National Institute Of Materials Physics - Romania

Bortezomib is an inhibitor of proteasomes and an anti-cancer drug. Although bortezomib is considered a safe drug, as confirmed by cytotoxicity assays, recent reports highlighted the possibility of interaction between bortezomib and cellular components, with detrimental long-term effects. The evaluation of the interaction between bortezomib and dsDNA was investigated in bulk solution and using a dsDNA electrochemical biosensor. The binding of bortezomib to dsDNA involved its electroactive centers and led to small morphological modifications in the dsDNA double helix, which were electrochemically identified through changes in the guanine and adenine residue oxidation peaks and confirmed by electrophoretic and spectrophotometric measurements. The redox product of bortezomib amino group oxidation was electrochemically generated in situ on the surface of the dsDNA electrochemical biosensor. The redox product of bortezomib was shown to interact primarily with guanine residues, preventing their oxidation and leading to the formation of bortezomib-guanine adducts, which was confirmed by control experiments with polyhomonucleotides electrochemical biosensors and mass spectrometry. An interaction mechanism between dsDNA and bortezomib is proposed, and the formation of the bortezomib redox product-guanine adduct explained.

In the view of the advantages of using P, N, Si and graphene oxide (GO) for the development of flame retardants materials, a multi-structure synergistic composite was synthesized by grafting a novel nitrogen-containing polyhedral oligomeric silsesquioxane (HAK) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) on the surface of GO nanosheet. In the first step, 2-hydroxyethyl acrylate was selectively reacted, and then, HAK was synthetized by the condensation of the aza-Michael addition product with 3-(methacryloyloxy)propyltrimethoxysilane. Finally, the GO obtained by an innovative variant of Marcano-Tour improved exfoliation method was functionalized, first with DOPO, and then with HAK. The structural, morphological and surface properties of GO and GO-DOPO-HAK were investigated by means of XRD, TEM-EDX, FT-IR, Raman, zeta potential and XPS techniques, and it was evidenced the functionalization of GO with DOPO, and then with HAK. The performed microscale combustion calorimetry (MCC) and TG measurements indicated a great potential of the GO-DOPO-HAK as flame retardant material as the obtained residual weight for this sample was found to be the highest one compared to the other investigated samples. MCC analyses further revealed a major decrease in heat release capacity (HRC) and a significant increase in char yield, results that confirm the great potential of GO-DOPO-HAK as flame retardancy material. [GRAPHICS] .

We studied here the influence of Li+ ions on the benzene rings of nematic mixture E7, which is electrochemically adsorbed onto gold electrode surface, to highlight the ability of this mixture for the applications in the field of the rechargeable Li+-ion batteries. Raman spectra support the changes observed in electrochemical analyses while contact angle measurements show that wetting properties of E7 layer were modified after deposition of this mixture onto gold support and the doping with Li+ ions.

Novel biomaterials with promising bone regeneration potential, derived from rich, renewable, and cheap sources, are reported. Thus, thin films were synthesized from marine-derived (i.e., from fish bones and seashells) hydroxyapatite (MdHA) by pulsed laser deposition (PLD) technique. Besides the physical-chemical and mechanical investigations, the deposited thin films were also evaluated in vitro using dedicated cytocompatibility and antimicrobial assays. The morphological examination of MdHA films revealed the fabrication of rough surfaces, which were shown to favor good cell adhesion, and furthermore could foster the in-situ anchorage of implants. The strong hydrophilic behavior of the thin films was evidenced by contact angle (CA) measurements, with values in the range of 15-18 degrees. The inferred bonding strength adherence values were superior (i.e., similar to 49 MPa) to the threshold established by ISO regulation for high-load implant coatings. After immersion in biological fluids, the growth of an apatite-based layer was noted, which indicated the good mineralization capacity of the MdHA films. All PLD films exhibited low cytotoxicity on osteoblast, fibroblast, and epithelial cells. Moreover, a persistent protective effect against bacterial and fungal colonization (i.e., 1- to 3-log reduction of E. coli, E. faecalis, and C. albicans growth) was demonstrated after 48 h of incubation, with respect to the Ti control. The good cytocompatibility and effective antimicrobial activity, along with the reduced fabrication costs from sustainable sources (available in large quantities), should, therefore, recommend the MdHA materials proposed herein as innovative and viable solutions for the development of novel coatings for metallic dental implants.

Using the microwave-assisted sol-gel method, Zn- and Cu-doped TiO2 nanoparticles with an anatase crystalline structure were prepared. Titanium (IV) butoxide was used as a TiO2 precursor, with parental alcohol as a solvent and ammonia water as a catalyst. Based on the TG/DTA results, the powders were thermally treated at 500 degrees C. XRD and XRF revealed the presence of a single-phase anatase and dopants in the thermally treated nanoparticles. The surface of the nanoparticles and the oxidation states of the elements were studied using XPS, which confirmed the presence of Ti, O, Zn, and Cu. The photocatalytic activity of the doped TiO2 nanopowders was tested for the degradation of methyl-orange (MO) dye. The results indicate that Cu doping increases the photoactivity of TiO2 in the visible-light range by narrowing the band-gap energy.

The current study was focused on the potential of pure P25 TiO2 nanoparticles (NPs) and Fe(1%)-N co-doped P25 TiO2 NPs to induce cyto- and genotoxic effects in MRC-5 human pulmonary fibroblasts. The oxidative lesions of P25 NPs were reflected in the amount of 8-hydroxydeoxyguanosine accumulated in DNA and the lysosomal damage produced, but iron-doping partially suppressed these effects. However, neither P25 nor Fe(1%)-N co-doped P25 NPs had such a serious effect of inducing DNA fragmentation or activating apoptosis signaling. Moreover, oxo-guanine glycosylase 1/2, a key enzyme of the base excision repair mechanism, was overexpressed in response to the oxidative DNA deterioration induced by P25 and P25-Fe(1%)-N NPs.

Due to the emergence of antibiotic-resistant pathogens, the need to find new, efficient antimicrobial agents is rapidly increasing. Therefore, in this study, we report the development of new biocomposites based on zinc-doped hydroxyapatite/chitosan enriched with essential oil of Artemisia dracunculus L. with good antimicrobial activity. Techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR) were used in order to evaluate their physico-chemical properties. Our studies revealed that biocomposite materials with nanometric dimension and homogeneous composition could be obtained through an economic and cost-effective synthesis method. The biological assays demonstrated that ZnHA (zinc-doped hydroxyapatite), ZnHACh (zinc-doped hydroxyapatite/chitosan) and ZnHAChT (zinc-doped hydroxyapatite/chitosan enriched with essential oil of Artemisia dracunculus L.) did not exhibit a toxic effect on the cell viability and proliferation of the primary osteoblast culture (hFOB 1.19). Moreover, the cytotoxic assay also highlighted that the cell morphology of the hFOB 1.19 was not altered in the presence of ZnHA, ZnHACh or ZnHAChT. Furthermore, the in vitro antimicrobial studies emphasized that the samples exhibited strong antimicrobial properties against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923 and Candida albicans ATCC 10231 microbial strains. These results are encouraging for the following development of new composite materials with enhanced biological properties that could promote the osteogenic process of bone healing and also exhibit good antimicrobial properties.

Extensive attention and considerable efforts have been made to construct efficient heterogeneous nano -particulate systems for surface chemical reactions to be active in solar light-driven photodegradation. This work addresses current deficiencies of the nanoparticles-focused systems intended for visible light photodegradation by developing a newly-formulated innovative chemically-engineered multi-component system that functions as a recyclabe, nontoxic, active and inexpensive catalyst for photodegradation of tetracyclne antibiotic. Here, we show a straightforward FeOOH nanografting of Al-based SrTiO3 perovskite material as core-shell nanoflower-like heteronanostructure with enhanced solar light-driven photodegradation capability over harmful antibi-otics. A persuasive surface formation mechanism is proposed based on systematic investigation of the assembly process. In-depth caracterization of structural, optical and morphological properties of the prepared samples was investigated using a series of complementary analytical techniques, such as XRD, FE-SEM, HR-TEM, synchrotron XPS, as well as hard and soft XAS in both total electron yield (TEY) and fluorescence yield (TFY). The oxygen -deficient nature of core and shell interface indicates its n-doping and the availability of free charges in core which can be either transferred to the shell or create localized absorption levels into the valence band. This study provides a real opportunity to rationally photocatalysts design with very promising performance in water treatment.

Sodium hexatitanate (Na2Ti6O13) nanoparticles have been synthesized by the hydrothermal method with microwave and conven-tional heating, after which their photocatalytic properties toward an azo dye pollutant degradation have been investigated. Insights into the dynamics and reactivity of the species involved in the photocatalytic mechanism of the (Na2Ti6O13) samples were precisely investigated, for the first time, by X-band electron paramagnetic resonance (EPR) spectroscopy under different experimental conditions. X-ray diffraction structural analysis revealed that all samples crystallized in a monoclinic C2/m structure, with different short-range structural order according to the employed heating, as indicated by Raman. Field-emission scanning electron microscopy and transmission electron microscopy results revealed the formation of rod-and fiber-like nanoparticles with different diameters and lengths. EPR measurements indicated the presence of different Ti3+ point defects and F centers in the samples. X-ray photoelectron spectroscopy analysis proved the presence of oxygen-related defects, but no Ti3+ was detected on the surface. Spin trapping experiments monitored the generation of hydroxyl (OH center dot) radicals over UV-irradiation time. Various parameters contribute to the photocatalytic activity of the samples; however, the type of defect and particle morphology appeared as key factors for enhanced efficiency. Our study provides significant information about paramagnetic defects in Na2Ti6O13 materials and their role in photocatalysis to design other Ti-based photocatalysts.

Nonmagnetic chiral crystals are a new class of systems hosting Kramers-Weyl Fermions, arising from the combination of structural chirality, spin- orbit coupling (SOC), and time-reversal symmetry. These materials exhibit nontrivial Fermi surfaces with SOC-induced Chern gaps over a wide energy range, leading to exotic transport and optical properties. In this study, we investigate the electronic structure and transport properties of CdAs2, a newly reported chiral material. We use synchrotron-based angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT) to determine the Fermiology of the (110)-terminated CdAs2 crystal. Our results, together with complementary magnetotransport measurements, suggest that CdAs2 is a promising candidate for novel topological properties protected by the structural chirality of the system. Our work sheds light on the details of the Fermi surface and topology for this chiral quantum material, providing useful information for engineering novel spintronic and optical devices based on quantized chiral charges, negative longitudinal magnetoresistance, and nontrivial Chern numbers.