with higher Ge content near the top. Full article

Black phosphorus is a promising thermoelectric (TE) material because of its high Seebeck coefficient and high electrical conductivity. In this work, the TE performance of bulk black phosphorus and single-layer phosphorene under uniaxial strain is studied using first-principles calculations and Boltzmann transport theory. The results show relatively excellent TE performance along the armchair direction for both black phosphorus and phosphorene in our study. However, high lattice thermal conductivity is the key adverse factor for further enhancing the TE performance of phosphorus. The ZT value can only reach up to 0.97 and 0.73 for n- and p-type black phosphorus at 700 K, respectively. Owing to quantum size effects, black phosphorene has lower lattice thermal conductivity than black phosphorus. At the same time, two-dimensional (2D) phosphorene exhibits increased electronic energy compared with bulk black phosphorus, resulting in a larger bandgap and reduced electrical conductivity due to the quantum confinement effect. Thus, the TE performance of n-type phosphorene can be partially improved, and the ZT value reaches up to 1.41 at 700 K. However, the ZT value decreases from 0.73 to 0.70 for p-type phosphorene compared with bulk phosphorus at 700 K. To further improve the TE performance of phosphorene, a tensile strain is applied along the armchair direction. Subsequent work indicates that uniaxial strain can further optimize phosphorene’s TE properties by tuning hole relaxation time to improve electrical conductivity. Strikingly, the ZT values exceed 1.7 for both n- and p-type phosphorene under 4.5% tensile strain along the armchair direction at 700 K because of increased electrical conductivity and decreased lattice thermal conductivity. Full article

Circulating fluidized bed combustion flue gas desulfurization generates large volumes of dry desulfurization ash requiring sustainable management. This study evaluated the impacts of substituting desulfurization ash for mineral powder filler in asphalt mastic on low-temperature rheological properties. Asphalt mastics were produced with 0–100% ash replacing mineral powder at 0.8–1.2 powder-binder mass ratios. Ductility and bending beam rheometer testing assessed flexibility and crack resistance. Burgers’ model fitted bending creep compliance to derive relaxation time, m(t)/S(t) index, and low-temperature compliance parameter for analytical insight. Scanning electron microscopy and Fourier transform infrared spectroscopy probed microstructural development and interaction mechanisms. Results showed that the inclusion of desulfurization ash reduced the low-temperature performance of the asphalt mastic compared to the mineral powder asphalt mastic. Additionally, as the temperature decreased further, the effect of the powder-to-gum ratio on the slurry’s crack resistance became less pronounced. Desulfurization ash primarily interacted with the base bitumen through physical means, and the performance of desulfurization ash asphalt slurry mainly depended on the degree of swelling between the desulfurization ash and the base asphalt. Full article

Recent research on the use of heptazine-based polymeric carbon nitride materials as potential photocatalysts for hydrogen evolution has made significant progress. However, the impact of the water cluster’s size on the time-dependent photochemical mechanisms during the water splitting process of heptazine–water clusters remains largely unexplored. Here, we present a Landau–Zener trajectory surface hopping dynamics calculation for heptazine–(H₂O)₄ clusters at the ADC(2) level. The electron-driven proton transfer (EDPT) mechanism reaction from water to hydrogen-bonded heptazine–water clusters was confirmed using this method, yielding a heptazinyl radical and an OH biradical as products. The calculated quantum yield of the EDPT for the heptazine–(H₂O)₄ complex was 6.5%, which was slightly lower than that of the heptazine–H₂O complex (9%), suggesting that increasing the water cluster size does not significantly enhance the efficiency of hydrogen transfer. Interestingly, our results show that the de-excitation of the heptazine–water complex from the excited state to the ground state via the EDPT process follows both fast and slow decay modes, which govern population relaxation and facilitate the photochemical water splitting reaction. This newly identified differential decay behavior offers valuable insights that could help deepen our understanding of the EDPT process, potentially improving the efficiency of water splitting under sunlight. Full article