Miran Mozetič

Titanium nanostructures for biomedical applications

Titanium and titanium alloys exhibit a unique combination of strength and biocompatibility, which enables their use in medical applications and accounts for their extensive use as implant materials in the last 50 years. Currently, a large amount of research is being carried out in order to determine the optimal surface topography for use in bioapplications, and thus the emphasis is on nanotechnology for biomedical applications. It was recently shown that titanium implants with rough surface topography and free energy increase osteoblast adhesion, maturation and subsequent bone formation. Furthermore, the adhesion of different cell lines to the surface of titanium implants is influenced by the surface characteristics of titanium; namely topography, charge distribution and chemistry. The present review article focuses on the specific nanotopography of titanium, i.e. titanium dioxide (TiO2) nanotubes, using a simple electrochemical anodisation method of the metallic substrate and other processes such as the hydrothermal or sol-gel template. One key advantage of using TiO2 nanotubes in cell interactions is based on the fact that TiO2 nanotube morphology is correlated with cell adhesion, spreading, growth and differentiation of mesenchymal stem cells, which were shown to be maximally induced on smaller diameter nanotubes (15 nm), but hindered on larger diameter (100 nm) tubes, leading to cell death and apoptosis. Research has supported the significance of nanotopography (TiO2 nanotube diameter) in cell adhesion and cell growth, and suggests that the mechanics of focal adhesion formation are similar among different cell types. As such, the present review will focus on perhaps the most spectacular and surprising one-dimensional structures and their unique biomedical applications for increased osseointegration, protein interaction and antibacterial properties.

Spontaneous Growth of Superstructure α‐Fe2O3 Nanowire and Nanobelt Arrays in Reactive Oxygen Plasma

One-dimensional a-Fe2O3 is a promising nanomaterial for advanced applications in catalysis and water splitting, environmental protection, sensors, dye solar cells, magnetic storage media, bioprocessing, and controlled drug delivery and detection, especially as carriers of antigens for prion detection and PCR manipulation. a-Fe2O3 nanowires have been successfully synthesized by various methods based on templates, hydrothermal conditions, sol–gel-mediated reactions, solvothermal conditions, gas decomposition, direct thermal oxidation (in a gas atmosphere of CO2, SO2, O2, and NO2), [7] chemical vapor deposition (CVD), and plasmaenhanced chemical vapor deposition (PECVD). The methods based on direct thermal oxidation, gas decomposition, and CVD reported to date require long synthesis times and high temperatures and therefore limit the efficiency of oxide nanowire synthesis. The application and commercialization of nanowires or nanobelts requires simple synthetic methods that can be scaled for both large areas and large quantities. Recently, we discovered a new universal method for the synthesis of transition metal oxide nanowires and nanobelts by direct plasma oxidation of bulk materials. It has been successfully applied for the rapid synthesis of high-density niobium oxide nanowires. In this process, there is no

The surface modification of cellulose fibres to create super-hydrophobic, oleophobic and self-cleaning properties

The surface modification of cellulose fibres was performed with the use of low-pressure water vapour plasma, followed by the application of a pad-dry-cure sol-gel coating with the water- and oil-repellent organic-inorganic hybrid precursor fluoroalkyl-functional siloxane (FAS), with the aim of creating the “lotus effect” on the cotton fabric surface. The tailored “lotus effect” was confirmed by measurements of the contact angle of water (154°) and n-hexadecane (140°), as well as by measurements of the water sliding angle (7°), which were used to identify the super-hydrophobic, oleophobic and self-cleaning properties of the modified fibres. The chemical and morphological changes caused by modifications of the fibres were investigated by XPS, FTIR, AFM and SEM. The results show that the plasma pre-treatment simultaneously increased the surface polarity, average roughness, and surface area of the fabric. The application of the FAS coating after plasma pre-treatment caused only a slight increase in the surface roughness, accompanied by a decrease in the surface area, indicating that the architecture of the surface was significantly changed. This result suggests that the surface pattern affected the “lotus effect” more than the average surface roughness. The plasma pre-treatment increased the effective concentration of the FAS network on the fabric, which resulted in enhanced repellency before and after repetitive washing, compared with that of the FAS-coated fabric sample without the plasma pre-treatment. Despite the fact that the plasma pre-treatment increased the concentration of the oxygen-containing functional groups on the fabric surface, this phenomenon insignificantly contributed to the adhesion ability and, consequently, the washing fastness of the FAS coating.

The influence of substrate material on bacteria sterilization in an oxygen plasma glow discharge

A critical approach to plasma sterilization is presented with the aim of sterilizing biocompatible materials such as TiO2 and polymer implants. Oxygen plasma was applied to sterilize glass and aluminium samples containing Bacillus subtilis spores. Sterilization was performed with a low pressure weakly ionized oxygen plasma created with a RF generator with an output power of 300 W and frequency 27.12 MHz. The density of charged particles, density of neutral oxygen atoms and the electron temperature were about 1 × 1016 m−3, 1.5 × 1022 m−3 and 5 eV, respectively. The sterilization effects were observed by SEM and by bacterial cultivation. It was found that the surface recombination of O-atoms plays an important role, since it causes temperature changes in the substrate. The sterilization efficiency increased with increasing plasma exposure time. The results showed that the sterilization efficiency is not necessarily just the effect of oxygen plasma radical interactions, but also of the sample heating due to radical interaction with the substrate. Plasma sterilization should be done differently according to the substrate material used for sterilization.

Modification of ink-jet paper by oxygen-plasma treatment

A study on oxygen-plasma treatment of ink-jet paper is presented. Paper was exposed to a weakly ionized, highly dissociated oxygen plasma with an electron temperature of 5?eV, a positive-ion density of 8 ? 1015?m?3 and a density of neutral oxygen atoms of 5 ? 1021?m?3. Optical emission spectroscopy (OES) was applied as a method for detection of the reaction products during the plasma treatment of the paper. OES spectra between 250 and 1000?nm were measured continuously during the plasma treatment. The wettability of the samples before and after the plasma treatment was determined by measuring the contact angle of a water drop. The appearance of the surface-functional groups was determined by using high-resolution x-ray photoelectron spectroscopy (XPS), while changes in the surface morphology were monitored with scanning electron microscopy (SEM). Already after 1?s of the plasma treatment the surface, which was originally hydrophobic, changed to hydrophilic, as indicated by a high absorption rate of a water drop into the paper. The OES showed a rapid increase of the CO and OH bands for the first few seconds of the plasma treatment, followed by a slow decrease during the next 40?s. The intensity of the O atom line showed reversed behaviour. The XPS analyses showed a gradual increase of oxygen-rich functional groups on the surface, while SEM analyses did not show significant modification of the morphology during the first 10?s of the plasma treatment. The results were explained by degradation of the alkyl ketene dimer sizing agent during the first few seconds of the oxygen-plasma treatment.

CF4 plasma and silver functionalized cotton

In an attempt to use minimal concentrations, initially, of silver nanoparticles for loading onto textiles and to achieve maximum concentrations on the material, CF4 low-pressure plasma was used on bleached and mercerized cotton fabric. The concentrations of silver on the fabrics were determined by the ICP-MS method (inductively coupled plasma-mass spectrometry), the morphology of fiber surfaces was observed with a scanning electron microscope (SEM), and an x-ray photoelectron spectroscopy (XPS) study was used for the evaluation of surface chemical changes. The antibacterial effect of silver loaded fabrics was tested against Enterococcus faecalis and Pseudomonas aeruginosa. The best results were found for plasma-treated cotton fabric functionalized with 30 nm silver particles. The results show effective plasma etching of the fabric surface, which caused excellent adhesion of silver particles. Color measurements of dyed samples showed that CF 4 plasma does not affect the color of dyed cotton. The mechanical properties of cotton remain unaltered after plasma treatment.

Optical emission spectroscopy characterization of oxygen plasma during treatment of a PET foil

Optical emission spectroscopy (OES) analysis of inductively coupled RF oxygen plasma during plasma treatment of a 23 µm thick polyethylene terephthalate (PET) foil is presented. Plasma was generated in pure oxygen at a pressure of 75 Pa with a RF generator at a frequency of 27.12 MHz and an output power of 300 W. The electron temperature was about 6 eV, the density of charged particles about 1016 m−3 and the density of neutral O atoms about 1022 m−3. Spectra were measured in the range from 250 to 950 nm by means of an optical spectrometer. For the first 10 s of plasma treatment the OES showed the presence of oxygen radicals only. Later, the OES spectra became richer with significant emission from CO and OH, which was attributed to PET oxidation. Simultaneously, the O peaks decreased significantly. After prolonged plasma treatment, the O peaks recovered, the CO band vanished while the OH and H peaks still persisted. In the final period of the treatment only atomic oxygen lines remained. The results showed that OES analysis was a powerful method for studying the evolution of PET oxidation by plasma treatment.

Degradation of Staphylococcus aureus bacteria by neutral oxygen atoms

The degradation of Staphylococcus aureus bacteria during treatment with neutral oxygen atoms was monitored by scanning electron microscopy. Experiments were performed in an afterglow chamber made from borosilicate glass. The source of oxygen atoms was remote inductively coupled radiofrequency oxygen plasma. The density of atoms at the samples was 8×1020 m−3. The treatment was performed at room temperature. The first effect was the removal of dried capsule. Capsule on exposed parts of bacteria was removed after receiving the dose of 6×1023 at./m2, while the parts of capsule filling the gaps between bacteria were removed after receiving the dose of 2.4×1024 m−2. After removing the capsule, degradation continued as etching of bacterial cell wall. The etching was rather nonuniform as holes with diameter of several 10 nm were observed. The cell wall was removed after receiving the dose of about 7×1024 m−2. The etching probabilities were about 2×10−5 for the capsule and 2×10−6 for the cell wall. The results wer...

Comparison of NO titration and fiber optics catalytic probes for determination of neutral oxygen atom concentration in plasmas and postglows

A comparative study of two different absolute methods NO titration and fiber optics catalytic probe (FOCP) for determination of neutral oxygen atom density is presented. Both methods were simultaneously applied for measurements of O density in a postglow of an Ar/O2 plasma created by a surfatron microwave generator with the frequency of 2.45 GHz an adjustable output power between 30 and 160 W. It was found that the two methods gave similar results. The advantages of FOCP were found to be as follows: it is a nondestructive method, it enables real time measuring of the O density, it does not require any toxic gas, and it is much faster than NO titration. The advantage of NO titration was found to be the ability to measure O density in a large range of dissociation of oxygen molecules.

Synergistic effect of gold nanoparticles and cold plasma on glioblastoma cancer therapy

Gold nanoparticles (AuNPs) have been investigated as a promising reagent for cancer therapy in various fields. In the meantime, cold atmospheric plasma has shown exquisite selectivity towards cancer cells. In this paper, we demonstrate that there is a synergy between gold nanoparticles and cold atmospheric plasma in cancer therapy. Specifically, the concentration of AuNPs plays an important role on plasma therapy. At an optimal concentration, gold nanoparticles can significantly induce glioblastoma (U87) cell death up to a 30% overall increase compared to the control group with the same plasma dosage but no AuNPs applied. The reactive oxygen species (ROS) intensity of the corresponding conditions has a reversed trend compared to cell viability. This matches with the theory that intracellular ROS accumulation results in oxidative stress, which further changes the intracellular pathways, causing damage to the proteins, lipids and DNA. Our results show that this synergy has great potential in improving the efficiency of cancer therapy and reducing harm to normal cells.