Effects of Atmospheric Pressure Plasma Jet on 3D-Printed Acrylonitrile Butadiene Styrene (ABS).

Polymers are essential in several sectors, yet some applications necessitate surface modification. One practical and eco-friendly option is non-thermal plasma exposure. The present research endeavors to examine the impacts of dielectric barrier discharge atmospheric pressure plasma on the chemical composition and wettability properties of acrylonitrile butadiene styrene surfaces subject to the action of additive manufacturing. The plasma source was produced by igniting either helium or argon and then adjusted to maximize the operational conditions for exposing polymers. The drop in contact angle and the improvement in wettability after plasma exposure can be due to the increased oxygen-containing groups onto the surface, together with a reduction in carbon content. The research findings indicated that plasma treatment significantly improved the wettability of the polymer surface, with an increase of up to 60% for both working gases, while the polar index increased from 0.01 up to 0.99 after plasma treatment. XPS measurements showed an increase of up to 10% in oxygen groups at the surface of He-plasma-treated samples and up to 13% after Ar-plasma treatment. Significant modifications were observed in the structure that led to a reduction of its roughness by 50% and also caused a leveling effect after plasma treatment. A slight decrease in the glass and melting temperature after plasma treatment was pointed out by differential scanning calorimetry and broadband dielectric spectroscopy. Up to a 15% crystallinity index was determined after plasma treatment, and the 3D printing process was measured through X-ray diffraction. The empirical findings encourage the implementation of atmospheric pressure plasma-based techniques for the environmentally sustainable manipulation of polymers for applications necessitating higher levels of adhesion and specific prerequisites.

Atmospheric Pressure Plasma Jet Exposure of Polylactic Acid Surfaces for Better Adhesion: Plasma Parameters towards Polymer Properties.

Polymers play a crucial role in multiple industries; however, surface modification is necessary for certain applications. Exposure to non-thermal plasma provides a viable and environmentally beneficial option. Fused deposition molding utilizes biodegradable polylactic acid, although it encounters constraints in biomedical applications as a result of inadequate mechanical characteristics. This study investigates the effects of atmospheric pressure plasma generated by a dielectric barrier discharge system using helium and/or argon on the modification of polylactic acid surfaces, changes in their wettability properties, and alterations in their chemical composition. The plasma source was ignited in either He or Ar and was tailored to fit the best operational conditions for polymer exposure. The results demonstrated the enhanced wettability of the polymer surface following plasma treatment (up to 40% in He and 20% in Ar), with a marginal variation observed among treatments utilizing different gases. The plasma treatments also caused changes in the surface topography, morphology, roughness, and hydrophilicity. Plasma exposure also resulted in observable modifications in the dielectric characteristics, phase transition, and structure. The experimental findings endorse the utilization of plasma technologies at normal air pressure for environmentally friendly processing of polymer materials, specifically for applications that necessitate enhanced adhesion and have carefully selected prerequisites.

Dextran coated iron oxide nanoparticles loaded with protocatechuic acid as multifunctional therapeutic agents.

Nowadays, there is a growing interest in multifunctional therapeutic agents as valuable tools to improve and expand the applicability field of traditional bioactive compounds. In this context, the synthesis and main characteristics of dextran-coated iron oxide nanoparticles (IONP-Dex) loaded with both an antioxidant, protocatechuic acid (PCA), and an antibiotic, ceftazidime (CAZ) or levofloxacin (LEV) are herein reported for the first time, with emphasis on the potentiation effect of PCA on drugs activity. All nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, vibrating sample magnetometry, differential scanning calorimetry and dynamic light scattering. As evidenced by DPPH method, IONP-Dex loaded with PCA and LEV had similar antioxidant activity like those with PCA only, but higher than PCA and CAZ loaded ones. A synergy of action between PCA and each antibiotic co-loaded on IONP-Dex has been highlighted by an enhanced activity against reference bacterial strains, such as S. aureus and E. coli after 40 min of incubation. It was concluded that PCA, which is the main cause of the antioxidative properties of loaded nanoparticles, further improves the antimicrobial activity of IONP-Dex nanoparticles when was co-loaded with CAZ or LEV antibiotics. All constructs also showed a good biocompatibility with normal human dermal fibroblasts.

Ferronematic Co(II) Complex: An Active Filler for Magnetically Actuated Soft Materials.

Ferronematics that are generally based on nematic liquid crystals (LCs) doped with magnetic nanoparticles, synergistically taking advantage of the anisotropic and flow characteristics of the nematic host and the magnetic susceptibility of the dopant, have powerful applications as magnetically actuated soft materials. In this work, a Co(II) complex, which alone presents both characteristics, is built with a salen-type ligand 3,5-dichlorosubstituted at the aromatic nuclei and has a tetramethyldisiloxane spacer, which makes it one of the few metallomesogens containing this structural motif. Paramagnetic crystals, through heat treatment above 110 °C, change into magnetic nematic LCs. Applying a perpendicular magnetic field of 50 mT, the nematic droplets align two by two through dipole-dipole interactions. By incorporating it into a silicone matrix consisting mainly of polydimethylsiloxane, a 3D printable ink is formulated and crosslinked under various shapes. In this environment, the cobalt complex is stabilized in an LC state at room temperature and, due to its anisotropy, facilitates the mechanical response to magnetic stimuli. The resulting objects can be easily manipulated on fluid or rough surfaces using external magnetic fields, behave like magnets by themselves, and show reversible locomotion.

Surface Degradation of DGEBA Epoxy Resins Cured with Structurally Different Amine Hardeners: Effects of UV Radiation.

In this study, the effects of three diamine curing agents (aromatic, cycloaliphatic, aliphatic) on the photochemical behavior of bisphenol A diglycidyl ether networks were comparatively examined. In order to monitor structural changes and study the curing agents' action mode, the cured epoxy resins were characterized before and after photoirradiation by means of Fourier-transform infrared spectroscopy, contact angle, differential scanning calorimetry, scanning electron microscopy, and energy-dispersive X-ray analysis, mass loss, and color modification measurements. Water absorption tests were also conducted. The cured epoxy resins are to be used in different multicomponent polymer materials for outdoor protection. The presence of the cycloaliphatic hardener led to reduced water absorption, and after UV irradiation, an increase in the glass transition temperature and lowest mass loss of the corresponding cured epoxy resin compared to the ones cured with aromatic and aliphatic hardener.

Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity.

Natural deep eutectic solvents (NADES)-hydroxypropyl cellulose (HPC) self-assembled gels with potential for pharmaceutical applications are prepared. FT-IR, 1HNMR, DSC, TGA and rheology measurements revealed that hydrogen bond acceptor−hydrogen bond donor interactions, concentration of NADES and the water content influence significantly the physico-chemical characteristics of the studied gel systems. HPC-NADES gel compositions have thermal stabilities lower than HPC and higher than NADES components. Thermal transitions reveal multiple glass transitions characteristic of phase separated systems. Flow curves evidence shear thinning (pseudoplastic) behavior. The flow curve shear stress vs. shear rate were assessed by applying Bingham, Herschel−Bulkley, Vocadlo and Casson rheological models. The proposed correlations are in good agreement with experimental data. The studied gels evidence thermothickening behavior due to characteristic LCST (lower critical solution temperature) behavior of HPC in aqueous systems and a good biocompatibility with normal cells (human gingival fibroblasts). The order of antibacterial and antifungal activities (S.aureus, E.coli, P. aeruginosa and C. albicans) is as follows: citric acid >lactic acid > urea > glycerol, revealing the higher antibacterial and antifungal activities of acids.

Effect of Hardener Type on the Photochemical and Antifungal Performance of Epoxy and Oligophosphonate S-IPNs.

Due to their highly reactive character and multiple crosslinking capacity, epoxy resins are one of the worldwide market-dominating classes of thermosetting polymers and are present in a wide range of technical applications, including structural adhesives, coatings and polymer matrices for composite materials. Despite their excellent features, epoxy resins are known to be highly flammable and possess low thermal stability and a brittle character and crack easily under impact forces. An efficient approach towards eliminating such drawbacks resides in obtaining epoxy-based semi-interpenetrating polymer networks, which possess excellent control over the morphology. The article describes the comparative effect of three hardeners (aromatic, cycloaliphatic and aliphatic) in the presence of an oligophosphonate (-R-O-PO(C6H5)-O-) (2 wt.% phosphorus) on the photochemical, fire and antifungal performance of bisphenol A diglycidyl ether semi-interpenetrating polymer networks. The networks are designed as future potential outdoor protective coatings for different substrates. The fire resistance capacity of the networks was undertaken with microscale combustion calorimetry before and after photochemical aging. Structural changes during photoirradiation were monitored via color modification studies, Fourier-transform infrared spectroscopy, differential scanning calorimetry, morphological assessment through scanning electron microscopy and mass loss measurements in order to propose the action mode of the hardeners and the oligophosphonate on the material properties. Microbiological testing was also undertaken with the aid of three specific wood decaying fungi as a first substrate.

Hydroxypropyl Cellulose/Pluronic-Based Composite Hydrogels as Biodegradable Mucoadhesive Scaffolds for Tissue Engineering.

Recently, the development of new materials with the desired characteristics for functional tissue engineering, ensuring tissue architecture and supporting cellular growth, has gained significant attention. Hydrogels, which possess similar properties to natural cellular matrixes, being able to repair or replace biological tissues and support the healing process through cellular proliferation and viability, are a challenge when designing tissue scaffolds. This paper provides new insights into hydrogel-based polymeric blends (hydroxypropyl cellulose/Pluronic F68), aiming to evaluate the contributions of both components in the development of new tissue scaffolds. In order to study the interactions within the hydrogel blends, FTIR and 1HNMR spectroscopies were used. The porosity and the behavior in moisture medium were highlighted by SEM and DVS analyses. The biodegradability of the hydrogel blends was studied in a simulated biological medium. The hydrogel composition was determinant for the scaffold behavior: the HPC component was found to have a great influence on the BET and GAB areas, on the monolayer values estimated from sorption-desorption isotherms and on mucoadhesivity on small intestine mucosa, while the Pluronic F68 component improved the thermal stability. All blends were also found to have good mechanical strength and increased biocompatibility on the NHDF cell line. Based on their particular compositions and increased mucoadhesivity on small intestine mucosa, these polymeric blends could be effective in the repair or recovery of damaged cell membranes (due to the contribution of Pluronic F68) or in control drug-delivery intestinal formulations.

Binary Silicone Elastomeric Systems with Stepwise Crosslinking as a Tool for Tuning Electromechanical Behavior.

Interpenetrating polymer networks (IPNs) represent an interesting approach for tuning the properties of silicone elastomers due to the possible synergism that may occur between the networks. A new approach is presented, which consists of mixing two silicone-based networks with different crosslinking pathways; the first network being cured by condensation route and the second network by UV curing. The networks were mixed in different ratios and the resulted samples yield good mechanical properties (improved elongations, up to 720%, and Young's modulus, 1 MPa), thermal properties (one glass transition temperature, ~-123 °C), good dielectric strength (~50 V/µm), and toughness (63 kJ/m3).

Photochemical Stability of a Cotton Fabric Surface Dyed with a Reactive Triphenodioxazine Dye.

The paper describes the photochemical stability of a commercial triphenodioxazine dye (Reactive Blue_204) linked onto a cotton fabric. Preliminary studies have shown that as a result of irradiation, the dye and its photodegradation products can pass directly onto the skin under conditions that mimic human perspiration and cause side-effects. The cotton dyed fabric was photo irradiated at different time intervals. Standard methods were employed to evaluate the color strength at various levels of pH, temperature, dyeing contact time, and salt concentration. The influence of UV radiation at different doses (λ > 300 nm) on the structural and color modifications of the dyed cotton fabrics was studied. Structural modifications before and after irradiation were compared by applying FTIR, UV-Vis, and near infrared chemical imaging (NIR-CI) techniques. Color modifications were investigated with the CIELAB system. Color differences significantly increased with the irradiation dose. High irradiation doses caused changes in the dye structure.

Dynamic Mechanical Analysis and Thermal Expansion of Lignin-Based Biopolymers.

Biodegradable materials investigation has become a necessity and a direction for many researchers worldwide. The main goal is to find sustainable alternatives which gradually replace plastics based on fossil resources from the market, because they are very harmful to the environment and to overall quality of life. In order to get to the stage of obtaining different functional parts from biodegradable materials, it is necessary to study their properties. Taking into account these shortcomings, this paper aims at the mechanical characterization (DMA-Dynamic Mechanical Analysis) and thermal degradation (thermogravimetric analysis (TGA)) of lignin-based biopolymers: Arboform LV3 Nature®, Arboblend® V2 Nature, and Arbofill® Fichte Arboform® LV3 Nature reinforced with aramid fibers. The tested samples were obtained by using the most common fabrication technique for polymers-injection molding. The obtained results for the DMA analysis showed separate polymeric-specific regions for each material and, based on the tanδ values between (0.37-0.54), a series of plastics could be proposed for replacement. The mechano-dynamic behavior could be correlated with the thermal expansion of biopolymers for temperatures higher than 50/55 °C, which are thermally stable up to temperatures of at least 250 °C.

Antibacterial Polysiloxane Polymers and Coatings for Cochlear Implants.

Within this study, new materials were synthesized and characterized based on polysiloxane modified with different ratios of N-acetyl-l-cysteine (NAC) and crosslinked via UV-assisted thiol-ene addition, in order to obtain efficient membranes able to resist bacterial adherence and biofilm formation. These membranes were subjected to in vitro testing for microbial adherence against S. pneumoniae using standardized tests. WISTAR rats were implanted for 4 weeks with crosslinked siloxane samples without and with NAC. A set of physical characterization methods was employed to assess the chemical structure and morphological aspects of the new synthetized materials before and after contact with the microbiological medium.

Effect of Thermal Aging on the Physico-Chemical and Optical Properties of Poly(ester urethane) Elastomers Designed for Passive Damping (Pads) of the Railway.

The aim of this study consists of monitoring the effect of thermal aging on the physico-chemical and optical properties of poly(ester urethane) elastomers designed as damping materials for railways. The materials were obtained by polyaddition in two stages in melt, resulting in regular structures. The structural modifications during the thermal aging of the samples were monitored using FTIR, color changes, TGA in non-isothermal and isothermal conditions, DSC and physico-mechanical measurements. The structural regularity of the rigid and flexible segments maintained the good mechanical properties of the structures up to 200 h of thermal aging at the elevated temperatures of 40 °C, 70 °C, 100 °C and 130 °C. It was observed that at 40 °C and low exposure times, changes occur mainly to the carbonyl groups of the soft segments. At higher temperatures and longer exposure times urethane groups were affected. Extended thermal aging led to significant changes in thermo-mechanical and optical properties.

A new sponge-type hydrogel based on hyaluronic acid and poly(methylvinylether-alt-maleic acid) as a 3D platform for tumor cell growth.

A new sponge-type hydrogel was obtained by cross-linking hyaluronic acid (HA) and poly(methylvinylether-alt-maleic acid) P(MVE-alt-MA) through a solvent-free thermal method. The sponge-type hydrogel was characterized and checked as a support for cell growth. The influence of concentration and weight ratio of polymers on the morphology and hydrogel stability was investigated. The total polymers concentration of 3% (w/w) and the weight ratio of 1:1 were optimal for the synthesis of a stable hydrogel (HA3P50) and to promote cell proliferation. The swelling measurements revealed a high-water absorption capacity of the hydrogel in basic medium. Diphenhydramine (DPH), lidocaine (Lid) and propranolol (Prop) were loaded within the hydrogel as a model drugs to investigate the ability of drug transport and release. In vitro studies revealed that HA3P50 hydrogel promoted the adhesion and proliferation of human hepatocellular carcinoma cell line HepG2, providing a good support for 3D cell culture to obtain surrogate tumor scaffold suitable for preclinical anti-cancer drug screening.

Radiation Processing and Characterization of Some Ethylene-propylene-diene Terpolymer/Butyl (Halobutyl) Rubber/Nanosilica Composites.

Composites based on ethylene-propylene-diene terpolymer (EPDM), butyl/halobutyl rubber and nanosilica were prepared by melt mixing and subjected to different doses of electron beam irradiation. The effect of irradiation dose on the mechanical properties, morphology, glass transition temperature, thermal stability and water uptake was investigated. The efficiency of the crosslinking by electron beam irradiation was analyzed by Charlesby-Pinner parameter evaluation and crosslink density measurements. The scanning electron microscopy data showed a good dispersion of nanosilica in the rubber matrix. An improvement in hardness and 100% modulus was revealed by increasing irradiation dose up to 150 kGy. The interaction between polymer matrix and nanosilica was analyzed using the Kraus equation. Additionally, these results indicated that the mechanical properties, surface characteristics, and water uptake were dependent on crosslink characteristics.

Superadsorbents for Strontium and Cesium Removal Enriched in Amidoxime by a Homo-IPN Strategy Connected with Porous Silica Texture.

In light of the fact that two with good compatibility are better than one, the homo-interpenetrating polymer network (IPN) strategy was used in this work to design novel amidoxime (AOX)-interpenetrating networks into porous silica (PSi) with the final aim to enhance the sorption performances of composite sorbents toward Cs+ and Sr2+. To achieve this goal, first, a homo-IPN of poly(acrylonitrile) (PAN) was constructed inside the channels of two kinds of porous silica, one mesoporous (PSi1) and one macroporous (PSi2), the textural properties of silica being exploited in controlling the sorption performances of the composites. The novel composites were fully characterized by thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and the nitrogen sorption/desorption isotherms (Brunauer-Emmett-Teller (BET) analysis). The sorption properties of the PSi1/AOX and PSi2/AOX composite sorbents for Sr2+ and Cs+ were investigated in the batch mode to determine the effect of solution pH, contact time, initial metal ion concentration, temperature, and the presence of competitive ions on the adsorption performances. The fast kinetics of sorption was supported by the fact that ∼80% of Sr2+ and ∼65% of Cs+ were adsorbed in the first 30 min, the kinetic data being better described by the pseudo-second-order kinetic model. The experimental isotherms were well fitted by the Langmuir and Sips isotherm models. The superadsorption of Sr2+ and Cs+ is demonstrated by the values of the maximum sorption capacity of the best sorbent constructed with mesoporous silica (PSi1/IPN-AOX), which were 344.23 mg Cs+/g and 360.23 mg Sr2+/g. The sorption process was spontaneous and endothermic for both metal ions. The presence of interfering cations (Na+, K+, Ca2+, and Mg2+), at a concentration of 10-2 M, only slightly influenced the sorption capacity for the main cation. The composite sorbents were still highly efficient after five sorption/desorption cycles.

Blends of sodium deoxycholate-based poly(ester ether)urethane ionomer and hydroxypropylcellulose with mucosal adhesiveness.

New mucoadhesive blends of sodium deoxycholate-based poly(ester ether)urethane ionomer (PU) and hydroxypropyl cellulose (HPC) are prepared. The presence of the intermolecular interactions between the polymeric components has been investigated by FTIR spectroscopy indicating their miscibility in the solid phase. DSC studies also revealed a single glass transition of the blends, which is indicative of miscibility of PU and HPC in the amorphous phase. The amount of HPC in the blends influences strongly the physicochemical and mucoadhesion/bioadhesion properties. It was found that the value of area attributed to ordered hydrogen bonding (FTIR), the onset temperature values of thermal degradation in N2 flow (TG/DTG), the values of the sorption capacity (Dynamic Vapor Sorption-DVS), the values of the apparent viscosity (rheological measurements) and mucoadhesion/bioadhesion properties increased by increasing the HPC content in the blends. Complex viscosity revealed shear thinning behavior for all the studied solutions evidencing the contributive role of polymer viscoelasticity on mucoadhesion. It was found that both G' and G" increase with an increase in angular frequency and G">G' which is characteristic for liquid-like (sol state) behavior for all blended solutions and this behavior is helpful in the adhesion with mucosa surface. Mucoadhesion of PU/HPC blends was assessed in the stomach mucosa at pH 2.6 and 37 °C. Bioadhesion test was performed at pH 7.4 and 37 °C and revealed a stronger interaction of PU/HPC blends with cellulose membrane than with stomach mucosa. The similar nature of the HPC and cellulose membrane determines additional adhesion forces and implicity high adhesion properties. The HPC component increases the hydrophilicity of the blends as DVS analysis revealed, but also leads to hydrolytic degradation. FTIR spectroscopy analysis was used to evaluate the hydrolytic stability in acid (pH 2.6) and slightly alkaline (pH 7.4) PBS media and a mechanism of degradation has been proposed.

Development of antioxidant and antimicrobial xanthan-based cryogels with tuned porous morphology and controlled swelling features.

Novel porous films based on xanthan gum (XG), poly(vinyl alcohol) (PVA), and red grape pomace (RGP), as entrapped natural antioxidant agent, were prepared by freeze/thawing, a versatile and non-destructive method. The stability of XG/PVA films was dependent on the crystalline zones created by PVA under freeze/thawing treatment. After three cryogenic cycles, the introduction of RGP into the 3D polymer matrix plays a major role by hindering the access of water into the cavities already formed during the first and second cryogenic cycles. By contrast, XG/PVA-based cryogels with enhanced mechanical strength were obtained when the number of freeze/thawing cycles increased from three to seven, while pores stability was improved by entrapment of RGP. The remarkable antioxidant and antimicrobial activity of XG/PVA/RGP cryogel films compared to the XG/PVA films, indicates the potential application of these systems in food packaging.

Epoxy Coatings Based on Modified Vegetable Oils for Wood Surface Protection against Fungal Degradation.

The study describes the curing and thermal behavior of a new castor oil maleic anhydride adduct/epoxy oils/5-Bromosalicylic acid coatings and their composites with wood. The epoxidized oils were flax and hemp. The kinetic parameters of the curing and thermal degradation processes were calculated. The resistance of the coated wood surfaces against Cladosporium cladosporioides, Aspergillus brasiliensis, and Penicillium chrysogenum was tested. Color changes, FT-IR and SEM were conducted before and after fungal attack. The decay resistance and color change of raw wood and wood treated samples against fungi was tested. Based on the color changes and according to ASTM D 2017, the decay resistance rating for covered samples was considered as "highly resistant". Chemical resistance and coating performance tests were also undertaken. The obtained results recommend the described materials for applications in wood protective coatings.

Duodenoscope-Associated Infections beyond the Elevator Channel: Alternative Causes for Difficult Reprocessing.

OBJECTIVES: Duodenoscopes have been widely used for both diagnostic and therapeutic endoscopic retrograde cholangiopancreatography (ERCP) procedures, but recently, numerous outbreaks of multidrug-resistant organisms (MDRO) infections have been reported which has led to extensive research for their possible causes. Consequently, the aim of this study is to search for possible duodenoscope surface damages that could provide an alternative and plausible source of infections. MATERIALS AND METHODS: In order to assess both outer and inner surfaces, a duodenoscope was dismantled and samples were taken from the outer resin polymer and from the air/water, elevator, and working (biopsy) channels that were characterized by FTIR, DSC, TGA, AFM, SEM techniques and the antimicrobial activity were tested. RESULTS: Alterations were noticed on both the coating and working channel polymers, with external alterations increasing progressively from the proximal sample to the distal sample near the tip of the scope. However, the results showed that the coating surface was still efficient against bacterial adhesion. Changes in surface texture and also morphological changes were shown. CONCLUSIONS: The study describes the impact of routine procedural use and reprocessing cycles on the duodenoscope, showing that these may possibly make it susceptible to bacterial contamination and MDRO biofilm formation due to difficult reprocessing of the altered surfaces.