Sulfation of furcellaran and its effect on hemocompatibility in vitro.

In this study, furcellaran (FUR) obtained from Furcellaria lumbricalis was firstly employed for sulfation via various methods, including SO3-pyridine (SO3∙Py) complex in different aprotic solvents, chlorosulfonic acid and sulfuric acid with a "coupling" reagent N,N'-Dicyclohexylcarbodiimide. Structural characterization through FT-IR, GPC, XPS and elemental analyses confirmed the successful synthesis of 6-O-sulfated FUR derivates characterized by varying degrees of sulfation (DS) ranging from 0.15 to 0.91 and molecular weight (Mw) spanning from12.5 kDa to 2.7 kDa. In vitro clotting assays, partial thromboplastin time (aPTT), thrombin time (TT), and prothrombin time (PT) underscored the essential role of sulfate esters in conferring anticoagulant activity whereas FUR prepared via chlorosulfonic acid with DS of 0.91 reached 311.4 s in aPPT showing almost 4-fold higher anticoagulant activity than native FUR at the concentration 2 mg/mL. MTT test showed all tested samples decreased cell viability in a dose dependent manner while all of them are non-cytotoxic up to the concentration of 0.1 mg/mL. Furthermore, sulfated derivates deposited onto polyethylene terephthalate surface presented substantial decrease in platelet adhesion, as well as absence of the most activated platelet stages. These findings support the pivotal role of O-6 FUR sulfates in enhancing hemocompatibility and provide valuable insights for a comparative assessment of effective sulfating approaches.

Comparison of Plasma-Polymerized Thin Films Deposited from 2-Methyl-2-oxazoline and 2-Ethyl-2-oxazoline: I Film Properties.

Poly(2-oxazoline) is a promising new class of polymeric materials due to their antibiofouling properties and good biocompatibility. Poly(2-oxazoline) coatings can be deposited on different substrates via plasma polymerization, which can be more advantageous than other coating methods. The aim of this study is to deposit poly(2-oxazoline) coatings using a surface dielectric barrier discharge burning in nitrogen at atmospheric pressure using 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline vapours as monomers and compare the film properties. For the comparison, the antibacterial and cytocompatibility tests were peformed according to ISO norms. The antibacterial tests showed that all the deposited films were highly active against Staphylococcus aureus and Escherichia coli bacteria. The chemical composition of the films was studied using FTIR and XPS, and the film surface's properties were studied using AFM and surface energy measurement. The cytocompatibility tests showed good cytocompatibility of all the deposited films. However, the films deposited from 2-methyl-2-oxazoline exhibit better cytocompatibility. This difference can be explained by the different chemical compositions and surface morphologies of the films deposited from different monomers.

Atmospheric Pressure Plasma Polymerized 2-Ethyl-2-oxazoline Based Thin Films for Biomedical Purposes.

Polyoxazoline thin coatings were deposited on glass substrates using atmospheric pressure plasma polymerization from 2-ethyl-2-oxazoline vapours. The plasma polymerization was performed in dielectric barrier discharge burning in nitrogen at atmospheric pressure. The thin films stable in aqueous environments were obtained at the deposition with increased substrate temperature, which was changed from 20 ∘C to 150 ∘C. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. The chemical composition of polyoxazoline films was studied by FTIR and XPS, the mechanical properties of films were studied by depth sensing indentation technique and by scratch tests. The film surface properties were studied by AFM and by surface energy measurement. After tuning the deposition parameters (i.e., monomer flow rate and substrate temperature), stable films, which resist bacterial biofilm formation and have cell-repellent properties, were achieved. Such antibiofouling polyoxazoline thin films can have many potential biomedical applications.

Cold atmospheric pressure plasma: simple and efficient strategy for preparation of poly(2-oxazoline)-based coatings designed for biomedical applications.

Poly(2-oxazolines) (POx) are an attractive material of choice for biocompatible and bioactive coatings in medical applications. To prepare POx coatings, the plasma polymerization represents a fast and facile approach that is surface-independent. However, unfavorable factors of this method such as using the low-pressure regimes and noble gases, or poor control over the resulting surface chemistry limit its utilization. Here, we propose to overcome these drawbacks by using well-defined POx-based copolymers prepared by living cationic polymerization as a starting material. Chemically inert polytetrafluoroethylene (PTFE) is selected as a substrate due to its beneficial features for medical applications. The deposited POx layer is additionally post-treated by non-equilibrium plasma generated at atmospheric pressure. For this purpose, diffuse coplanar surface barrier discharge (DCSBD) is used as a source of "cold" homogeneous plasma, as it is operating at atmospheric pressure even in ambient air. Prepared POx coatings possess hydrophilic nature with an achieved water contact angle of 60°, which is noticeably lower in comparison to the initial value of 106° for raw PTFE. Moreover, the increased fibroblasts adhesion in comparison to raw PTFE is achieved, and the physical and biological properties of the POx-modified surfaces remain stable for 30 days.

Fast Surface Hydrophilization via Atmospheric Pressure Plasma Polymerization for Biological and Technical Applications.

Polymeric surfaces can benefit from functional modifications prior to using them for biological and/or technical applications. Surfaces considered for biocompatibility studies can be modified to gain beneficiary hydrophilic properties. For such modifications, the preparation of highly hydrophilic surfaces by means of plasma polymerization can be a good alternative to classical wet chemistry or plasma activation in simple atomic or molecular gasses. Atmospheric pressure plasma polymerization makes possible rapid, simple, and time-stable hydrophilic surface preparation, regardless of the type and properties of the material whose surface is to be modified. In this work, the surface of polypropylene was coated with a thin nanolayer of plasma-polymer which was prepared from a low-concentration mixture of propane-butane in nitrogen using atmospheric pressure plasma. A deposition time of only 1 second was necessary to achieve satisfactory hydrophilic properties. Highly hydrophilic, stable surfaces were obtained when the deposition time was 10 seconds. The thin layers of the prepared plasma-polymer exhibit highly stable wetting properties, they are smooth, homogeneous, flexible, and have good adhesion to the surface of polypropylene substrates. Moreover, they are constituted from essential elements only (C, H, N, O). This makes the presented modified plasma-polymer surfaces interesting for further studies in biological and/or technical applications.

The Effect of Plasma Pretreatment and Cross-Linking Degree on the Physical and Antimicrobial Properties of Nisin-Coated PVA Films.

Stable antimicrobial nisin layers were prepared on the carrying medium-polyvinyl alcohol (PVA) films, crosslinked by glutaric acid. Surface plasma dielectric coplanar surface barrier discharge (DCSBD) modification of polyvinyl alcohol was used to improve the hydrophilic properties and to provide better adhesion of biologically active peptide-nisin to the polymer. The surface modification of films was studied in correlation to their cross-linking degree. Nisin was attached directly from the salt solution of the commercial product. In order to achieve a stable layer, the initial nisin concentration and the following release were investigated using chromatographic methods. The uniformity and stability of the layers was evaluated by means of zeta potential measurements, and for the surface changes of hydrophilic character, the water contact angle measurements were provided. The nisin long-term stability on the PVA films was confirmed by tricine polyacrylamide gel electrophoresis (SDS-PAGE) and by antimicrobial assay. It was found that PVA can serve as a suitable carrying medium for nisin with tunable properties by plasma treatment and crosslinking degree.

Adaptive Control of Ion Yield in Femtosecond Laser Post-ionization for Secondary Ion Mass Spectrometry.

Secondary ion mass spectrometry is an excellent technique of analytical chemistry, where primary ions sputter a solid sample generating the secondary ions which are determined. Although the ion yield is inherently low, it can be enhanced by using a post-ionization of sputtered neutral species. Our novel approach integrates this technique with a near infrared femtosecond laser post-ionization based on an adaptive control through a laser pulse shaper. The shaping of the laser pulse provides adaptive control to select a mass peak of interest and to enhance this peak intensity. Versatility is confirmed by optimizing the ion yield for different molecules (tryptophan, anthracene, polyethylene, and oxalic acid) with focus on parent ion enhancement, fragmentation process, sublimation effect, and excited secondary species. This proof-of-concept experiment provides not only a nonspecific increase of the overall ion yield, but also the selection of specific secondary species and the adaptive enhancement of their intensities on the order of 100, potentially simplifying data interpretation. Such tailored spectra might advance the (secondary ion) mass spectrometry to new capabilities.

Infrared femtosecond laser preionization in secondary ion mass spectrometry of silver surface.

An alternative secondary ion mass spectrometry utilizing laser preionization is introduced. The native Ag sample surface is first irradiated with laser pulse (100 fs duration, 10(10)-10(11) W/cm(2) intensity, 1240 nm wavelength) and subsequently bombarded with primary ions (Bi(3)(+), 10 ns duration, 25 keV energy). Multiple correlation patterns are observed in the mass spectra, confirming the mutual laser-secondary ion mass spectrometry (SIMS) interplay in the preionization mechanism. The Ag(+), C(3)H(5)(+), C(3)H(5)O(3)(+), and AgOH(+), C(4)H(5)O(4)(+) are observed with the shallow and steep increasing of intensities at 1.3 × 10(11) W/cm(2) and 1.5 × 10(11) W/cm(2), respectively. Two ionization mechanisms are identified, the ion sputtering regime for intensities of less than 1.4 × 10(11) W/cm(2) and the multiphoton ionization at higher intensities. The Ag saturation intensity obtained from fitting is 2.4 × 10(13) W/cm(2), close to the one reported for postionization. The proposed preionization approach might eliminate the need for high peak power/high intensity laser source and, moreover, the experiment geometry ensures that large areas of the sample are affected by the laser beam.

Fullerenes, nanotubes, and graphite as matrices for collision mechanism in secondary ion mass spectrometry: determination of cyclodextrin.

A technique for improving the sensitivity of high mass molecular analysis is described. Three carbon species, fullerenes, single walled carbon nanotubes, and highly ordered pyrolytic graphite are introduced as matrices for the secondary ion mass spectrometry analysis of cyclodextrin (C(42)H(70)O(35), 1134 u). The fullerene and nanotubes are deposited as single deposition, and 10, 20, or 30 deposition films and cyclodextrin is deposited on top. The cyclodextrin parent-like ions and two fragments were analyzed. A 30 deposition fullerene film enhanced the intensity of cationized cyclodextrin with Na by a factor of 37. While the C(6)H(11)O(5) fragment, corresponding to one glucopyranose unit, increased by a factor of 16. Although fragmentation on fullerene is not suppressed, the intensity is twice as low as the parent-like ion. Deprotonated cyclodextrin increases by 100× and its C(8)H(7)O fragment by 10×. While the fullerene matrix enhances secondary ion emission, the nanotubes matrix film generates a basically constant yield. Graphite gives rise to lower intensity peaks than either fullerene or nanotubes. Scanning electron microscopy and atomic force microscopy provide images of the fullerene and nanotubes deposition films revealing flat and web structured surfaces, respectively. A "colliding ball" model is presented to provide a plausible physical mechanism of parent-like ion enhancement using the fullerene matrix.