Polymers, Volume 15, Issue 21 (November-1 2023) – 143 articles

Heavy metal contamination in water resources is a major issue worldwide. Metals released into the environment endanger human health, owing to their persistence and absorption into the food chain. Cadmium is a highly toxic heavy metal, which causes severe health hazards in human beings as well as in animals. To overcome the issue, current research focused on cadmium ion removal from the polluted water by using porous magnetic chitosan composite produced from Kaphal (Myrica esculenta) leaves. The synthesized composite was characterized by BET, XRD, FT-IR, FE-SEM with EDX, and VSM to understand the structural, textural, surface functional, morphological-compositional, and magnetic properties, respectively, that contributed to the adsorption of Cd. The maximum Cd adsorption capacities observed for the Fe₃O₄ nanoparticles (MNPs) and porous magnetic chitosan (MCS) composite were 290 mg/g and 426 mg/g, respectively. Both the adsorption processes followed second-order kinetics. Batch adsorption studies were carried out to understand the optimum conditions for the fast adsorption process. Both the adsorbents could be regenerated for up to seven cycles without appreciable loss in adsorption capacity. The porous magnetic chitosan composite showed improved adsorption compared to MNPs. The mechanism for cadmium ion adsorption by MNPs and MCS has been postulated. Magnetic-modified chitosan-based composites that exhibit high adsorption efficiency, regeneration, and easy separation from a solution have broad development prospects in various industrial sewage and wastewater treatment fields. Full article

The chemically synthesized polymer polyacrylamide (HPAM) has achieved excellent oil displacement in conventional reservoirs, but its oil displacement is poor in extreme reservoir environments. To develop a biopolymer oil flooding agent suitable for extreme reservoir conditions, the viscosity changes and rheological properties of three biopolymers, diutan gum, xanthan gum, and scleroglucan, were studied under extreme reservoir conditions (high salt, high temperature, strong acid, and alkali), and the effects of temperature, mineralization, pH, and other factors on their viscosities and long-term stability were analyzed and compared. The results show that the three biopolymers had the best viscosity-increasing ability at temperatures of 90 °C and below. The viscosity of the three biopolymers was 80.94 mPa·s, 11.57 mPa·s, and 59.83 mPa·s, respectively, when the concentration was 1500 mg/L and the salinity 220 g/L. At the shear rate of 250 s⁻¹, 100 °C~140 °C, scleroglucan had the best viscosification. At 140 °C, the solution viscosity was 19.74 mPa·s, and the retention rate could reach 118.27%. The results of the long-term stability study showed that the solution viscosity of scleroglucan with a mineralization level of 220 mg/L was 89.54% viscosity retention in 40 days, and the diutan gum could be stabilized for 10 days, with the viscosity maintained at 90 mPa·s. All three biopolymers were highly acid- and alkali-resistant, with viscosity variations of less than 15% in the pH3~10 range. Rheological tests showed that the unique double-helix structure of diutan gum and the rigid triple-helix structure of scleroglucan caused them to have better viscoelastic properties than xanthan gum. Therefore, these two biopolymers, diutan gum, and scleroglucan, have the potential for extreme reservoir oil displacement applications. It is recommended to use diutan gum for oil displacement in reservoirs up to 90 °C and scleroglucan for oil displacement in reservoirs between 100 °C and 140 °C. Full article

It is known that complexes based on natural polysaccharides are able to eliminate bone defects. Prolonged hyperglycemia leads to low bone regeneration and a chronic inflammatory response. The purpose of this study was to increase the efficiency of early bone formation in a cavity of critical size in diabetes mellitus in the experiment. The polyelectrolyte complex contains high-molecular ascorbate of chitosan, chondroitin sulfate, sodium hyaluronate, heparin, adgelon serum growth factor, sodium alginate and amorphous nanohydroxyapatite (CH–SA–HA). Studies were conducted on five groups of white female Wistar rats: group 1—regeneration of a bone defect in healthy animals under a blood clot; group 2—regeneration of a bone defect under a blood clot in animals with diabetes mellitus; group 3—bone regeneration in animals with diabetes mellitus after filling the bone cavity with a collagen sponge; group 4—filling of a bone defect with a CH–SA–HA construct in healthy animals; group 5—filling of a bone defect with a CH–SA–HA construct in animals with diabetes mellitus. Implantation of the CH–SA–HA construct into bone cavities in type I diabetic rats can accelerate the rate of bone tissue repair. The inclusion of modifying polysaccharides and apatite agents in the construction may be a prospect for further improvement of the properties of implants. Full article

This study aimed at formulating the antiglaucoma agent, Bimatoprost (BMT), into niosomal in situ gel (BMT-ISG) for ocular delivery. Niosomes containing cholesterol/span 60 entrapping BMT were fabricated using a thin-film hydration method. The fabricated niosomes were optimized and characterized for entrapment efficiency (%EE) and size. The optimized BMT-loaded niosomal formulation prepared at a cholesterol/span 60 ratio of 1:2 exhibited the highest entrapment (81.2 ± 1.2%) and a small particle size (167.3 ± 9.1 nm), and they were selected for incorporation into in situ gelling systems (BMT-ISGs) based on Pluronic F127/Pluronic F68. Finally, the in vivo efficiency of the BMT-ISG formulation, in terms of lowering the intraocular pressure (IOP) in normotensive male albino rabbits following ocular administration, was assessed and compared to that of BMT ophthalmic solution. All the formulated BMT-ISGs showed sol–gel transition temperatures ranging from 28.1 °C to 40.5 ± 1.6 °C. In addition, the BMT-ISG formulation sustained in vitro BMT release for up to 24 h. Interestingly, in vivo experiments depicted that topical ocular administration of optimized BMT-ISG formulation elicited a significant decline in IOP, with maximum mean decreases in IOP of 9.7 ± 0.6 mm Hg, compared to BMT aqueous solution (5.8 ± 0.6 mm Hg). Most importantly, no signs of irritation to the rabbit’s eye were observed following topical ocular administration of the optimized BMT-ISG formulation. Collectively, our results suggested that niosomal in situ gels might be a feasible delivery vehicle for topical ocular administration of anti-glaucoma agents, particularly those with poor ocular bioavailability. Full article

Polypropylene melt-blown nonwoven fabric (PP MNF) masks can effectively block pathogens in the environment from entering the human body. However, the adhesion of surviving pathogens to masks poses a risk of human infection. Thus, embedding safe and efficient antibacterial materials is the key to solving pathogen infection. In this study, stable chlorinated poly(methacrylamide-N,N′-methylenebisacrylamide) polypropylene melt-blown nonwoven fabrics (PP-P(MAA-MBAA)-Cl MNFs) have been fabricated by a simple UV cross-link and chlorination process, and the active chlorine content can reach 3500 ppm. The PP-P(MAA-MBAA)-Cl MNFs show excellent hydrophilic and antibacterial properties. The PP-P(MAA-MBAA)-Cl MNFs could kill all bacteria (both Escherichia coli and Staphylococcus aureus) with only 5 min of contact. Therefore, incorporating PP-P(MAA-MBAA)-Cl MNF as a hydrophilic antimicrobial layer into a four-layer PP-based mask holds great potential for enhancing protection and comfort. Full article

Although fumed silica/siloxane suspensions are commonly employed in additive manufacturing technology, the interplay between shelf life, storage conditions, and printability has yet to be explored. In this work, direct ink writing (DIW) was used to print unique three-dimensional structures that required suspensions to retain shape and form while being printed onto a substrate. Suspensions containing varying concentrations of hydrophobic and hydrophilic silica were formulated and evaluated over a time span of thirty days. Storage conditions included low (8%) and high (50%) relative humidity and temperatures ranging from 4 °C to 25 °C. The shelf life of the suspensions was examined by comparing the print quality of pristine and aged samples via rheology, optical microscopy, and mechanical testing. Results showed a significant decrease in printability over time for suspensions containing hydrophilic fumed silica, whereas the printability of suspensions containing hydrophobic fumed silica remained largely unchanged after storage. The findings in this work established the following recommendations for extending the shelf life and printability of suspensions commonly used in DIW technology: (1) higher fumed silica concentrations, (2) low humidity and low temperature storage environments, and (3) the use of hydrophobic fumed silica instead of hydrophilic fumed silica. Full article

Continuous fiber-reinforced composite truss structures have broad application prospects in aerospace engineering owing to their high structural bearing efficiency and multifunctional applications. This paper presents the design and fabrication of multilayer truss structures with controlled mechanical properties based on continuous fiber-reinforced thermoplastic composite 3D printing. Continuous fiber composite pyramid trusses fabricated by 3D printing have high specific stiffness and strength, with maximum equivalent compression modulus and strength of 401.91 MPa and 30.26 MPa, respectively. Moreover, the relative density of a truss structure can be as low as 1.45%. Additionally, structural units can be extended in any direction to form a multilayer truss structure. Structural performance can be controlled by designing the parameters of each layer. This study offers a novel approach for designing a multifunctional multilayer truss structure, a structure with low-density needs and unique load-bearing effects. Full article

Cardiovascular tissue engineering is providing many solutions to cardiovascular diseases. The complex disease demands necessitating tissue-engineered constructs with enhanced functionality. In this study, we are presenting the production of a dexamethasone (DEX)-loaded electrospun tubular polymeric poly(l-lactide) (PLA) or poly(d,l-lactide-co-glycolide) (PLGA) construct which contains iPSC-CMs (induced pluripotent stem cell cardiomyocytes), HUVSMCs (human umbilical vein smooth muscle cells), and HUVECs (human umbilical vein endothelial cells) embedded in fibrin gel. The electrospun tube diameter was calculated, as well as the DEX release for 50 days for 2 different DEX concentrations. Furthermore, we investigated the influence of the polymer composition and concentration on the function of the fibrin gels by imaging and quantification of CD31, alpha-smooth muscle actin (αSMA), collagen I (col I), sarcomeric alpha actinin (SAA), and Connexin 43 (Cx43). We evaluated the cytotoxicity and cell proliferation of HUVECs and HUVSMCs cultivated in PLA and PLGA polymeric sheets. The immunohistochemistry results showed efficient iPSC-CM marker expression, while the HUVEC toxicity was higher than the respective HUVSMC value. In total, our study emphasizes the combination of fibrin gel and electrospinning in a functionalized construct, which includes three cell types and provides useful insights of the DEX release and cytotoxicity in a tissue engineering perspective. Full article

When drilling into a reservoir, the drilling fluid containing bentonite is prone to solid phase invasion, causing serious damage to the reservoir, and the conventional API barite suspension stability is poor, which makes it easy to cause sedimentation and blockage. Therefore, in order to avoid accidents, we use ultrafine barite to obtain a good suspension stability. More importantly, the method of modifying zwitterionic polymers on the surface of nano-silica is used to develop a temperature-resistant and salt-resistant fluid loss reducer FATG with a core-shell structure, and it is applied to ultra-fine clay-free water-based drilling fluid (WBDF). The results show that the filtration loss of clay-free drilling fluid containing FATG can be reduced to 8.2 mL, and AV can be reduced to 22 mPa·s. Although the viscosity is reduced, FATG can reduce the filter loss by forming a dense mud cake. The clay-free drilling fluid system obtained by further adding sepiolite can reduce the filtration loss to 3.8 mL. After aging at 220 °C for 15 d, it still has significant salt tolerance, the filtration loss is only 9 mL, the viscosity does not change much, a thinner and denser mud cake is formed, and the viscosity coefficient of the mud cake is smaller. The linear expansion test and permeability recovery evaluation were carried out. The hydration expansion inhibition rate of bentonite can reach 72.5%, and the permeability recovery rate can reach 77.9%, which can meet the long-term drilling fluid circulation work in the actual drilling process. This study can provide guidance for technical research in related fields such as reservoir protection. Full article

Low-dielectric constant polymers are widely used in various microelectronic materials. With the development of 5G communication technology, there is an urgent need for polymer materials with low dielectric constant at high frequency, good thermal resistance, and mechanical properties. In this study, four novel poly (aryl ether ketone) (PAEK) containing different numbers of methylene groups were synthesized via nucleophilic polycondensation reaction. At 10 GHz, these polymer films exhibit excellent dielectric properties with dielectric constants as low as 2.76. The relationship between the dielectric constant and the number of methylene groups is illustrated by constructing the amorphous accumulation cell model. In addition, methylene groups provided the polymer with favorable mechanical performance, including Young’s modulus in the range of 2.17–2.21 GPa, the tensile strength from 82.0 to 88.5 MPa and the elongation at the break achieved 7.94%, respectively. Simultaneously, the polymer maintains good thermal resistance with a glass transition temperature (T_g) reaching 216 °C. The result indicates that the obtained novel PAEK is potentially valuable in the field of high-frequency communications. Full article

Halocynthia roretzi, a member of Ascidiacea, is covered with its own tunic, which is composed of polysaccharides, such as cellulose Iβ and sulfated chitin. H. roretzi has an open-vessel system, whose blood vessels and hemocytes are found in the tunic, so that the mechanical environment of the tunic could be carefully controlled because of its influence on hemocyte behaviors. While active deformation of the tunic and related phenomena have been previously reported, the mechanical environment in the tunic, which directly influences its deformation, has been rarely investigated. Meanwhile, the developments of actuators based on cellulose and chitin have been frequently reported. However, a cellulose–sulfated chitin actuator has not been proposed. In this study, the mechanical environment of the tunic, which has been rarely investigated despite its importance in the active deformation of the tunic, was evaluated using finite element analysis. A finite element model of the tunic, based on its histological characteristics as well as deformation patterns, was developed. The results showed that the shape of the tunic, the pattern of fiber distribution, and control of the water content influenced the mechanical environment. Full article

The elaboration of a low-cost and effective approach to synthesize hybrid composite materials based on the conventional thermoplastics and natural biopolymers is a sustainable alternative to the production of “traditional” plastics. Cellulose is one of the most abundant biopolymers. Its fibrils possess outstanding mechanical characteristics and, hence, attract considerable interest of researchers during recent decades. However, modification of the hydrophobic polymer matrix by cellulose fibrils is significantly complicated by the hydrophilic nature of the latter. In this study, we propose an effective and low-cost approach to the synthesis of polystyrene at the cellulose microfibrils composite material via the emulsion polymerization method. The obtained fibrous composite was comprehensively analyzed with FTIR spectroscopy, SEM, TGA, and DSC, and was further employed to produce sponge hybrid materials. We investigated the influence of the cellulose/polystyrene ratio on the density, porosity, pore volume, and water uptake of the obtained sponge materials. The sample containing 70 wt.% of cellulose demonstrated the best water absorption properties while preserving its shape, even after 24 h of floating on water. The produced sponge materials might be employed as sorption materials for the purification and desalination of waters of various origins, filtration, and collection of undesirable elements under specific industrial or natural conditions. Full article

In recent years, there has been a growing interest in the use of gelatin nanoparticles (GNPs) for the treatment of infectious diseases. The inherent properties of these nanoparticles make them attractive options for drug delivery. Their biocompatibility ensures that they can interact with biological systems without causing adverse reactions, while their biodegradability ensures that they can break down harmlessly in the body once their function is performed. Furthermore, their capacity for controlled drug release ensures that therapeutic agents can be delivered over a sustained period, thereby enhancing treatment efficacy. This review examines the current landscape of GNP-based drug delivery, with a specific focus on its potential applications and challenges in the context of infectious diseases. Key challenges include controlling drug release rates, ensuring nanoparticle stability under physiological conditions, scaling up production while maintaining quality, mitigating potential immunogenic reactions, optimizing drug loading efficiency, and tracking the biodistribution and clearance of GNPs in the body. Despite these hurdles, GNPs hold promising potential in the realm of infectious disease treatment. Ongoing research and innovation are essential to overcome these obstacles and completely harness the potential of GNPs in clinical applications. Full article

This research work studies the self-healing ability, mechanical properties, and shape memory of the polymer Surlyn^® 8940 with and without multiwall carbon nanotubes (MWCNTs) as a nanoreinforcement. This polymer comes from a partially neutralized poly(ethylene-co-methacrylic acid) (EMAA) ionomer copolymer. MWCNTs and the polymer went through a mixing process aimed at achieving an excellent dispersion. Later, an optimized extrusion method was used to produce a uniform reinforced filament, which was the input for the 3D-printing process that was used to create the final test samples. Various concentrations of MWCNTs (0.0, 0.1, 0.5, and 1.0 wt.%) were used to evaluate and compare the mechanical properties, self-healing ability, and shape memory of unreinforced and nanoreinforced materials. Results show an enhancement of the mechanical properties and self-healing ability through the addition of MWCNTs to the matrix of polymer, and the specimens showed shape memory events. Full article

Methotrexate or amethopterin or 4-amino-N10-methyl pteroylglutamic acid is used for treating autoimmune diseases, as well as certain malignancies. Drug delivery systems, which are based on biopolymers, can be developed to improve the therapeutic and pharmacological properties of topically administered drugs. Biopolymers improve the therapeutic effect of drugs, mainly by improving their biodistribution and modulating drug release. This study presents the synthesis of membranes based on anionic polysaccharides and cationic polysaccharides for transdermal delivery of the active ingredient methotrexate, as well as a compatibility study between methotrexate and each of the components used in the prepared membranes. The obtained membranes based on different marine polysaccharides, namely κ-carrageenan and chitosan, for the release of the active ingredient methotrexate were characterized using techniques such as TG, FTIR, UV–Vis spectrophotometry, FTIR microscopy, water absorption capacity, water vapor permeability, and biodegradation rate. Following the studies, the membranes suitable for the transdermal release of the active substance were validated. Full article

The influences of ethylene-based elastomer (EE) and the compatibilizer agent ethylene-butyl acrylate-glycidyl methacrylate (EBAGMA) on the thermal degradation of PLA/EE blends were evaluated by the thermal degradation kinetics and thermodynamic parameters using thermogravimetry. The presence of EE and EBAGMA synergistically improved the PLA thermal stability. The temperature of 10% of mass loss (T_10%) of PLA was around 365 °C, while in the compatibilized PLA/EE blend, this property increased to 370 °C. The PLA average activation energy ($\overline{{\mathrm{E}}_{\mathrm{a}}}$) reduced in the PLA/EE blend (from 96 kJ/mol to 78 kJ/mol), while the presence of EBAGMA in the PLA/EE blend increased the $\overline{{\mathrm{E}}_{\mathrm{a}}}$ due to a better blend compatibilization. The solid-state thermal degradation of the PLA and PLA/EE blends was classified as a D-type degradation mechanism. In general, the addition of EE increased the thermodynamic parameters when compared to PLA and the compatibilized blend due to the increase in the collision rate between the components over the thermal decomposition. Full article

Beer bagasse is a residue waste produced in great amounts; nevertheless, it is still underestimated in the industry. The aim of this paper is to develop an innovative and efficient methodology to recycle the beer bagasse by producing Poly-lactic acid(PLA)-based bio-composites, in the forms of pellets and filaments, to be used in additive manufacturing processes. To assess the suitability of beer bagasse for extrusion-based 3D printing techniques, it was, firstly, physically and chemically characterized. Then, it was added in combination with different kinds of plasticizers to PLA to make bio-composites, analyzing their thermal and physical properties. The results prove the great potential of bagasse, evidencing its printability. Both composites’ pellets and filaments were used in two different 3D printing machines and the mechanical properties of the 3D-printed models were evaluated as a function of the composition and the kind of technology used. All the used plasticizers improved processability and the polymer–bagasse interface. Compared to neat PLA, no changes in thermal properties were detected, but a lowering of the mechanical properties of the 3D-printed composites compared to the neat polymers was observed. Finally, a comparison between the efficiency of the two 3D printing techniques to be used with the bio-based composites was performed. Full article

Bio-solids (biological sludge) from wastewater treatment plants are a significant source of the emission of microplastics (MPs) into the environment. Weakening the structure of MPs before they enter the environment may accelerate their degradation and reduce the environmental exposure time. Therefore, we studied the effect of UV-A and UV-C, applied at 70 °C, on three types of MPs, polypropylene (PP), polyethylene (PE), and polyethylene terephthalate (PET), that are commonly found in sewage sludge, using three shapes (fibers, lines, granules). The MPs were exposed to UV radiation in bio-solid suspensions, and to air and water as control. The structural changes in and degradation of the MPs were investigated using Attenuated Total Reflectance–Fourier Transform Infrared Spectrometry (ATR-FTIR) and surface morphology was performed with SEM analysis. UV exposure led to the emergence of carbonyl and hydroxyl groups in all of the PP samples. In PE and PET, these groups were formed only in the bio-solid suspensions. The presence of carbonyl and hydroxyl groups increased with an increasing exposure time. Overall, UV radiation had the greatest impact on the MPs in the bio-solids suspension. Due to the surface-to-volume ratio of the tested samples, which influences the degradation rate, the fibers were more degraded than the other two plastic shapes. UV-A was slightly more effective at degrading the MPs than UV-C. These findings show that ultraviolet radiation in combination with an elevated temperature affects the structure of polymers in wastewater bio-solids, which can accelerate their degradation. Full article

Coating is a technique to surround a target substance with a thin layer to obtain desirable properties. Polyvinyl alcohols (PVAs) are biodegradable plastics and have shown good applicability as a coating or film material. Cellulose nanocrystals are a promising green nanomaterial that has been shown to enhance the properties of PVA after blending. However, these PVA/CNC films have concerns in a moist environment due to high hydrophilicity. To overcome this issue, the current study incorporated beeswax into PVA/CNC films and investigated the effect of CNC and beeswax on the properties of the coatings and films. Results showed that the addition of corn stover-derived CNCs to PVA films increased tensile strength (from 11 to 25 MPa) and Young’s modulus (from 32 to 173 MPa) and reduced water vapor transmission rate (from 25 to 20 g h⁻¹ m⁻²). Beeswax added to PVA/CNC films further improved water vapor barrier properties (from 20 to 9 g h⁻¹ m⁻²) and maintained Young’s modulus (from 173 to 160 MPa), though it caused a reduction in the tensile strength (from 25 to 11 MPa) of the films. This information can help to select materials for blending with PVAs by obtaining the desirable endmost properties depending on applications. Full article

Some photosensitive resins have poor mechanical properties after 3D printing. To overcome these limitations, a polyurethane acrylate oligomer (PUA) microsphere was prepared using the Pickering emulsion template method and ultraviolet (UV) curing technology in this paper. The prepared PUA microspheres were added to PUA-1,6-hexanediol diacrylate (HDDA) photosensitive resin system for digital light processing (DLP) 3D printing technology. The preparation process of PUA microspheres was discussed based on micromorphology, and it was found that the oil-water ratio of the Pickering emulsion and the emulsification speed had a certain effect on the microsphere size. As the oil-water ratio and the emulsification speed increased, the microsphere particle size decreased to a certain extent. Adding a suitable proportion of PUA microspheres to the photosensitive resin can improve the mechanical properties and thermal stability. When the modified photosensitive resin microsphere content was 0.5%, the tensile strength, elongation at break, bending strength, and initial thermal decomposition temperature were increased by 79.14%, 47.26%, 26.69%, and 10.65%, respectively, compared with the unmodified photosensitive resin. This study provides a new way to improve the mechanical properties of photosensitive resin 3D printing. The resin materials studied in this work have potential application value in the fields of ceramic 3D printing and dental temporary replacement materials. Full article

In addition to measuring the strain, stress, and Young’s modulus of materials through tension and compression, in-plane shear modulus measurement is also an important part of parameter testing of composites. Tensile testing of ±45° composite laminates is an economical and effective method for measuring in-plane shear strength. In this paper, the in-plane shear modulus of T800 carbon fiber/epoxy composites were measured through tensile tests of ±45° composite laminates, and acoustic emission (AE) was used to characterize the damage of laminates under in-plane shear loading. Factor analysis (FA) on acoustic emission parameters was performed and the reconstructed factor scores were clustered to obtain three damage patterns. Finally, the development and evolution of the three damage patterns were characterized based on the cumulative hits of acoustic emission. The maximum bearing capacity of the laminated plate is about 17.54 kN, and the average in-plane shear modulus is 5.42 GPa. The damage modes of laminates under in-plane shear behavior were divided into three types: matrix cracking, delamination and fiber/matrix interface debonding, and fiber fracture. The characteristic parameter analysis of AE showed that the damage energy under in-plane shear is relatively low, mostly below 2000 mV × ms, and the frequency is dispersed between 150–350 kHz. Full article

Volatile organic compounds (VOCs), often invisible but potentially harmful, are prevalent in industrial and laboratory settings, posing health risks. Detecting VOCs in real-time with high sensitivity and low detection limits is crucial for human health and safety. The optical sensor, utilizing the gasochromic properties of sensing materials, offers a promising way of achieving rapid responses in ambient environments. In this study, we investigated the heterostructure of SnO₂/WO₃ nanoparticles and employed it as the primary detection component. Using the electrospinning technique, we fabricated a sensing fiber containing Ag NPs, poly(methyl methacrylate) (PMMA), and SnO₂/WO₃ (PMMA-Ag-SnO₂/WO₃) for acetone vapor detection. Following activation via UV/ozone treatment, we observed charge migration between WO₃ and SnO₂, resulting in a substantial generation of superoxide radicals on SnO₂ nanoparticles. This phenomenon facilitates structural deformation of the fiber and alters the oxidation state of tungsten ions, ultimately leading to a significant change in extinction when exposed to acetone vapor. As a result, PMMA-Ag-SnO₂/WO₃ fiber achieves a detection limit of 100 ppm and a response time of 1.0 min for acetone detection. These findings represent an advancement in the development of sensitive and selective VOC sensing devices. Full article

Natural cyclodextrins (CDs) can be formed by 6, 7, or 8 glucose molecules (α-, β-, and γ-, respectively) linked in a ring, creating a cone shape. Its interior has an affinity for hydrophobic molecules, while the exterior is hydrophilic and can interact with water molecules. This feature has been used to develop active packaging applied to food, interacting with the product or its environment to improve one or more aspects of its quality or safety. It also provides monitoring information when food is optimal for consumption, as intelligent packaging is essential for the consumer and the merchant. Therefore, this review will focus on discerning which packaging is most appropriate for each situation, solubility and toxicological considerations, characterization techniques, effect on the guest properties, and other aspects related to forming the inclusion complex with bioactive molecules applied to packaging. Full article

In this review, we summarize and discuss our experimental data published in a number of papers on the transfer reactions of polymer chains in the polymerization of ethylene, propylene, and hexene-1, and the copolymerization of ethylene with α-olefins over multisite supported titanium–magnesium catalysts (TMC). Three groups of transfer reactions are discussed in the review: (1) transfer reactions with AlEt₃ cocatalyst, (2) transfer reactions with hydrogen, and (3) transfer reactions with participation of α-olefins in the case of ethylene copolymerization with α-olefins. We have found polymerization conditions where it is possible to observe heterogeneity of active sites of TMC for all three groups of the indicated reactions. It is shown that (1) the transfer reaction with AlEt₃ proceeds with higher reactivity on the active sites that produce polymers with low molecular weight; (2) the transfer reaction with hydrogen, in the case of α-olefin polymerization and copolymerization of ethylene with α-olefins, proceeds with higher reactivity on the active sites which produce polymers with high molecular weight; (3) the transfer reaction with α-olefins proceed with higher reactivity on the active sites that produce high molecular weight polymers. Full article

Gradient porous materials, particularly carbon-based materials, hold immense potential in the fields of batteries, energy storage, electrocatalysis, and sensing, among others, by synergistically combining the attributes associated with each pore size within a unified structural framework. In this study, we developed a gradient porous aramid (GP-Aramid) by incorporating cellulose acetate as a porosity promoter in the polymer casting solution in different proportions. These GP-Aramids were subsequently transformed into their pyrolyzed counterparts (GP-Pyramids), retaining their original structures while displaying diverse cellular or dense microstructures inherited from the parent aramid, as confirmed via scanning electron microscopy. X-ray diffraction spectra provided evidence of the conversion of aramids into carbonaceous materials. The materials showed structural defects observed through the intensity ratio of the G and D bands (ID/IG = 1.05) in the Raman spectra, while X-ray photoelectron spectra (XPS) revealed that the carbonization process yielded pyrolyzed carbon materials unusually rich in nitrogen (6%), oxygen (20%), and carbon (72%), which is especially relevant for catalysis applications. The pyrolyzed materials showed bulk resistivities from 5.3 ± 0.3 to 34.2 ± 0.6 depending on the meta- or para-orientation of the aramid and the porous structure. This work contributes to understanding these gradient porous aromatic polyamides’ broader significance and potential applications in various fields. Full article

This paper describes a new methodology for carrying out quantitative extraction of cloxacillin from drinking and river water samples using a molecularly imprinted polymer (MIP) as a selective sorbent for solid-phase extraction (MISPE). Several polymers were synthesized via thermal polymerization using cloxacillin as a template, methacrylic acid (MAA) as a functional monomer, ethyleneglycoldimethacrylate (EGDMA) as a cross-linker and different solvents as porogens. Binding characteristics of the adequate molecularly imprinted and non-imprinted (NIP) polymers were evaluated via batch adsorption assays following the Langmuir and Freundlich isotherms and Scatchard assays. The parameters related to the extraction approach were studied to select the most appropriate polymer for cloxacillin determination. Using the optimized MIP as the SPE sorbent, a simple sample treatment methodology was combined with high-performance liquid chromatography (HPLC) to analyze cloxacillin residues in drinking and river water. Under the optimum experimental conditions, the MISPE methodology was validated using spiked samples. The linearity for cloxacillin was assessed within the limits of 0.05–1.5 µg L⁻¹ and the recovery percentage was higher than 98% (RSD < 4%). The limits of detection and limits of quantification were 0.29 and 0.37 µg L⁻¹ and 0.8 and 0.98 µg L⁻¹ for drinking and river water, respectively. The selectivity of MIP against other ß-lactam antibiotics with similar structures (oxacillin, cefazoline, amoxicillin and penicillin V) was studied, obtaining a good recovery higher than 85% for all except cefazoline. The proposed MISPE-HPLC methodology was successfully applied for the detection of cloxacillin in drinking water from Canal de Isabel II (Madrid) and river water from the Manzanares River (Madrid). Full article

The destruction of polymers under the influence of ultraviolet (UV) radiation is the cause of their aging and deterioration of strength properties. Asphaltenes are low-value waste products after the refining and deasphalting of heavy crude oil, which absorb UV radiation well. Asphaltenes require rational utilization, which suggests their use as UV stabilizing agents for polymers. In this work, asphaltenes were used to prevent UV aging of polypropylene (PP) by adding them in a mass fraction from 5% to 30% within an asphaltene/PP composite material. Rheometry, calorimetry, X-ray diffraction analysis, and tensile strength of PP films containing asphaltenes were performed before and after their intense UV irradiation for accelerated aging. Asphaltenes slightly reduce the viscosity, crystallinity, and mechanical strength of the initial PP due to their plasticizing effect. However, this deterioration in properties is more than compensated when studying UV-aged samples. Intense UV aging causes multiple catastrophic drops in the viscosity and strength of pure PP with the preservation of crystallinity due to the break of polymer chains and a decrease in molecular weight by approximately eight times. Asphaltenes suppress the destruction of PP, which is expressed in a significantly smaller decline in its viscosity and strength due to UV aging. The most optimal content of asphaltenes is 20%, which suppresses UV destruction by six times and best preserves the strength properties of PP. Full article

Polymeric materials show great promise for use in a variety of dental applications. Manufacturers generally provide flexural strength information based on standardized (ISO and ASTM) specimen dimensions and loading conditions. It is not clear, however, if flexural strength data are predictive of the clinical performance of dental crowns. The objectives of this study were, therefore, to determine whether flexural strengths, as measured via three-point bending (3PB), would be predictive of failure loads assessed via crunch-the-crown (CTC) tests. Three brands of polymers (Trilor, Juvora, and Pekkton) were fabricated into rectangular bars and fully contoured crowns (10 specimens of each polymer brand, 30 specimens of each shape). Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and burn off tests were used to characterize/confirm the materials. Bars were tested blindly in 3PB to determine flexural strength, and crowns were CTC-tested to determine failure load after luting to resin abutments. The statistical significance of the test results was evaluated via one-way ANOVA (α = 0.05) and Pearson’s correlation coefficient, while regression analysis was used to test for a correlation between 3PB and CTC results. The fracture mechanisms and failure surface characteristics were characterized using scanning electron microscopy (SEM). There were significant differences (p < 0.05) in the mean crown failure loads (Trilor (7033 N) > Juvora (5217 N) > Pekkton (3023 N)) and mean flexural strengths of the bars (Trilor (468 MPa) > Juvora (197 MPa) = Pekkton (192 MPa)). The mode of crown fracture was different between the materials and included deformation (Juvora), ductile-to-brittle fracture (Pekkton), and a combination of cracks and deformation (Trilor). Flexural strengths did not correlate with the corresponding crown failure loads for any of the materials tested. These results suggest that dental practitioners should not rely on the flexural strengths reported from three-point bending tests, as advertised by the manufacturer, to predict the performance of polymeric crowns. Full article

There is a constant need to predict the dynamic properties of composite materials already at the design stage. A particularly attractive tool for achieving this goal is mesoscale finite element modeling. This paper presents the mesoscale modeling of the dynamic properties of polymer concrete. The method is based on finite element modeling and substructural identification. Substructural identification is a model updating technique based on frequency response functions. It enables the identification of model dynamic properties considering damping. The presented method is used to model the dynamic properties of a polymer concrete beam. In the first step, the mesoscale finite element model is built and then it is decoupled into substructures: a polymer matrix, aggregates, and an interfacial transition zone (ITZ). Next, the dynamic properties of the polymer matrix substructure are updated, and the model is reassembled. Then, second-stage updating takes place, which consists of determining the parameters of the aggregates and the ITZ. The use of substructural identification made it possible to determine the parameters of substructures that do not exist in an independent, isolated form like the ITZ. Moreover, it allows for determining the amount of damping that ITZ brings to the structure. Full article

In the present paper, a scalable, economically feasible, and continuous process for making cellulose-based carbon fibers (CFs) is described encompassing precursor spinning, precursor additivation, thermal stabilization, and carbonization. By the use of boric acid (BA) as an additive, the main drawback of cellulose-based CFs, i.e., the low carbon yield, is overcome while maintaining a high level of mechanical properties. This is demonstrated by a systematic comparison between CFs obtained from a BA-doped and an un-doped cellulose precursor within a temperature range for carbonization between 1000 and 2000 °C. The changes in chemical composition (via elemental analysis) and physical structure (via X-ray scattering) as well as the mechanical and electrical properties of the resulting CFs were investigated. It turned out that, in contrast to current opinion, the catalytic effect of boron in the formation of graphite-like structures sets in already at 1000 °C. It becomes more and more effective with increasing temperature. The catalytic effect of boron significantly affects crystallite sizes (L_a, L_c), lattice plane spacings (d₀₀₂), and orientation of the crystallites. Using BA, the carbon yield increased by 71%, Young’s modulus by 27%, and conductivity by 168%, reaching 135,000 S/m. At the same time, a moderate decrease in tensile strength by 25% and an increase in density of 14% are observed. Full article