Search Results (82)

Despite its broad application due to its affordability, biodegradability, and natural antimicrobial and antioxidant activities, chitosan (CS) still exhibits limitations in mechanical strength and barrier effectiveness. Owing to its unique chemical characteristics, itaconic acid (IT) presents potential as a compatibilizing agent in polymeric blend formulations. Biodegradable polymers composed of chitosan (CS), itaconic acid (IT), and starch (S) were synthesized using two polymerization methods. The first method involved grafting IT onto CS at varying ratios of IT (4%, 6%, and 8% wt.), using 1% v/v acetic acid/water as the solvent and potassium persulfate as the initiator. In the second approach, starch (S) was blended with the copolymer P(CS-g-IT) at concentrations of 1%, 3%, and 5%, utilizing water as the solvent and glacial acetic acid as a catalyst. The resulting biodegradable films underwent characterization through FTIR, TGA, SEM, and mechanical property analysis. To further explore the effects of combining IT, starch, and carbon black, the blends, referred to as P[(CS-g-IT)-b-S], were also loaded with carbon black. This allowed for the evaluation of the materials’ physicomechanical properties, such as viscosity, tensile strength, elongation, and contact angle. The findings demonstrated that the presence of IT, starch, and carbon black collectively improved the films’ mechanical performance, physical traits, and biodegradability. Among the samples, the blended copolymer with 1% starch exhibited the highest mechanical properties, followed by the grafted copolymer with 8% IT and the blended copolymer mixed with carbon black at 7%. In contrast, the blended copolymer with 5% starch showed the highest hydrophilicity and the shortest degradation time compared to the grafted copolymer with 8% IT and the blended copolymer mixed with 7% carbon black. Full article

Novel amphiphilic block copolymers of N-vinyl pyrrolidone (NVP) and either n-hexyl methacrylate (HMA, PNVP-b-PHMA) or stearyl methacrylate (SMA, PNVP-b-PSMA) were prepared by RAFT polymerization techniques and the sequential addition of monomers starting from the polymerization of NVP and using two different Chain Transfer Agents, CTAs. PNVP-b-PHMA are amorphous block copolymers containing constituent blocks with both high and low Tg values, whereas PNVP-b-PSMA are amorphous–semi-crystalline copolymers. Samples with different molecular weights and compositions were obtained. The copolymers were microphase-separated, but partial mixing was also observed. The presence of the amorphous PNVP block reduced the crystallinity of the PSMA blocks in the PNVP-b-PSMA copolymers. The thermal stability of the blocks was influenced by both constituents. The self-assembly behavior in THF, which is a selective solvent for polymethacrylate blocks, and in aqueous solutions, where PNVP was soluble, was examined. Unimolecular or low-aggregation-number micelles were obtained in THF for both types of samples. On the contrary, high-aggregation-number, spherical, and compact micelles were revealed in aqueous solutions. The increase in the steric hindrance of the side ester group of the polymethacrylate chain led to slightly lower degrees of association. The hydrophobic compound curcumin was efficiently encapsulated within the micellar core of the supramolecular structures in aqueous solutions. Micelles with higher aggregation numbers were more efficient in the encapsulation of curcumin. The results of this study were compared with those obtained from other block copolymers based on PNVP. Full article

This paper reviews the research progress on ionogels in flexible pressure sensors. Ionogels comprise solid carrier networks and ionic liquids (ILs) dispersed therein and have good non-volatility, high conductivity, thermal stability, a wide electrochemical window, and mechanical properties. These characteristics give ionogels broad application prospects in wearable electronic devices, intelligent robots, and healthcare. The article first introduces the classification of ionogels, including the classification based on ILs and solid carrier networks. Then, the preparation methods and processing technologies of ionogels, such as the direct mixing method, in situ polymerization/gel method, and solvent exchange method, are discussed. Subsequently, the article expounds in detail on the properties and modification methods of ionogels, including toughness, conductivity, hydrophobicity, self-healing, and adhesiveness. Finally, the article focuses on the application of ionogels in flexible pressure sensors and points out the challenges faced in future research. The language of this mini-review is academic but not overly technical, making it accessible to even researchers new to the field and establishing an overall impression of research. We believe this mini-review serves as a solid introductory resource for a niche topic, with large and clear references for further research. Full article

A multifunctional paper-based composite of paper coated with a polypyrrole@lignocellulosic slurry (PPy@LS) and carboxymethyl cellulose (CMC) was developed. PPy@LS was prepared via the polymerization of pyrrole onto a lignocellulosic slurry derived from hemp stalks prepared using deep eutectic solvents. The PPy@LS slurry was mixed with the required amount of CMC and vacuum-filtered onto filter paper to fabricate the composite (PPy@LS/CMC). The resulting composite paper exhibited excellent multifunctional properties, including electrical conductivity, photothermal conversion, and antibacterial properties. These properties are stable against external environments, such as water and abrasion, due to the addition of CMC. The electrical conductivity of PPy@LS/CMC varied in the dry (1.6 × 10⁻⁴ S/cm) and wet (4.8 × 10⁻⁶ S/cm) states, suggesting its potential application in humidity sensing. Notably, the PPy@LS/CMC paper achieved significant photothermal activity under light irradiation, as demonstrated by the measured surface temperature exceeding 80 °C in 10 min. Moreover, the composite paper exhibited > 99.9% antibacterial activity against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). The combination of the inherent characteristics of filter paper along with the photothermal property of PPy enable the PPy@LS/CMC composite appropriate for solar interfacial evaporation application. These multifunctional composite papers with innovative combinations of properties have great potential for applications in smart packaging, humidity sensing, biomedicine, and solar-driven water purifications. Full article

Although chitosan (CS) is used in many industries because of its low cost, biodegradability, nontoxic, antibacterial, and antioxidant qualities, it lacks sufficient mechanical and barrier properties. Biodegradable polymers based on CS, polyvinyl alcohol (PVA), and starch (S) were prepared at various ratios (1/3/6 and 1/5/4) via a blending polymerization process in the presence of water as the solvent and glacial acetic acid as the catalyst. The obtained biodegradable polymers were characterized via FTIR, TGA, SEM, and mechanical tests. The biodegradable polymers were mixed with rice straw and carbon black to study the effects of rice straw and carbon black on the physicomechanical properties of the biodegradable polymer films, including viscosity, tensile strength, elongation, and contact angle. The incorporation of rice straw and carbon black into a polymer blend significantly enhanced the physical and mechanical properties while also boosting their biodegradability by 36% and 15%, respectively, due to their biological activity. Notably, the CS/PVA/S blend with a ratio of 1/5/4, combined with rice straw, emerged as the standout performer. It exhibited superior mechanical strength and the shortest degradation time, outperforming the CS/PVA/S blended with a ratio of 1/3/6 mixed with carbon black. According to these findings, the biodegradable polymers became more soluble as the temperature increased from 30 to 45 °C. Full article

Scaffolds for regenerative therapy can be made from natural or synthetic polymers, each offering distinct benefits. Natural biopolymers like chitosan (CS) are biocompatible and biodegradable, supporting cell interactions, but lack mechanical strength. Synthetic polymers like polyvinyl alcohol (PVA) provide superior mechanical strength and cost efficiency but are not biodegradable or supportive of cell adhesion. Combining these polymers optimizes their advantages while adding metal oxide nanoparticles like calcium oxide (CaO NPs) enhances antimicrobial properties by damaging bacterial membranes. In this study, we obtained the formation of CaO NPs by calcinating eggshells, which were mixed in a polymeric network of CS and PVA to obtain four different membrane formulations for subdermal tissue regeneration. The spherical nanoparticles measured 13.43 ± 0.46 nm in size. Their incorporation into the membranes broadened the hydroxyl bands in the Fourier transform infrared (FTIR) analysis at 3331 cm⁻¹. X-ray diffraction (XRD) analysis showed changes in the crystalline structure, with new diffraction peaks at 2θ values of 7.2° for formulations F2, F3, and F4, likely due to the increased amorphous nature and concentration of CaO NPs. Additionally, higher CaO NPs concentrations led to a reduction in thermal properties and crystallinity. Scanning electron microscopy (SEM) revealed a heterogeneous morphology with needle-like structures on the surface, resulting from the uniform dispersion of CaO NPs among the polymer chains and the solvent evaporation process. A histological examination of the implanted membranes after 60 days indicated their biocompatibility and biodegradability, facilitated by incorporating CaO NPs. During the degradation process, the material fragmented and was absorbed by inflammatory cells, which promoted the proliferation of collagen fibers and blood vessels. These findings highlight the potential of incorporating CaO NPs in soft tissue regeneration scaffolds. Full article

The starting point for the preparation of polymeric membranes by phase inversion is having a thermodynamically stable solution. Ternary diagrams for the polymer, solvent, and non-solvent can predict this stability by identifying the phase separation and describing the thermodynamic behavior of the membrane formation process. Given the lack of data for the ternary system water (H₂O)/hydrochloric acid (HCℓ)/polyamide 66 (PA66), this work employed the Flory–Huggins theory for the construction of the ternary diagrams (H₂O/HCℓ/PA66 and H₂O/formic acid (FA)/PA66) by comparing the experimental data with theoretical predictions. Pure polymer and the membranes produced by phase inversion were characterized to provide the information required to create the ternary diagrams. PA66/FA and PA66/HCℓ solutions were also evaluated regarding their classification as true solutions, and the universal quasi-chemical functional group activity coefficient (UNIFAC) method was used for determining non-solvent/solvent interaction parameters (g₁₂). Swelling measurements determined the polymer/non-solvent interaction parameter (χ₁₃) for H₂O/PA66 and the solvent/polymer interaction parameter (χ₂₃) for PA66/FA and PA66/HCℓ. The theoretical cloud point curve was calculated based on “Boom’s LCP Correlation” and compared to the curve of the experimental cloud point. The ternary Gibbs free energy of mixing and χ₂₃ indicated FA as the best solvent for the PA66. However, for HCℓ, the lower concentration (37–38%), volatility, and fraction volume of dissolved PA66 (ϕ₃) indicated that HCℓ is also adequate for PA66 solubilization based on the similar membrane morphology observed when compared to the PA66/FA membrane. Full article

CO₂ separation is an important environmental method mainly used in reducing CO₂ emissions to mitigate anthropogenic climate change. The use of mixed-matrix membranes (MMMs) arrives as a possible answer, combining the high selectivity of inorganic membranes with high permeability of organic membranes. However, the combination of these materials is challenging due to their opposing nature, leading to poor interactions between polymeric matrix and inorganic fillers. Many additives have been tested to reduce interfacial voids, some of which showed potential in dealing with compatibility problems, but most of them lack further studies and optimization. Deep eutectic solvents (DESs) have emerged as IL substitutes since they are cheaper and environmentally friendly. Choline chloride-based deep eutectic solvents were studied as additives in polyethersulfone (PES)/SAPO-34 membranes to improve CO₂ permeability and CO₂/N₂ and CO₂/CH₄ selectivity. SAPO-34 crystals of 150 nm with a high surface area and microporosity were synthesized using dry-gel methodology. The PES/SAPO-34 membranes were optimized following previous work and used in a defined composition, using 5 or 10 w/w% of DES during membrane preparation. All MMMs were characterized by their ideal gas permeability using N₂ and CO₂ pure gasses. Selected membranes were also tested using CH₄ pure gas. The results presented that 5 w/w%, in polymer mass, of ChCl–glycerol presented the best result over the synthesized membranes. An increase of 200% in CO₂ permeability maintains the CO₂/N₂ selectivity for the non-modified PES/SAPO-34 membrane. A CO₂/CH₄ selectivity of 89.7 was obtained in PES/SAPO-34/ChCl-glycerol membranes containing 5 w/w% of this DES, which is an outstanding ideal separation performance for MMMs when compared to other results in the literature. FTIR analysis reiterates the presence of glycerol in the membranes prepared. Dynamic Mechanical Thermal Analysis (DMTA) shows that the addition of 5 w/w% of DES does not impact the membrane flexibility or polymer structure. However, in concentrations higher than 10 w/w%, the inclusion of DES could lead to high membrane rigidification without impacting the overall thermal resistance. SEM analysis of DES-enhanced membranes presented asymmetric final membranes and reaffirmed the results obtained in DMTA about rigidified structures and lower zeolite–polymer interaction with higher concentrations of DES. Full article

Furanoate polyesters are an extremely promising new class of materials for packaging applications, particularly furanoate-based nanocomposites, which have gained a high interest level in research and development in both academia and industries. The monomers utilised for the synthesis of furanoate-based polyesters were derived from lignocellulosic biomass, which is essential for both eco-friendliness and sustainability. Also, these polyesters have a lower carbon footprint compared to fossil-based plastics, contributing to greenhouse gas reduction. The furanoate-based nanocomposites exhibit enhanced performance characteristics, such as high thermal stability, excellent mechanical strength, superior barrier resistance, and good bacteriostatic rate, making them suitable for a wide range of industrial applications, especially for food-packaging applications. This paper reviews the recent trends in the synthesis routes of monomers, such as the various catalytic activities involved in the oxidation of 5(hydroxymethyl)furfural (HMF) into 2,5-furandicarboxylic acid (FDCA) and its ester, dimethyl furan-2,5-dicarboxylate (DMFD). In addition, this review explores the fabrication of different furanoate-based nanocomposites prepared by in situ polymerization, by melt mixing or solvent evaporation methods, and by using different types of nanoparticles to enhance the overall material properties of the resulting nanocomposites. Emphasis was given to presenting the effect of these nanoparticles on the furanoate polyester’s properties. Full article

Previous research highlights the potential of polyaniline-based biocomposites as unique adsorbents for humidity sensors. This study examines several preparative routes for creating polyaniline (PANI) and chitosan (CHT) composites: Type 1—in situ polymerization of aniline with CHT; Type 2—molecular association in acidic aqueous media; and a control, Type 3—physical mixing of PANI and CHT powders (without solvent). The study aims to differentiate the bonding nature (covalent vs. noncovalent) within these composites, which posits that noncovalent composites should exhibit similar physicochemical properties regardless of the preparative route. The results indicate that Type 1 composites display features consistent with covalent and hydrogen bonding, which result in reduced water swelling versus Type 2 and 3 composites. These findings align with spectral and thermogravimetric data, suggesting more compact structure for Type 1 materials. Dye adsorption studies corroborate the unique properties for Type 1 composites, and ¹H NMR results confirm the role of covalent bonding for the in situ polymerized samples. The structural stability adopts the following trend: Type 1 (covalent and noncovalent) > Type 2 (possible trace covalent and mainly noncovalent) > Type 3 (noncovalent). Types 2 and 3 are anticipated to differ based on solvent-driven complex formation. This study provides greater understanding of structure-function relationships in PANI-biopolymer composites and highlights the role of CHT as a template that involves variable (non)covalent contributions with PANI, according to the mode of preparation. The formation of composites with tailored bonding modalities will contribute to the design of improved adsorbent materials for environmental remediation to versatile humidity sensor systems. Full article

The rapid design of advanced materials depends on synthesis parameters and design. A wide range of materials can be synthesized using precursor reactions based on chelated gel and organic polymeric gel pathways. The desire to develop high-performance lithium-ion rechargeable batteries has motivated decades of research on the synthesis of battery active material particles with precise control of composition, phase-purity, and morphology. Among the most common methods reported in the literature to prepare precursors for lithium-ion battery active materials, sol-gel is characterized by simplicity, homogeneous mixing, and tuning of the particle shape. The chelate gel and organic polymeric gel precursor-based sol-gel method is efficient to promote desirable reaction conditions. Both precursor routes are commonly used to synthesize lithium-ion battery cathode active materials from raw materials such as inorganic salts in aqueous solutions or organic solvents. The purpose of this review is to discuss synthesis procedure and summarize the progress that has been made in producing crystalline particles of tunable and complex morphologies by sol-gel synthesis that can be used as active materials for lithium-ion batteries. Full article

Glyphosate is the most used herbicide in agriculture. Its major metabolite is AMPA (aminomethylphosphonic acid), but N-acetyl-AMPA and N-acetylglyphosate are also metabolites of interest. For risk assessment, a general residue definition was proposed as the sum of glyphosate, AMPA, N-acetyl-glyphosate and N-acetyl-AMPA, expressed as glyphosate. A confirmatory method for glyphosate in fat, liver and kidneys, as well as a confirmatory method for AMPA and N-acetyl-glyphosate in all matrices, are still missing. In this paper, we present a method for the quantitative determination of glyphosate residues and its metabolites AMPA, N-acetyl-AMPA and N-acetyl-glyphosate by liquid chromatography–mass spectrometry (LC-MS/MS) in adipose tissue, liver, eggs, milk and honey without derivatization. Different chromatographic columns were tested, with the Hypercarb column providing the best results. The analytes were eluted with mobile phases of acidified water with 1.2% formic acid and 0.5% formic acid in acetonitrile. Sample purification procedures were also optimized by varying the solvent extraction mixtures (water, methanol and mixture ψ (methanol, water) = 1:1, each with the addition of 1% formic acid (v/v)), using different sorbents in solid phase extraction (SPE) (polymeric cationic (PCX) and anionic (PAX)) and using dispersive solid phase extraction (dSPE) (C18 and PSA) by modifying the extraction procedures. Finally, the analytes were extracted from the samples with 1% formic acid in water (v/v). Milk and adipose tissue were purified by the addition of dichloromethane, while liver and egg samples were purified by SPE with a mixed cation exchange sorbent and ultrafiltration with cut-off filters. The proposed analytical procedures were validated according to SANTE/11312/2021 guidelines: linearity, limits of quantification, precision and accuracy were determined for all matrices. The limits of quantification (LOQs) ranged from 0.025 to 0.2 mg kg⁻¹. Precision, expressed as relative standard deviation, was <20%, while accuracy, expressed as analytical recovery, ranged from 70% to 120%. During method validation, the measurement uncertainty was estimated to be <50% for all analytes. Good validation parameters according to the SANTE document were achieved for all analytes. Therefore, the method can be considered reliable and sensitive enough for routine monitoring of polar pesticides. The application of the accredited method in routine analysis will provide data that are useful for the re-evaluation of risk assessment studies in foods of animal origin. Full article

Using dodecyl acrylate as a raw material and 2-Cyanoprop-2-yl-dithiobenzoate as a chain transfer agent, poly(dodecyl acrylate) is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. Using poly(dodecyl acrylate) as stabilizers, narrowly dispersed poly(ε-caprolactone) microspheres with particle sizes ranging from 0.5 to 1.5 μm are successfully synthesized by ring-opening dispersion polymerization. The effects of the molecular weight of poly(dodecyl acrylate), the volume proportion of mixed solvent (i.e., 1,4-dioxane/heptane), and the reaction temperature on the particle size and its distribution are investigated. With careful control of the synthesis condition, microspheres can be obtained with a particle size distribution of 1.09 (D_w/D_n). The average particle size of poly(ε-caprolactone) microspheres decreased with the increase in the molecular weight of poly(dodecyl acrylate) and increased with the increase in the relative content of 1,4-dioxane. The uniformity of microspheres decreased with the increase in the polymerization temperature. Full article

This study aimed to develop composite hydrogels with exceptional piezoelectric properties and pressure sensitivity. To achieve the objective, this study created a deep eutectic solvent (DES) by mixing choline chloride (ChCl), acrylamide (AM), and acrylic acid (AA). Barium titanate nanoparticles (BTNPs) were incorporated as fillers into the deep eutectic solvents (DES) to synthesize the composite hydrogels using frontal polymerization (FP). The mechanical and piezoelectric properties of the resulting composite hydrogels were analyzed using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). This study found that the BTNPs/P(AM-co-AA) composite hydrogels exhibited excellent mechanical and piezoelectric properties. This is attributed to the high dielectric constant of BTNPs and the electrode polarization phenomenon when subjected to pressure. With a BTNPs content of 0.6 wt%, the maximum compressive strength increased by 3.68 times compared with the hydrogel without added BTNPs. Moreover, increasing the BTNPs content to 0.6 wt% resulted in a 1.48 times increase in generated voltage under the same pressure, compared with the hydrogel with only 0.2 wt% BTNPs. This study provides a method for preparing composite hydrogels with outstanding piezoelectric properties and pressure sensitivity. Full article

Hybrid nanocomposites based on poly(3,6-dianiline-2,5-dichloro-1,4-benzoquinone) (PDACB) in salt form and graphene oxide (GO) have been obtained for the first time, and the significant influence of the preparation method on the composition and structure of nanocomposites and their functional properties has been demonstrated. Nanocomposites were prepared in three ways: via ultrasonic mixing of PDACB and GO; via in situ oxidative polymerization of 3,6-dianiline-2,5-dichloro-1,4-benzoquinone (DACB) in the presence of GO; and by heating a suspension of previously prepared PDACB and GO in DMF with the removal of the solvent. The results of the study of the composition, chemical structure, morphology, thermal stability and electrical properties of nanocomposites obtained via various methods are presented. Nanocomposites obtained by mixing the components in an ultrasonic field demonstrated strong intermolecular interactions between PDACB and GO both due to the formation of hydrogen bonds and π-stacking, as well as through electrostatic interactions. Under oxidative polymerization of DACB in the presence of GO, the latter participated in the oxidative process, being partially reduced. At the same time, a PDACB polymer film was formed on the surface of the GO. Prolonged heating for 4 h at 85 °C of a suspension of PDACB and GO in DMF led to the dedoping of PDACB with the transition of the polymer to the base non-conductive form and the reduction of GO. Regardless of the preparation method, all nanocomposites showed an increase in thermal stability compared to PDACB. All nanocomposites were characterized by a hopping mechanism of conductivity. Direct current (dc) conductivity σ_dc values varied within two orders of magnitude depending on the preparation conditions. Full article