Laser Desorption/Ionization Mass Spectrometry as a Potential Tool for Evaluation of Hydroxylation Degree of Various Types of Titanium Dioxide Materials.

For many applications, TiO2 must have a unique surface structure responsible for its desirable physicochemical properties. Therefore the fast and easy methods of TiO2 surface characterization are of great interest. Heated TiO2 samples and dye-modified TiO2 samples were analyzed by laser desorption/ionization mass spectrometry. In the negative ion mode, two types of ions were detected, namely (TiO2)n- and (TiO2)nOH-. It has been established that the samples can be differentiated based on the relative ion abundances, especially with respect to the free hydroxyl group population. It indicates that laser desorption ionization mass spectrometry has the potential for the investigation of the surface properties of various TiO2 materials.

Transcriptional profiling of catalase genes in juglone-treated seeds of maize (Zea mays L.) and wheat (Triticum aestivum L.).

The major aim of the present study was to investigate the influence of juglone (JU; 5-hydroxy-1,4-naphthoquinone) treatments on the expression level of Cat1, Cat2 and Cat3 genes, encoding the respective catalase isozymes in maize (Zea mays L.) and wheat (Triticum aestivum L.) seeds. In parallel, germination efficiency, catalase (CAT) activity and hydrogen peroxide (H2O2) content in juglone-exposed cereal seeds were assessed. Juglone applications significantly stimulated abundance of three target catalase transcripts as well as induced CAT activity and generation of H2O2 in both maize and wheat kernels. Furthermore, germination process of juglone-affected maize seeds was more severe suppressed than in case of wheat kernels. The role of juglone in triggering the oxidative stress as well as antioxidative responses in seeds of the studied model cereal species are discussed.

Surface-Attached Poly(oxanorbornene) Hydrogels with Antimicrobial and Protein-Repellent Moieties: The Quest for Simultaneous Dual Activity.

By copolymerizing an amphiphilic oxanorbornene monomer bearing N- tert-butyloxycarbonyl (Boc) protected cationic groups with an oxanorbornene-functionalized poly(ethylene glycol) (PEG) macromonomer, bifunctional comb copolymers were obtained. Varying the comonomer ratios led to copolymers with PEG contents between 5⁻25 mol %. These polymers were simultaneously surface-immobilized on benzophenone-bearing substrates and cross-linked with pentaerythritoltetrakis(3-mercaptopropionate). They were then immersed into HCl to remove the Boc groups. The thus obtained surface-attached polymer hydrogels (called SMAMP*-co-PEG) were simultaneously antimicrobial and protein-repellent. Physical characterization data showed that the substrates used were homogeneously covered with the SMAMP*-co-PEG polymer, and that the PEG moieties tended to segregate to the polymer⁻air interface. Thus, with increasing PEG content, the interface became increasingly hydrophilic and protein-repellent, as demonstrated by a protein adhesion assay. With 25 mol % PEG, near-quantitative protein-adhesion was observed. The antimicrobial activity of the SMAMP*-co-PEG polymers originates from the electrostatic interaction of the cationic groups with the negatively charged cell envelope of the bacteria. However, the SMAMP*-co-PEG surfaces were only fully active against E. coli, while their activity against S. aureus was already compromised by as little as 5 mol % (18.8 mass %) PEG. The long PEG chains seem to prevent the close interaction of bacteria with the surface, and also might reduce the surface charge density.

Simultaneously Antimicrobial, Protein-repellent and Cell-compatible Polyzwitterion Networks: More Insight on Bioactivity and Physical Properties.

A poly(oxanorbornene)-based polyzwitterion with primary ammonium and carboxylate groups (PZI) has been reported previously as the first simultaneously antimicrobial and protein-repellent polyzwitterion. Here, additional physical and biological properties of three poly(oxanorbornene)-based polyzwitterions with different functional groups (PZI, the polycarboxybetaine PCB, and the polysulfobetaine PSB) are compared to understand the molecular origins of this unusual bioactivity. Additionally, the three polyzwitterions and the antimicrobial, polycationic SMAMP are exposed to proteins, bacteria suspensions, human plasma and serum. These interactions are investigated by surface plasmon resonance spectroscopy. In protein adhesion studies, neither fibrinogen nor lysozyme adhere irreversibly to PZI, yet reversible interaction with lysozyme is observed at pH 7 and 8. In the presence of bivalent cations, reversible fibrinogen adhesion on PZI and PSB is observed, but not on PCB. This might explain why mammalian cells grow on PZI and PSB, but not on PCB. PZI does not show human plasma adhesion, while PCB and PSB have 0.27 and 0.48 ng mm-2 adhered plasma, and SMAMP even 6.3 ng mm-2. Both PZI and SMAMP show strong serum adhesion, while no serum adhered to PCB, and only little to PSB. This could be related to the pH difference between serum and plasma, to which the pH-responsive primary ammonium groups are susceptible, while the permanently charged NR4 + groups are unaffected. Both PZI and PCB showed none or only little bacterial adhesion. PCB is also intrinsically antimicrobial against E. coli and S. aureus bacteria and thus is also simultaneously protein-repellent and antimicrobially active. Thus, while the carboxylate groups of PZI and PCB seems to be a prerequisite for the dual antimicrobial activity and protein-repellency, the pH-responsiveness of the primary ammonium group seems to make the PZI molecule vulnerable for protein adhesion in fluids that are slightly out of the physiological range.

Evaluation of Game Performance in Elite Male Sitting Volleyball Players.

The aims of the current study were (a) to analyze the differences in game performances of sitting volleyball athletes representing the different types of disabilities and (b) to assess whether the seated position vertical reach is one of the crucial factors in the game performance level of sitting volleyball athletes. One hundred male athletes from various national teams participating in the European Championships in Sitting Volleyball (2009) took part in this study. The athletes were categorized according to type of disability and the results of the vertical reach in a seated position. Thirtysix games were analyzed using the Game Performance Sheet for Sitting Volleyball. Twenty-three game performance parameters were studied. In addition, the sum and effectiveness of attacks, blocks, block services, services, ball receiving, and defensive actions were calculated. The main results indicated significant differences between athletes with minimal disability and athletes with single amputations from above the knee in the level of defensive performances and the summation of defensive actions. There was also a significant difference between athletes in relation to their vertical reach during activity and attacking actions, blocks, and ball receiving. In addition, there were strong relationships between the players' vertical reach scores and their activity and effectiveness in sitting volleyball. In conclusion, the accuracy of the World Organization Volleyball for Disabled classification systems for sitting volleyball players was confirmed. There is a strong relationship between players' vertical reach and their effectiveness in sitting volleyball.

A Simultaneously Antimicrobial, Protein-Repellent, and Cell-Compatible Polyzwitterion Network.

A simultaneously antimicrobial, protein-repellent, and cell-compatible surface-attached polymer network is reported, which reduces the growth of bacterial biofilms on surfaces through its multifunctionality. The coating was made from a poly(oxonorbornene)-based zwitterion (PZI), which was surface-attached and cross-linked in one step by simultaneous UV-activated CH insertion and thiol-ene reaction. The process was applicable to both laboratory surfaces like silicon, glass, and gold and real-life surfaces like polyurethane foam wound dressings. The chemical structure and physical properties of the PZI surface and the two reference surfaces SMAMP ("synthetic mimic of an antimicrobial peptide"), an antimicrobial but protein-adhesive polymer coating, and PSB (poly(sulfobetaine)), a protein-repellent but not antimicrobial polyzwitterion coating were characterized by Fourier transform infrared spectroscopy, ellipsometry, contact angle measurements, photoelectron spectroscopy, swellability measurements (using surface plasmon resonance spectroscopy, SPR), zeta potential measurements, and atomic force microscopy. The time-dependent antimicrobial activity assay (time-kill assay) confirmed the high antimicrobial activity of the PZI; SPR was used to demonstrate that it was also highly protein-repellent. Biofilm formation studies showed that the material effectively reduced the growth of Escherichia coli and Staphylococcus aureus biofilms. Additionally, it was shown that the PZI was highly compatible with immortalized human mucosal gingiva keratinocytes and human red blood cells using the Alamar Blue assay, the live-dead stain, and the hemolysis assay. PZI thus may be an attractive coating for biomedical applications, particularly for the fight against bacterial biofilms on medical devices and in other applications.

Fluorescent ROMP Monomers and Copolymers for Biomedical Applications.

The synthesis and characterization of a series of green, blue and red-fluorescent exo-oxanorbornene acid and imide monomers carrying nitrobenzofurazan, coumarin, and Rhodamin B, respectively, as fluorophores is presented. These monomers carry oxanorbornene as polymerizable unit, and were readily copolymerized with bioactive functional oxanorbornene monomers by ring-opening metathesis polymerization (ROMP), as demonstrated by gel permeation chromatography and NMR spectroscopy. Due to the ease of synthesis of these monomers, and their cost-effectiveness compared many to other fluorescent probes, they are useful for biomaterials applications.