Enhancing Graphene Nanoplatelet Reactivity through Low-Temperature Plasma Modification.

Graphene-based materials have great potential for applications in many fields, but their poor dispersion in polar solvents and chemical inertness require improvements. Low-temperature plasma allows the precise modification of materials, improving the physicochemical properties of the surface and thus creating the possibility of their potential use. Plasma treatment offers the possibility of introducing oxygen functional groups simply, rapidly, and in a controlled way. In this work, a systematic investigation of the effect of plasma modification on graphene nanoplatelets has been carried out to determine the optimal plasma parameters, especially the exposure time, for introducing the highest amount of oxygen functional groups on a surface. Different gases (O2, CO2, air, Ar, and C2H4) were used for this purpose. The chemical nature of the introduced oxygen-containing functionalities was characterized by X-ray photoelectron spectroscopy, and the structural properties of the materials were studied by Raman spectroscopy. The plasma-induced changes have been shown to evolve as the surface functionalities observed after plasma treatment are unstable. The immersion of the materials in liquids was carried out to check the reactivity of carbons in postplasma reactions. Stabilization of the material's surface after plasma treatment using CH3COOH was the most effective for introducing oxygen functional groups.

Nanostructured Pr-Rich CexPr1-xO2-δ Mixed Oxides for Diesel Soot Combustion: Importance of Oxygen Lability.

Soot combustion experiments with 5%O2/He were conducted using model soot, and four distinct compositions of CexPr1-xO2-δ oxides of varying nominal cerium compositions (x = 0, 0.2, 0.3, and 1) were prepared. The catalyst samples were comprehensively characterized using techniques such as XRD, Raman spectroscopy, HR-TEM, N2 adsorption at -196 °C, XPS, O2-TPD, H2-TPR, and work function measurements. The Pr-rich compositions, ranging from Ce0.3Pr0.7O2-δ to PrO2-δ, resulted in a significant increase in the total evolved O2 amounts and enhanced catalyst reducibility. However, a decrease in the textural properties of the catalysts was noted, which was particularly important for the pure praseodymia under the synthesis route conducted. The catalytic activity was investigated under the two following contact modes of mixing between soot and catalyst: loose and tight. The results revealed that the catalytic performance is associated with the surface contact in tight contact mode and with the combination of surface/subsurface/bulk oxygen mobility and the BET surface area in loose contact mode. Notably, the temperatures estimated at 10% and 50% of the conversion (T10 and T50) parameters were achieved at much lower temperatures than the uncatalyzed soot combustion, even under loose contact conditions. Specifically, the 50% conversion was achieved at 511 °C and 538 °C for Ce0.3Pr0.7O2 and Ce0.2Pr0.8O2, respectively. While no direct correlation between catalytic activity and work function was observed, a significant relationship emerges between work function values and the formation of oxygen vacancies, whatever the conditions used for these measurements. On the other hand, the ability to generate a high population of oxygen vacancies at low temperatures, rather than the direct activation of gas-phase O2, influences the catalytic performance of Pr-doped ceria catalysts, highlighting the importance of surface/subsurface oxygen vacancy generation, which was the parameter that showed a better correlation with the catalytic activity, whatever the soot conversion value or the mode of contact considered.

Improving Biocompatibility of Polyurethanes Apply in Medicine Using Oxygen Plasma and Its Negative Effect on Increased Bacterial Adhesion.

Polyurethanes (PUs) are versatile polymers used in medical applications due to their high flexibility and fatigue resistance. PUs are widely used for synthetic blood vessels, wound dressings, cannulas, and urinary and cardiovascular catheters. Many scientific reports indicate that surface wettability is crucial for biocompatibility and bacterial adhesion. The use of oxygen plasma to modify PUs is advantageous because of its effectiveness in introducing oxygen-containing functional groups, thereby altering surface wettability. The purpose of this study was to investigate the effect of the modification of the oxygen plasma of polyurethane on its biocompatibility with lung tissue (A549 cell line) and the adhesion of Gram-positive bacteria (S. aureus and S. epidermidis). The results showed that the modification of polyurethane by oxygen plasma allowed the introduction of functional groups containing oxygen (-OH and -COOH), which significantly increased its hydrophilicity (change from 105° ± 2° to 9° ± 2°) of PUs. Surface analysis by atomic force microscopy (AFM) showed changes in PU topography (change in maximum height from ∼110.3 nm to ∼32.1 nm). Moreover, biocompatibility studies on A549 cells showed that on the PU-modified surface, the cells exhibited altered morphology (increases in cell surface area and length, and thus reduced circularity) without concomitant effects on cell viability. However, serial dilution and plate count and microscopic methods confirmed that plasma modification significantly increased the adhesion of S. aureus and S. epidermidis bacteria. This study indicate the important role of surface hydrophilicity in biocompatibility and bacterial adhesion, which is important in the design of new medical biomaterials.

Revealing bactericidal events on graphene oxide nano films deposited on metal implant surfaces.

At the time when pathogens are developing robust resistance to antibiotics, the demand for implant surfaces with microbe-killing capabilities has significantly risen. To achieve this goal, profound understanding of the underlying mechanisms is crucial. Our study demonstrates that graphene oxide (GO) nano films deposited on stainless steel (SS316L) exhibit superior antibacterial features. The physicochemical properties of GO itself play a pivotal role in influencing biological events and their diversity may account for the contradictory results reported elsewhere. However, essential properties of GO coatings, such as oxygen content and the resulting electrical conductivity, have been overlooked so far. We hypothesize that the surface potential and electrical resistance of the oxygen content in the GO-nano films may induce bacteria-killing events on conductive metallic substrates. In our study, the GO applied contains 52 wt% of oxygen, and thus exhibits insulating properties. When deposited as a nano film on an electrically conducting steel substrate, GO flakes generate a Schottky barrier at the interface. This barrier, consequently, impedes the transfer of electrons to the underlying conductive substrate. As a result, this creates reactive oxygen species (ROS), leading to bacterial death. We confirmed the presence of GO coatings and their hydrolytic stability by using X-ray photoelectron spectroscopy (XPS), µRaman spectroscopy, scanning electron microscopy (SEM), and Kelvin probe force microscopy (KPFM) measurements. The biological evaluation was performed on the MG63 osteoblast-like cell line and two selected bacteria species: S. aureus and P. aeruginosa, demonstrating both the cytocompatibility and antibacterial behavior of GO-coated SS316L substrates. We propose a two-step bactericidal mechanism: electron transfer from the bacteria membrane to the substrate, followed by ROS generation. This mechanism finds support in changes observed in contact angle, surface potential, and work function, identified as decisive factors. By addressing overlooked factors and effectively bridging the gap between understanding and practicality, we present a transformative approach for implant surfaces, combating microbial resistance, and offering new application possibilitie.

In Vitro and In Silico Studies of Functionalized Polyurethane Surfaces toward Understanding Biologically Relevant Interactions.

The solid-aqueous boundary formed upon biomaterial implantation provides a playground for most biochemical reactions and physiological processes involved in implant-host interactions. Therefore, for biomaterial development, optimization, and application, it is essential to understand the biomaterial-water interface in depth. In this study, oxygen plasma-functionalized polyurethane surfaces that can be successfully utilized in contact with the tissue of the respiratory system were prepared and investigated. Through experiments, the influence of plasma treatment on the physicochemical properties of polyurethane was investigated by atomic force microscopy, attenuated total reflection infrared spectroscopy, differential thermal analysis, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and contact angle measurements, supplemented with biological tests using the A549 cell line and two bacteria strains (Staphylococcus aureus and Pseudomonas aeruginosa). The molecular interpretation of the experimental findings was achieved by molecular dynamics simulations employing newly developed, fully atomistic models of unmodified and plasma-functionalized polyurethane materials to characterize the polyurethane-water interfaces at the nanoscale in detail. The experimentally obtained polar and dispersive surface free energies were consistent with the calculated free energies, verifying the adequacy of the developed models. A 20% substitution of the polymeric chain termini by their oxidized variants was observed in the experimentally obtained plasma-modified polyurethane surface, indicating the surface saturation with oxygen-containing functional groups.

Sonochemical Deposition of Gentamicin Nanoparticles at the PCV Tracheostomy Tube Surface Limiting Bacterial Biofilm Formation.

BACKGROUND: The use of nanotechnology in the production of medical equipment has opened new possibilities to fight bacterial biofilm developing on their surfaces, which can cause infectious complications. In this study, we decided to use gentamicin nanoparticles. An ultrasonic technique was used for their synthesis and immediate deposition onto the surface of tracheostomy tubes, and their effect on bacterial biofilm formation was evaluated. METHODS: Polyvinyl chloride was functionalized using oxygen plasma followed by sonochemical formation and the embedment of gentamicin nanoparticles. The resulting surfaces were characterized with the use of AFM, WCA, NTA, FTIR and evaluated for cytotoxicity with the use of A549 cell line and for bacterial adhesion using reference strains of S. aureus (ATCC® 25923™) and E. coli (ATCC® 25922™). RESULTS: The use of gentamicin nanoparticles significantly reduced the adhesion of bacterial colonies on the surface of the tracheostomy tube for S. aureus from 6 × 105 CFU/mL to 5 × 103 CFU/mL and for E. coli from 1.655 × 105 CFU/mL to 2 × 101 CFU/mL, and the functionalized surfaces did not show a cytotoxic effect on A549 cells (ATTC CCL 185). CONCLUSIONS: The use of gentamicin nanoparticles on the polyvinyl chloride surface may be an additional supporting method for patients after tracheostomy in order to prevent the colonization of the biomaterial by potentially pathogenic microorganisms.

Speciation of Oxygen Functional Groups on the Carbon Support Controls the Electrocatalytic Activity of Cobalt Oxide Nanoparticles in the Oxygen Evolution Reaction.

The effective use of the active phase is the main goal of the optimization of supported catalysts. However, carbon supports do not interact strongly with metal oxides, thus, oxidative treatment is often used to enhance the number of anchoring sites for deposited particles. In this study, we set out to investigate whether the oxidation pretreatment of mesoporous carbon allows the depositing of a higher loading and a more dispersed cobalt active phase. We used graphitic ordered mesoporous carbon obtained by a hard-template method as active phase support. To obtain different surface concentrations and speciation of oxygen functional groups, we used a low-temperature oxygen plasma. The main methods used to characterize the studied materials were X-ray photoelectron spectroscopy, transmission electron microscopy, and electrocatalytic tests in the oxygen evolution reaction. We have found that the oxidative pretreatment of mesoporous carbon influences the speciation of the deposited cobalt oxide phase. Moreover, the activity of the electrocatalysts in oxygen evolution is positively correlated with the relative content of the COO-type groups and negatively correlated with the C═O-type groups on the carbon support. Furthermore, the high relative content of COO-type groups on the carbon support is correlated with the presence of well-dispersed Co3O4 nanoparticles. The results obtained indicate that to achieve a better dispersed and thus more catalytically active material, it is more important to control the speciation of the oxygen functional groups rather than to maximize their total concentration.

Functionalization of Graphite with Oxidative Plasma.

Surface-modified graphite is studied as an electrode material, an adsorbent, and a membrane component, among other applications. Modifying the graphite with plasma can be used to create relevant surface functionalities, in particular, various oxygen groups. The application of surface-oxidized graphite often requires its use in an aqueous environment. The application in an aqueous environment is not an issue for acid-oxidized carbons, but a discrepancy in the structure-activity relationship may arise because plasma-oxidized carbons show a time-dependent decrease in the degree of functionalization and related properties. Moreover, plasma-oxidized materials are often characterized in terms of their chemical and physical properties, most notably their degree of functionalization after plasma treatment, without contact with water. In this study, we used low-temperature plasma oxidation with pure oxygen and carbon dioxide and sample-washing with concentrated nitric and sulfuric acids. To evaluate the electronic properties of modified graphite, the work function changes and surface oxygen content were measured just after plasma modification and after water immersion. We show that water immersion drastically decreases the work function of plasma-treated samples, which is accompanied by a decrease in the number of radicals introduced by plasma. Our results demonstrate that the increase in stable work function as a result of plasma treatment, brought about by an increase in the surface oxygen species concentration, can be realized most effectively for the acid-washed graphite.

Preparation of 3DOM ZrTiO4 Support, WxCeMnOδ/3DOM ZrTiO4 Catalysts, and Their Catalytic Performance for the Simultaneous Removal of Soot and NOx.

As an efficient and durable engine, a diesel engine has a broad application. However, soot particles (PM) and nitrogen oxides (NOx) coming from diesel engines are the main causes of air pollution, so it is necessary to design and prepare an effective catalyst for the simultaneous elimination of PM and NOx. In this work, a novel 3DOM ZrTiO4 support and a series of WxCeMnOδ/3DOM ZrTiO4 catalysts (where x indicates the wt% of W) were designed and fabricated by the colloidal crystal template technique. Among the as-prepared catalysts, the W1CeMnOδ/3DOM ZrTiO4 catalyst exhibits the highest NO conversion rate (52%) at the temperature of maximum CO2 concentration (474°C) and achieves 90% NO conversion in the temperature range of 250-396°C. The excellent catalytic performance is associated with the macroporous structure, abundant oxygen vacancies, sufficient acid sites, and the synergistic effect among the active components. The possible reaction mechanisms of WxCeMnOδ/3DOM ZrTiO4 catalysts were also discussed based on the characterization results.

Microbiological analysis of tracheostomy tube biofilms and antibiotic resistance profiles of potentially pathogenic microorganisms.

<b>Introduction:</b> In hospitalized patients, tracheostomy tubes (TTs) are susceptible to colonization by biofilm- producing potentially pathogenic microorganisms (PPMs). Contact with TTs, which are situated in a critical region of the body with enormous microbial exposure, may lead to the emer-gence of resistant respiratory infections.</br></br> <b>Objective:</b> Our study aimed to isolate and identify Gram-positive and Gram-negative PPMs, mark their antibiotic resistance and determine the bacteriological pattern of the biofilm colonizing the TTs. </br></br> <b>Methods:</b> The study was conducted on 45 tracheostomy tubes obtained from 45 hospitalized adult patients with tracheostomy with intubation periods ranging from 1 to 28 days. Tracheal aspirates (TA) obtained from polyvinyl chloride (PVC) TTs were used for the analysis. Bacteria in biofilms were identified by standard microbiological techniques, tested for antibiotic resistance and phenotypic resistance according to the EUCAST guidelines and visualized by SEM.</br></br> <b>Results:</b> Out of 45 TTs, 100% were found to be positive in bacterial cultures with 58 PPM isolates (10 spe-cies) correlating well with the SEM findings. Overall, 72% of isolates were Gram-negative bacilli, followed by Gram-positive cocci (28%). Staphylococcus aureus was the predominant bacterium (identified in 35.5% of patients), followed by Klebsiella pneumoniae (identified in 23.8%). Among the Gram-negative PPMs, 50% of isolates were identified as multidrug-resistant (MDR), 8.6% as extremely drug-resistant (XDR) and 5.2% were pandrug-resistant (PDR).</br></br><b>Conclusions:</b> Our study showed a rapid colonization of the TT surface by biofilm- producing PPMs. Patients with tracheosto- mies, also those with non-infectious conditions, were mainly colonized with highly re-sistant bacteria.

Carbon-Based Composites as Electrocatalysts for Oxygen Evolution Reaction in Alkaline Media.

This review paper presents the most recent research progress on carbon-based composite electrocatalysts for the oxygen evolution reaction (OER), which are of interest for application in low temperature water electrolyzers for hydrogen production. The reviewed materials are primarily investigated as active and stable replacements aimed at lowering the cost of the metal electrocatalysts in liquid alkaline electrolyzers as well as potential electrocatalysts for an emerging technology like alkaline exchange membrane (AEM) electrolyzers. Low temperature electrolyzer technologies are first briefly introduced and the challenges thereof are presented. The non-carbon electrocatalysts are briefly overviewed, with an emphasis on the modes of action of different active phases. The main part of the review focuses on the role of carbon-metal compound active phase interfaces with an emphasis on the synergistic and additive effects. The procedures of carbon oxidative pretreatment and an overview of metal-free carbon catalysts for OER are presented. Then, the successful synthesis protocols of composite materials are presented with a discussion on the specific catalytic activity of carbon composites with metal hydroxides/oxyhydroxides/oxides, chalcogenides, nitrides and phosphides. Finally, a summary and outlook on carbon-based composites for low temperature water electrolysis are presented.

Covalently bonded surface functional groups on carbon nanotubes: from molecular modeling to practical applications.

The aim of this work was to investigate how chemical functionalization affects the electronic properties of multi-walled carbon nanotubes, altering the electrophoretic deposition process: a method of choice for the fabrication of high quality, all-carbon nanotube (CNT) layers. Wet chemistry methods were applied to modify the surfaces of CNTs by insertion of various oxygen- and nitrogen-containing groups. Transmission electron microscopy revealed no significant changes in the material morphology, while X-ray photoelectron spectroscopy and Raman spectroscopy showed that changes in the chemical composition did not translate to the changes in the structure. Molecularly modelled optimized surface functional group geometries and electron density distributions allowed the calculation of the dipole moments (-COOH = 0.77; -OH = 1.65; -CON(CH3CH2)2 = 3.33; -CONH2 = 2.00; -NH2 = 0.78). Due to their polarity, the introduction of surface functional groups resulted in significant modifications of the electronic properties of CNTs, as elucidated by work function measurements via the Kelvin method and ultraviolet photoelectron spectroscopy. The work function changed from 4.6 eV (raw CNTs) to 4.94 eV for the -OH functionalized CNTs and 4.3 eV for the CNTs functionalized with -CON(CH3CH2), and was inversely proportional to the dipole moment values. Finally, using CNT dispersions, electrophoretic deposition was conducted, allowing the correlation of the work function of CNTs and the measured electrophoretic current with the impact on the deposits' qualities. Thus, a rational background for the development of carbon-based biomaterials was provided.

Demonstration of the Influence of Specific Surface Area on Reaction Rate in Heterogeneous Catalysis.

Heterogeneous catalysis plays an important role in many chemical reactions, especially those applied in industrial processes, and therefore, its theoretical foundations are introduced not only to students majoring in chemical engineering or catalysis but also as part of general chemistry courses. The consideration of catalytic activity of various solids and mechanisms of catalytic reactions requires the introduction of the concept of an active site, which together with the catalyst specific surface area are discussed as key parameters controlling the reaction rate. There are many known demonstrations of heterogeneous catalysis phenomena that can be performed live in a lecture hall, but all of them focus only on the general idea of catalytic processes and are not suitable for quantitative analysis. Therefore, herein we present a simple demonstration of the influence of the specific surface area of a catalyst on the rate of a catalytic reaction. This demonstration is based on a model reaction of hydrogen peroxide decomposition catalyzed by cobalt spinel (Co3O4) calcined at various temperatures. The differences in reaction rates can be monitored visually, and the obtained data can be used directly for a simple kinetic analysis, including comparison of numerical values of the reaction rate constants.

Characterization of Partially Covered Self-Expandable Metallic Stents for Esophageal Cancer Treatment: In Vivo Degradation.

Partially covered self-expandable metallic esophageal stent (SEMS) placement is the most frequently applied palliative treatment in esophageal cancer. Structural characterization of explanted 16 nitinol-polyurethane SEMS (the group of 6 females, 10 males, age 40-80) was performed after their removal due to dysfunction. The adverse bulk changes in the polymer structure were identified using differential scanning calorimetry (DSC), differential mechanical thermal analysis (DMTA), and attenuated total reflectance infrared spectroscopy (ATR-IR) and discussed in terms of melting point shift (9 °C), glass-transition shift (4 °C), differences in viscoelastic behavior, and systematic decrease of peaks intensities corresponding to C-H, C═O, and C-N polyurethane structural bonds. The scanning electron and confocal microscopic observations revealed all major types of surface degradation, i.e., surface cracks, peeling off of the polymer material, and surface etching. The changes in the hydrophobic polyurethane surfaces were also revealed by a significant decrease in wettability (74°) and the corresponding increase of the surface free energy (31 mJ/m2). To understand the in vivo degradation, the in vitro tests in simulated salivary and gastric fluids were performed, which mimic the environments of proximal and distal ends, respectively. It was concluded that the differences in the degradation of the proximal and distal ends of prostheses strongly depend on the physiological environment, in particular stomach content. Finally, the necessity of the in vivo tests for SEMS degradation is pointed out.

Conductive all-carbon nanotube layers: Results on attractive physicochemical, anti-bacterial, anticancer and biocompatibility properties.

Physicochemical, electrochemical and biological performance of 4 types of all-carbon nanotube layers was studied. Higher oxidation state of carbon was responsible for micro-scaled uniformity of the layers and excellent electrical conductivity, while nitrogen containing functional groups yielded materials with anisotropy similar to natural tissues and reduced work function. All materials were cytocompatible with mammalian fibroblasts (viability >80%, cytotoxicity <3% at day 7) and human dermal fibroblast (viability of cells >70% at day 1), while reducing bacterial and cancer cells proliferation without adding any drug. After 8 h culture, a ~50% depletion in the number of Gram-positive bacteria was observed on materials with lower work function, while Gram-negative bacteria were more sensitive towards carbon coordination number and presence of nitrogen atoms (cell depletion of up to 48% on amidized carbon nanotubes). After 1-day culture, >80% reduction in the melanoma cells number, connected with enhanced production of reactive oxygen species (ROS) was observed. All-carbon nanotube layers decreased bacteria and cancer cell functions without negatively influencing mammalian cells nor using drugs and we believe that this can be explained by various sensitivity of the tested cells towards exogenous ROS overproduction. As the concerns over implant-related infections as well as rates of antibiotic-resistant bacteria and chemotherapeutic-resistant cancer cells are growing, such materials should pave the way for a wide range of biomedical applications.

Graphene-based materials enhance cardiomyogenic and angiogenic differentiation capacity of human mesenchymal stem cells in vitro - Focus on cardiac tissue regeneration.

Cell-based therapies have recently emerged as promising strategies for the treatment of cardiovascular disease. Mesenchymal stem cells (MSCs) are a promising cell type that represent a class of adult stem cells characterized by multipotency, high proliferative capacity, paracrine activity, and low immunogenicity. To improve the functional and therapeutic efficacy of MSCs, novel biomaterials are considered as scaffolds/surfaces that promote MSCs growth and differentiation. One of them are graphene-based materials, including graphene oxide (GO) and reduced graphene oxide (rGO). Due to the unique physical, chemical, and biological properties of graphene, scaffolds comprising GO/rGO have been examined as novel platforms to improve the differentiation potential of human MSCs in vitro. We verified different i) size of GO flakes, ii) reduction level, and iii) layer thickness to select the most suitable artificial niche for MSCs culture. The results revealed that graphene-based substrates constitute non-toxic substrates for MSCs. Surfaces with large flakes of GO as well as low reduced rGO are the most biocompatible for MSCs propagation and do not affect their proliferation and survival. Interestingly, small GO flakes and highly reduced rGO decreased MSCs proliferation and induced their apoptosis. We also found that GO and rGO substrates did not alter the MSCs phenotype, cell cycle progression and might modulate the adhesive capabilities of these cells. Importantly, we demonstrated that both materials promoted the cardiomyogenic and angiogenic differentiation capacity of MSCs in vitro. Thus, our data indicates that graphene-based surfaces represent promising materials that may influence the therapeutic application of MSCs via supporting their pro-regenerative potential.

Functionalization of the Parylene C Surface Enhances the Nucleation of Calcium Phosphate: Combined Experimental and Molecular Dynamics Simulations Approach.

Interactions at the solid-body fluid interfaces play a vital role in bone tissue formation at the implant surface. In this study, fully atomistic molecular dynamics (MD) simulations were performed to investigate interactions between the physiological components of body fluids (Ca2+, HPO42-, H2PO4-, Na+, Cl-, and H2O) and functionalized parylene C surface. In comparison to the native parylene C (-Cl surface groups), the introduction of -OH, -CHO, and -COOH surface groups significantly enhances the interactions between body fluid ions and the polymeric surface. The experimentally observed formation of calcium phosphate nanocrystals is discussed in terms of MD simulations of the calcium phosphate clustering. Surface functional groups promote the clustering of calcium and phosphate ions in the following order: -OH > -CHO > -Cl (parent parylene C) ≈ -COO-. This promoting role of surface functional groups is explained as stimulating the number of Ca2+ and HPO42- surface contacts as well as ion chemisorption. The molecular mechanism of calcium phosphate cluster formation at the functionalized parylene C surface is proposed.

Biofunctional catheter coatings based on chitosan-fatty acids derivatives.

Multifunctional and biofunctional coatings for medical devices are an attractive strategy towards tailoring the interactions of the device with the body, thereby influencing the host response, and the susceptibility to microbial colonization. Here we describe the development of a coating process to yield amphiphilic, lubricious coatings, resistant to bacterial colonization, based on chitosan. Chitosan-fatty acid derivatives were obtained by simultaneous N,O-acylation of chitosan with either linoleic, α-linolenic, or dilinoleic acid. Chemical characterization of new materials was carried out using 1H NMR, FTIR, and XPS. Surface properties of coated polyester samples were studied using SEM and contact angle measurements, which indicated that the incorporation of hydrophobic constituents into chitosan macromolecules led to a decrease of both surface roughness and water contact angle. Importantly, tribological testing demonstrated that these new coatings decrease the coefficient of friction due to the self-organization of fatty acid (from 0.53 for the neat chitosan to 0.35 for chitosan-fatty acid derivative). Meanwhile, preliminary bacterial colonization tests indicated significant-over 80%-reduction in E. coli colonization following coating with chitosan-linoleic and chitosan-α-linolenic derivatives. Finally, cytotoxicity and hemocompatibility studies confirmed that all amphiphilic chitosan-fatty acid derivatives were non-toxic and non-hemolytic. Collectively, our results demonstrate the potential of the developed coating strategy, particularly the chitosan-linoleic and chitosan-α-linolenic acid derivatives, for applications as biofunctional catheter coatings.

Investigation of the surface species during temperature dependent dehydrogenation of naphthalene on Ni(111).

The temperature dependent dehydrogenation of naphthalene on Ni(111) has been investigated using vibrational sum-frequency generation spectroscopy, X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory with the aim of discerning the reaction mechanism and the intermediates on the surface. At 110 K, multiple layers of naphthalene adsorb on Ni(111); the first layer is a flat lying chemisorbed monolayer, whereas the next layer(s) consist of physisorbed naphthalene. The aromaticity of the carbon rings in the first layer is reduced due to bonding to the surface Ni-atoms. Heating at 200 K causes desorption of the multilayers. At 360 K, the chemisorbed naphthalene monolayer starts dehydrogenating and the geometry of the molecules changes as the dehydrogenated carbon atoms coordinate to the nickel surface; thus, the molecule tilts with respect to the surface, recovering some of its original aromaticity. This effect peaks at 400 K and coincides with hydrogen desorption. Increasing the temperature leads to further dehydrogenation and production of H2 gas, as well as the formation of carbidic and graphitic surface carbon.

One-step sonochemical fabrication and embedding of gentamicin nanoparticles into parylene C implant coating: towards controlled drug delivery.

A facile one-step sonochemical method was employed for the first time for gentamicin nanoparticles (GNPs) fabrication and embedding into the surface of parylene C implant coating. The developed system was thoroughly characterized in terms of particle size (NTA, STEM/EDX), surface dispersion (IR-image) and drug release kinetics (UV-Vis). It was revealed that the optimization of the applied ultrasound conditions resulted in the formation of GNPs with an average size in the narrow range of 30-70 nm and their docking into the parylene C nanopores, while the molecular structure of the antibiotic was preserved as confirmed by the FTIR spectra. The obtained surface morphology resulted in controlled elution of the drug up to 7 days, and the kinetics followed the Korsmeyer-Peppas model. The apparent benefits of the proposed sonochemical approach (short preparation time, direct drug accessibility, lack of chemical wastes) are pointed out.