The adsorption behavior of the Tet-124 antimicrobial peptide and the Tet-124peptide modified at the C- and N-terminus with the sequence glycine-3,4-dihydroxyphenylalanine-glycine (G-DOPA-G) on titanium surfaces was studied using quartz crystal micro balance with dissipation (QCM-D). At a low pH level(4.75) Tet-124 and Tet-124-G-DOPA-G form rigid layers. This is attributed to the electrostatic interactions of the positively charged lysine and arginine residues in the peptide sequence with the negatively charged titanium oxide layer. At an elevated pH level (6.9) Tet-124 shows a lower mass adsorption at the surface than Tet-124-G-DOPA-G. This is attributed to the interaction of the catechol due to the formation of complexes with the titanium oxide and titanium surface layer. The C terminal and N terminal modification with the sequence G-DOPA-G shows similar adsorption rate and mass adsorption coverage at saturation; however it is presented a more loosely layers on the G-DOPA-G-TeT-124. Fibroblast adhesion and the biocompatibility test of both the surfaces following modification withTet-124-G-DOPA-G and the titanium alloy control showed similar results. In addition, no changes in the adhesion of E. colibacteria due to the modification of the surface were detected
A robust procedure for the surface bio-functionalization of carbon surfaces was developed. It consists on the modification of carbon materials in contact with an aqueous suspension of the enzyme laccase from Trametes versicolor and the lyophilization agent maltodextrin, with the pH value adjusted close to the isoelectric point of the enzyme. We report in-situ investigations applying Quartz Crystal Microbalance with Dissipation (QCM-D) for carbon-coated sensor surfaces and, moreover, ex-situ measurements with static contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Scanning Force Microscopy (SFM) for smooth Highly Oriented Pyrolytic Graphite (HOPG) substrates, for contact times between the enzyme formulation and the carbon material surface ranging from 20 s to 24 h. QCM-D studies reveals the formation of rigid layer of biomaterial, a few nanometers thin, which shows a strongly improved wettability of the substrate surface upon contact angle measurements. Following spectroscopic characterization, these layers are composed of mixtures of laccase and maltodextrin. The formation of these adsorbates is attributed to attractive interactions between laccase, the maltodextrin-based lyophilization agent and the hydrophobic carbon surfaces; a short-term contact between the aqueous laccase mixture suspension and HOPG surfaces is shown to merely result in de-wetting patterns influencing the results of contact angle measurements. The new enzyme-based surface modification of carbon-based materials is suggested to be applicable for the improvement of not only the wettability of low energy substrate surfaces with fluid formulations like coatings or adhesives, but also their adhesion in contact with hardened polymers
Surface engineering of magnesium alloys requires adequate strategies, processes and materials permitting corrosion protection. Liquid formulations containing corrosion inhibitors often are to be optimized according to the demands of the respective substrate and following the service conditions during its application. As an interdisciplinary approach, a combination of several techniques for instantly monitoring or elaborately analyzing the surface state of magnesium was accomplished in order to characterize the performance of new adsorbing sustainable amphiphilic polymers which recently were developed to facilitate a multi-metal corrosion protection approach. The application of established techniques like Contact Angle measurements and X-ray Photoelectron Spectroscopy investigations was supplemented by introducing related and yet faster online-capable and larger-scale techniques like Aerosol Wetting Test and Optically Stimulated Electron Emission. Moreover, an inexpensive setup was configured for scaling the inset and the extent of degradation processes which occur at local electrochemical circuits and lead to hydrogen bubble formation. Using these analytical tools, changes of the surface state of emeried AM50 samples were investigated. Even in contact with water, being a moderate corrosive medium, the online techniques facilitated detecting surface degradation of the unprotected magnesium alloy within * Corresponding author. L. M. G. Gonçalves et al. 283 some seconds. In contrast, following contact with a 1 weight% formulation of a polymeric corrosion inhibitor, surface monitoring indicated a delay of the onset of degradation processes by approximately two orders of magnitude in time. Mainly based on the spectroscopic investigations, the corrosion inhibiting effects of the investigated polymer are attributed to the adsorption of a primary polymer layer with a thickness of a few nanometers which occurs within some seconds. Immersion of magnesium for several hours brings up a protective film with around ten nanometers thickness.
Staphylococcus epidermidis is a gram-positive bacterium, and one of the most prevalent causes of nosocomial infections due to its strong ability to form biofilms on catheters and surgical implants. Here we explore the antimicrobial properties of Tet-124 peptides, which are part of the innate defense against different multicellular organisms in nature. Two different Tet-124 peptides were immobilized on a polyethylenimine (PEI) film to determine their impact on the antimicrobial properties: KLWWMIRRW (Tet-124), which contains only natural amino acids, and KLWWMIRRWG-(F-Br)-G (F-Br = 4-Bromophenylalanine), a modified Tet-124 sequence with the addition of an unnatural amino acid. The immobilization was obtained as a result of the electrostatic interaction between PEI amino groups and the C-terminal carboxylic groups of tryptophan and glycine amino acids of Tet-124 and Tet-124-Br peptides, respectively. The process was monitored and studied by water contact angle, Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Quartz Crystal Microbalance with Dissipation (QCM-D) measurements. The antibacterial effect of our samples against S. epidermis was evaluated by the spread plate counting method, and cytotoxicity was tested using fibroblast cultures. Our results indicate the feasibility to immobilize electrostatically both Tet-124 peptides for biomedical applications.
Quality assured surface pre-treatment may greatly enhance adhesive interactions and, thus, the performance and durability of material joints. This holds true as well for substrates used in coating processes as for adherents introduced into bonding processes. Wet table polymeric wetting agents—shortly called polymeric interfactants—contribute to modifying surfaces and governing the properties of interphases. This is demonstrated for amphiphilic polymers directing the adsorption of graphene oxide(GO) nano-sheets from aqueous dispersion on alumina surfaces. In this contribution, contact angle measurements as well as X-ray photoelectron spectroscopy and scanning force microscopy investigations are applied for the characterization of thin films. GO is adsorbed either from a buffered dispersion on pristine aluminum oxide surfaces or on alumina modified with a few nanometers thin layer of a polymeric interfactant. Laterally extended nanoparticles and GO nano-sheets are preferentially found on interfactant layers whereas on pristine aluminum oxide smaller adsorbates dominate. The driving forces directing the GO attachment are discussed using a phenomenological model based on polymer/substrate interactions governing the sticking probabilities of GO nano-sheets with different sizes
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