Search Results (215)

Photodynamic therapy (PDT) is a highly selective, clinically approved, minimally invasive technique that effectively eliminates cancer cells. Its effectiveness is limited by poor light penetration into tissue and the hydrophobic nature of photosensitizers, highlighting the need for new approaches to treatment. Here, a theranostic upconversion nanoplatform, consisting of a NaYF₄:Yb,Er,Tm,Fe core and a NaHoF₄ shell codoped with Yb, Nd, Gd and Tb ions, was designed to enhance PDT outcomes by integrating multi-wavelength upconversion luminescence, T₂-weighted magnetic resonance imaging (MRI) and PDT. The synthesized core–shell upconversion nanoparticles (CS-UCNPs) were coated with new verteporfin (VP)-conjugated alendronate-terminated poly(N,N-dimethylacrylamide-co-2-aminoethyl acrylate) [Ale-P(DMA-AEA)] grafted with poly(ethylene glycol) (PEG). Under 980 nm NIR irradiation, CS-UCNP@Ale-P(DMA-AEA)-PEG-VP nanoparticles generated reactive oxygen species (ROS) due to the efficient energy transfer between CS-UCNPs and VP. In a pilot preclinical study, intratumoral administration of nanoparticle conjugates to mice, followed by exposure to NIR light, induced necrosis of pancreatic tumor and suppressed its growth. Full article

The rational design of transition metal oxides with tailored electronic structures and defect chemistries is critical for advancing high-performance supercapacitors. Herein, we report the engineering of cobalt oxide (Co₃O₄) gels through controlled sol–gel synthesis and rare earth (RE) incorporation using neodymium (Nd), gadolinium (Gd), and dual neodymium/gadolinium (Nd/Gd) doping. X-ray diffraction (XRD) confirmed the preservation of the cubic spinel structure with systematic peak shifts and broadening, evidencing lattice strain, oxygen vacancy generation, and defect enrichment. Field-emission scanning electron microscopy (FE-SEM) analyses revealed distinct morphological evolution from compact nanoparticle assemblies in pristine Co₃O₄ to highly porous, interconnected frameworks in Nd/Gd–Co₃O₄ (Nd/Gd-Co). X-ray photoelectron spectroscopy (XPS) verified the stable incorporation of RE ions, accompanied by electronic interaction with the Co–O matrix and enhanced oxygen defect states. Electrochemical measurements demonstrated that the Nd/Gd–Co electrode achieved a remarkable areal capacitance of 25 F/cm² at 8 mA/cm², superior ionic diffusion coefficients, and the lowest equivalent series resistance (0.26 Ω) among all samples. Long-term cycling confirmed 84.35% capacitance retention with 94.46% coulombic efficiency after 12,000 cycles. Furthermore, the asymmetric pouch-type supercapacitor (APSD) constructed with Nd/Gd–Co as the positive electrode and activated carbon as the negative electrode delivered a wide operational window of 1.5 V, an areal capacitance of 140 mF/cm², an energy density of 0.044 mWh/cm², and 89.44% retention after 7000 cycles. These findings establish Nd/Gd-Co gels as robust and scalable electrode materials and demonstrate that RE co-doping is an effective strategy for bridging high energy density with long-term electrochemical stability in asymmetric supercapacitors. Full article

The chromium-free oxide precursor strategy effectively avoids chromium volatilization and electrode contamination in metal-supported solid oxide fuel cells (MS-SOFCs), while enabling high-temperature co-sintering in air to simplify the fabrication process. However, the drastic microstructural coarsening, dimensional shrinkage, and thermal expansion mismatch with adjacent components of such substrates during high-temperature sintering, reduction, and thermal cycling collectively contribute to the interfacial instability and structural degradation of MS-SOFCs. Herein, we address these issues by incorporating a small amount of Gd_0.1Ce_0.9O_1.95 (GDC) to the NiO-Fe₂O₃ (NFO) substrate. The incorporation of GDC significantly enhances the sintering compatibility and reduction stability of the MS-SOFCs, alleviating the stress-induced warping and distortion. Moreover, the GDC phase has a pinning effect to suppressing the coarsening of the substrates during high-temperature sintering and reduction processes, enhancing mechanical integrity and structural robustness of the single cell. With 15 wt% GDC incorporated into the NiFe substrate, the corresponding MS-SOFC with GDC electrolyte film achieves a peak power density of 0.56 W cm⁻² at 600 °C, along with markedly improved structural integrity and operational reliability. This work demonstrates a viable pathway for designing heterophase-engineered supports with matched thermomechanical properties, offering promising prospects for enhancing the durability of MS-SOFCs. Full article

The ionization of ferrocene (Fc) remains an active topic of interest due to its complex, ulti-electron character. Accurate prediction of its first ionization potential (IP) requires methods that go beyond single-particle approximations, as Koopmans’ theorem, Janak’s theorem, and the outer valence Green function (OVGF) approach prove inadequate. Using the ΔSCF method, the first IP of Fc was calculated to be ~6.9 ± 0.1 eV, which is in close agreement with experimental values (6.72–6.99 eV). To benchmark computational accuracy, 42 models were evaluated using the CCSD, CCSD(T), and B3LYP methods with Pople and Dunning basis sets, including Fe-specific modifications to better capture 3d electron behavior. The results underscore the importance of proper treatment of Fe 3d orbitals, with B3LYP/m6-31G(d) offering the best compromise between accuracy and computational efficiency. Notably, the singly occupied molecular orbital (SOMO) in Fc⁺ is identified as the 8a₁’ orbital, which is dominated by its Fe 3d character. This orbital, although not the α-HOMO in Fc⁺, becomes the LUMO upon ionization. Analysis of the excess orbital energy spectrum (EOES) reveals substantial energy shifts upon ionization, particularly in Fe-centered orbitals spanning both the core and valence regions. Theoretical momentum distribution (TMD) analysis of the 8a₁’ orbital further quantifies orbital differences before and after ionization, providing complementary insights in momentum space. Finally, energy decomposition analysis (EDA) shows that while most interaction energy components become less stabilizing upon ionization, steric and Pauli terms contribute a small stabilizing effect. Full article

Oxygen transport membranes (OTMs) have gained a lot of attention for their application in different innovative fields, but the development of new materials able to combine high oxygen permeability and good chemical stability is crucial to boost the exploitation of such membrane-based technologies. Perovskite oxides are widely studied as mixed ionic-electronic conductors for the realization of OTMs. In this article, we focus on _Sr1-xCa_xTi_0.8Fe_0.2O_3-ẟ (SCTF) perovskites and investigate the effect of Ca content on the A-site of the permeation properties, both in single-phase SCTF membranes and in dual-phase membranes obtained by combining SCTF and the ionic conductor Ce_0.8Gd_0.2O₂ (CGO). In single-phase samples, we observed that the substitution of 40% Ca preserves the permeation performances of the non-substituted SrTi_0.8Fe_0.2O_3−ẟ membrane while allowing for a substantial decrease in the sintering temperature, thus facilitating membrane manufacturing. In dual-phase membranes, the increase in the Ca content in the perovskite causes an increase in grain size. The permeation is, at least partially, controlled by the kinetics of the surface exchange reactions. This limitation can be overcome by the addition of an activation layer; however, the permeance of activated CGO-SCTF membranes still remains lower compared to the single-phase parent perovskitic membranes. Full article

Iron(III) (Fe(III)) complexes have recently emerged as safer alternatives to magnetic resonance imaging (MRI) contrast agents (CAs), reigniting interest in biomedical research. Although gadolinium Gd(III)-based contrast agents (CAs) have been widely used in MRI over the past four decades, their use in the current clinical routine is severely constrained due to concerns about high toxicity and environmental impact. Research is now focusing on synthesizing safer contrast agents with alternative paramagnetic ions like Fe(III) or Mn(II). MRI CAs with integrated potent therapeutic moieties may offer synergistic advantages over traditional contrast agents in clinical use. The study explored the use of salinomycin-ferrihydrite composites as possible effective ensembles of imaging and therapeutic units in the same molecule, evaluating their anticancer activity and influence on the signal in MRI. The composites were characterized using Mössbauer spectroscopy and ICP-MS for iron content determination. The in vitro relaxivity measurements in a high-field MR scanner demonstrated the potency of the composites as T₂ enhancers. The antitumor activity of one selected Sal-ferrihydrite composite was tested in three human cancer cell lines: A549 (non-small cell lung cancer); SW480 (colon cancer); and CH1/PA1 (ovarian teratocarcinoma) by the MTT cell viability assay. The new Sal-ferrihydrite composite showed a pronounced cytotoxicity in all three human cancers in line with enhanced signal in MRI, which makes it a promising candidate for future biomedical applications. The superior cytotoxic effect, together with the strong signal enhancement, makes these compounds promising candidates for further detailed investigations as future theranostic agents. Full article

This article investigates the connection between the process parameters of solid hydrogenation, disproportionation (HD), desorption, and recombination (DR) (HDDR) in sintered (Nd,Pr,Gd)-Fe-B magnets, as well as their phase composition and degree of texture (DoT). During HD, hydrogen pressures of 10–50 kPa were applied at temperatures ranging from 700 to 785 °C for reaction times ranging from 3 to 11 h. DR was performed at 750–850 °C. The HD reaction was observed across the full range of hydrogen pressure and temperature. The phase composition of the disproportionation products depends on the depth in the sample. Applying HDDR treatment at a pressure of 10 kPa is an effective way to increase the DoT of magnets. Magnets are anisotropic following the HDDR treatment across the parameter ranges. The dependence of the DoT value on HDDR treatment parameters is complicated, with the main trend being a decline in DoT with increasing hydrogen pressure. The DoT is determined by the disproportionation and recombination temperatures, as well as the depth at 50 kPa pressure. The recombined phase is isotropic near the sample surface and highly anisotropic within the sample after 50 kPa is applied. Full article

Petrological knowledge on weathering processes controlling the mobility of chemical elements is still limited in the dry tropical zone of Cameroon. This study aims to investigate the mobility of major and trace elements during rhyolite weathering and soil formation in Mobono by understanding the mineralogical and elemental vertical variation. The studied soil was classified as Cambisols containing mainly quartz, K-feldspar, plagioclase, smectite, kaolinite, illite, calcite, lepidocrocite, goethite, sepiolite, and interstratified clay minerals. pH values ranging between 6.11 and 8.77 indicated that hydrolysis, superimposed on oxidation and carbonation, is the main process responsible for the formation of secondary minerals, leading to the formation of iron oxides and calcite. The bedrock was mainly constituted of SiO₂, Al₂O₃, Na₂O, Fe₂O₃, Ba, Zr, Sr, Y, Ga, and Rb. Ce and Eu anomalies, and chondrite-normalized La/Yb ratios were 0.98, 0.67, and 2.86, respectively. SiO₂, Al₂O₃, Fe₂O₃, Na₂O, and K₂O were major elements in soil horizons. Trace elements revealed high levels of Ba (385 to 1320 mg kg⁻¹), Zr (158 to 429 mg kg⁻¹), Zn (61 to 151 mg kg⁻¹), Sr (62 to 243 mg kg⁻¹), Y (55 to 81 mg kg⁻¹), Rb (1102 to 58 mg kg⁻¹), and Ga (17.70 to 35 mg kg⁻¹). LREEs were more abundant than HREEs, with LREE/HREE ratio ranging between 2.60 and 6.24. Ce and Eu anomalies ranged from 1.08 to 1.21 and 0.58 to 1.24 respectively. The rhyolite-normalized La/Yb ratios varied between 0.56 and 0.96. Mass balance revealed the depletion of Si, Ca, Na, Mn, Sr, Ta, W, U, La, Ce, Pr, Nd, Sm, Gd and Lu, and the accumulation of Al, Fe, K, Mg, P, Sc, V, Co, Ni, Cu, Zn, Ga, Ge, Rb, Y, Zr, Nb, Cs, Ba, Hf, Pb, Th, Eu, Tb, Dy, Ho, Er, Tm and Yb during weathering along the soil profile. Full article

The alloy Pr₂Fe_16.75Ni_0.25 has been examined to investigate its structural properties, critical behavior, and magnetocaloric effects. Rietveld’s refinement of X-ray diffraction patterns has revealed a rhombohedral structure with an $R\overline{3}m$ space group. Pr₂Fe_16.9Ni_0.25 also demonstrates a direct magnetocaloric effect near room temperature, accompanied by a moderate magnetic entropy change ($-\mathrm{\Delta }{S}_M^{\max }$ = 5.5 J kg⁻¹ K⁻¹ at ${\mu }_0\mathrm{\Delta }H=5$ T) and a broad working temperature range. Furthermore, the Relative Cooling Power (RCP) is approximately 89% of the widely recognized gadolinium (Gd) for ${\mu }_0\mathrm{\Delta }H=2$ T. This compound exhibits a commendable magnetocaloric response, on par with or even surpassing that of numerous other intermetallic alloys. Critical behavior was analyzed using thermo-magnetic measurements, employing methods such as the modified Arrott plot, critical isotherm analysis, and Kouvel-Fisher techniques. The obtained critical exponents ($\beta$, $\gamma$, and $\delta$) exhibit similarities to those of the 3D-Ising model, characterized explicitly by intermediate range interactions. Full article

Co_0.95R_0.05Fe₂O₄ nanoparticles were synthesized using a sol-gel approach incorporating bio-based agents and were found to be single phases adopting a cubic Fd-3m structure. XPS shows the presence of Gd³⁺ and Ho³⁺ ions. The spin–orbit splitting of about 15.4 eV observed in Co 2p core-level spectra is an indication that Co is predominantly present as Co³⁺ state, while the satellite structures located at about 6 eV higher energies than the main lines confirm the existence of divalent Co in Co_0.95R_0.05Fe₂O₄. The positions of the Co 3s and Fe 3s main peaks obtained by curve fitting and the exchange splitting obtained values for Co 3s and Fe 3s levels point to the high Co³⁺/Co²⁺ and Fe³⁺/Fe²⁺ ratios in both samples. The saturation magnetizations are smaller for the doped samples compared to the pristine ones. For theoretical magnetization calculation, we have considered that the heavy rare earths are in octahedral sites and their magnetic moments are aligned antiparallelly with 3d transition magnetic moments. ZFC-FC curves shows that some nanoparticles remain superparamagnetic, while the rest are ferrimagnetic, ordered at room temperature, and showing interparticle interactions. The M_S/Ms ratio at room temperature is below 0.5, indicating the predominance of magnetostatic interactions. Full article

Addressing the limitations of poor piezoelectric photocatalytic activity and insufficient magnetic recovery in pure BiFeO₃ nanoparticles, Gd and Zr co-doped BiFeO₃ nanoparticles were synthesized via the sol-gel method. The structural characterization revealed a rhombohedral-to-orthorhombic phase transition with reduced grain size (~35 nm) and lattice distortion due to dopant incorporation. An XPS analysis confirmed Fe³⁺ dominance and oxygen vacancy enrichment, while optimized BGFZ9 exhibited enhanced remanent magnetization (0.1753 emu/g, 14.14 increase) compared to undoped BFO. The synergistic piezo-photocatalytic system achieved 81.08% Ofloxacin degradation within 120 min (rate constant: 0.0136 min⁻¹, 1.26 higher than BFO) through stress-induced piezoelectric fields that promoted electron transfer for ·O₂⁻/·OH radical generation via O₂ reduction. The Ofloxacin degradation efficiency decreased to 24.36% after four cycles, with structural integrity confirmed by XRD phase stability. This work demonstrates a triple-optimization mechanism (crystal phase engineering, defect modulation, and magnetic enhancement) for designing magnetically recoverable multiferroic catalysts in pharmaceutical wastewater treatment. Full article

Magnetic resonance imaging (MRI) is widely used as a medical imaging technique due to its non-invasive nature, high spatial contrast, and virtually unlimited depth of penetration. Different modalities can be used for contrast in MRI, including T₁ (spin–lattice) and T₂ or T₂ * (spin–spin) proton relaxation times, and specific contrast agents (CAs) have been developed that locally enhance the contrasts in MRI images. We present a method combining T₁- and T₂-specific CAs in a single imaging technique, referred to as correlation MRI. This technique allows different CAs to be used simultaneously to visualize contrast between multiple types of tissue in the same image when applied as targeted CAs. An obstacle for the quantitative use of correlation MRI is that T₁ and T₂ relaxivity changes generated by CAs are not independent of each other. Here, we measured relaxivities in mixtures with various concentrations of Cas, including Magnevist (Gd³⁺-based, primarily a T₁ CA) and Feridex (Fe²⁺- and Fe³⁺-based, primarily a T₂ CA), and compared them to theoretically predicted values. It was found that, at clinically relevant concentrations, relaxivities of the mixtures deviate from linearly added values. We finally propose a three-dimensional calibration curve to quantitatively determine the concentration in mixtures of CAs, based on the measured relaxivities. Full article

Background: The role of the periarticular muscles of the knee joint in ensuring body balance is still ambiguous. Therefore, we conducted clinical and biomechanical assessments on 52 older adults (36 women and 16 men, age of 67.58 ± 7.30 years, body weight of 75.10 ± 13.42 kg, and height of 163.92 ± 8.80 cm) to determine the role of the knee muscles in balance maintenance. Methods: The clinical examination included the Dizziness Handicap Inventory (DHI), the Geriatric Depression Scale (GDS), the Performance-Oriented Mobility Assessment (POMA), the Functional Reach Test (FRT), the Falls Efficacy Scale—International (FES-I), and bioimpedance parameters (skeletal muscle mass—SMM—and its derived parameter—Diff SMM). The biomechanical assessment involved parameters that characterize muscle torques of knee joint extensors and flexors in isokinetic and isometric conditions, as well as changes in the centre of pressure (COP) position while standing with eyes open and closed. Results: Based on treatment history and DHI results (>10 points), 26 participants were identified as having balance disorders, while the remaining participants formed the control group. Statistical analysis was performed to determine differences between the groups. The groups significantly differed in terms of the results obtained from the DHI (p < 0.001) and GDS (p = 0.04) questionnaires as well as FES-I (p < 0.001) and POMA (p = 0.002) tests. While SMM (p = 0.012) was similar in the groups, Diff SMM (p = 0.04) significantly differed. The multiple regression analysis confirmed the knee joint extensor parameters’ significant role in predicting the COP path (p = 0.03 and p = 0.04 for two assumed models). Conclusions: The obtained results proved that the muscle torques of knee extensors can be used in the diagnostic process of older patients with balance disorders, indicating possible rehabilitation directions. Full article

This study explores the structural, magnetic, and magnetocaloric properties of ${\mathrm{Ce}}_2$(Fe, Co${)}_{17}$ (x = 0, 0.5, 0.6, and 0.7) compounds synthesized via arc melting under high temperatures exceeding 2300 K. The as-cast ingots are subsequently sealed and subjected to a heat treatment at 1323 K to improve homogeneity and crystallinity. Detailed analyses using X-ray diffraction and magnetometry reveal that cobalt substitution significantly impacts the structural and magnetic behavior, enabling precise tuning of the magnetic transition temperature and magnetic order. The substitution induces an anisotropic increase in cell parameters and shifts the magnetocaloric effect (MCE) from low temperatures (200 K for x = 0) to near room temperature (285 K for x = 0.7), enhancing the operating temperature range. The magnetocaloric effect is studied across different magnetic transitions: a metamagnetic and ferro-antiferromagnetic transition followed by a paramagnetic state in one sample, and a direct ferro-paramagnetic transition in another. The compounds exhibit a second-order magnetic phase transition, ensuring a reversible MCE, with a relative cooling power (RCP) that is approximately 85% of that of pure Gd. Moreover, the use of cerium, the most cost-effective rare-earth element (5 $/kg), combined with its low atomic concentration (10%) in these intermetallics, enhances the sustainability and affordability of these materials. These findings underline the potential of iron-rich Ce-based compounds for next-generation refrigeration and energy-harvesting applications. Full article

Carbonaceous shale has garnered significant interest as a viable alternative source of rare earth elements (REEs) besides conventional REE-bearing ores. This study characterized rare earth element + Yttrium+ Scandium (REYs) enrichment in the 11 core samples of carbonaceous shale (7) and coal (4) collected from Arnot Mine. Major elements of the studied carbonaceous shale (CS) and coal showed high amounts of SiO₂, Al₂O₃, and Fe₂O₃, indicating a high content of aluminosilicate and iron-rich minerals. The plots Na₂O + K₂O against SiO₂ suggested alkali granite, granite, and granodiorite provenance sources for the studied shale and coal. The samples showed enrichment in low and heavy rare elements crystallized from a low potassium tholeiitic and medium calc-alkaline magma based on the plots of La_N/Yb_N and K₂O vs. SiO₂. The mineralogical and maceral analysis revealed the dominant presence of kaolinite (15%–45%), and it was suggested as the cation exchange site resulting from the isomorphous substitution of Al³⁺ for Si⁴⁺. Additionally, siderite was suggested as one of the REY hosts due to the Fe³⁺ site forming a complex with the REE³⁺ ions. Furthermore, the samples were classified as lignite to sub-bituminous coal category with dominant minerals including kaolinite, quartz, and siderite. The outlook coefficient (Coutl) of REY in CS revealed a promising area for economically viable, having two enrichment types, including low (La, Ce, Pr, Nd, and Sm) and heavy (Ho, Er, Tm, Yb, and Lu). The Eu_N/Eu_N* and Ce_N/Ce_N* ratio for the current studied samples exhibited a weak negative to no anomaly, and most of the studied samples were characterized by distinctive positive Gd anomalies derived from sediment source regions weathered from alkali granite, granite, and granodiorite provenance formed from a low potassium tholeiitic and medium calc-alkaline magma. Full article