Carboxymethylated and Sulfated Furcellaran from Furcellaria lumbricalis and Its Immobilization on PLA Scaffolds.

This study involved the creation of highly porous PLA scaffolds through the porogen/leaching method, utilizing polyethylene glycol as a porogen with a 75% mass ratio. The outcome achieved a highly interconnected porous structure with a thickness of 25 µm. To activate the scaffold's surface and improve its hydrophilicity, radiofrequency (RF) air plasma treatment was employed. Subsequently, furcellaran subjected to sulfation or carboxymethylation was deposited onto the RF plasma treated surfaces with the intention of improving bioactivity. Surface roughness and water wettability experienced enhancement following the surface modification. The incorporation of sulfate/carboxymethyl group (DS = 0.8; 0.3, respectively) is confirmed by elemental analysis and FT-IR. Successful functionalization of PLA scaffolds was validated by SEM and XPS analysis, showing changes in topography and increases in characteristic elements (N, S, Na) for sulfated (SF) and carboxymethylated (CMF). Cytocompatibility was evaluated by using mouse embryonic fibroblast cells (NIH/3T3).

Recent Progress in Cellulose Hydrophobization by Gaseous Plasma Treatments.

Cellulose is an abundant natural polymer and is thus promising for enforcing biobased plastics. A broader application of cellulose fibers as a filler in polymer composites is limited because of their hydrophilicity and hygroscopicity. The recent scientific literature on plasma methods for the hydrophobization of cellulose materials is reviewed and critically evaluated. All authors focused on the application of plasmas sustained in fluorine or silicon-containing gases, particularly tetrafluoromethane, and hexamethyldisiloxane. The cellulose materials should be pre-treated with another plasma (typically oxygen) for better adhesion of the silicon-containing hydrophobic coating. In contrast, deposition of fluorine-containing coatings does not require pre-treatment, which is explained by mild etching of the cellulose upon treatment with F atoms and ions. The discrepancy between the results reported by different authors is explained by details in the gas phase and surface kinetics, including the heating of samples due to exothermic surface reactions, desorption of water vapor, competition between etching and deposition, the influence of plasma radiation, and formation of dusty plasma. Scientific and technological challenges are highlighted, and the directions for further research are provided.

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.

Antibacterial Thin Films Deposited from Propane-Butane Mixture in Atmospheric Pressure Discharge.

Antibacterial coatings on biomedical instruments are of great interest because they can suppress bacterial colonization on these instruments. In this study, antibacterial polymeric thin coatings were deposited on teflon substrates using atmospheric pressure plasma polymerization from a propane-butane mixture. The plasma polymerization was performed by means of surface dielectric barrier discharge burning in nitrogen at atmospheric pressure. The chemical composition of plasma polymerized propane-butane films was studied by energy-dispersive X-ray spectroscopy (EDX) and FTIR. The film surface properties were studied by SEM and by surface energy measurement. The EDX analysis showed that the films consisted of carbon, nitrogen and oxygen from ambient air. The FTIR analysis confirmed, in particular, the presence of alkyl, nitrile, acetylene, imide and amine groups. The deposited films were hydrophilic with a water contact angle in the range of 13-23°. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. On the other hand, the films were cytocompatible, reaching more than 80% of the cell viability threshold compared to reference polystyrene tissue.

Effect of Saccharides Coating on Antibacterial Potential and Drug Loading and Releasing Capability of Plasma Treated Polylactic Acid Films.

More than half of the hospital-associated infections worldwide are related to the adhesion of bacteria cells to biomedical devices and implants. To prevent these infections, it is crucial to modify biomaterial surfaces to develop the antibacterial property. In this study, chitosan (CS) and chondroitin sulfate (ChS) were chosen as antibacterial coating materials on polylactic acid (PLA) surfaces. Plasma-treated PLA surfaces were coated with CS either direct coating method or the carbodiimide coupling method. As a next step for the combined saccharide coating, CS grafted samples were immersed in ChS solution, which resulted in the polyelectrolyte complex (PEC) formation. Also in this experiment, to test the drug loading and releasing efficiency of the thin film coatings, CS grafted samples were immersed into lomefloxacin-containing ChS solution. The successful modifications were confirmed by elemental composition analysis (XPS), surface topography images (SEM), and hydrophilicity change (contact angle measurements). The carbodiimide coupling resulted in higher CS grafting on the PLA surface. The coatings with the PEC formation between CS-ChS showed improved activity against the bacteria strains than the separate coatings. Moreover, these interactions increased the lomefloxacin amount adhered to the film coatings and extended the drug release profile. Finally, the zone of inhibition test confirmed that the CS-ChS coating showed a contact killing mechanism while drug-loaded films have a dual killing mechanism, which includes contact, and release killing.

Enzyme-Catalyzed Polymerization Process: A Novel Approach to the Preparation of Polyaniline Colloidal Dispersions with an Immunomodulatory Effect.

A green, nature-friendly synthesis of polyaniline colloidal particles based on enzyme-assisted oxidation of aniline with horseradish peroxidase and chitosan or poly(vinyl alcohol) as steric stabilizers was successfully employed. Physicochemical characterization revealed formation of particles containing the polyaniline emeraldine salt and demonstrated only a minor effect of polymer stabilizers on particle morphology. All tested colloidal particles showed in vitro antioxidation activity determined via scavenging of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals. In vitro, they were able to reduce oxidative stress and inhibit the production of reactive oxygen species by neutrophils and inflammatory cytokines by macrophages. The anti-inflammatory effect observed was related to their antioxidant activity, especially in the case of neutrophils. The particles can thus be especially advantageous as active components of biomaterials modulating the early stages of inflammation. In addition to the immunomodulatory effect, the presence of intrinsically conducting polyaniline can impart cell-instructive properties to the particles. The approach to particle synthesis that we employed─an original one using environmentally friendly and biocompatible horseradish peroxidase─represents a smart way of preparing conducting particles with unique properties, which can be further modified by the stabilizers used.

Furcellaran Surface Deposition and Its Potential in Biomedical Applications.

Surface coatings of materials by polysaccharide polymers are an acknowledged strategy to modulate interfacial biocompatibility. Polysaccharides from various algal species represent an attractive source of structurally diverse compounds that have found application in the biomedical field. Furcellaran obtained from the red algae Furcellaria lumbricalis is a potential candidate for biomedical applications due to its gelation properties and mechanical strength. In the present study, immobilization of furcellaran onto polyethylene terephthalate surfaces by a multistep approach was studied. In this approach, N-allylmethylamine was grafted onto a functionalized polyethylene terephthalate (PET) surface via air plasma treatment. Furcellaran, as a bioactive agent, was anchored on such substrates. Surface characteristics were measured by means of contact angle measurements, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Subsequently, samples were subjected to selected cell interaction assays, such as antibacterial activity, anticoagulant activity, fibroblasts and stem cell cytocompatibility, to investigate the Furcellaran potential in biomedical applications. Based on these results, furcellaran-coated PET films showed significantly improved embryonic stem cell (ESC) proliferation compared to the initial untreated material.

Novel Slippery Liquid-Infused Porous Surfaces (SLIPS) Based on Electrospun Polydimethylsiloxane/Polystyrene Fibrous Structures Infused with Natural Blackseed Oil.

Hydrophobic fibrous slippery liquid-infused porous surfaces (SLIPS) were fabricated by electrospinning polydimethylsiloxane (PDMS) and polystyrene (PS) as a carrier polymer on plasma-treated polyethylene (PE) and polyurethane (PU) substrates. Subsequent infusion of blackseed oil (BSO) into the porous structures was applied for the preparation of the SLIPS. SLIPS with infused lubricants can act as a repellency layer and play an important role in the prevention of biofilm formation. The effect of polymer solutions used in the electrospinning process was investigated to obtain well-defined hydrophobic fibrous structures. The surface properties were analyzed through various optical, macroscopic and spectroscopic techniques. A comprehensive investigation of the surface chemistry, surface morphology/topography, and mechanical properties was carried out on selected samples at optimized conditions. The electrospun fibers prepared using a mixture of PDMS/PS in the ratio of 1:1:10 (g/g/mL) using tetrahydrofuran (THF) solvent showed the best results in terms of fiber uniformity. The subsequent infusion of BSO into the fabricated PDMS/PS fiber mats exhibited slippery behavior regarding water droplets. Moreover, prepared SLIPS exhibited antibacterial activity against Staphylococcus aureus and Escherichia coli bacterium strains.

Controlled release of enrofloxacin by vanillin-crosslinked chitosan-polyvinyl alcohol blends.

In transdermal drug delivery applications uniform drug distribution and sustained release are of great importance to decrease the side effects. In this direction in the present research, vanillin crosslinked chitosan (CS) and polyvinyl alcohol (PVA) blend based matrix-type transdermal system was prepared by casting and drying of aqueous solutions for local delivery of enrofloxacin (ENR) drug. Subsequently, the properties including the morphology, chemical structure, thermal behavior, tensile strength, crosslinking degree, weight uniformity, thickness, swelling and drug release of the CS-PVA blend films before and after crosslinking were characterized. In vitro drug release profiles showed the sustained release of ENR by the incorporation of vanillin as a crosslinker into the CS-PVA polymer matrix. Furthermore, the release kinetic profiles revealed that the followed mechanism for all samples was Higuchi and the increase of vanillin concentration in the blend films resulted in the change of diffusion mechanism from anomalous transport to Fickian diffusion. Overall, the obtained results suggest that the investigated vanillin crosslinked CS-PVA matrix-type films are potential candidates for transdermal drug delivery system.

Plasma Mediated Chlorhexidine Immobilization onto Polylactic Acid Surface via Carbodiimide Chemistry: Antibacterial and Cytocompatibility Assessment.

The development of antibacterial materials has great importance in avoiding bacterial contamination and the risk of infection for implantable biomaterials. An antibacterial thin film coating on the surface via chemical bonding is a promising technique to keep native bulk material properties unchanged. However, most of the polymeric materials are chemically inert and highly hydrophobic, which makes chemical agent coating challenging Herein, immobilization of chlorhexidine, a broad-spectrum bactericidal cationic compound, onto the polylactic acid surface was performed in a multistep physicochemical method. Direct current plasma was used for surface functionalization, followed by carbodiimide chemistry to link the coupling reagents of N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDAC) and N-Hydroxysuccinimide (NHs) to create a free bonding site to anchor the chlorhexidine. Surface characterizations were performed by water contact angle test, X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM). X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM). The antibacterial activity was tested using Staphylococcus aureus and Escherichia coli. Finally, in vitro cytocompatibility of the samples was studied using primary mouse embryonic fibroblast cells. It was found that all samples were cytocompatible and the best antibacterial performance observed was the Chlorhexidine immobilized sample after NHs activation.

Modulation of Differentiation of Embryonic Stem Cells by Polypyrrole: The Impact on Neurogenesis.

The active role of biomaterials in the regeneration of tissues and their ability to modulate the behavior of stem cells in terms of their differentiation is highly advantageous. Here, polypyrrole, as a representantive of electro-conducting materials, is found to modulate the behavior of embryonic stem cells. Concretely, the aqueous extracts of polypyrrole induce neurogenesis within embryonic bodies formed from embryonic stem cells. This finding ledto an effort to determine the physiological cascade which is responsible for this effect. The polypyrrole modulates signaling pathways of Akt and ERK kinase through their phosphorylation. These effects are related to the presence of low-molecular-weight compounds present in aqueous polypyrrole extracts, determined by mass spectroscopy. The results show that consequences related to the modulation of stem cell differentiation must also be taken into account when polypyrrole is considered as a biomaterial.

Slippery Liquid-Infused Porous Polymeric Surfaces Based on Natural Oil with Antimicrobial Effect.

Many polymer materials have found a wide variety of applications in biomedical industries due to their excellent mechanical properties. However, the infections associated with the biofilm formation represent serious problems resulting from the initial bacterial attachment on the polymeric surface. The development of novel slippery liquid-infused porous surfaces (SLIPSs) represents promising method for the biofilm formation prevention. These surfaces are characterized by specific microstructural roughness able to hold lubricants inside. The lubricants create a slippery layer for the repellence of various liquids, such as water and blood. In this study, effective antimicrobial modifications of polyethylene (PE) and polyurethane (PU), as commonly used medical polymers, were investigated. For this purpose, low-temperature plasma treatment was used initially for activation of the polymeric surface, thereby enhancing surface and adhesion properties. Subsequently, preparation of porous microstructures was achieved by electrospinning technique using polydimethylsiloxane (PDMS) in combination with polyamide (PA). Finally, natural black seed oil (BSO) infiltrated the produced fiber mats acting as a lubricating layer. The optimized fiber mats' production was achieved using PDMS/PA mixture at ratio 1:1:20 (g/g/mL) using isopropyl alcohol as solvent. The surface properties of produced slippery surfaces were analyzed by various microscopic and optics techniques to obtain information about wettability, sliding behavior and surface morphology/topography. The modified PE and PU substrates demonstrated slippery behavior of an impinged water droplet at a small tilting angle. Moreover, the antimicrobial effects of the produced SLIPs using black seed oil were proven against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli).

Conducting composite films based on chitosan or sodium hyaluronate. Properties and cytocompatibility with human induced pluripotent stem cells.

Novel composite films combining biocompatible polysaccharides with conducting polyaniline (PANI) were prepared via the in-situ polymerization of aniline hydrochloride in the presence of sodium hyaluronate (SH) or chitosan (CH). The composite films possess very good cytocompatibility in terms of adhesion and proliferation of two lines of human induced pluripotent stem cells (hiPSC). Moreover, the cardiomyogenesis and even formation of beating clusters were successfully induced on the films. The proportion of formed cardiomyocytes demonstrated excellent properties of composites for tissue engineering of stimuli-responsive tissues. The testing also demonstrated antibacterial activity of the films against E. coli and PANI-SH was able to reduce bacterial growth from 2 × 105 to < 1 cfu cm-2. Physicochemical characterization revealed that the presence of polysaccharides did not notably influence conductivities of the composites being ∼1 and ∼2 S cm-1 for PANI-SH and PANI-CH respectively; however, in comparison with neat PANI, it modified their topography making the films smoother with mean surface roughness of 4 (PANI-SH) and 14 nm (PANI-CH). The combination of conductivity, antibacterial activity and mainly cytocompatibility with hiPSC opens wide application potential of these polysaccharide-based composites.

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.

Degradable Poly(ethylene oxide)-Like Plasma Polymer Films Used for the Controlled Release of Nisin.

Poly(ethylene oxide) (PEO)-like thin films were successfully prepared by plasma-assisted vapor thermal deposition (PAVTD). PEO powders with a molar weight (Mw) between 1500 g/mol and 600,000 g/mol were used as bulk precursors. The effect of Mw on the structural and surface properties was analyzed for PEO films prepared at a lower plasma power. Fourier transform (FTIR-ATR) spectroscopy showed that the molecular structure was well preserved regardless of the Mw of the precursors. The stronger impact of the process conditions (the presence/absence of plasma) was proved. Molecular weight polydispersity, as well as wettability, increased in the samples prepared at 5 W. The influence of deposition plasma power (0-30 W) on solubility and permeation properties was evaluated for a bulk precursor of Mw 1500 g/mol. The rate of thickness loss after immersion in water was found to be tunable in this way, with the films prepared at the highest plasma power showing higher stability. The effect of plasma power deposition conditions was also shown during the permeability study. Prepared PEO films were used as a cover, and permeation layers for biologically active nisin molecule and a controlled release of this bacteriocin into water was achieved.

The biocompatibility of polyaniline and polypyrrole 2: Doping with organic phosphonates.

Conducting polymers (CP) can be used as pH- and/or electro-responsive components in various bioapplications, for example, in 4D smart scaffolds. The ability of CP to maintain conductivity under physiological conditions is, therefore, their crucial property. Unfortunately, the conductivity of the CP rapidly decreases in physiological environment, as their conducting salts convert to non-conducting bases. One of the promising solutions how to cope with this shortcoming is the use of alternative "doping" process that is not based on the protonation of CP with acids but on interactions relying in acidic hydrogen bonding. Therefore, the phosphonates (dimethyl phosphonate, diethyl phosphonate, dibutyl phosphonate, or diphenyl phosphonate) were used to re-dope two most common representatives of CP, polyaniline (PANI) and polypyrrole (PPy) bases. As a result, PANI doped with organic phosphonates proved to have significantly better stability of conductivity under different pH. It has also been shown that cytotoxicity of studied materials determined on embryonic stem cells and their embryotoxicity, determined as the impact on cardiomyogenesis and erythropoiesis, depend both on the polymer and phosphonate types used. With the exception of PANI doped with dibutyl phosphonate, all PPy-based phosphonates showed better biocompatibility than the phosphonates based on PANI.

Polymer Biointerfaces.

Polymer biointerfaces are considered suitable materials for the improvement and development of numerous applications [...].