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1.
Thermal study of APTES-functionalized magnetite nanoparticles with citric acid and polyacrylic acid for advanced forward osmosis systems
Matjaž Kristl, Urška Ostroško, Irena Ban, Irena Petrinić, Janja Stergar, 2024, original scientific article

Abstract: Iron-based magnetic nanoparticles (MNPs) have attracted considerable attention as promising draw solutes in forward osmosis processes due to various advantages. In the present study, magnetite (Fe3O4) nanoparticles (MNPs) with diameters in the range of 12±2 nm were synthesized by applying the coprecipitation method and stabilized using (3-aminopropyl) triethoxysilane (APTES). The amino groups of APTES were further functionalized with various amounts of citric acid (CA) and poly(acrylic acid) (PAA) to achieve higher osmotic pressure. The as-prepared and functionalized nanoparticles were characterized using diferent methods: Fourier-transform infrared spectroscopy (FTIR) confrmed the binding of APTES and CA/PAA on the surface of the MNPs, while the size of the particles was determined by transmission electron microscopy (TEM) and X-ray powder difraction. The isoelectric point, zeta potential, and the particle size in suspension were determined by dynamic light scattering (DLS)/zeta potential measuring system. The amount of free –COOH groups was determined by conductometric titrations. The amount of organic matter (APTES, CA, and PAA) bound on the surface was determined by thermogravimetric analysis (TG), giving results between 7.6% for samples stabilized with APTES only and 17.5% for samples functionalized with APTES+PAA. TG provides a simple and efcient method for determining the amount of organic compounds bound to the surface of MNPs. The osmotic pressure measurements of double-layer coated MNPs provided encouraging results of up to 28 bar, enabling using the samples as draw solutions in an experimental forward osmosis system.
Keywords: magnetic nanoparticles, magnetite, citrit acid, poly(acrylic acid), forward osmosis
Published in DKUM: 14.08.2024; Views: 105; Downloads: 3
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Fabrication of poly(ethylene furanoate)/silver and titanium dioxide nanocomposites with improved thermal and antimicrobial properties
Johan Stanley, Eleftheria Xanthopoulou, Lidija Fras Zemljič, Panagiotis A. Klonos, Apostolos Kyritsis, Dimitra A. Lambropoulou, Dimitrios Bikiaris, 2024, original scientific article

Abstract: Poly(ethylene furanoate) (PEF)-based nanocomposites were fabricated with silver (Ag) and titanium dioxide (TiO2) nanoparticles by the in-situ polymerization method. The importance of this research work is to extend the usage of PEF-based nanocomposites with improved material properties. The PEF-Ag and PEF-TiO2 nanocomposites showed a significant improvement in color concentration, as determined by the color colorimeter. Scanning electron microscopy (SEM) photographs revealed the appearance of small aggregates on the surface of nanocomposites. According to crystallinity investigations, neat PEF and nanocomposites exhibit crystalline fraction between 0–6%, whereas annealed samples showed a degree of crystallinity value above 25%. Combining the structural and molecular dynamics observations from broadband dielectric spectroscopy (BDS) measurements found strong interactions between polymer chains and nanoparticles. Contact angle results exhibited a decrease in the wetting angle of nanocomposites compared to neat PEF. Finally, antimicrobial studies have been conducted, reporting a significant rise in inhibition of over 15% for both nanocomposite films against gram-positive and gram-negative bacteria. From the overall results, the synthesized PEF-based nanocomposites with enhanced thermal and antimicrobial properties may be optimized and utilized for the secondary packaging (unintended food-contact) materials.
Keywords: active agents, antimicrobial studies, biobased polymers, crystallinity, poly(ethylene 2, 5-furandicarboxylate)
Published in DKUM: 03.04.2024; Views: 214; Downloads: 8
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6.
Kraft lignin/tannin as a potential accelerator of antioxidant and antibacterial properties in an active thermoplastic polyester-based multifunctional material
Klementina Pušnik Črešnar, Alexandra Zamboulis, Dimitrios Bikiaris, Alexandra Aulova, Lidija Fras Zemljič, 2022, original scientific article

Abstract: This research focuses on key priorities in the field of sustainable plastic composites that will lead to a reduction in CO2 pollution and support the EU’s goal of becoming carbon neutral by 2050. The main challenge is to develop high-performance polyphenol-reinforced thermoplastic composites, where the use of natural fillers replaces the usual chemical additives with non-toxic ones, not only to improve the final performance but also to increase the desired multifunctionalities (structural, antioxidant, and antibacterial). Therefore, poly (lactic acid) (PLA) composites based on Kraft lignin (KL) and tannin (TANN) were investigated. Two series of PLA composites, PLA-KL and PLA-TANN, which contained natural fillers (0.5%, 1.0%, and 2.5% (w/w)) were prepared by hot melt extrusion. The effects of KL and TANN on the PLA matrices were investigated, especially the surface physicochemical properties, mechanical properties, and antioxidant/antimicrobial activity. The surface physicochemical properties were evaluated by measuring the contact angle (CA), roughness, zeta potential, and nanoindentation. The results of the water contact angle showed that neither KL nor TANN caused a significant change in the wettability, but only a slight increase in the hydrophilicity of the PLA composites. The filler loading, the size of the particles with their available functional groups on the surfaces of the PLA composites, and the interaction between the filler and the PLA polymer depend on the roughness and zeta potential behavior of the PLA-KL and PLA-TANN composites and ultimately improve the surface mechanical properties. The antioxidant properties of the PLA-KL and PLA-TANN composites were determined using the DPPH (2,2′-diphenyl-1-picrylhydrazyl) test. The results show an efficient antioxidant behavior of all PLA-KL and PLA-TANN composites, which increases with the filler content. Finally, the KL- and PLA-based TANN have shown resistance to the Gram-negative bacteria, E. coli, but without a correlation trend between polyphenol filler content and structure.
Keywords: poly (lactic acid), Kraft lignin, tannin, multifunctionality of PLA composites, surface mechanical properties, antioxidant/antibacterial activity
Published in DKUM: 18.09.2023; Views: 495; Downloads: 24
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7.
Synthesis of PMMA/ZnO nanoparticles composite used for resin teeth
Danica Popović Antić, Rajko Bobovnik, Silvester Bolka, Miroslav Vukadinovič, Vojkan Lazić, Rebeka Rudolf, 2017, original scientific article

Abstract: Wear resistance is one of the most important physical properties of the artificial teeth used in acrylic dentures. The goal of this research was to synthesize a new composite material made of matrix Poly-(methyl methacrylate)-PMMA with different percentages (2 % and 3 % of volume fractions) of zinc-oxide nanoparticles (ZnO NPs) as reinforcing elements, to improve its mechanical properties. The dynamic mechanical behaviour of this composite was studied through the DMA method in comparison to the pure PMMA supported by the characterization of their microstructures. Then the wear resistance was analysed on the samples, which were prepared in the form of teeth. In this context their vertical height loss was measured after 100,000 chewing cycles on a chewing simulator, before and after the artificial thermal ageing. Investigations showed that the PMMA/ZnO NP composites dampened the vibrations better than the pure PMMA, which could be assigned to the homogenous distribution of ZnO NPs in the PMMA matrix. It was found that the mean vertical height loss for the pure PMMA teeth was significantly higher (more than 4 times) compared to composite teeth made with ZnO NPs. Introducing the thermal artificial ageing led to the finding that there was no effect on the height loss by the composite material with 3 % of volume fractions of ZnO NPs. Based on this it was concluded that PMMA/ZnO NPs composites showed improved in-vitro wear resistance compared to acrylic-resin denture teeth, so this new composite material should be preferred when occlusal stability is considered to be of high priority.
Keywords: poly-methyl methacrylate, PMMA, zinc-oxide nanoparticles, composite, resin teeth
Published in DKUM: 12.12.2017; Views: 1876; Downloads: 437
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8.
Effect of peptides' binding on the antimicrobial activity and biocompatibility of ‎protein-based substrates ‎
Maja Kaisersberger Vincek, 2017, doctoral dissertation

Abstract: This work reveals the effect of coupling approach (chemical by using carbodiimide chemistry ‎and grafting-to vs. grafting-from synthesis routes, and enzymatic by using transglutaminase) ‎of a hydrophilic ε-poly-L-lysine (εPL) and an amphiphilic oligo-acyl-lysyl (OAK) derivative (K-7α12-OH) to wool fibers and gelatine (GEL) macromolecules, respectively, and substrates ‎antibacterial activity against Gram-negative E. coli and Gram-positive S. aureus bacteria ‎after 1–24 h of exposure, as well as their cytotoxicity. Different spectroscopic (ultraviolet-‎visible, infrared, fluorescence and electron paramagnetic resonance) and separation ‎techniques (size-exclusion chromatography and capillary zone electrophoresis) as well as ‎zeta potential and potentiometric titration analysis, were performed to confirm the covalent ‎coupling of εPL/OAK, and to determine the amount and orientation of its immobilisation.‎ The highest and kinetically the fastest level of bacterial reduction was achieved with ‎wool/GEL functionalised with εPL/OAK by chemical grafting-to approach. This effect ‎correlated with both the highest grafting yield and conformationally the highly-flexible ‎(brush-like) orientation linkage of εPL/OAK, implicating on the highest amount of accessible ‎amino groups interacting with bacterial membrane. However, OAK`s amphipathic structure, ‎the cationic charge and the hydrophobic moieties, resulted to relatively high reduction of S. ‎aureus for grafting-from and the enzymatic coupling approaches using OAK-functionalised ‎GEL. ‎ The εPL/OAK-functionalised GEL did not induce toxicity in human osteoblast cells, even at ‎‎~25-fold higher concentration than bacterial minimum inhibitory (MIC) concentration of ‎εPL/OAK, supporting their potential usage in biomedical applications.‎ It was also shown that non-ionic surfactant adsorbs strongly onto the wool surface during ‎the process of washing, thereby blocking the functional sites of immobilized εPL and ‎decreases its antibacterial efficiency. ‎ ‎
Keywords: wool, gelatine, antimicrobial peptides, ε-poly-L-lysine, oligo-acyl-lysyl, grafting chemistry, ‎grafting approach, peptide orientation, antibacterial activity, cytotoxicity‎
Published in DKUM: 17.08.2017; Views: 1931; Downloads: 175
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Covalent binding of heparin to functionalized PET materials for improved haemocompatibility
Metod Kolar, Miran Mozetič, Karin Stana-Kleinschek, Mirjam Fröhlich, Boris Turk, Alenka Vesel, 2015, original scientific article

Abstract: The hemocompatibility of vascular grafts made from poly(ethylene terephthalate) (PET) is insufficient due to the rapid adhesion and activation of blood platelets that occur upon incubation with whole blood. PET polymer was treated with NHx radicals created by passing ammonia through gaseous plasma formed by a microwave discharge, which allowed for functionalization with amino groups. X-ray photoelectron spectroscopy characterization using derivatization with 4-chlorobenzaldehyde indicated that approximately 4% of the –NH2 groups were associated with the PET surface after treatment with the gaseous radicals. The functionalized polymers were coated with an ultra-thin layer of heparin and incubated with fresh blood. The free-hemoglobin technique, which is based on the haemolysis of erythrocytes, indicated improved hemocompatibility, which was confirmed by imaging the samples using confocal optical microscopy. A significant decrease in number of adhered platelets was observed on such samples. Proliferation of both human umbilical vein endothelial cells and human microvascular endothelial cells was enhanced on treated polymers, especially after a few hours of cell seeding. Thus, the technique represents a promising substitute for wet-chemical modification of PET materials prior to coating with heparin.
Keywords: poly(ethylene terephthalate), vascular graft, biocompatibility, heparin, plasma, functionalization, haemolysis, platelet adhesion, endothelization
Published in DKUM: 21.06.2017; Views: 1344; Downloads: 348
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10.
Modification of PET-polymer surface by nitrogen plasma
Rok Zaplotnik, Metod Kolar, Aleš Doliška, Karin Stana-Kleinschek, 2011, original scientific article

Abstract: Low pressure weakly nitrogen plasma was applied for incorporation of nitrogen-containing functional groups onto poly(ethylene terephthalate) - PET polymer. Nitrogen plasma was created in an electrode-less radiofrequency discharge at the nominal power of 200 W and the frequency of 27.12 MHz. Nitrogen molecules entered the discharge region were highly excited, partially dissociated and weakly ionized. Transformation into the state of plasma allowed for creation of chemically reactive particles with a high potential energy while the kinetic energy remained close to the value typical for room temperature. The chemical reactivity allowed for rapid functionalization with nitrogen-rich functional groups. The appearance of these groups was monitored by X-ray photoelectron spectroscopy - XPS. The polymer surface was quickly saturated with nitrogen indicating that the modification was limited to an extremely thin surface film.
Keywords: poly(ethylene terephthalate), nitrogen plasma, surface modification, functional groups, X-ray photoelectron spectroscopy
Published in DKUM: 17.03.2017; Views: 1358; Downloads: 103
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