Surface Analysis by Photoelectrons – Computer Control of Experiments

Dizertační práce se zabývá metodami pro výzkum povrchů pevných látek za použití fotoelektronů emitovaných rentgenovým zářením. Jedná se o metody rentgenové fotolektronové spektroskopie - XPS, úhlově závislé XPS - ARXPS a rentgenové fotoelektronové difrakce - XPD. Práce se zaměřuje především na metodu ARXPS, která slouží k analýze hloubkového složení povrchu vzorků. Pro získávání informace o hloubkovém složení z naměřených spekter ARXPS byl vytvořen výpočetní software v prostředí Matlab, který byl testován na simulovaných datech a také na reálných vzorcích. Pro realizaci uvedených fotoelektronových metod byl navržen kompletní manipulační systém, který zabezpečuje transport vzorků ve vakuové aparatuře a také realizaci experimentů uvedenými metodami. Systém je z velké části řízen elektronicky pomocí vytvořeného ovládacího softwaru v počítači a umožňuje provádět tyto experimenty automatizovaně.Doctoral thesis is dealing with the methods for analysis of surfaces by photoelectrons being emitted by X-ray radiation. The methods are: X-ray Photoelectron Spectroscopy - XPS, Angle-resolved XPS - ARXPS and X-ray Photoelectron Diffraction - XPD. The work is especially focused on a method of ARXPS, which is used for the depth compositional analysis of sample surfaces. To obtain an information about the depth composition from the measured ARXPS spectra, a calculation software in the Matlab environment has been developed. The software has been tested both for simulated and real sample data. For an experimental implementation of these methods, a complete manipulation system has been developed. It ensures the transport of samples inside a vacuum apparatus and the experiment itself. The system is controlled mainly by a software and enables to run the experiments automatically.

Multifunctional Molecule-Grafted V₂C MXene as High-Kinetics Potassium-Ion-Intercalation Anodes for Dual-Ion Energy Storage Devices

Constructing dual-ion energy storage devices using anion-intercalation graphite cathodes offers the unique opportunity to simultaneously achieve high energy density and output power density. However, a critical challenge remains in the lack of proper anodes that match with graphite cathodes, particularly in sustainable electrolyte systems using abundant potassium. Here, a surface grafting approach utilizing multifunctional azobenzene sulfonic acid is reported, which transforms V2C MXene into a high-kinetics K+-intercalation anode (denoted ASA-V2C) for dual-ion energy storage devices. Importantly, the grafted azobenzene sulfonic acid offers extra K+-storage centers and fast K+-hopping sites, while concurrently acting as a buffer between V2C layers to mitigate the structural distortion during K+ intercalation/de-intercalation. These functionalities enable the V2C electrode with significantly enhanced specific capacity (173.9 mAh g−1 vs 121.5 mAh g−1 at 0.05 A g−1), rate capability (43.1% vs 12.0% at 20 A g−1), and cycling stability (80.3% vs 45.2% after 900 cycles at 0.05 A g−1). When coupled with an anion-intercalation graphite cathode, the ASA-V2C anode demonstrates its potential in a dual-ion energy storage device. Notably, the device depicts a maximum energy density of 175 Wh kg−1 and a supercapacitor-comparable power density of 6.5 kW kg−1, outperforming recently reported Li+-, Na+-, and K+-based dual-ion devices

Comparison of Different Approaches to Surface Functionalization of Biodegradable Polycaprolactone Scaffolds

Due to their good mechanical stability compared to gelatin, collagen or polyethylene glycol nanofibers and slow degradation rate, biodegradable poly-epsilon-caprolactone (PCL) nanofibers are promising material as scaffolds for bone and soft-tissue engineering. Here, PCL nanofibers were prepared by the electrospinning method and then subjected to surface functionalization aimed at improving their biocompatibility and bioactivity. For surface modification, two approaches were used: (i) COOH-containing polymer was deposited on the PCL surface using atmospheric pressure plasma copolymerization of CO2 and C2H4, and (ii) PCL nanofibers were coated with multifunctional bioactive nanostructured TiCaPCON film by magnetron sputtering of TiC-CaO-Ti3POx target. To evaluate bone regeneration ability in vitro, the surface-modified PCL nanofibers were immersed in simulated body fluid (SBF, 1x) for 21 days. The results obtained indicate different osteoblastic and epithelial cell response depending on the modification method. The TiCaPCON-coated PCL nanofibers exhibited enhanced adhesion and proliferation of MC3T3-E1 cells, promoted the formation of Ca-based mineralized layer in SBF and, therefore, can be considered as promising material for bone tissue regeneration. The PCL-COOH nanofibers demonstrated improved adhesion and proliferation of IAR-2 cells, which shows their high potential for skin reparation and wound dressing

Immobilization of Platelet-Rich Plasma onto COOH Plasma-Coated PCL Nanofibers Boost Viability and Proliferation of Human Mesenchymal Stem Cells

The scaffolds made of polycaprolactone (PCL) are actively employed in different areas of biology and medicine, especially in tissue engineering. However, the usage of unmodified PCL is significantly restricted by the hydrophobicity of its surface, due to the fact that its inert surface hinders the adhesion of cells and the cell interactions on PCL surface. In this work, the surface of PCL nanofibers is modified by Ar/CO2/C2H4 plasma depositing active COOH groups in the amount of 0.57 at % that were later used for the immobilization of platelet-rich plasma (PRP). The modification of PCL nanofibers significantly enhances the viability and proliferation (by hundred times) of human mesenchymal stem cells, and decreases apoptotic cell death to a normal level. According to X-ray photoelectron spectroscopy (XPS), after immobilization of PRP, up to 10.7 at % of nitrogen was incorporated into the nanofibers surface confirming the grafting of proteins. Active proliferation and sustaining the cell viability on nanofibers with immobilized PRP led to an average number of cells of 258+-12.9 and 364+-34.5 for nanofibers with ionic and covalent bonding of PRP, respectively. Hence, our new method for the modification of PCL nanofibers with PRP opens new possibilities for its application in tissue engineering

Different concepts for creating antibacterial yet biocompatible surfaces: Adding bactericidal element, grafting therapeutic agent through COOH plasma polymer and their combination

Antibacterial coatings have become a rapidly developing field of research, strongly stimulated by the increasing urgency of identifying alternatives to the traditional administration of antibiotics. Such coatings can be deposited onto implants and other medical devices and prevent the inflammations caused by hospital-acquired infections. Nevertheless, the design of antibacterial yet biocompatible and bioactive surfaces is a challenge that biological community has faced for many years but the "materials of dream" have not yet been developed. In this work, the biocompatible yet antibacterial multi-layered films were prepared by a combination of magnetron sputtering (TiCaPCON film), ion implantation (Ag-doped TiCaPCON film), plasma polymerization (COOH layer), and the final immobilization of gentamicin (GM) and heparin (Hepa) molecules. The layer chemistry was thoroughly investigated by means of FTIR and X-ray photoelectron spectroscopies. It was found that the immobilization of therapeutic components occurs throughout the entire thickness of the plasma-deposited COOH layer. The influence of each type of bactericide (Ag+ ions, GM, and Hepa) on antibacterial activity and cell proliferation was analyzed. Our films were cytocompatible and demonstrated superior bactericidal efficiency toward antibioticresistant bacterial E. coli K261 strain. Increased toxicity while using the combination of Ag nanoparticles and COOH plasma polymer is discussed

Low-energy electron microscopy of graphene outside UHV: electron-induced removal of PMMA residues used for graphene transfer

Two-dimensional materials, such as graphene, are usually prepared by chemical vapor deposition (CVD) on selected substrates, and their transfer is completed with a supporting layer, mostly polymethyl methacrylate (PMMA). Indeed, the PMMA has to be removed precisely to obtain the predicted superior properties of graphene after the transfer process. We demonstrate a new and effective technique to achieve a polymer-free CVD graphene - by utilizing low-energy electron irradiation in a scanning low-energy electron microscope (SLEEM). The influence of electron-landing energy on cleaning efficiency and graphene quality was observed by SLEEM, Raman spectroscopy (the presence of disorder D peak) and XPS (the deconvolution of the C 1s peak). After removing the absorbed molecules and polymer residues from the graphene surface with slow electrons, the individual graphene layers can also be distinguished outside ultra-high vacuum conditions in both the reflected and transmitted modes of a scanning low-energy (transmission) electron microscope

Antibacterial activity of therapeutic agent-immobilized nanostructured TiCaPCON films against antibiotic-sensitive and antibiotic-resistant Escherichia coli strains

The development of flexible and low-cost methods of surface functionalization to fight infection at the early stage is an urgent scientific task. Herein, polymerization in low-pressure plasma rich in COOH species and carbodii-mide chemistry methods were utilized to immobilize four different therapeutic agents (antibiotic (gentamicin), antimicrobial peptide (indolicidin), anti-adhesive molecules (heparin) and nitroxide radicals (2,2,5,5-tetramethyl-3-carboxyl-pyrrolidine-1-oxyl)) on the surface of nanostructured biocompatible TiCaPCON films to impart antibacterial characteristics. The polymers deposited from COOH-rich plasma showed decent stability in phosphate-buffered saline solution and were successfully used for the immobilization of different therapeutic agents via ionic or covalent bond. The bactericide attachment was proved by FTIR spectroscopy and XPS analysis. All samples with grafted therapeutic agents were hydrophilic with water contact angle values in the range of 26-56 degrees. Bactericide release tests indicated the maximum concentration of therapeutic agents in the case of ionic immobilization. In case of covalent immobilization, fast initial release observed over 24 h was followed by slower leaching in the next 24 h (indolicidin), 48 h (heparin), and 96 h (gentamicin). The pH-sensitive COOH plasma polymer degradation and gentamicin release were demonstrated. The bactericide-linked films showed noticeable reduction of the antibiotic-sensitive E. coli U20 strain and, except indolicidin-immobilized samples, effectively inhibited growth of the antibiotic-resistant E. coli K261 strain at their initial concentration of 10(4) CFU/mL. The films with nitroxide radicals not only exhibited the highest antibacterial activity against E. coli K261 cells (100% after 8 h), but also prevented the biofilm formation