National Institute Of Materials Physics - Romania

This study describes the development of a pyruvate kinase (PyK)-biosensor for the evaluation of PyK activity, as a diagnostic tool for early cancer screening and detection of kinase inhibitors used in cancer treatment, with the evaluation of the inhibition mechanism. The biosensor was constructed by co-immobilizing the enzymes PyK and pyruvate oxidase (PyOx) on Au film electrodes by crosslinking with glutaraldehyde (GA) and evaluated electrochemically by cyclic voltammetry (CV) and fixed potential amperometry (CA). First, the experimental conditions were optimized in terms of applied potential, enzyme ratio PyK:PyOx and enzyme substrate concentration: phosphoenolpyruvate (PEP) and adenosine diphosphate (ADP). The biosensor sensitivity towards PEP detection was 2.11 +/- 0.08 mu A mM- 1 cm- 2, with very high reproducibility and repeatability, which made it suitable for inhibition studies of PyK inhibitor. The inhibition mechanism of shikonin was determined in relation to both PEP and ADP, with the calculation of IC50 values and binding constants (Ki). Detection of shikonin was possible at very low concentrations in the linear range of 0.1-4.0 pM. The electrochemical results were validated by UV-Vis spectrophotometry. The developed biosensor is a valuable tool for drug screening by enabling enzyme catalytic function examination with applicability to identify inhibitors, estimate their affinity, inhibition mechanism linked to their molecular mechanisms of action and evaluate selectivity, of great interest in both pharmaceutical and medical domains.

Bilayer metallic electrodes of magnesium and zinc-aluminum alloys Mg/Zn:Al were prepared using combined laser-thermionic vacuum arc methods. Plasma diagnosis suggests laser-plasma interaction by increasing the discharge voltage when the laser is on, which is converted by thermal annealing of plasma ions. A magnesium thin film with a lower work function, covered with a Zn:Al (4:1) layer was successfully used for efficient charge injection into electroluminescent diodes. The zinc-aluminum combination preserved the electrical conductivity of the thin magnesium film and protected it against oxidation. The capacitance-voltage measurements confirmed the integrity of the magnesium layer, whereas the work function was not affected. The zinc-aluminum alloy obtained through a thermionic vacuum arc exhibits good conductivity compared to pure zinc layers and better stability against degradation.

Understanding the behavior of biomaterials under physiological conditions is essential for the development of new materials for implants and bone regeneration. This study addresses the critical need to evaluate how exposure to simulated body fluid (SBF) affects hydroxyapatite (HAp) and dextran-coated hydroxyapatite (HApDx) nanoparticles, which are widely considered for biomedical applications due to their bioactivity and biocompatibility. Structural, morphological, and surface property changes induced by SBF immersion were systematically investigated for the first time using advanced characterization techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), FT-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and fractal and Minkowski functional analyses. The results revealed that SBF immersion significantly influenced both HAp and HApDx, leading to reduced crystallite sizes, surface smoothening, and enhanced structural homogeneity. FTIR and FT-Raman spectra indicated subtle structural modifications, while SEM and AFM analyses confirmed the formation of a biomimetic apatite layer and a decrease in surface roughness. These changes are indicative of improved bioactivity, suggesting enhanced potential for osteoconductivity and cellular interaction. Biological evaluations using MG63 osteoblast-like cells demonstrated favorable cell viability and adhesion across 24, 48, and 72 h, particularly for the samples immersed in SBF. AFM further confirmed that surface modifications supported the cell attachment and proliferation. Overall, our findings underscore the importance of SBF exposure in enhancing the physicochemical and biological performance of HAp-based materials, reinforcing their promise for biomedical applications.

This study investigates the development of electrochemical genosensors using gold-coated electrospun polymeric fibers electrodes, Au/PMMA/PET and immobilized phosphorothioated oligonucleotides. Scanning electron microscopy (SEM) with energy-dispersive X-rays spectroscopy (EDS) revealed a uniform distribution of oligonucleotides on the fibers, contrary to planar gold electrodes Au/Ti/SiO2/Si, where network-like films were observed. X-ray photoelectron spectroscopy (XPS) confirmed the successful immobilization of the phosphorothioated oligonucleotides via strong covalent gold-sulfur bonds, while surface plasmon resonance (SPR) indicated superior binding affinity, with significantly lower equilibrium dissociation constants, when compared to unmodified probes. The detection of BCR/ABL fusion gene of chronic myeloid leukemia using differential pulse voltammetry and methylene blue as electroactive indicator, showed that the Au/PMMA/PET electrodes achieved a sensitivity of 379 +/- 12 mu A cm(-)(2) pM(-)(1) and a limit of detection of similar to 5.00 +/- 0.01 fM, outperforming the Au/Ti/SiO2/Si planar electrodes. Reduced non-specific adsorption was observed on the Au/PMMA/PET electrodes and attributed to the inherent charges introduced during the electrospinning process, which created localized electrostatic fields that repelled weakly adsorbing molecules. These findings demonstrate the potential of Au/PMMA/PET electrodes as a robust platform for further development of high-performance clinical diagnostic devices.

Understanding the behavior of biomaterials under physiological conditions is essential for the development of new materials for implants and bone regeneration. This study addresses the critical need to evaluate how exposure to simulated body fluid (SBF) affects hydroxyapatite (HAp) and dextran-coated hydroxyapatite (HApDx) nanoparticles, which are widely considered for biomedical applications due to their bioactivity and biocompatibility. Structural, morphological, and surface property changes induced by SBF immersion were systematically investigated for the first time using advanced characterization techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), FT-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and fractal and Minkowski functional analyses. The results revealed that SBF immersion significantly influenced both HAp and HApDx, leading to reduced crystallite sizes, surface smoothening, and enhanced structural homogeneity. FTIR and FT-Raman spectra indicated subtle structural modifications, while SEM and AFM analyses confirmed the formation of a biomimetic apatite layer and a decrease in surface roughness. These changes are indicative of improved bioactivity, suggesting enhanced potential for osteoconductivity and cellular interaction. Biological evaluations using MG63 osteoblast-like cells demonstrated favorable cell viability and adhesion across 24, 48, and 72 h, particularly for the samples immersed in SBF. AFM further confirmed that surface modifications supported the cell attachment and proliferation. Overall, our findings underscore the importance of SBF exposure in enhancing the physicochemical and biological performance of HAp-based materials, reinforcing their promise for biomedical applications.

In the present work, an essential advance in the preparation of novel nanocomposites based on functionalized V2O5 nanostructures with reduced graphene oxide by hydrothermal method, which has great potential for use in photocatalytic processes related to environmental remediation. XRD analysis confirmed V2O5 in an orthorhombic structure. SEM images showed transparent RGO layers well anchored onto the surface of the V2O5 with a homogeneous distribution. Raman spectroscopy further explained the hybridization and interaction between the components. The photocatalytic activity of Rhodamine-B in aqueous solutions has been studied upon irradiation with visible light. A high RhB degradation was obtained using the V2O5/RGO photocatalyst (82 %), compared to the degradation obtained with only V2O5 (60 %). First-principles Density Functional Theory (DFT) simulations reveal a strong interaction between V2O5 molecules and graphene surfaces, with an adsorption energy of -1.673 eV and a significant charge transfer of 0.367 e- to RGO. This interaction modifies the electronic structure, creating semi-metallic behavior near the Fermi level and enhancing catalytic activity through improved charge carrier dynamics and active sites for photocatalytic applications.

A spin-coating technique was used to produce new thin films of fluoride-doped hydroxyapatite (HApF) and fluoride-doped hydroxyapatite in a dextran matrix (HApF-Dx) with the potential to be used as nanocoatings for various biomedical implants. The stability of the suspensions used in obtaining the thin films was confirmed by ultrasonic measurements with double-distilled water as a reference. The HApF and HApF-Dx thin films obtained by spin-coating showed diffraction patterns corresponding to hexagonal hydroxyapatite. The X-ray photoelectron spectroscopy studies confirmed the partial substitution of hydroxyl groups (-OH) by fluoride ions. The FTIR studies were conducted in order to highlight the presence of the functional group specific for the HAp in the samples and the influence of the dextran addition on the vibrational characteristics. The surface morphologies of the HApF and HApF-Dx thin films were explored using scanning electron microscopy (SEM), atomic force microscopy (AFM), and metallographic microscopy (MM). The surfaces of the HApF and HApF-Dx thin films were found to be smooth, homogenous, and nanostructured. The biocompatibility assays on HGF-1 cells confirmed that both coatings exhibited good cell viability for all the tested time intervals (24 and 48 h). The findings highlighted the potential of HApF and HApF-Dx coatings for biomedical applications. Additional information about the HGF-1 adherence and development on the surface of the HApF and HApF-Dx coatings was obtained using metallographic microscopy, scanning electron microscopy, and atomic force microscopy techniques. This research demonstrates that the spin-coating method can be successfully used to fabricate HApF and HApF-Dx nanocoatings for potential biomedical applications.

The Ni49+xMn32-2xGa19+x (x = 0; 2) Heusler ferromagnetic shape memory alloys were prepared using spark plasma sintering using raw flake-type powders obtained by soft grinding melt-spun ribbons. Samples were characterized using x-ray diffraction, electron microscopy, thermal analysis, and bending tests. Although the properties of ribbons and corresponding powders show similar properties' tendencies, they are opposite in the bulk sintered alloys when compared with precursor powders. Namely, Ni49Mn32Ga19 bulk shows a higher enthalpy (5.8 J g-1), an increased martensitic transformation (MT) temperature (by 9 K), and a reduced hysteresis span (5 K). Conversely, for the Ni51Mn28Ga21 sintered sample, a lower enthalpy (2 J g-1), a significant decrease (by 40 K) in the MT starting temperature, and a broadening of the hysteresis range (26 K) were observed. This difference is analyzed versus specific features of the microstructure. Moreover, the activation energy and the pre-exponential factor of the MT, extracted through kinetic analysis within two non-isothermal models, Kissinger and Friedman, complement and sustain these findings. Fractography details of the sintered samples are discussed in relation to the stress-strain curves from the bending tests. The Ni49Mn32Ga19 bulk sample exhibits a higher bending strength (260 MPa) and a lower strain (0.55%) than the Ni51Mn28Ga21 sample (177 MPa and 0.61%). The observed dependence of functional characteristics on preparation enables the possibility of property control required for various applications and suggests that the proposed route is promising in this regard for further investigations.

Amyloid beta (A(3) peptide aggregates are well-established biomarkers for Alzheimer's disease, though the complete etiology of this disorder remains elusive. Developing biointerfaces to elucidate the physiological roles of these peptides is essential. This study investigates the aggregation, fibrillation, and interaction of A(3 peptides with conductive, biocompatible nanostructured materials designed for applications involving neuronal cells. Various conductive, rigid, and flexible surfaces, both functionalized and non-functionalized with A(340 fibrils, were fabricated. These included glass substrates and poly(methyl methacrylate) electrospun fiber networks coated with gold via magnetron sputtering. The substrates were also functionalized through physical adsorption with poly-L-lysine and collagen, known to support cell proliferation, as well as with the inverse-A(340 peptide and an Amyloid Protein Non-A(3 Component, and the results were compared. The scaffolds were characterized using scanning electron microscopy, X-ray diffraction, atomic force microscopy, contact angle and electrical measurements, while their biological interactions were assessed using MTS assays, fluorescence imaging, and scanning electron microscopy. Fibroblast L929 and neuroblastoma SH-SY5Y cell lines were used as models, with results indicating an elevated cell viability, comparable to the control. The developed nanostructured surfaces are highly promising for integration into advanced neuromorphic engineering devices, as they have proven capable of maintaining their structural integrity when exposed to proteases.

The present study investigates the influence of strontium (Sr) content on the intrinsic properties of barium strontium titanate (Ba1-xSrxTiO3, BST) which was successfully prepared by the conventional solid-state reaction with different concentrations of strontium (x = 0, 0.3, 0.5, 0.6, 0.7, 1). The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and diffuse reflectance spectroscopy, the dielectric properties being also investigated. Structural and vibrational analyses reveal a structural phase transition from tetragonal to cubic at x = 0.4, with a linear decline of the tetragonality ratio as well as a shrinkage in the unit cell volume that occur with increasing Sr content. The morphological study shows that the grain size decreases as the Sr content increases in the tetragonal phase. Yet, upon the phase transition from tetragonal to cubic, the grain size initially increases, followed by a subsequent decrease with further Sr addition. It has been found that the band gap shows a decrease as Sr content increases. The temperature dependence of the dielectric parameters reveals that the Curie temperature as well as the dielectric constant and the loss tangent are strongly affected by the addition of Sr. The activation energy derived from the dielectric response, was found to be in the range 0.685-1.065eV, suggesting the dominance of doubly ionized oxygen vacancy for conduction and relaxation mechanism. Ab initio calculations were done employing the Linear Combination of Atomic Orbitals (LCAO) method. The bandgap energy (Eg) and the structural parameters were calculated using various types of exchange-correlation functionals (PWGGA, PBE, B3LYP and PBE0). A good agreement with the experimental results is achieved using the PBE0 functional. This study contributes to a better understanding of the structure-property relationship in BaSrTiO3 and provides valuable insights for optimizing its performance in various technological applications.