Iwona Malka

Highly biocompatible, nanocrystalline hydroxyapatite synthesized in a solvothermal process driven by high energy density microwave radiation.

A microwave, solvothermal synthesis of highly biocompatible hydroxyapatite (HAp) nanopowder was developed. The process was conducted in a microwave radiation field having a high energy density of 5 W/mL and over a time less than 2 minutes. The sample measurements included: powder X-ray diffraction, density, specific surface area, and chemical composition. The morphology and structure were investigated by scanning electron microscopy as well as transmission electron microscopy (TEM). The thermal behavior analysis was conducted using a simultaneous thermal analysis technique coupled with quadruple mass spectrometry. Additionally, Fourier transform infrared spectroscopy tests of heated samples were performed. A degradation test and a biocompatibility study in vitro using human osteoblast cells were also conducted. The developed method enables the synthesis of pure, fully crystalline hexagonal HAp nanopowder with a specific surface area close to 240 m2/g and a Ca/P molar ratio equal to 1.57. TEM measurements showed that this method results in particles with an average grain size below 6 nm. A 28-day degradation test conducted according to the ISO standard indicated a 22% loss of initial weight and a calcium ion concentration at 200 μmol/dm3 in the tris(hydroxymethyl)aminomethane hydrochloride test solution. The cytocompatibility of the obtained material was confirmed in a culture of human bone derived cells, both in an indirect test using the material extract, and in direct contact. A quantitative analysis was based on the 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide. Viability assay as well as on DNA content measurements in the PicoGreen test. Indirect observations were performed at one point in time according to the ISO standard for in vitro cytotoxicity (ie, after 24 hours of cell exposure to the extracts). The direct contact tests were completed at three time points: after 24 hours, on day 7, and on day 14 of a culture in an osteogenic medium. All of the tests revealed good tolerance of cells toward the material; this was also shown by means of live/dead fluorescent staining. Both quantitative results and morphological observations revealed much better cell tolerance toward the obtained HAp compared to commercially available HAp NanoXIM, which was used as a reference material.

Size-dependent density of zirconia nanoparticles

Summary The correlation between density and specific surface area of ZrO2 nanoparticles (NPs) was studied. The NPs were produced using a hydrothermal process involving microwave heating. The material was annealed at 1100 °C which resulted in an increase in the average grain size of the ZrO2 NPs from 11 to 78 nm and a decrease in the specific surface area from 97 to 15 m2/g. At the same time, the density increased from 5.22 g/m3 to 5.87 g/m3. This effect was interpreted to be the result of the presence of a hydroxide monolayer on the NP surface. A smaller ZrO2 grain size was correlated with a larger contribution of the low density surface layer to the average density. To prove the existence of such a layer, the material was synthesized using 50% heavy water. Fourier transform infrared spectroscopy (FTIR) permitted the identification of the –OD groups created during synthesis. It was found that the –OD groups persisted on the ZrO2 surface even after annealing at 1100 °C. This hydroxide layer is responsible for the decrease in the average density of the NPs as their size decreases. This study of the correlation between particle size and density may be used to assess the quality of the NPs. In most cases, the technological aim is to avoid an amorphous layer and to obtain fully crystalline nanoparticles with the highest density possible. However, due to the effect of the surface layers, there is a maximum density which can be achieved for a given average NP diameter. The effect of the surface layer on the NP density becomes particularly evident for NPs smaller than 50 nm, and thus, the density of nanoparticles is size dependent.

On the Heat Stability of Amyloid-Based Biological Activity: Insights from Thermal Degradation of Insulin Fibrils

Formation of amyloid fibrils in vivo has been linked to disorders such as Alzheimer’s disease and prion-associated transmissible spongiform encephalopathies. One of the characteristic features of amyloid fibrils is the high thermodynamic stability relative both to native and disordered states which is also thought to underlie the perplexingly remarkable heat resistance of prion infectivity. Here, we are comparing high-temperature degradation of native and fibrillar forms of human insulin. Decomposition of insulin amyloid has been studied under helium atmosphere and in the temperature range from ambient conditions to 750°C using thermogravimetry and differential scanning calorimetry coupled to mass spectrometry. While converting native insulin into amyloid does upshift onset of thermal decomposition by ca. 75°C, fibrils remain vulnerable to covalent degradation at temperatures below 300°C, as reflected by mass spectra of gases released upon heating of amyloid samples, as well as morphology and infrared spectra of fibrils subjected to incubation at 250°C. Mass spectra profiles of released gases indicate that degradation of fibrils is much more cooperative than degradation of native insulin. The data show no evidence of water of crystallization trapped within insulin fibrils. We have also compared untreated and heated amyloid samples in terms of capacity to seed daughter fibrils. Kinetic traces of seed-induced insulin fibrillation have shown that the seeding potency of amyloid samples decreases significantly already after exposure to 200°C, even though corresponding electron micrographs indicated persisting fibrillar morphology. Our results suggest that amyloid-based biological activity may not survive extremely high temperature treatments, at least in the absence of other stabilizing factors.

Hydriding properties of Mg- -Al- -Zn quasicrystal powder produced by mechanical alloying

Abstract The stable quasicrystal belonging to the Bergman class based on Mg–Al–Zn (Mg44Al15Zn41) was prepared by the mechanical alloying of elemental powders. The phase structure, chemical composition and hydriding properties of the obtained quasicrystal were investigated by XRD, SEM, EDS, DSC and the volumetric Sievert method. Our results have shown that the Mg44Al15Zn41 quasicrystal is unstable while hydriding above 200 °C and decomposes irreversibly into different Mg–Zn based intermetallic compounds. While being hydrided at 200 °C, where the quasicrystal is stable, Mg44Al15Zn41 decomposes mainly into the MgZn2 based intermetallic compound with MgH2 but above 300 °C, where the 2/1 approximant is stable, Mg44Al15Zn41 transforms mainly into the Frank-Kasper phase with MgH2.

The role of Mg2FeH6 formation on the hydrogenation properties of MgH2-FeFx composites

AbstractThe hydrogenation properties of magnesium hydride mechanically milled with iron fluorides (FeF2 and FeF3), were investigated by Temperature Programmed Desorption (TPD) and volumetric methods using a Sieverts-type apparatus, as prepared upon dehydrogenation and finally upon subsequent hydrogenation. The activation energy of hydrogen desorption (Ea), calculated from the Kissinger formula using TPD measurements obtained with different heating rates, showed significant decreases of Ea in comparison to that of milled MgH2 without any dopants. Moreover, the influence of these metal fluorides on the thermodynamics of the decomposition process was also examined. In the case of the FeF2 dopant, rehydrogenation following desorption caused the complete decomposition of the iron fluoride to BCC iron and the formation of a predominant MgH2 phase. In contrast to FeF2, the addition of FeF3 led to the formation of β-MgH2 as a major phase coexisting with Mg2FeH6 and MgF2 compounds. The presence of pure Fe in the MgH2+FeF2 composite, as opposed to MgH2+FeF3 containing Mg2FeH6 and MgF2, did not cause any significant influence on the sorption properties of MgH2. Moreover, the original material doped with FeF3 predominantly showed iron in the Mg2FeH6 compound, while the FeF2 dopant iron mostly showed the nearly pure BCC metallic phase

Hollow microtubes made of carbon, boron and gold: novel semiconducting nanocomposite material for applications in electrochemistry and temperature sensing

Carbon based nanocomposites have recently been intensively investigated as a new class of functional hybrid materials. Here, we present a procedure to obtain a new nanocomposite material made of carbon, boron and gold for applications in electrochemistry and electronics. The presented fabrication protocol uses cellulose fibers as a template that is first modified with an inorganic nanocomposite material consisting of gold nanoparticles (AuNPs) embedded in a polyoxoborate matrix, and then is subjected to the process of thermal decomposition. The as obtained material has a form of tubes with a diameter of a couple of micrometers that are composed of carbonized cellulose coated with the polyoxoborate–AuNP nanocomposite. This inorganic shell, which covers the outer surface of the carbon microtubes, serves as a scaffold that makes the structure stable. The obtained material exhibits electrical properties of a semiconductor with the width of the band gap of about 0.6 eV, and forms Schottky contact with a metal electrode. We show that the new material is suitable for preparation of the NCT-type thermistor. We also demonstrate application of the new nanocomposite in electrochemistry for modification of the surface of a working electrode. Experiments carried out with three exemplary redox probes show that the electrochemical performance of the modified electrode depends greatly on the amount of AuNPs in the nanocomposite.