National Institute Of Materials Physics - Romania

Magnesium-doped hydroxyapatite/chitosan composite coatings produced by the radio-frequency magnetron sputtering technique were exposed to 5 MeV electron beams of 8 and 30 Gy radiation doses in a linear electron accelerator. The surfaces of unirradiated layers are smooth, while the irradiated ones exhibit nano-structures with sizes that increase from 60 nm at a 8 Gy dose to 200 nm at a 30 Gy dose. Young's modulus and the stiffness of the layers decrease from 58.9 GPa and 10 mu N/nm to 5 GPa and 2.2 mu N/nm, respectively, when the radiation doses are increased from 0 to 30 Gy. These data suggest the diminishing of the contribution of the chitosan to the elasticity of the magnesium-doped hydroxyapatite/chitosan composite layers after electron beam irradiation. The biological capabilities of the coatings were assessed before and after their immersion in RPMI-1640 cell culture medium for 7 and 14 days, respectively, and further cultured with a MG63 cell line (ATCC CRL1427) in Dulbecco's Modified Eagle Medium supplemented with fetal bovine serum, penicillin-streptomycin, and L-glutamine. Thus, 1 mu m spherical structures were developed on the surfaces of the layers exposed to a 30 Gy radiation dose and immersed for 14 days in the RPMI-1640 biological medium. The molecular structures of all the RPMI-1640 immersed samples were modified by the growth of a carbonated hydroxyapatite layer characterized by a B-type substitution, as Fourier Transform Infrared Spectroscopy revealed. The biological assay proved the increased biocompatibility of the layers kept in RPMI-1640 medium and enhanced MG63 cell attachment and proliferation. Atomic force microscopy analysis indicated the elongated fibroblastic cell morphology of MG63 cells with minor alteration at 30 Gy irradiation doses as a result of layer biocompatibility modifications.

In the last decade, it has been observed that the field of biomaterials has gained the attention of the researchers. This study presents the physicochemical and biological properties of coatings based on chromium-doped hydroxyapatite (CrHAp) and chromium-doped hydroxyapatite enriched with amoxicillin (CrHApAx). The coatings were obtained for the first time using the dip coating technique, beginning from dense suspensions of CrHAp and CrHApAx. The obtained layers were then analyzed by various methods in order to have a comprehensive overview of their physicochemical properties. Stability studies performed using ultrasound measurements showed that the CrHAp suspension has very good stability (S = 6.8610-6 s-1) compared to double-distilled water. The CrHApAx suspension (S = 0.00025 s-1) shows good but weaker stability compared to that of the CrHAp suspension. Following XRD studies, a single hydroxyapatite-specific phase was observed in the CrHAp sample, while in the case of the CrHApAx sample, an amoxicillin-specific peak was also observed. The AFM results showed that the CrHAp coatings had a surface topography of a homogenous and uniform layer, with no significant cracks and fissures, while the CrHApAx coatings exhibited a surface morphology of homogenous layers formed of particles conglomerates. The biocompatibility of CrHAp and CrHApAx coatings was assessed using the MG63 cell line. The cytotoxicity of the coatings was evaluated by measuring cell viability with the aid of an MTT assay after 24, 48, and 72 h of incubation with the CrHAp and CrHApAx coatings. The results demonstrated that both CrHAp and CrHApAx coatings exhibited good biocompatibility for all the tested time intervals. The in vitro antibacterial activity of the coatings was also assessed against Pseudomonas aeruginosa 27853 ATCC (P. aeruginosa) bacterial cells. The potential of P. aeruginosa bacterial cells to adhere and develop on the surfaces of CrHAp and CrHApAx coatings was also investigated using AFM analysis. The findings of the biological assays suggest that CrHAp and CrHApAx coatings could be considered as promising candidates for biomedical applications, including the development of novel antimicrobial materials.

In this work, we report for the first time the development and complex characterization of new bioceramics based on hydroxyapatite (HAp, Ca10(PO4)6(OH)2). On the other hand, the lyophilization process was used for the first time in this research. The samples were obtained by a modified coprecipitation method and were dried by lyophilization (lyophilized hydroxyapatite (HApLF) and lyophilized zinc-doped hydroxyapatite (5ZnHApLF)). Valuable information about the HApLF and 5ZnHApLF stability was obtained through nondestructive ultrasound measurements. The X-ray diffraction (XRD) studies revealed the phase and the effects of the incorporation of Zn ions into the HAp structure. The chemical composition of the samples was evaluated by energy dispersive X-ray analysis (EDS) and X-ray photoelectron spectroscopy (XPS). Information about the functional groups present in the HApLF and 5ZnHApLF was obtained using Fourier Transform Infrared Spectroscopy (FTIR) studies. The morphology of HApLF and 5ZnHApLF pellets was observed by scanning electron microscopy (SEM). The surface topography of HApLF and 5ZnHApLF pellets was studied with the aid of atomic force microscopy (AFM). Details regarding the roughness of the samples were also obtained using AFM topographies and SEM images. A complementary study was also carried out on a larger analysis surface using a Scanning Acoustic Microscope (SAM). The SAM was used for the first time to analyze the surface of HAp and 5ZnHAp pellets. The biological properties of the HApLF and 5ZnHApLF pellets was investigated with the aid of MG63 and human gingival fibroblasts (HGF-1) cell lines. The results of the cell viability assay highlighted that both the HApLF and 5ZnHApLF pellets exhibited good biological activity. Moreover, SEM and AFM studies were conducted in order to emphasize the development of MG63 and HGF-1 cells on the pellet's surface. Both SEM and AFM images depicted that the pellets' surface favored the cell attachment and development of MG63 and HGF-1 cells. Furthermore, the antimicrobial properties of the HApLF and 5ZnHApLF were evaluated against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923, and Candida albicans ATCC 10231. The results of the antimicrobial assays highlighted that the 5ZnHApLF exhibited a strong antimicrobial activity against the tested microbial strains. The results of the biological assays suggested that the samples show great potential for being used in the development of novel materials for biomedical applications.

A methodology for the quantitative estimation of the drug loading of iron oxide-based magnetic nanoparticles by corroborating magnetometry and M & ouml;ssbauer spectroscopy investigations is reported. The proposed methodology is exemplified in the case of two series of nanoparticles, namely Fe3O4 nanoparticles covered with citric acid molecules and further functionalized with doxorubicin, and Fe3O4 nanoparticles covered with L-Cysteine molecules and further functionalized with doxorubicin. The general idea of the proposed methodology is to probe the real magnetic structure of the magnetic core via low-temperature M & ouml;ssbauer spectroscopy for the correct estimation of the spontaneous magnetization of the magnetic core. It subsequently uses the ratio between the spontaneous magnetization of the covered nanoparticles and that of the magnetic core for the reliable and nondestructive evaluation of the nanoparticle loading by organic molecules. Although the methodology is exemplified in the case of magnetite-based nanoparticles, it can be successfully considered for a large class of medicine-loaded Fe-containing magnetic nanoparticles where 57Fe M & ouml;ssbauer spectroscopy can be applied.

When used as the active layers-either as a light absorber in photovoltaic devices or as an electroluminescent material in light-emitting devices-lead-free perovskites significantly impact the performance of optoelectronic devices. This study focuses on antimony-based perovskites, which are promising for lighting applications. These types of perovskites enable the formation of self-trapped excitons (STEs) with higher dissociation energy than lead-based perovskites, which generate excitons with lower dissociation energy. The (CH3NH3)3Sb2I9 crystals are synthesized using two methods, resulting in distinct spatial configurations - dimer and dimer/layered mixtures, each exhibiting unique structural and spectroscopic properties, as revealed by comprehensive multi-parametric complementary analyses. Their emissive properties underscore the efficiency of the STE photoluminescence, driven by electron-phonon interactions and influenced by Sb-Sb distances in (CH3NH3)3Sb2I9 powder, whether dispersed in polymethyl-methacrylate or solution. The phase transition from monoclinic to hexagonal (dimer) and trigonal (layered) structures enabled the tuning of the optical properties in direct correlation with the structural and electrical features. The photoluminescence behavior of the STEs, analyzed in conjunction with the Raman spectroscopy, elucidates the dynamic process of the electron-phonon coupling effects in the dimer (face-capping Sb-I octahedra) and layered (corner-sharing Sb-I octahedra) crystallographic structures.

In this paper, we present the development of magnesium-doped hydroxyapatite in chitosan matrix (MHA_Ch) powder by an adapted coprecipitation method. The MHA_Ch powder was then deposited as thin layers by radio frequency magnetron sputtering. The MHA_Ch layers were exposed to various irradiation doses and immersed in Dulbecco's Modified Eagle's Medium (DMEM) for various time intervals. We report, for the first time, the effects of DMEM on irradiated layers of magnesium-doped hydroxyapatite in a chitosan matrix. The surface morphology of the layers before and after irradiation and immersion in DMEM was evaluated by SEM, AFM, and MM studies. Additionally, data about the functional groups present in the layers and the changes induced by exposure of the layers to irradiation and DMEM were obtained by FTIR studies. In vitro biological assays were conducted using an MG63 cell line (ATCC CRL1427). Our results suggest that the magnesium-doped hydroxyapatite in chitosan matrix layers may be suitable candidates for applications in the biomedical domain.

Biodegradable templates are sought for targeted antibiotic administration/delivery in bone infections to avoid detrimental reactions during bone regeneration. We investigated two key-aspects in this direction: 1) the optimal antibiotic delineation, with thermal stability equivalent to the temperature involved for templates preparation and 2) the antibacterial templates development by a two-step homogenization process. The selected antibiotic - ampicillin (AMP) was mechanically and then thermally mixed with the prime materials: poly(lactic acid) (PLA) - the polymeric matrix, biogenic bovine bone-derived hydroxyapatite (HA, particles <40 mu m), and graphene nanoplatelets (GnP, micrometric range). For the first time, all materials were used in simultaneous modulated ratios for the synthesis of PLA/AMP (1-5 wt.%)/HA (0-30 wt.%)/GnP (0-3 wt.%) composites. The influence of the concomitant materials modulation was surveyed through several assays. The FTIR-ATR spectroscopy depicted a three-level model of overlapping structures asserting the solid molecular cross-linking between all materials, without structural alterations induced to any material (XRD analysis). The addition of AMP to the PLA matrix caused a slight particle conglomeration, alleviated through GnP addition. The microporous HA particles supported the adhesion to the PLA matrix and promoted the AMP particles' entrapment/attachment. Linked to the enhanced wettability of the composite materials, the phosphate buffered saline solution (PBS) degradation profiles revealed a pronounced burst during the first 14-28 days of incubation and a long-term, low-level process hereafter. Thus, the formation of pores and cavities were signalled along with the HA particles' fragmentation. The released AMP (percentage) pictured an ascending trendline during the 24 h of analysis, at all targeted ratios. The preservation of AMP features at 200 degrees C was endorsed by the strong antibacterial activity of composite materials against Staphylococcus aureus (S. Aureus) growth and the medium response against Escherichia coli (E. Coli) - the higher the drug release, the higher the inhibitory effect on bacteria evolution.

The paper presents the features of the magnetization decay of proton-irradiated MgB2 bulk samples. Irradiation was performed with protons of energies between 8.6 and 15.07 MeV at different fluences. The creep activation energy is sensitive to the ratio between proton range and sample thickness. Experimental data show that the creep exponents are different from the theoretical predictions. When the proton range is shorter than the sample thickness (protons of 8.6 MeV), the thermomagnetic instabilities are strongly emphasized and affect the creep behavior.

Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti3C2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti3C2, hydroamination exhibits almost complete selectivity for the anti-Markovnikov regioisomer, for both aliphatic amines and less-reactive aromatic amines. Ti3C2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C-C multiple bonds is a reaction with complete atom efficiency that may form C-N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti3C2 nanosheets is quantified by thermoprogrammed NH3 desorption. The measured TOF values are on the order of 102 h-1, with the highest TOF value being 350 h-1 for 1-hexyne hydroamination by n -butylamine. Therefore, Ti3C2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.

Herein we present a comparative study among different spray-coated nanometric mesoporous electron transporting layers (ETLs) in perovskite solar cells (PSC), namely m-TiO2, 2 , m-SnO2 2 and m-SnO2 2 quantum dots (mSnO2QDs). 2 QDs). The solutions used for deposition were prepared from commercial pastes and colloidal suspensions for m-TiO2 2 and m-SnO2. 2 . For m-SnO2QDs 2 QDs in-house QDs solutions were prepared. The formamidiniummethylamonium-potassium (FAMA@10 K) has been used as light absorber material in the fabricated PSCs. The structural, compositional and morphological studies, correlated with the photovoltaic performance of PSCs, indicate that the m-SnO2 2 QDs layer is the best candidate among the three investigated mesoporous ETLs. Compared with the suspensions used for the other two ETLs, the in-house prepared SnO2 2 QDs solution presents smaller agglomerates of nanoparticles and results in the formation of a thinner, more uniform and compact mesoporous ETL. The FAMA@10 K perovskite deposited on m-SnO2 2 QDs ETL presents a lower roughness, better uniformity and a higher amount of PbI2. 2 . Our work unveils that the SnO2 2 QDs solution can be easily produced in laboratory and when is deposited as mesoporous scaffold in a PSC with FAMA@10 K perovskite, the power conversion efficiency increases up to 14.90 %, being with up to 27 % larger than in the PSCs with m-TiO2 2 and mSnO2 2 ETLs prepared from commercial solutions. By modeling the J-V dynamic hysteresis with more than 90 % match between the calculated and experimental J-V data, for all three types of mesoporous ETLs, the relevant parameters that explain the hysteresis magnitude and account for ionic-induced recombination processes in PSCs were determined.