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PEGylated palladium nanocubes as nanomaterials sensitizing glioblastoma cells to proton irradiation

The increasing incidence of cancer emphasizes the urgent need for the development of novel and more effective therapeutic strategies. Glioblastoma multiforme remains one of the most aggressive and treatment-resistant tumors with a dismal prognosis. In this study, 12 nm cubic palladium nanoparticles (Pd NCs) were synthesized as a cost-effective alternative to gold nanoparticles (Au NPs) for use as nano-radiosensitizers in high-energy proton beam therapy. To further improve their biocompatibility and stability in biological environments, Pd NCs were covalently functionalized with thiolated poly(ethylene glycol) (PEG-SH). In vitro assays (MTS test and clonogenic assay) on LN229 and U118 glioblastoma cell lines demonstrated that PEGylation significantly reduced cytotoxicity. For LN229 cells, Pd NCs and PEGylated Pd NCs (Pd NCs-PEG) exhibited comparable radiosensitizing effects at equivalent concentrations, whereas in U118 cells, Pd NC-PEG induced a significantly stronger effect. Holotomographic microscopy confirmed larger NP uptake in U118 compared to LN229 cells, suggesting cell-line-dependent internalization efficiency. Finally, Fouriertransform infrared spectroscopy (FTIR) revealed NP- and/or proton beam-induced biochemical changes in glioblastoma cells, particularly in protein and carbohydrate content. These findings indicate that Pd NCs possess promising radiosensitizing properties and that PEGylation enhances their biocompatibility, offering a potential strategy to improve the overall efficacy of proton therapy outcomes for glioblastoma.

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Evaluation of the contribution of the mean free path in Co to the magnetoresistance in Co/Cu multilayers

The mean free path (MFP) within the cobalt (Co) layer is systematically varied over a broad range, from 10 Å to 500 Å, in order to investigate its influence on the current-in-plane magnetoresistance (MR) in ultrathin Co/Cu multilayers. This variation enables a detailed analysis of electron transport mechanisms as a function of spin-dependent scattering within the magnetic layers. The study also examines the effect of surface roughness, which plays a crucial role in electron reflection and scattering at both external and internal boundaries. By incorporating roughness at the outer surfaces and at the Co/Cu interfaces, the model captures realistic structural features often present in experimentally fabricated multilayers. To further isolate the role of interfacial disorder, two distinct interface configurations are considered: a smooth, idealized interface and a rough interface incorporating morphological irregularities. This comparative approach reveals that interface quality significantly modifies the magnetic transport properties of the system. Numerical simulations indicate that MR decreases monotonically with increasing MFP in the case of smooth interfaces, due to reduced spin-dependent scattering. However, for rough interfaces, MR behavior becomes non-monotonic: it may increase or decrease with MFP depending on the dominant spin diffusion and reflection mechanisms at the interface. Overall, the magnitude of MR is found to be highly sensitive to both the degree of surface roughness and the microscopic nature of interfacial scattering, underscoring their fundamental importance in tuning MR effects in magnetic multilayers.

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Initial stages of oxide formation on titanium surfaces during oxygen bombardment at room temperature: An XPS study

In this work, we investigated the oxidation of metal titanium (Ti) induced by ion bombardment using X-ray photoelectron spectroscopy (XPS). The UNIFIT program was used for data processing and analysis, which enables the precise numerical deconvolution of XPS spectra. The photoemission spectra were numerically deconvoluted using a combination of Gaussian and Lorentzian functions to determine the different oxidation states of the elements and to monitor the early stages of the oxidation process. The analysis of the photoemission spectra revealed significant transformations of the titanium electronic structure during the oxidation process. Before exposing the sample to oxygen ions, the spectrum around the Ti 2p atomic level showed only the metallic phase of titanium. However, with an increase in the bombardment time, Ti 2p photoemission spectra reveal the presence of different titanium oxides (TiO, and TiO2), indicating the progressive coverage of the titanium surface with oxide layers. After 180 minutes of bombardment with ions, the TiO2 phase becomes dominant, although metallic Ti and lower oxides are still present on the sample's surface. These conclusions were further confirmed by the analysis of XPS spectra around the valence band, which, with the increasing oxygen irradiation time, showed a decrease in the intensity of the peak characteristic for metallic titanium and an increase in the intensities of the features associated with TiO2. Our analysis shows that an increase in the thickness of the TiO2 surface layer follows, consistent with Wagner's theory. In addition, our study suggests that the mechanism of titanium oxidation is primarily influenced by the diffusion transport of Ti cations through singly charged cation vacancies, formed during the bombardment of the material.

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Effect of Surface Printing on the Release Kinetics of Gentamicin from Gradient Samples for Bone Applications

The aim of this study was to investigate the release kinetics of gentamicin from a gradient-structured sample intended for bone applications and to assess the influence of surface printing on the antibiotic release profile. The base sample was designed with a spatial gradient of porosity, enabling controlled fluid penetration and gradual release of the active substance. Such a gradient structure was expected to combine an initial therapeutic concentration with a sustained delivery phase. In addition to the base design, selected samples were modified through surface printing with a gentamicin-containing layer. This approach aimed to further prolong drug release by introducing an additional diffusion barrier and altering surface properties. The release studies were carried out under static conditions in phosphate-buffered saline (PBS) at 37 °C to simulate physiological temperature. Gentamicin concentration in the release medium was quantified at predetermined time intervals using a validated spectrophotometric method. The obtained results demonstrated clear differences in release profiles between the unmodified gradient sample and the surface-printed variant. In the surface-printed samples, the initial concentration of the drug in the medium was reduced compared to the base gradient structure, while the subsequent release phase was more uniform and extended over time. These findings indicate that surface printing represents an effective strategy for tailoring drug release kinetics from gradient materials, with potential applications in local bone infection treatment and implant-associated antimicrobial protection.

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Effect of deposition time on the optical properties of CdSe nanostructured films
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Cadmium selenide nanostructured films were prepared using the high-frequency (HF) magnetron sputtering method. All samples were deposited on quartz substrates in disk form with a radius of 16 mm. The temperature of the substrate was maintained at 180 °C for all samples. The deposition times were 3, 6, 9, 12 and 20 min. The effect of deposition time on the optical properties of CdSe nanostructured films was investigated by X-ray diffraction (XRD), optical absorption spectra (OAS), a scanning electron microscope (SEM) and an energy-dispersive X-ray analyser (EDX). XRD analysis of the obtained samples exhibited a cubic structure with a preferred (200) orientation. The average crystallite size of the CdSe nanostructured films was determined using the Scherrer equation. An increase in deposition time was found to result in a corresponding increase in crystallite size. The EDX showed that the CdSe nanostructured films were formed from the desired elements, and their distribution was uniform. SEM analysis showed that the surface morphologies of the CdSe nanostructured films were dependent on the deposition time. OAS was analysed using the Tauc model. The absorption spectrum fitting (ASF) method was applied to estimate the optical band gap and Urbach energy of the CdSe nanostructured films. The optical band gap and Urbach energy were found to decrease with increasing deposition time. This behavior is ascribed to the growth in particle size.

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Relationship between biopolymer properties

Biopolymers are gaining importance as they tackle the plastics problem and are being recognized as a possible alternative. However, some issues such as their thermomechanical, barrier properties, and biodegradation are putting them at risk as replacements of traditional polymers. All the aforementioned properties were analysed for five biopolymers: PLA, PBS, PVA, starch, and PBAT.

A strong correlation (0.98) was found between the elongation at break and the ultimate tensile strength (UTS); however, none of these properties were connected with the Young modulus. This could be because during plastic deformation the polymer undergoes atom displacement and breakage of the bonds, that keeps moving further away until rupture occurs; this is related to the viscoelastic properties of the polymers. On the other hand, during elastic behavior, the displacement comes back to their original state so that the polymer structure does not change. The Young modulus (MPa) was 28.77 for starch, 134.45 for PBAT, 141.18 for PBS, 461.07 for PVA, and 701.67 for PLA.

The Young modulus is related to the water vapor transmission rate (WVTR). It is inversely proportional (-0.79), which means that the greater the permeation, the weaker the material. It could be explained by picturing the polymer with its crosslinks, where the more crosslinks are present, the harder it would be for the water to cross through the polymer and the stiffer the polymer would be as the chains would not unfold so easily. The WVTR in g/daym2 for the biopolymers was 43.35 for PLA, 43.8 for PVA, 222.2 for PBS, 457.5 for PBAT, and 901.37 for PBAT.

As for biodegradation, all polymers biodegraded between 7 and 28 days; this was done by composting at 60ºC following ISO 20200: 2015. PVA degraded at 15 days, PLA and starch at 21, and PBS and PBAT at 28 days.

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Magnetic ordering and electronic structure of GdRhIn

In recent decades, ternary intermetallic compounds of the equiatomic RTX-type, which are composed of a rare earth, a transition metal and a p-element, have been studied intensively due to a variety of possible chemical compositions, crystal structure types and outstanding physical properties. Our study presents a theoretical investigation of the electronic and magnetic properties of the intermetallic compound GdRhIn using the DFT+U method. Strong electron correlations in the 4f shell of gadolinium were accounted for using the GGA+U approach, with structural optimization confirming a hexagonal Fe₂P-type lattice and equilibrium parameters. The compound exhibits a ferromagnetic (FM) ground state, though the antiferromagnetic G-type (AFM-G) configuration lies only 3.51 meV/f.u. higher in energy, indicating competing exchange interactions mediated by the RKKY mechanism. This proximity suggests potential magnetic switching under external stimuli, making GdRhIn promising for spintronics and magnetocaloric applications. The A-type and C-type AFM orderings are less stable, lying 2.97 meV/f.u. and 0.76 meV/f.u. above the AFM-G state, respectively. Analysis of the electronic structure reveals strongly localized 4f states of Gd, responsible for the magnetic moment of 7.1 μB, in agreement with experimental data. The Rh and In sublattices remain non-magnetic, with the conduction band near the Fermi level formed by hybridized Rh 4d and In 5p states. The density of states and band structure confirm minimal spin polarization for Rh and In, while the Gd 4f states dominate the magnetic behavior. The FM and AFM-G configurations exhibit nearly identical band dispersions, with only minor differences in the Gd 4f splitting, further highlighting the system’s magnetic flexibility. These findings align with experimental observations. The material’s tunable magnetic state makes it promising for spintronic and magnetocaloric applications. This work was supported by the state assignment of the Ministry of Science and Higher Education of the Russian Federation for IMP UrB RAS.

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Investigating the 8CB Liquid Crystal–Insulin Interaction: The Role of the Smectic A Phase in Enhancing Detection Sensitivity

Liquid crystal (LC) biosensors have emerged as a viable platform for protein detection due to their distinct optical and dielectric features. These biosensors make use of LC's responsiveness to external stimuli, which includes interactions with biomolecules such as proteins. LC’s molecular alignment and order are extremely sensitive to changes in their surroundings, allowing for highly sensitive and selective protein identification. This study presents the first comprehensive multi-technique investigation of human insulin (HI) detection using octyl-4-biphenylcarbonitrile (8CB) liquid crystal, highlighting the enhanced sensitivity achieved when 8CB operates in its smectic A phase compared to its nematic homologs. The importance of this work rests in providing basic insights into how LC-phase molecular ordering governs protein–LC interactions, rather than in establishing a new standard for biosensing sensitivity. Polarizing optical microscopy (POM) revealed two primary configurations, focal conic and radial, in 8CB-LC upon interaction with HI at concentrations of 20 μM–300 μM. Dielectric studies showed significant changes in impedance, loss tangent, relaxation time, and capacitive behavior, while Raman spectroscopy revealed shifts in vibrational modes, correlating with HI interactions. Molecular docking provided insights into the binding behavior of 8CB-LC with HI. Among cyanobiphenyl LCs, 8CB’s smectic A phases enhanced molecular ordering and sensitivity, detecting HI at concentrations of 20 μM, which is lower than the LOD of other cyanobiphenyl LCs. These findings demonstrate 8CB’s high specificity and sensitivity, positioning it as a strong candidate for label-free insulin biosensing.

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PFOS and PFOA Interaction with Organic Chromophore-Bound Serum Albumin

PFOS and PFOA are persistent in nearly all water bodies and are very thermally and chemically stable, making them non-biodegradable and posing health risks. When bound with proteins, this relationship can affect human health. Several detection methods involving gas chromatography, mass spectrometry, and other PFOS detection procedures are time-consuming and require expensive instrumentation. Consequently, fluorescence spectroscopy was used to quantify PFOS by utilizing an SQ-BSA complex based on the sulfonated-squaraine dye (SQ) absorption and fluorescence properties. The SQ dye (blue-solid) was prepared by reacting with squaric acid and the synthesis of 3-(2-Methylbenzo[D]Thiazol-3-ium-3-yl)-propane-1-sulfonate in a Dean-Stark apparatus containing 5 mL of anhydrous pyridine, 4 mL of n-butanol, and 4 mL of toluene. The system was refluxed at 175°C for 5 hours, after which the reaction mixture was purified via recrystallization in methanol twice and then finally characterized by 1H NMR. It interacted with bovine serum albumin (BSA) to form the SQ-BSA complex, which was then investigated separately and showed fluorescence turn-on. The complex emission continuously increases as the BSA concentration rises, accompanied by a corresponding wavelength shift from 640 nm to 660 nm due to a non-covalent interaction. However, subsequent PFOS and PFOA additions revealed a gradual fluorescence turn-on and turn-off, respectively, which continued to increase along these two directions up to a 20 µM concentration. Overall, the detection of these sequentially studied tri-component systems (SQ, BSA, PFOS/PFOA) relies on the different interacting behaviors of SQ with PFOS and PFOA, thereby providing a complementary approach for detecting PFOS and PFOA in water. Therefore, the demonstrated very strong discrimination ability of PFOS and PFOA by the SQ-BSA complex becomes ascribed to the obviously known differing interacting abilities of these two harmful pollutants with BSA amongst various studies.

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Spin transitions of [FeII(phen)2(NCS)2] spin crossover complex in ethylene glycol matrix

Introduction. Spin crossover (SCO) materials, which are capable of spin-state switching between high spin and low spin states, are of significant focus in material science research for possible applications in spin-based devices. Here, we investigated spin transitions of Fe(II)-based spin crossover (SCO) complex [FeII(phen)2(NCS)2], which shows spin state bi-stability between its high spin (HS, S=2) and low spin (LS, S=0) embedded in ethylene glycol matrix.

Methods. The SCO complex is synthesized by the solgel method with a judicious choice of reacting materials and the materials are further characterized by X-ray powder diffraction, temperature dependent currentvoltage (I-V) and current vs. time (I-t) measurements. Magnetic characterisations are also performed with electron paramagnetic resonance in the temperature range of 110-280K.

Results. Electrical measurement obtained by acquiring temperature-dependent I-V data shows thermal spin-state switching with prominent hysteresis loop. The low temperature (T=90 K) data show an LS state with higher conductivity, whereas at high temperatures, it shows lower conductivity in the HS state. The measured I-t data under dark and illumination at 300 K and 90 K, respectively, provide a better photo-induced response at lower temperature. The EPR data of 280 K show a prominent peak at ~2900 Gauss with g=2.1, along with an additional peak at~ 2300 Gauss corresponding to g=2.9. The additional peak is smeared out with a lowering in temperature, indicating HS to LS spin transition. Embedding polymer reduces the transition temperature by ~160 K, which is slightly lower than that of bulk (176 K), which may arise due to the reduction in strong co-operative interaction between the π-π or H bonding of the complex.

Conclusion. We demonstrated the spin transition characteristics of the SCO complex in the ethylene glycol matrix with features different from that of the bulk, which may be quite important in designing future applications.

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