Search Results (63)

This study investigates the combined use of electron beam irradiation (EBI) and nanotechnology to develop improved food packaging films. EBI, commonly applied for sterilization, can alter polymer microstructure, while irradiated cellulose nanocrystals (CNCs) offer enhanced functionality when incorporated into biopolymer matrices. Here, CNCs were irradiated with doses up to 50 kGy, leading to the formation of carboxyl and aldehyde groups, confirmed by FTIR analysis, as a consequence of the initial formation of free radicals and peroxides that may subsist in that original form or be converted into various carbonyl groups. Flexible films were obtained by incorporating pristine and EB-irradiated CNCs in an internal mixer, using minute amounts of poly(ethylene oxide) (PEO) to facilitate the dispersion of the filler within the polymer matrix. The resulting PLA/PEO/CNC films were evaluated for their mechanical, thermal, barrier, and antioxidant properties. The results showed that structural modifications of CNCs led to significant enhancements in the performance of the composite films, including a 30% improvement in water barrier properties and a 50% increase in antioxidant activity. These findings underscore the potential of irradiated CNCs as effective additives in biopolymer-based active packaging, offering a sustainable approach to reduce dependence on synthetic preservatives and potentially extend the shelf life of food products. Full article

Microplastics (MPs) are emerging contaminants that can significantly impact soil nutrient dynamics, particularly phosphorus (P) cycling, which is critical for maintaining soil fertility and ecosystem productivity. However, limited information is available on how different microplastic types and concentrations specifically influence phosphorus dynamics and microbial enzyme activity in soils. Microplastic contamination may alter P cycling by directly supplying phosphorus or indirectly influencing microbial activity and enzyme function through changes in soil structure and aggregation. This study examined the short-term impacts of three widely used microplastic polymers—polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET)—on soil phosphorus forms and alkaline phosphatase activity (APA), a key enzyme in phosphorus transformation. Incubation experiments were conducted at two concentrations (0.5% and 5%) over 30 and 60 days. The results indicated that the impact of microplastics on soil phosphorus dynamics varied according to both polymer type and contamination dose. Microplastics increased available phosphorus (AP) and APA levels compared to control soils, indicating a stimulatory effect on microbial processes. This may be due to the temporary accumulation of phosphorus on MP surfaces, which can stimulate phosphatase activity. Over time, however, both AP and APA levels declined, suggesting that degradation products released from MPs and organic matter may have altered the activity of the microbial communities responsible for P cycling. FTIR analysis revealed clear degradation of microplastics, with PET showing the most pronounced chemical transformation. PP exhibited moderate degradation, while PE demonstrated the highest resistance to environmental breakdown. These degradation processes likely released functional groups (e.g., carboxyl, carbonyl, hydroxyl) and low-molecular-weight compounds into the soil, modifying microbial processes and phosphorus chemistry. Particularly in PET-amended soils, these degradation products may have enhanced phosphate complexation or mobilization, contributing to higher levels of available phosphorus at the end of the incubation time. Understanding the polymer-specific and concentration-dependent effects of microplastics is critical for accurate ecological risk assessment in terrestrial ecosystems. Full article

Glycerol is a biogenic waste that is generated in both the biodiesel and oleo-chemical industries. The value addition of surplus glycerol is of utmost importance for making these industries economically profitable. In line with this, glycerol is converted into glycerol carbonate, a potential candidate for the industrial production of polymers and biobased non-isocyanate polyurethanes. In addition, glycerol can also be converted into solketal, which is the protected form of glycerol with a primary hydroxyl functional group. In this contribution, we developed a microwave-assisted solvent and catalyst-free method for converting solketal into solketal carbonate. Under conventional heating conditions, the reaction of solketal with dimethyl carbonate resulted in 70% solketal carbonate in 48 h. However, under microwave heating, 90% solketal carbonate was obtained in just 30 min. From the perspective of sustainability and green chemistry, biomass-derived heterogeneous catalysts are gaining importance. Therefore, in this project, several green catalysts, such as molecular sieves (MS, 4Å), Hβ-Zeolite, Montmorillonite K-10 clay, activated carbon from groundnut shell (Arachis hypogaea), biochar prepared from the pyrolysis of sawdust, and silica gel, were successfully used for the carbonyl transfer reaction. The obtained solketal carbonate was thoroughly characterized by ¹H NMR, ¹³C NMR, IR, and MS. The method presented here is facile, clean, and environmentally benign, as it eliminates the use of complicated procedures, toxic solvents, and toxic catalysts. Full article

The amorphization and crystallization of citric acid in the presence of a variety of polymers were investigated. Polymers were chosen for their different physicochemical features, including hygroscopicity, glass transition temperature (T_g), and functional groups capable of forming intermolecular non-covalent interactions with citric acid. Citric acid solutions with varying amounts of pectin (PEC), guar gum (GG), κ-carrageenan (KG), gelatin (GEL), (hydroxypropyl)methylcellulose (HPMC), and carboxymethylcellulose sodium (CMC-Na) were lyophilized. Dispersions were stored for up to 6 months in controlled temperature and relative humidity environments and periodically monitored using powder X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopy. Moisture sorption isotherms and moisture contents were determined. Amorphous solid dispersions of citric acid were successfully formed in the presence of ≥20% w/w CMC-Na and PEC or ≥30% w/w of the other polymers except KG which required a minimum of 40% polymer. All samples remained amorphous even in their rubbery state at 0% RH (25 °C and 40 °C), but increasing the RH to 32% RH resulted in citric acid crystallization in the KG dispersions, and further increasing to 54% RH resulted in crystallization in all samples. Polymer effectiveness for inhibiting citric acid crystallization was CMC-Na > PEC ≥ GEL > HPMC > GG > KG. To create and maintain amorphous citric acid, polymer traits in order of effectiveness were as follows: greater propensity for intermolecular non-covalent interactions (both ionic and hydrogen bonding) with the citric acid, carbonyl groups, higher T_g, and then lower hygroscopicity. Full article

The aim of this research was to obtain two-layer polymer composites with favorable mechanical and functional properties. The composites consisted of one lower layer of polymer with less elastic properties, containing no admixtures, and one upper layer of polymer with more elastic properties, containing plant admixtures, in the amount of 10% by weight of either goldenrod (Solidago virgaurea L.), or of turmeric (Curcuma longa L.). The admixtures S. virgaurea and C. longa were intended to introduce new biodegradable and medicinal properties without causing too much deterioration of physical or mechanical properties. Some polymer composites additionally contained magnetic particles in the form of carbonyl iron (Fe) in the amount of 20% by weight. The tests of mechanical tensile strength of the composites, water absorption, frost resistance, and surface contact angle were performed. Microscopic examinations determined the roughness of the cross-sectional surfaces. A constant magnetic field with magnetic induction B, which was an additional external factor changing the properties and structure of two-layer polymer composites, was also used in the research. Full article

Glassy carbon (GC) microelectrodes have been successfully used for the detection of electroactive neurotransmitters such as dopamine and serotonin through voltammetry. However, non-electroactive neurotransmitters such as glutamate, lactate, and gamma-aminobutyric acid (GABA) are inherently unsuitable for detection through voltammetry techniques without functionalizing the surface of the microelectrodes. To this end, we present here the immobilization of the L-glutamate oxidase (GluOx) enzyme on the surface of GC microelectrodes to enable the catalysis of a chemical reaction between L-glutamate, oxygen, and water to produce H₂O₂, an electroactive byproduct that is readily detectable through voltammetry. This immobilization of GluOx on the surface of bare GC microelectrodes and the subsequent catalytic reduction in H₂O₂ through fast-scan cyclic voltammetry (FSCV) helped demonstrate the indirect in vitro detection of glutamate, a non-electroactive molecule, at concentrations as low as 10 nM. The functionalized microelectrodes formed part of a four-channel array of microelectrodes (30 μm × 60 μm) on a 1.6 cm long neural probe that was supported on a flexible polymer, with potential for in vivo applications. The types and strengths of the bond between the GC microelectrode surface and its functional groups, on one hand, and glutamate and the immobilized functionalization matrix, on the other hand, were investigated through molecular dynamic (MD) modeling and Fourier transform infrared spectroscopy (FTIR). Both MD modeling and FTIR demonstrated the presence of several covalent bonds in the form of C-O (carbon–oxygen polar covalent bond), C=O (carbonyl), C-H (alkenyl), N-H (hydrogen bond), C-N (carbon–nitrogen single bond), and C≡N (triple carbon–nitrogen bond). Further, penetration tests on an agarose hydrogel model confirmed that the probes are mechanically robust, with their penetrating forces being much lower than the fracture force of the probe material. Full article

The development of dressings based on electrospun membranes with polymers and plant extracts is an interesting approach to skin regeneration, providing elements to prevent contamination and a matrix that accelerates the healing process. We developed a membrane composed of polyvinylpyrrolidone (PVP), gel and Aloe vera peel extract via the electrospinning technique. Additionally, an optimal ratio of PVP/Av gel/Av skin extract was determined to facilitate membrane formation. Electrospun membranes were obtained with fiber diameters of 1403 ± 57.4 nm for the PVP and 189.2 ± 11.4 nm for PVP/Av gel/Av peel extract, confirming that the use of extracts generally reduced the fiber diameter. The incorporation of gel and peel extract of Aloe vera into the electrospun membrane was analyzed via FTIR and UV–Vis spectroscopies. FTIR revealed the presence of functional groups associated with phenolic compounds such as aloin, aloe-emodin, emodin and aloesin, which was confirmed by UV–Vis, revealing absorption bands corresponding to aloin, phenols and carbonyl groups. This finding provides evidence of the effective integration and prevalence of bioactive compounds of a phenolic and polysaccharide nature from the gel and the Av skin extract in the electrospun fibers, resulting in an advanced membrane that could improve and accelerate the healing process and protect the wound from bacterial infections. Full article

This work proposes for the first time protecting–reflecting on both sides of plated mirrors and a solution to polycarbonate surface vulnerability to weathering and scratching using tungsten disulfide (WS₂) by mechanical polishing. The ability of the dynamic chemical plating (DCP) technique to deposit Ag films at the nanometer scale on a polycarbonate (PC) substrate and its characteristics to be metallized is also shown. These deposits hold significant promise for concentrated solar power (CSP) applications. Complementarily, the application of WS₂ as a reflective film for CSP by mechanical polishing on smooth polycarbonate surfaces is both novel and practical. This technique is innovative and scalable without needing reactants or electrical potential, making it highly applicable in real-world scenarios, including, potentially, on-site maintenance. The effects of surface morphology and adhesion, and the reflectivity parameters of the silver metallic surfaces were investigated. Wettability was investigated because it is important for polymeric surfaces in the activation and metal deposition immediately after redox reactions. The flame technique improved wettability by modifying the surface with carbonyl and carboxyl functional groups, with PC among the few industrial polymers that resisted such a part of the process. The change in the chemical composition, roughness, and wettability of the surfaces effectively improved the adhesion between the Ag film and the PC substrate. However, it did not significantly affect the adhesion between PC and WS₂ and showed its possible implementation as a first surface mirror. Overall, this work provides a scalable, innovative method for improving the durability and reflectivity of polycarbonate-based mirrors, with significant implications for CSP applications. Full article

This paper presents the thermal behavior of polymer microspheres based on glycidyl methacrylate (GMA) and crosslinking agents benzene-1,4-diylbis(2-methylprop-2-enoate) (1,4DMB) and trimethylolpropane trimethacrylate (TRIM) before and after functionalization with thioglycolic acid (TGA). The thermal stability of the polymers was determined using thermogravimetric analysis and differential scanning calorimetry under non-oxidizing conditions. The evolved gases were detected by FTIR and NMR spectroscopy, and the chemical structure of solid residues after preheating was assessed by FTIR/ATR spectroscopy. The post-functionalized microspheres showed higher thermal stability (within 270–290 °C) than the initial copolymers (within 240–250 °C). In this paper, examples of decomposition patterns of polymer microspheres before and after functionalization are presented. The decomposition of the initial microspheres starts with the emission of GMA monomers, acrolein, carbon dioxide, and the formation of unsaturated bonds in the solid residue. In the case of functionalized microspheres, degradation involves the transesterification of ester groups with the -SH groups, resulting in the emission of carbonyl sulfide, acrolein and carbon dioxide. Furthermore, lactone groups are created in the solid residue. The degradation of the functionalized copolymers is a complex process due to their crosslinked structure, rendering the identification of all the degradation products unattainable. Full article

This research concerns the modification of commercially available epoxy resin with flame retardants in order to obtain aging-resistant and antimicrobial polymeric materials with a plant stabilizer dedicated to use in rail transport. Polymer compositions based on epoxy resin, fiberglass fabric, and naringenin were prepared. Naringenin was added as a natural stabilizer at 2, 4, and 8 phr. The materials were subjected to solar aging lasting 800 h. The hardness of the samples, surface energy, and carbonyl indexes were determined, and the color change in the composition after aging was analyzed. In addition, microscopic observations, analyses of mechanical properties, and microbiological tests were performed. The hardness determination showed that the samples retained their functional properties after solar aging. The increase in the polar component of the surface energy of all materials indicated the beginning of the degradation process of the composites. The tensile one-directional tests were carried out for plane samples taken in three directions (0, 90, and 45 degrees referred to a plate edge) before and after the aging process. The addition of naringenin did not affect the functional and surface properties of the epoxy resin-based materials. Polyphenol stabilized polymer composites, as evidenced by the results of carbonyl indexes. Moreover, the obtained samples showed good antimicrobial properties for E. coli and C. albicans in the field of testing the viability of microbial cells in contact with the tested surfaces. Full article

The aim of this research was to obtain new polymer composites with a silicone rubber matrix, having favorable mechanical and functional properties. They contained admixtures in the amount of 10% by weight of expanded graphite (EG) or birch bark (BB). Additionally, some composites contained magnetic particles in the form of carbonyl iron in the amount of 20% by weight. The tensile strength, water absorption, frost resistance, surface contact angle, and free surface energy were examined. Microscopic images were taken using the SEM method and the content of some elements in selected microareas was determined using the EDXS method. In the study, a constant magnetic field with magnetic induction B was used, by means of which the properties and structure of polymer composites were modified. Scientific research in the field of polymers is the driving force behind the progress of civilization. Smart materials are able to respond to external stimuli, such as magnetic fields, with significant changes in their properties. The magnetic field affects not only chemical reactions, but also the crystallographic structure and physicochemical properties of the final products. Owing to their unique properties, such materials can be used in the space industry, automotive industry, or electrical engineering. Full article

The depletion of natural resources and increasing environmental apprehension regarding the reduction of harmful isocyanates employed in manufacturing polyurethanes (PUs) have generated significant attention from both industrial and academic sectors. This attention is focused on advancing bio-based non-isocyanate polyurethane (NIPU) resins as viable and sustainable substitutes, possessing satisfactory properties. This review presents a comprehensive analysis of the progress made in developing bio-based NIPU polymers for wood adhesive applications. The main aim of this paper is to conduct a comprehensive analysis of the latest advancements in the production of high-performance bio-based NIPU resins derived from lignin and tannin for wood composites. A comprehensive evaluation was conducted on scholarly publications retrieved from the Scopus database, encompassing the period from January 2010 to April 2023. In NIPU adhesive manufacturing, the exploration of substitute materials for isocyanates is imperative, due to their inherent toxicity, high cost, and limited availability. The process of demethylation and carbonation of lignin and tannin has the potential to produce polyphenolic compounds that possess hydroxyl and carbonyl functional groups. Bio-based NIPUs can be synthesized through the reaction involving diamine molecules. Previous studies have provided evidence indicating that NIPUs derived from lignin and tannin exhibit enhanced mechanical properties, decreased curing temperatures and shortened pressing durations, and are devoid of isocyanates. The characterization of NIPU adhesives based on lignin and tannin was conducted using various analytical techniques, including Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), matrix-assisted laser desorption/ionization with time-of-flight (MALDI-TOF) mass spectrometry, and gel permeation chromatography (GPC). The adhesive performance of tannin-based NIPU resins was shown to be superior to that of lignin-based NIPUs. This paper elucidates the potential of lignin and tannin as alternate sources for polyols in the manufacturing of NIPUs, specifically for their application as wood adhesives. Full article

This article reports the characterisation of pyrolysis of automotive shredder residue using in situ synchrotron IR, gas-phase IR, and thermal analyses to explore if the automotive shredder residue can be converted into value-added products. When heating to ~600 °C at different heating rates, thermal analyses suggested one- to two-stage pyrolysis. Transformations in the first stage, at lower temperatures, were attributed to the degradation of carbonyl, hydroxyl, or carboxyl functional stabilisers (aldehyde and ether impurities, additives, and stabilisers in the ASR). The second stage transformations, at higher temperatures, were attributed to the thermal degradation of the polymer char. Simultaneous thermal analyses and gas-phase IR spectroscopy confirmed the evolution of the gases (alkanes (CH₄), CO₂, and moisture). The synchrotron IR data have demonstrated that a high heating rate (such as 150 °C/min) results in an incomplete conversion of ASRs unless sufficient time is provided. The thermogravimetry data fit the linearised multistage kinetic model at different heating rates. The activation energy of reactions varied between 24.98 and 124.94 kJ/mol, indicating a surface-controlled reaction exhibiting high activation energy during the initial stages and a diffusion and mass transfer control showing lower activation energy at the final stages. The corresponding frequency factors were in the range of 3.34 × 10¹³–5.68 × 10¹ mg⁻¹/min for different pyrolysis stages. The evolution of the functional groups decreased with an increase in the heating rate. Full article

Due to their high abundance, polymeric character, and chemical tunability, polysaccharides are perfect candidates for the stabilization of photoactive nanoscale objects, which are of great interest in modern science but can be unstable in aqueous media. In this work, we have demonstrated the relevance of oxidized dextran polysaccharide, obtained via a simple reaction with H₂O₂, towards the stabilization of photoactive octahedral molybdenum and tungsten iodide cluster complexes [M₆I₈}(DMSO)₆](NO₃)₄ in aqueous and culture media. The cluster-containing materials were obtained by co-precipitation of the starting reagents in DMSO solution. According to the data obtained, the amount and ratio of functional carbonyl and carboxylic groups as well as the molecular weight of oxidized dextran strongly affect the extent of stabilization, i.e., high loading of aldehyde groups and high molecular weight increase the stability, while acidic groups have some negative impact on the stability. The most stable material based on the tungsten cluster complex exhibited low dark and moderate photoinduced cytotoxicity, which together with high cellular uptake makes these polymers promising for the fields of bioimaging and PDT. Full article

Researchers in the field of tissue engineering are always searching for new scaffolds for bone repair. Polyetheretherketone (PEEK) is a chemically inert polymer that is insoluble in conventional solvents. PEEK’s great potential in tissue engineering applications arises from its ability to not induce adverse reactions when in contact with biological tissues and its mechanical properties, which are similar to those of human bone. These exceptional features are limited by the bio-inertness of PEEK, which causes poor osteogenesis on the implant surface. Here, we demonstrated that the covalent grafting of the sequence (48–69) mapped on the BMP-2 growth factor (GBMP1α) significantly enhances the mineralization and gene expression of human osteoblasts. Different chemical methods were employed for covalently grafting the peptide onto 3D-printed PEEK disks: (a) the reaction between PEEK carbonyls and amino-oxy groups inserted in the peptides’ N-terminal sites (oxime chemistry) and (b) the photoactivation of azido groups present in the peptides’ N-terminal sites, which produces nitrene radicals able to react with PEEK surface. The peptide-induced PEEK surface modification was assessed using X-ray photoelectron measurements, while the superficial properties of the functionalized material were analyzed by means of atomic force microscopy and force spectroscopy. Live and dead assays and SEM measurements showed greater cell cover on functionalized samples than the control, without any cytotoxicity induction. Moreover, functionalization improved the rate of cell proliferation and the amount of calcium deposits, as demonstrated by the AlamarBlue™ and alizarin red results, respectively. The effects of GBMP1α on h-osteoblast gene expression were assayed using quantitative real-time polymerase chain reaction. Full article