Comparative study of iodine-doped and undoped pyrrole grafting with plasma on poly (glycerol sebacate) scaffolds and its human dental pulp stem cells compatibility.

This study addresses the morphological and chemical characterization of PGS scaffolds after (6, 12, 18, 24, and 30 min) residence in undoped pyrrole plasma (PGS-PPy) and the evaluation of cell viability with human dental pulp stem cells (hDPSCs). The results were compared with a previous study that used iodine-doped pyrrole (PGS-PPy/I). Analyses through SEM and AFM revealed alterations in the topography and quantity of deposited PPy particles. FTIR spectra of PGS-PPy scaffolds confirmed the presence of characteristic absorption peaks of PPy, with higher intensities observed in the nitrile and -C≡C- groups compared to PGS-PPy/I scaffolds, while raman spectra indicated a lower presence of polaron N+ groups. On the other hand, PGS scaffolds modified with PPy exhibited lower cytotoxicity compared to PGS-PPy/I scaffolds, as evidenced by the Live/Dead assay. Furthermore, the PGS-PPy scaffolds at 6 and 12 min, and particularly the PGS-PPy/I scaffold at 6 min, showed the best results in terms of cell viability by the fifth day of culture. The findings of this study suggest that undoped pyrrole plasma modification for short durations could also be a viable option to enhance the interaction with hDPSCs, especially when the treatment times range between 6 min and 12 min.

Synthesis and Electrochemical Evaluation of MSNs-PbAE Nanocontainers for the Controlled Release of Caffeine as a Corrosion Inhibitor.

In this paper, a controlled-release system of caffeine as a corrosion inhibitor was obtained by encapsulating it in MCM-41 silica nanoparticles coated with a poly(ß-amino ester) (PbAE), a pH-sensible polymer. Encapsulation was verified using Fourier transform infrared spectroscopy (FTIR) and thermogravimetry (TGA). The release of caffeine from the nanocontainers was analyzed in electrolytes with pH values of 4, 5, and 7 using UV-Vis, showing a 21% higher release in acidic electrolytes than in neutral electrolytes, corroborating its pH sensitivity. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization were used to determine the inhibition mode and efficiency of the encapsulated and free caffeine. The caffeine released from the nanocontainers showed the highest efficiency, which was 85.19%. These results indicate that these nanocontainers could have potential use in smart anticorrosion coating applications.

Influence of Molecular Weight and Grafting Density of PEG on the Surface Properties of Polyurethanes and Their Effect on the Viability and Morphology of Fibroblasts and Osteoblasts.

Grafting polyethylene glycol (PEG) onto a polymer's surface is widely used to improve biocompatibility by reducing protein and cell adhesion. Although PEG is considered to be bioinert, its incorporation onto biomaterials has shown to improve cell viability depending on the amount and molecular weight (MW) used. This phenomenon was studied here by grafting PEG of three MW onto polyurethane (PU) substrata at three molar concentrations to assess their effect on PU surface properties and on the viability of osteoblasts and fibroblasts. PEG formed a covering on the substrata which increased the hydrophilicity and surface energy of PUs. Among the results, it was observed that osteoblast viability increased for all MW and grafting densities of PEG employed compared with unmodified PU. However, fibroblast viability only increased at certain combinations of MW and grafting densities of PEG, suggesting an optimal level of these parameters. PEG grafting also promoted a more spread cell morphology than that exhibited by unmodified PU; nevertheless, cells became apoptotic-like as PEG MW and grafting density were increased. These effects on cells could be due to PEG affecting culture medium pH, which became more alkaline at higher MW and concentrations of PEG. Results support the hypothesis that surface energy of PU substrates can be tuned by controlling the MW and grafting density of PEG, but these parameters should be optimized to promote cell viability without inducing apoptotic-like behavior.

Biocompatibility studies of polyurethane electrospun membranes based on arginine as chain extender.

Electrospun polymers are an example of multi-functional biomaterials that improve the material-cellular interaction and aimed at enhancing wound healing. The main objective of this work is to fabricate electrospun polyurethane membranes using arginine as chain extender (PUUR) in order to test the fibroblasts affinity and adhesion on the material and the polymer toxicity. Polyurethane membranes were prepared in two steps: (i) the polyurethane synthesis, and ii) the electrospinning process. The membranes were characterized by scanning electron microscopy (SEM), Fourier transforms infrared spectroscopy, gel permeation chromatography, and differential scanning calorimetry techniques. The evaluation of PUUR as a scaffolding biomaterial for growing and developing of cells on the material was realized by LIVE/DEAD staining. The results show that the fluorescent surface area of human fibroblasts (hFB), was greater in control dense membranes made from Tecoflex than in electrospun and dense PUUR. From SEM analysis, the electrospun membranes show relatively uniform attachment of cells with a well-spread shape, while Tecoflex dense membranes show a non-proliferating round shape, which is attributed to the fiber's structure in electrospun membranes. The cell morphology and the cell attachment assay results reveal the well spreading of hFB cells on the surface of electrospun PUUR membranes which indicates a good response related to cell adhesion.

Synthesis of Poly(2-Acrylamido-2-Methylpropane Sulfonic Acid) and its Block Copolymers with Methyl Methacrylate and 2-Hydroxyethyl Methacrylate by Quasiliving Radical Polymerization Catalyzed by a Cyclometalated Ruthenium(II) Complex.

The first example of quasiliving radical polymerization and copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) without previous protection of its strong acid groups catalyzed by [Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6 complex is reported. Nuclear magnetic resonance (RMN) and gel permeation chromatography (GPC) confirmed the diblock structure of the sulfonated copolymers. The poly(2-acryloamido-2-methylpropanesulfonic acid)-b-poly(methyl methacrylate) (PAMPS-b-PMMA) and poly(2-acryloamido-2-methylpropanesulfonic acid)-b-poly(2-hydroxyethylmethacrylate) (PAMPS-b-PHEMA) copolymers obtained are highly soluble in organic solvents and present good film-forming ability. The ion exchange capacity (IEC) of the copolymer membranes is reported. PAMPS-b-PHEMA presents the highest IEC value (3.35 mmol H+/g), but previous crosslinking of the membrane was necessary to prevent it from dissolving in aqueous solution. PAMPS-b-PMMA exhibited IEC values in the range of 0.58-1.21 mmol H+/g and it was soluble in methanol and dichloromethane and insoluble in water. These results are well correlated with both the increase in molar composition of PAMPS and the second block included in the copolymer. Thus, the proper combination of PAMPS block copolymer with hydrophilic or hydrophobic monomers will allow fine-tuning of the physical properties of the materials and may lead to many potential applications, such as polyelectrolyte membrane fuel cells or catalytic membranes for biodiesel production.

Increased Toxicity of Doxorubicin Encapsulated into pH-Responsive Poly(ß-Amino Ester)-Functionalized MCM-41 Silica Nanoparticles.

BACKGROUND: The encapsulation of anti-cancer drugs in stimulus-sensitive release systems may provide advantages such as enhanced drug toxicity in tumour tissue cells due to increased intracellular drug release. Encapsulation may also improve release in targeted tissue due to the response to a stimulus such as pH, which is lower in the tumour tissue microenvironment. Here, we evaluated the in vitro toxicity of the Drug Doxorubicin (DOX) loaded into a release system based on poly(ß-amino ester)- modified MCM-41 silica nanoparticles. METHODS: The MCM-41-DOX-PbAE release system was obtained by loading DOX into MCM-41 nanoparticles amino-functionalized with 3-aminopropyltriethoxysilane (APTES) and then coated with a pH-responsive poly(ß-amino ester) (PbAE). The physicochemical characteristics of the release system were evaluated through TEM, FTIR and TGA. Cytotoxicity assays were performed on the MCM-41- DOX-PbAE system to determine their effects on the inhibition of human MCF-7 breast cancer cell proliferation after 48 h of exposure through crystal violet assay; the investigated systems included MCF-7 cells with MCM-41, PbAE, and MCM-41-PbAE alone. Additionally, the release of DOX and the change in pH in vitro were determined. RESULTS: The physicochemical characteristics of the synthesized MCM-41-PbAE system were confirmed, including the nanoparticle size, spherical morphology, mesoporous ordered structure, and presence of PbAE on the surface of the MCM-41 nanoparticles. Likewise, we demonstrated that the release of DOX from the MCM-41-DOX-PbAE system promoted an important reduction in MCF-7 cell viability (~ 70%) compared to the values obtained with MCM-41, PbAE, and MCM-41-PbAE, as well as a reduction in the viability under treatment with just DOX (~ 50%). CONCLUSION: The results suggest that all the components of the release system are biocompatible and that the encapsulation of DOX in MCM-41-PbAE could allow better intracellular release, which would probably increase the availability and toxic effect of DOX.

Effect of different exposure times on physicochemical, mechanical and biological properties of PGS scaffolds treated with plasma of iodine-doped polypyrrole.

Polyglycerol sebacate (PGS) scaffolds obtained using a leaching technique were modified with iodine-doped polypyrrole (PPy-I) in a plasma reactor in order to study the effect of exposure time on the cell viability of hDPSCs. SEM analysis showed the formation and growth of PPy-I particles as the exposure time was increased, while FTIR and XPS analysis revealed the presence of -NH- and N+ groups in the chemical composition of the surfaces, relating to the increase in the amount of PPY-I particles. The water contact angle measurements showed an increase in the scaffold's hydrophilicity with greater exposure times which was also attributed to the rising of PPy-I particles. It was also observed that PPy-I promotes the rigidity of the treated PGS scaffolds. when in direct contact with treated PGS scaffolds, cell viability improved with respect to non-treated scaffolds, however only at shorter time exposures. Extracts of plasma-treated PGS scaffolds showed high cytotoxicity as the time exposure to plasma treatment was increased.

Controlled Phase Changes of Titania Using Nitrogen Plasma.

In this work, the development of a new crystallization technique is reported, using nitrogen plasma (AC) to obtain nanostructured anatase and rutile from amorphous titanium oxide (TiO2). This methodology increases throughput and minimizes thermal effects. Nanostructured amorphous TiO2 was obtained by the sol-gel method and subsequently subjected to AC treatment, at a controlled pressure, applying different powers and treatment times in order to obtain phase changes. The obtained samples were characterized using X-ray diffraction (XRD), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The results show the crystallization in parallel with anatase and rutile phases with a proportion that is directly related to the applied power in the plasma and the treatment time. This technique allows us to obtain smaller crystals in comparison with those of classic thermal methodologies. It is also demonstrated that the application of plasma represents a novel and innovative method to obtain phase polymorphic changes in titanium oxide without needing to apply prolonged heat treatments at high temperatures and can therefore be taken into consideration as a technique with low energy costs, in comparison with conventional heat treatments.