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Efficient adsorbents for excess bilirubin removal are extremely important for the treatment of hyperbilirubinemia. However, traditional adsorbents, such as activated carbons and ion-exchange resins, still suffer from dissatisfactory adsorption performance and poor blood compatibility. Herein, we adopted a rational design strategy guided by density functional theory (DFT) calculations to prepare blood-compatible quaternary ammonium group grafted electrospun polyacrylonitrile nanofiber adsorbents. The calculation analysis and adsorption experiments were used to investigate the structure–function relationship between group types and bilirubin adsorption, both indicating that quaternary ammonium groups with suitable configurations played a crucial role in bilirubin binding. The obtained nanofiber adsorbents showed the bilirubin removal efficiency above 90% even at a coexisting BSA concentration of 50 g L−1. The maximum adsorption capacities were 818.9 mg g−1 in free bilirubin solution and 163.7 mg g−1 in albumin bound bilirubin solution. The nanofiber adsorbents also showed considerable bilirubin removal in dynamic adsorption to reduce the bilirubin concentration to a normal level, which was better than commercial activated carbons. Our study demonstrates the high feasibility of a theory-driven design method for the development of grafted electrospun nanofibers, which have good potential as bilirubin adsorbents in hemoperfusion applications.

A hybrid synthetic-natural, thermoresponsive graft copolymer composed of poly(N-isopropyl acrylamide) (PNIPAM) side chains, prepared via RAFT polymerization, and a chitosan (Chit) polysaccharide backbone, was synthesized via radical addition-fragmentation reactions using the “grafting to” technique, in aqueous solution. ATR-FTIR, TGA, polyelectrolyte titrations and 1H NMR spectroscopy were employed in order to validate the Chit-g-PNIPAM copolymer chemical structure. Additionally, 1H NMR spectra and back conductometric titration were utilized to quantify the content of grafted PNIPAM side chains. The resulting graft copolymer contains dual functionality, namely both pH responsive free amino groups, with electrostatic complexation/coordination properties, and thermoresponsive PNIPAM side chains. Particle size measurements via dynamic light scattering (DLS) were used to study the thermoresponsive behavior of the Chit-g-PNIPAM copolymer. Thermal properties examined by TGA showed that, by the grafting modification with PNIPAM, the Chit structure became more thermally stable. The lower critical solution temperature (LCST) of the copolymer solution was determined by DLS measurements at 25–45 °C. Furthermore, dynamic and electrophoretic light scattering measurements demonstrated that the Chit-g-PNIPAM thermoresponsive copolymer is suitable of binding DNA molecules and forms nanosized polyplexes at different amino to phosphate groups ratios, with potential application as gene delivery systems.

This research focuses on modifying discarded feathers by grafting glycidyl methacrylate (GMA) onto their surface through thiolation, followed by an epoxy ring-opening reaction with N-methyl-D-glucamine (NMDG) to synthesize feather-based boron adsorbents. Optimization of the adsorbent preparation conditions was achieved through single-factor experiments, varying temperature, time, GMA concentration, and initiator dosage. The synthesized adsorbent (F-g-GMA-NMDG) underwent characterization using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The adsorption behavior of the adsorbent was studied, and its boron adsorption capacity at different temperatures was determined through static adsorption kinetic curves. Analysis of adsorption isotherms, kinetics, and thermodynamics was conducted. Results indicate that the boron adsorption process by F-g-GMA-NMDG follows a pseudo-second-order model. The adsorption process is endothermic, with higher temperatures promoting adsorption efficiency. Gibbs free energy (ΔG) confirms the spontaneity of the adsorption process. Enhanced adsorption efficacy was observed under neutral and acidic pH conditions. After four cycles, the adsorbent maintained its adsorption efficiency, demonstrating its stability and potential for reuse. This study provides novel insights into both the treatment of discarded feathers and the development of boron adsorbents.

A polyethylene (PE) film surface modification method is proposed via benzoic acid (BA) alkylation grafting to improve the surface affinity to polar substances. The procedure involves sequentially spraying AlCl3 and BA onto the heat-softened PE surface. The occurrence of the alkylation reaction was evaluated through comparative chemical, morphological, and thermal analyses. It was demonstrated that the grafting reaction of BA onto the PE film surface took place, limited to the surface layer, while preserving the bulk properties of PE. The reaction resulted in the formation of aluminum benzoate complexes, which improved the surface affinity to polar compounds. The impact of grafting on the surface properties of PE was further assessed by comparing the behavior of PE films treated with BA and untreated PE films when painted with watercolors. The PE film grafted with BA exhibited increased affinity towards watercolors, providing strong evidence of a change in surface polarity from hydrophobic to hydrophilic. These findings indicate that the proposed methodology effectively renders the PE surface paintable, even with non-toxic water-based inks, making it suitable for applications such as packaging.

Water scarcity and contamination have emerged as critical global challenges, requiring the development of effective and sustainable solutions for the treatment of contaminated water. Recently, functionalized polymer biomaterials have garnered significant interest because of their potential for a wide range of water treatment applications. Accordingly, this paper highlights the design of a new adsorbent material based on a cellulosic nonwoven textile grafted with two extracted biopolymers. The layer-by-layer grafting technique was used for the polyelectrolyte multi-layer (PEM) biosorbent production. Firstly, we extracted a Suaeda fruticosa polysaccharide (SFP) and confirmed its pectin-like polysaccharide structure via SEC, NMR spectroscopy, and chemical composition analyses. Afterward, the grafting was designed via an alternating multi-deposition of layers of SFP polymer and carrageenan crosslinked with 1,2,3,4-butanetetracarboxylic acid (BTCA). FT-IR and SEM were used to characterize the chemical and morphological characteristics of the designed material. Chemical grafting via polyesterification reactions of the PEM biosorbent was confirmed through FT-IR analysis. SEM revealed the total filling of material microspaces with layers of grafted biopolymers and a rougher surface morphology. The assessment of the swelling behavior revealed a significant increase in the hydrophilicity of the produced adsorbent system, a required property for efficient sorption potential. The evaluation of the adsorption capabilities using the methylene blue (MB) as cationic dye was conducted in various experimental settings, changing factors such as the pH, time, temperature, and initial concentration of dye. For the untreated and grafted materials, the greatest adsorbed amounts of MB were 130.6 mg/g and 802.6 mg/g, respectively (pH = 4, T = 22 C, duration = 120 min, and dye concentration = 600 mg/L). The high adsorption performance, compared to other reported materials, was due to the presence of a large number of hydroxyl, sulfonate, and carboxylic functional groups in the biosorbent polymeric system. The adsorption process fitted well with the pseudo-first-order kinetic model and Langmuir/Temkin adsorption isotherms. This newly developed multi-layered biosorbent shows promise as an excellent adsorption resultant and cheap-cost/easy preparation alternative for treating industrial wastewater.

An increase in plastic waste pollution and the strengthening of global environmental policies have heightened the need for research on biodegradable plastics. In this regard, polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are notable examples, serving as alternatives to traditional plastics. In this study, the compatibility and mechanical properties of PLA/PBAT blends were improved by the chemical grafting of maleic anhydride (MAH). In addition, qualitative analyses were conducted, dynamic mechanical properties were investigated, and the structure and mechanical characteristics of the blends were analyzed. With an increase in the MAH concentration, the grafting yield of the blends increased, and significantly improved the compatibility of the PLA/PBAT blend, with an ~2 and 2.9 times increase in the tensile strength and elongation at break, respectively. These findings indicate that the modified PLA/PBAT blend demonstrates potential for applications that require sustainable plastic materials, thereby contributing to the development of environmentally friendly alternatives in the plastics industry.

Radiation chemistry presents a unique avenue for developing innovative polymeric materials with desirable properties, eliminating the need for chemical initiators, which can be potentially detrimental, especially in sensitive sectors like medicine. In this investigation, we employed a radiation-induced graft polymerization process with N-vinylcaprolactam (NVCL) to modify lignocellulosic membranes derived from Agave salmiana, commonly known as maguey. The membranes underwent thorough characterization employing diverse techniques, including contact angle measurement, degree of swelling, scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier-transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), nuclear magnetic resonance (CP-MAS 13C-NMR), X-ray photoelectron spectroscopy (XPS), and uniaxial tensile mechanical tests. The membranes’ ability to load and release an antimicrobial glycopeptide drug was assessed, revealing significant enhancements in both drug loading and sustained release. The grafting of PNVCL contributed to prolonged sustained release by decreasing the drug release rate at temperatures above the LCST. The release profiles were analyzed using the Higuchi, Peppas–Sahlin, and Korsmeyer–Peppas models, suggesting a Fickian transport mechanism as indicated by the Korsmeyer–Peppas model.

A novel adsorbent–contaminant system was investigated for its ability to remove a contaminant of emerging concern, diclofenac potassium, from contaminated water. Bio-based crosslinked chitosan beads functionalized with poly(itaconic acid) side chains were examined for their potential to remove the emerging contaminant. To evaluate the impact of the polymeric microstructure on its adsorptive capacity, several adsorbent samples were prepared using different combinations of initiator and monomeric concentrations. Fourier Transform Infrared (FTIR) analysis confirmed the crosslinking of the chitosan chains and the incorporation of the carboxylic groups on the surface of the final chitosan beads. After the grafting copolymerization process, an additional peak at 1726 cm−1 corresponding to the carboxylic C=O groups of the grafted chains appeared, indicating the successful preparation of poly(IA)-g-chitosan. Thermal stability studies showed that the grafting copolymerization improved the thermal stability of the beads. X-ray and Scanning Electron Microscopy confirmed the successful grafting of the itaconic acid on the surface of the beads. The study revealed that the higher the initiator concentration, the greater the number of side chains, whereas the higher the monomeric concentration, the longer the length of these side chains. The adsorption mechanism involved hydrogen bonding to the carboxylic groups of the grafted chains along with n-π* stacking interaction between the amino group of the chitosan and the aromatic rings of diclofenac potassium. The adsorption efficiencies of diclofenac potassium onto the grafted beads were significantly improved compared to the unfunctionalized chitosan beads, reaching values above 90%. The removal efficiency of grafted chitosan increased with an increase in the concentration in the range of 10–30 ppm and then flattened out in the range of 30–50 ppm. The removal efficiencies of 1–50 ppm of DCF ranged between about 75% and 92% for the grafted chitosan and 30–45% for the crosslinked chitosan. Rapid adsorption occurred within 20 min for all grafted sample combinations, and the adsorption kinetics followed a pseudo-second-order model with qe values ranging from 28 to 44.25 g/mg and R2 values greater than 0.9915. The results highlight the potential of grafted chitosan beads in removing emerging contaminants from contaminated water without harming the environment.

Waterborne polyurethane-acrylate (WPUA) grafted with polyurethane was prepared to improve the film-forming ability of hard-type acrylic latex. To balance the film-formation ability and hardness, the WPUA latex was designed with a hard core (polyacrylate) and soft shell (polyurethane). The grafting ratio was controlled through varying the content of 2-hydroxyethyl methacrylate (HEMA) used to cap the ends of the polyurethane prepolymer. The morphologies of the latex particles, film surface, and fracture surface of the film were characterized through transmission electron microscopy, atomic force microscopy, and scanning electron microscopy, respectively. An increase in the grafting ratio resulted in the enhanced miscibility of polyurethane and polyacrylate but reduced adhesion between particles and increased minimum film formation temperature. In addition, grafting was essential to obtain transparent WPUA films. Excessive grafting induced defects such as micropores within the film, leading to the decreased hardness and adhesive strength of the film. The optimal HEMA content for the preparation of a WPUA coating with excellent film-forming ability and high hardness in ambient conditions was noted to be 50%. The final WPUA film was prepared without coalescence agents that generate volatile organic compounds.

Blend copolymers (PVA/S) were grafted with polyethylene glycol methyl methacrylate (PEGMA) with different ratios. Potassium persulfate was used as an initiator. The blend copolymer (PVA/S) was created by combining poly(vinyl alcohol) (PVA) with starch (S) in various ratios. The main idea was to study the effect of different ratios of the used raw materials on the biodegradability of plastic films. The resulting polymers (PVA/S/PEGMA) were analyzed using FTIR spectroscopy to investigate the hydrogen bond interaction between PVA, S, and PEGMA in the mixtures. TGA and SEM analyses were used to characterize the polymers (PVA/S/AA). The biodegradability and mechanical properties of the PVA/S/PEGMA blend films were evaluated. The findings revealed that the mechanical properties of the blend films are highly influenced by PEGMA. The time of degradation of the films immersed in soil and Coca-Cola increases as the contents of PVA and S and the molecular weight (MW) of PEGMA increase in the terpolymer. The M8 sample (PVA/S/PEGMA in the ratio of 3:1:2, respectively) with a MW of 950 g/mol produced the lowest elongation at break (67.5%), whereas M1 (PVA/S/PEGMA in the ratio of 1:1:1, respectively) with a MW of 300 g/mol produced the most (150%). The film’s tensile strength and elongation at break were improved by grafting PEGMA onto the blending polymer (PAV-b-S). Tg and Tm increased when the PEGMA MW increased from 300 to 950. Tg (48.4 °C) and Tm (190.9 °C) were the lowest in M1 (300), while Tg (84.8 °C) and Tm (190.9 °C) were greatest in M1 (950) at 209.3 °C. The increased chain and molecular weight of PEGMA account for the increase in Tg and Tm of the copolymers.

As the only renewable resource among the four basic materials (steel, cement, plastic, wood), wood itself and wood products have a “low carbon” value and play an important role in storing carbon. The moisture absorption and expansion properties of wood limit its application scope and shorten its service life. To enhance the mechanical and physical properties of fast-growing poplars, an eco-friendly modification procedure has been used. This was accomplished by the in situ modification of wood cell walls by vacuum pressure impregnation with a reaction of water-soluble 2-hydroxyethyl methacrylate (HEMA) and N,N’-methylenebis(acrylamide) (MBA). The anti-swelling efficiency of HEMA/MBA-treated wood was improved (up to 61.13%), whereas HEMA/MBA-treated wood presented a lower weight-gain rate (WG) and water-absorption rate (WAR). It was observed that the modulus of elasticity, hardness, density, and other properties of modified wood had improved significantly, as indicated by XRD analysis. Modifiers diffuse primarily within cell walls and cell interstices of wood, causing crosslinks between the modifiers and the cell walls, reducing its hydroxyl content and blocking the channels for water movement, thereby enhancing its physical properties. This result can be obtained by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDX), Nitrogen adsorption test imaging ATR-FTIR (Attenuated total reflection-Fourier-Transform Infrared) Spectroscopy, and nuclear magnetic resonance (NMR) and Nitrogen adsorption test. Overall, this straightforward, high-performance modification method is crucial for maximizing wood’s efficiency and the sustainable development of human society.

Chitosan is a polysaccharide extracted from animal sources such as crab and shrimp shells. In this work, chitosan films were modified by grafting them with a thermoresponsive polymer, poly(di(ethylene glycol) methyl ether methacrylate) (PMEO2MA). The films were modified to introduce functional groups useful as reversible addition–fragmentation chain transfer (RAFT) agents. PMEO2MA chains were then grown from the films via RAFT polymerization, making the chitosan films thermoresponsive. The degree of substitution of the chitosan-based RAFT agent and the amount of monomer added in the grafting reaction were varied to control the length of the grafted PMEO2MA chain segments. The chains were cleaved from the film substrates for characterization using 1H NMR and a gel permeation chromatography analysis. Temperature-dependent contact angle measurements were used to demonstrate that the hydrophilic–hydrophobic nature of the film surface varied with temperature. Due to the enhanced hydrophobic character of PMEO2MA above its lower critical solution temperature (LCST), the ability of PMEO2MA-grafted chitosan films to serve as a substrate for cell growth at 37 °C (incubation temperature) was tested. Interactions with cells (fibroblasts, macrophages, and corneal epithelial cells) were assessed. The modified chitosan films supported cell viability and proliferation. As the temperature is lowered to 4 °C (refrigeration temperature, below the LCST), the grafted chitosan films become less hydrophobic, and cell adhesion should decrease, facilitating their removal from the surface. Our results indicated that the cells were detached from the films following a short incubation period at 4 °C, were viable, and retained their ability to proliferate.

In this study, a heavy metal trapping gel with multiple ligand groups was prepared for the first time using response surface methodology. The gel was produced by condensing and grafting glutathione as a grafting monomer onto the main polyacrylamide chain, based on the Mannich reaction mechanism with formaldehyde. FTIR, SEM, TG-DSC, and zeta potentials were used to characterize the gel. The results demonstrated that the gel was morphologically folded and porous, with a net-like structure, which enhanced its net trapping and sweeping abilities, and that glutathione was used to provide sulfhydryl groups to boost the metal trapping ability of polyacrylamide. Coagulation experiments showed that the highest efficiency of the removal of Cd ions from water samples was achieved when the concentration of polyacrylamide–glutathione was 84.48 mgL−1, the concentration of Cd was 10.0 mgL−1, the initial turbidity was 10.40 NTU, and the initial pH was 9.0. Furthermore, the presence of two cations, Cu and Zn, had an inhibitory effect on the removal of Cd ions. In addition, analysis of the zeta potential revealed the flocculation of polyacrylamide–glutathione. The flocculation mechanism of glutathione is mainly chelation, adsorption bridging, and netting sweeping.

Efficient adsorbents for excess bilirubin removal are extremely important for the treatment of hyperbilirubinemia. However, traditional adsorbents, such as activated carbons and ion-exchange resins, still suffer from dissatisfactory adsorption performance and poor blood compatibility. Herein, we adopted a rational design strategy guided by density functional theory (DFT) calculations to prepare blood-compatible quaternary ammonium group grafted electrospun polyacrylonitrile nanofiber adsorbents. The calculation analysis and adsorption experiments were used to investigate the structure-function relationship between group types and bilirubin adsorption, both indicating that quaternary ammonium groups with suitable configurations played a crucial role in bilirubin binding. The obtained nanofiber adsorbents showed the bilirubin removal efficiency above 90% even at a coexisting BSA concentration of 50 g L -1 . The maximum adsorption capacities were 818.9 mg g -1 in free bilirubin solution and 163.7 mg g -1 in albumin bound bilirubin solution. The nanofiber adsorbents also showed considerable bilirubin removal in dynamic adsorption to reduce the bilirubin concentration to a normal level, which was better than commercial activated carbons. Our study demonstrates the high feasibility of a theory-driven design method for the development of grafted electrospun nanofibers, which have good potential as bilirubin adsorbents in hemoperfusion applications.

In this work, cellulose nanofibers (CNF) were surface treated by plasma and grafted with poly(ethylene glycol)methyl ether methacrylate (PEGMMA) for increasing mechanical strength and hydrophobicity. The surface characteristics of the sponges were studied by scanning electron microscopy, micro-computed tomography, and Fourier transform infrared spectroscopy, which demonstrated successful surface modification. Plasma treatment applied to CNF suspension led to advanced defibrillation, and the resulting sponges (CNFpl) exhibited smaller wall thickness than CNF. The grafting of PEGMMA led to an increase in the wall thickness of the sponges and the number of larger pores when compared with the non-grafted counterparts. Sponges with increased hydrophobicity demonstrated by an almost 4 times increase in the water contact angle and better mechanical strength proved by 2.5 times increase in specific compression strength were obtained after PEGMMA grafting of plasma treated CNF. Cells cultivated on both neat and PEGMMA-grafted CNF sponges showed high viability (>99%). Remarkably, CNF grafted with PEGMMA showed better cell viability as compared with the untreated CNF sample; this difference is statistically significant (p < 0.05). In addition, the obtained sponges do not trigger an inflammatory response in macrophages, with TNF-α secretion by cells in contact with CNFpl, CNF-PEGMMA, and CNFpl-PEGMMA samples being lower than that observed for the CNF sample. All these results support the great potential of cellulose nanofibers surface treated by plasma and grafted with PEGMMA for biomedical applications.

The plastic waste problem has recently attracted unprecedented attention globally. To reduce the adverse eff ects on environments, biodegradable polymers have been studied to solve the problems. Poly(ε-caprolactone) (PCL) is one of the common biodegradable plastics used on its own or blended with natural polymers because of its excellent properties after blending. However, PCL and natural polymers are difficult to blend due to the polymers’ properties. Grafted polymerization of maleic anhydride and dibenzoyl peroxide (DBPO) with PCL is one of the improvements used for blending immiscible polymers. In this study, we first focused on the effects of three factors (stirring time, maleic anhydride (MA) amount and benzoyl peroxide amount) on the grafting ratio with a maximum value of 4.16% when applying 3.000 g MA and 1.120 g DBPO to 3.375 g PCL with a stirring time of 18 h. After that, the grafting condition was studied based on the kinetic thermal decomposition and activation energy by the Coats–Redfern method. The optimal fitting model was confirmed by the determination coefficient of nearly 1 to explain the contracting volume mechanism of synthesized PCL-g-MA. Consequently, grafted MA hydrophilically augmented PCL as the reduced contact angle of water suggests, facilitating the creation of a plastic–biomaterial composite.

Gum katira polysaccharide is biocompatible and non-toxic, and has antioxidant, anti-microbial, and immunomodulatory properties. It is a natural polysaccharide and exudate derived from the stem bark of Cochlospermum reliogosum Linn. Additionally, it has many traditional medicinal uses as a sedative and for the treatment of jaundice, gonorrhea, syphilis, and stomach ailments. This article provides an overview of gum katira, including its extraction, separation, purification, and physiochemical properties and details of its characterization and pharmacognostic features. This paper takes an in-depth look at the synthetic methods used to modify gum katira, such as carboxymethylation and grafting triggered by free radicals. Furthermore, this review provides an overview of its industrial and phytopharmacological applications for drug delivery and heavy metal and dye removal, its biological activities, its use in food, and the potential use of gum katira derivatives and their industrial applications. We believe researchers will find this paper useful for developing techniques to modify gum katira polysaccharides to meet future demands.

Demand for direct chemical modification of functional material on a surface is increasing in various fields. A new approach for a functionalized surface is investigated by applying a conventional laser in order to generate chemical activation by photothermal energy. Poly(ethyleneimine) (PEI), with a high density of amino groups, is chemically grafted on poly(methyl methacrylate) (PMMA) by irradiation of a CO2 laser (10.6 μm). Laser parameters such as power, scan rate, and focal length are observed to play an important role in order to introduce effective photothermal energy for the chemical reaction between PEI and PMMA. By optimization of laser parameters, the amide compound is produced as a result of the reaction of amine from PEI and the ester of PMMA successfully. The PMMA surface modified with PEI is analyzed by XPS and TOF-SIMS to identify the functional groups. Furthermore, the surface is characterized in terms of wettability, adhesion force, and surface charge for various applications. Finally, reaction with dye and metal on the amine-terminated PMMA shows promising results in supplying a selective and reliable functional substrate.

This research focuses on modifying discarded feathers by grafting glycidyl methacrylate (GMA) onto their surface through thiolation, followed by an epoxy ring-opening reaction with N-methyl-D-glucamine (NMDG) to synthesize feather-based boron adsorbents. Optimization of the adsorbent preparation conditions was achieved through single-factor experiments, varying temperature, time, GMA concentration, and initiator dosage. The synthesized adsorbent (F-g-GMA-NMDG) underwent characterization using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The adsorption behavior of the adsorbent was studied, and its boron adsorption capacity at different temperatures was determined through static adsorption kinetic curves. Analysis of adsorption isotherms, kinetics, and thermodynamics was conducted. Results indicate that the boron adsorption process by F-g-GMA-NMDG follows a pseudo-second-order model. The adsorption process is endothermic, with higher temperatures promoting adsorption efficiency. Gibbs free energy (Δ G ) confirms the spontaneity of the adsorption process. Enhanced adsorption efficacy was observed under neutral and acidic pH conditions. After four cycles, the adsorbent maintained its adsorption efficiency, demonstrating its stability and potential for reuse. This study provides novel insights into both the treatment of discarded feathers and the development of boron adsorbents.

A hybrid synthetic-natural, thermoresponsive graft copolymer composed of poly( N -isopropyl acrylamide) (PNIPAM) side chains, prepared via RAFT polymerization, and a chitosan (Chit) polysaccharide backbone, was synthesized via radical addition-fragmentation reactions using the "grafting to" technique, in aqueous solution. ATR-FTIR, TGA, polyelectrolyte titrations and 1 H NMR spectroscopy were employed in order to validate the Chit- g -PNIPAM copolymer chemical structure. Additionally, 1 H NMR spectra and back conductometric titration were utilized to quantify the content of grafted PNIPAM side chains. The resulting graft copolymer contains dual functionality, namely both pH responsive free amino groups, with electrostatic complexation/coordination properties, and thermoresponsive PNIPAM side chains. Particle size measurements via dynamic light scattering (DLS) were used to study the thermoresponsive behavior of the Chit- g -PNIPAM copolymer. Thermal properties examined by TGA showed that, by the grafting modification with PNIPAM, the Chit structure became more thermally stable. The lower critical solution temperature (LCST) of the copolymer solution was determined by DLS measurements at 25-45 °C. Furthermore, dynamic and electrophoretic light scattering measurements demonstrated that the Chit- g -PNIPAM thermoresponsive copolymer is suitable of binding DNA molecules and forms nanosized polyplexes at different amino to phosphate groups ratios, with potential application as gene delivery systems.

A polyethylene (PE) film surface modification method is proposed via benzoic acid (BA) alkylation grafting to improve the surface affinity to polar substances. The procedure involves sequentially spraying AlCl 3 and BA onto the heat-softened PE surface. The occurrence of the alkylation reaction was evaluated through comparative chemical, morphological, and thermal analyses. It was demonstrated that the grafting reaction of BA onto the PE film surface took place, limited to the surface layer, while preserving the bulk properties of PE. The reaction resulted in the formation of aluminum benzoate complexes, which improved the surface affinity to polar compounds. The impact of grafting on the surface properties of PE was further assessed by comparing the behavior of PE films treated with BA and untreated PE films when painted with watercolors. The PE film grafted with BA exhibited increased affinity towards watercolors, providing strong evidence of a change in surface polarity from hydrophobic to hydrophilic. These findings indicate that the proposed methodology effectively renders the PE surface paintable, even with non-toxic water-based inks, making it suitable for applications such as packaging.

In this study, polycaprolactone (PCL)- and poly(acrylic acid) (PAA)-based electrospun nanofibers were prepared for the carriers of antimicrobials and designed composite nanofiber mats for chronic wound care. The PCL- and PAA-based electrospun nanofibers were prepared through in situ polymerization starting from PCL and acrylic acid (AA). Different amounts of AA were introduced to improve the hydrophilicity of the PCL electrospun nanofibers. A compatibilizer and a photoinitiator were then added to the electrospinning solution to form a grafted structure composed of PCL and PAA (PCL-g-PAA). The grafted PAA was mainly located on the surface of a PCL nanofiber. The optimization of the composition of PCL, AA, compatibilizer, and photoinitiator was studied, and the PCL-g-PAA electrospun nanofibers were characterized through scanning electron microscopy and 1H-NMR spectroscopy. Results showed that the addition of AA to PCL improved the hydrophilicity of the electrospun PCL nanofibers, and a PCL/AA ratio of 80/20 presented the best composition and had smooth nanofiber morphology. Moreover, poly[2 -(tert-butylaminoethyl) methacrylate]-grafted graphene oxide nanosheets (GO-g-PTA) functioned as an antimicrobial agent and was used as filler for PCL-g-PAA nanofibers in the preparation of composite nanofiber mats, which exerted synergistic effects promoted by the antibacterial properties of GO-g-PTA and the hydrophilicity of PCL-g-PAA electrospun nanofibers. Thus, the composite nanofiber mats had antibacterial properties and absorbed body fluids in the wound healing process, thereby promoting cell proliferation. The biodegradation of the PCL-g-PAA electrospun nanofibers also demonstrated an encouraging result of three-fold weight reduction compared to the neat PCL nanofiber. Our findings may serve as guidelines for the fabrication of electrospun nanofiber composites that can be used mats for chronic wound care.

This work proposes a new method for obtaining poly(3-hydroxybutyrate) (PHB)/microfibrillated cellulose (MC) composites with more balanced properties intended for the substitution of petroleum-based polymers in packaging and engineering applications. To achieve this, the MC surface was adjusted by a new chemical route to enhance its compatibility with the PHB matrix: (i) creating active sites on the surface of MC with γ-methacryloxypropyltrimethoxysilane (SIMA) or vinyltriethoxysilane (SIV), followed by (ii) the graft polymerization of methacrylic acid (MA). The high efficiency of the SIMA-MA treatment and the lower efficiency in the case of SIV-MA were proven by the changes observed in the Fourier transform infrared FTIR spectra of celluloses. All modified celluloses and the PHB composites containing them showed good thermal stability close to the processing temperature of PHB. SIMA-modified celluloses acted as nucleating agents in PHB, increasing its crystallinity and favoring the formation of smaller spherulites. A uniform dispersion of SIMA-modified celluloses in PHB as a result of the good compatibility between the two phases was observed by scanning electron microscopy and many agglomerations of fibers in the composite with unmodified MC. The dual role of SIMA-MA treatment, as both compatibilizer and plasticizer, was pointed out by mechanical and rheological measurements. This new method to modify MC and obtain PHB/MC composites with more balanced stiffness–toughness properties could be a solution to the high brittleness and poor processability of PHB-based materials.

Hydrogenated Nitrile Rubber (HNBR) is widely used in aerospace, petroleum exploration and other fields because of its excellent performances. However, there remains a challenge of balancing the oil resistance and the low temperature resistance for HNBR. In this work, a series of grafted carboxyl nitrile rubber (XNBR) was prepared by the esterification reaction between active functional groups (–COOH) of XNBR and alkanols of different molecular chain lengths (C8H17OH, C12H25OH, C16H33OH, C18H37OH) or Methoxypolyethylene glycols (MPEG) of different molecular weights (Mn = 350, 750, 1000). The structure and low temperature resistance of as-obtained grafted polymers were characterized by Fourier Transform Infrared (FTIR), 1H-NMR and Differential scanning calorimetry (DSC). It was found that the glass transition temperatures (Tg) of grafted XNBR were significantly decreased. MPEG grafted polymers with better low temperature resistance were then selected for hydrogenation. As-prepared hydrogenated XNBR grafted with MPEG-1000 (HXNBR-g-1000) showed the lowest Tg of −29.8 °C and the best low temperature resistance. This work provides a novel and simple preparation method for low temperature resistant HNBR, which might be used potentially in extremely cold environments.

Plant-based materials have found their application in the packaging with a yearly growing production rate. These naturally biodegradable polymers are obtained from renewable and sustainable natural resources with reduced environmental impact and affordable cost. These materials have found their utilization in fully-renewable plant-based packaging products, such as Tetra Pak®-like containers, by replacing commonly-used polyethylene as the polymer component. Poly(lactic acid) (PLA) is one of the representative plant-based polymers because of its eco-friendliness and excellent chemical and mechanical properties. In this work, a PLA surface was modified by various food additives, namely ascorbic acid (ASA) and fumaric acid (FA), using plasma-initiated grafting reactions in order to improve the surface and adhesion properties of PLA. Various analytical and microscopic techniques were employed to prove the grafting process. Moreover, the improved adhesion of the modified PLA foil to aluminum (Al) foil in a laminate configuration was proven by peel resistance measurements. The peel resistance of modified PLA increased by 74% and 184% for samples modified by ASA and FA, respectively, compared with untreated PLA.

This study reports the feasible use of chitosan as a thin film biosensor on the very sensitive quartz crystal micro balance system for detection of blends of multiple templates within a single matrix. The development of chitosan-based thin film materials with selectivity for nicotine derivatives is described. The molecular imprinting of a combination of nicotine derivatives in N-diacryloyl pipiradine-chitosan-methacrylic acid copolymer films on quartz crystal resonators was used to generate thin films with selectivity for nicotine and a range of nicotine analogues, particularly 3-phenylpyridine. The polymers were characterized by spectroscopic and microscopic evaluations; surface area, pore size, pore volume using Breuner-Emmet-Teller method. Temperature characteristics were also studied. The swelling and structure consistency of the Chitosan was achieved by grafting with methylmethacrylic acid and cross-linking with N-diacrylol pipiradine. A blend of 0.002 g (0.04 mmol) of Chitosan, 8.5 μL Methylmethacrylic Acid and 1.0 mg N-diacrylol pipradine (BAP) presented the best blend formulation. Detections were made within a time interval of 99 s, and blend templates were detected at a concentration of 0.5 mM from the Quartz crystal microbalance resonator analysis. The successful crosslinking of the biopolymers ensured successful control of the swelling and agglomeration of the chitosan, giving it the utility potential for use as thin film sensor. This successful crosslinking also created successful dual multiple templating on the chitosan matrix, even for aerosolized templates. The products can be used in environments with temperature ranges between 60 °C and 250 °C.

An eco-friendly strategy for the modification of polylactic acid (PLA) surface properties, using a solvent-free process, is reported. Reactive extrusion (REX) allowed the formation of new covalent bonds between functional molecules and the PLA polymeric matrix, enhancing its mechanical properties and modifying surface hydrophobicity. To this end, the PLA backbone was modified using two alkoxysilanes, phenyltriethoxysilane and N-octyltriethoxysilane. The reactive extrusion process was carried out under mild conditions, using melting temperatures between 150 and 180 °C, 300 rpm as screw speed, and a feeding rate of 3 kg·h−1. To complete the study, flat tapes of neat and functionalized PLA were obtained through monofilament melt extrusion to quantify the enhancement of mechanical properties and hydrophobicity. The results verified that PLA modified with 3 wt% of N-octyltriethoxysilane improves mechanical and thermal properties, reaching Young’s modulus values of 4.8 GPa, and PLA hydrophobic behavior, with values of water contact angle shifting from 68.6° to 82.2°.

Water scarcity and contamination have emerged as critical global challenges, requiring the development of effective and sustainable solutions for the treatment of contaminated water. Recently, functionalized polymer biomaterials have garnered significant interest because of their potential for a wide range of water treatment applications. Accordingly, this paper highlights the design of a new adsorbent material based on a cellulosic nonwoven textile grafted with two extracted biopolymers. The layer-by-layer grafting technique was used for the polyelectrolyte multi-layer (PEM) biosorbent production. Firstly, we extracted a Suaeda fruticosa polysaccharide (SFP) and confirmed its pectin-like polysaccharide structure via SEC, NMR spectroscopy, and chemical composition analyses. Afterward, the grafting was designed via an alternating multi-deposition of layers of SFP polymer and carrageenan crosslinked with 1,2,3,4-butanetetracarboxylic acid (BTCA). FT-IR and SEM were used to characterize the chemical and morphological characteristics of the designed material. Chemical grafting via polyesterification reactions of the PEM biosorbent was confirmed through FT-IR analysis. SEM revealed the total filling of material microspaces with layers of grafted biopolymers and a rougher surface morphology. The assessment of the swelling behavior revealed a significant increase in the hydrophilicity of the produced adsorbent system, a required property for efficient sorption potential. The evaluation of the adsorption capabilities using the methylene blue (MB) as cationic dye was conducted in various experimental settings, changing factors such as the pH, time, temperature, and initial concentration of dye. For the untreated and grafted materials, the greatest adsorbed amounts of MB were 130.6 mg/g and 802.6 mg/g, respectively (pH = 4, T = 22 C, duration = 120 min, and dye concentration = 600 mg/L). The high adsorption performance, compared to other reported materials, was due to the presence of a large number of hydroxyl, sulfonate, and carboxylic functional groups in the biosorbent polymeric system. The adsorption process fitted well with the pseudo-first-order kinetic model and Langmuir/Temkin adsorption isotherms. This newly developed multi-layered biosorbent shows promise as an excellent adsorption resultant and cheap-cost/easy preparation alternative for treating industrial wastewater.

Radiation chemistry presents a unique avenue for developing innovative polymeric materials with desirable properties, eliminating the need for chemical initiators, which can be potentially detrimental, especially in sensitive sectors like medicine. In this investigation, we employed a radiation-induced graft polymerization process with N-vinylcaprolactam (NVCL) to modify lignocellulosic membranes derived from Agave salmiana , commonly known as maguey. The membranes underwent thorough characterization employing diverse techniques, including contact angle measurement, degree of swelling, scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier-transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), nuclear magnetic resonance (CP-MAS 13 C-NMR), X-ray photoelectron spectroscopy (XPS), and uniaxial tensile mechanical tests. The membranes' ability to load and release an antimicrobial glycopeptide drug was assessed, revealing significant enhancements in both drug loading and sustained release. The grafting of PNVCL contributed to prolonged sustained release by decreasing the drug release rate at temperatures above the LCST. The release profiles were analyzed using the Higuchi, Peppas-Sahlin, and Korsmeyer-Peppas models, suggesting a Fickian transport mechanism as indicated by the Korsmeyer-Peppas model.

An increase in plastic waste pollution and the strengthening of global environmental policies have heightened the need for research on biodegradable plastics. In this regard, polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are notable examples, serving as alternatives to traditional plastics. In this study, the compatibility and mechanical properties of PLA/PBAT blends were improved by the chemical grafting of maleic anhydride (MAH). In addition, qualitative analyses were conducted, dynamic mechanical properties were investigated, and the structure and mechanical characteristics of the blends were analyzed. With an increase in the MAH concentration, the grafting yield of the blends increased, and significantly improved the compatibility of the PLA/PBAT blend, with an ~2 and 2.9 times increase in the tensile strength and elongation at break, respectively. These findings indicate that the modified PLA/PBAT blend demonstrates potential for applications that require sustainable plastic materials, thereby contributing to the development of environmentally friendly alternatives in the plastics industry.

Many bio-applicable materials, medical devices, and prosthetics combine both polymer and metal components to benefit from their complementary properties. This goal is normally achieved by their mechanical bonding or casting only. Here, we report an alternative easy method for the chemical grafting of a polymer on the surfaces of a metal or metal alloys using alkoxy amine salt as a coupling agent. The surface morphology of the created composites was studied by various microscopy methods, and their surface area and porosity were determined by adsorption/desorption nitrogen isotherms. The surface chemical composition was also examined by various spectroscopy techniques and electrokinetic analysis. The distribution of elements on the surface was determined, and the successful bonding of the metal/alloys on one side with the polymer on the other by alkoxy amine was confirmed. The composites show significantly increased hydrophilicity, reliable chemical stability of the bonding, even interaction with solvent for thirty cycles, and up to 95% less bacterial adhesion for the modified samples in comparison with pristine samples, i.e., characteristics that are promising for their application in the biomedical field, such as for implants, prosthetics, etc. All this uses universal, two-step procedures with minimal use of energy and the possibility of production on a mass scale.

This study is based upon the functionalization of polypropylene (PP) by radical polymerization to optimize its properties by influencing its molecular weight. Grafting of PP was done at different concentrations of maleic anhydride (MAH) and benzoyl peroxide (BPO). The effect on viscosity during and after the reaction was studied by torque rheometer and melt flow index. Results showed that a higher concentration of BPO led to excessive side-chain reactions. At a high percentage of grafting, lower molecular weight product was produced, which was analyzed by viscosity change during and after the reaction. Percentage crystallinity increased by grafting due to the shorter chains, which consequently led to an improvement in the chain’s packing. Prepared Maleic anhydride grafted polypropylene (MAH-g-PP) enhanced interactions in PP-PET blends caused a partially homogeneous blend with less voids.

The exploitation of epoxidized natural rubber (ENR) in electrochemical applications is approaching its limits because of its poor thermo-mechanical properties. These properties could be improved by chemical and/or physical modification, including grafting and/or crosslinking techniques. In this work, acrylonitrile (ACN) has been successfully grafted onto ENR- 25 by a radical photopolymerization technique. The effect of (ACN to ENR) mole ratios on chemical structure and interaction, thermo-mechanical behaviour and that related to the viscoelastic properties of the polymer was investigated. The existence of the –C≡N functional group at the end-product of ACN-g-ENR is confirmed by infrared (FT-IR) and nuclear magnetic resonance (NMR) analyses. An enhanced grafting efficiency (~57%) was obtained after ACN was grafted onto the isoprene unit of ENR- 25 and showing a significant improvement in thermal stability and dielectric properties. The viscoelastic behaviour of the sample analysis showed an increase of storage modulus up to 150 × 103 MPa and the temperature of glass transition (Tg) was between −40 and 10 °C. The loss modulus, relaxation process, and tan delta were also described. Overall, the ACN-g-ENR shows a distinctive improvement in characteristics compared to ENR and can be widely used in many applications where natural rubber is used but improved thermal and mechanical properties are required. Likewise, it may also be used in electronic applications, for example, as a polymer electrolyte in batteries or supercapacitor.

Silicone rubber (SR) is a material used for medical procedures, with a common example of its application being in implants for cosmetic or plastic surgeries. It is also an essential component for the development of medical devices. SR was functionalized with the polymeric prodrug of poly(2-methacryloyloxy-benzoic acid) (poly(2MBA)) to render the analgesic anti-inflammatory drug salicylic acid by hydrolysis. The system was designed by functionalizing SR films (0.5 cm × 1 cm) with a direct grafting method, using gamma irradiation (60Co source) to induce the polymerization process. The absorbed dose (from 20 to 100 kGy) and the monomer concentration (between 0.4 and 1.5 M) were critical in controlling the surface and the bulk modifications of SR. Grafting poly(2MBA) onto SR (SR-g-2MBA) were characterized by attenuated total reflectance Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy/energy-dispersive X-ray spectrometry, fluorescence microscopy, the contact angle, and the swelling. SR-g-2MBA demonstrated the drug’s sustained and pH-dependent release in simulated physiological mediums (pH = 5.5 and 7.4). The drug’s release was quantified by high-performance liquid chromatography and confirmed by gas chromatography–mass spectrometry. Finally, cytocompatibility was demonstrated in murine fibroblast and human cervical cancer cell lines. The developed systems provide new polymeric drug release systems for medical silicone applications.

In this work we aim to show that the overall surface potential is a key factor to understand and predict anti-fouling characteristics of a polymer membrane. Therefore, polyvinylidene fluoride membranes were modified by electron beam-induced grafting reactions forming neutral, acidic, alkaline or zwitterionic structures on the membrane surface. The differently charged membranes were investigated regarding their surface properties using diverse analytical methods: zeta potential, static and dynamic water contact angle, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Porosimetry measurements proved that there is no pore blocking due to the modifications. Monodisperse suspensions of differently charged polystyrene beads were synthesized by a radical emulsion polymerization reaction and were used as a model fouling reagent, preventing comparability problems known from current literature. To simulate membrane fouling, different bead suspensions were filtered through the membranes. The fouling characteristics were investigated regarding permeation flux decline and concentration of model fouling reagent in filtrate as well as by SEM. By considering electrostatic interactions equal to hydrophobic interactions we developed a novel fouling test system, which enables the prediction of a membrane’s fouling tendency. Electrostatic forces are dominating, especially when charged fouling reagents are present, and can help to explain fouling characteristics that cannot be explained considering the surface wettability.

A novel adsorbent-contaminant system was investigated for its ability to remove a contaminant of emerging concern, diclofenac potassium, from contaminated water. Bio-based crosslinked chitosan beads functionalized with poly(itaconic acid) side chains were examined for their potential to remove the emerging contaminant. To evaluate the impact of the polymeric microstructure on its adsorptive capacity, several adsorbent samples were prepared using different combinations of initiator and monomeric concentrations. Fourier Transform Infrared (FTIR) analysis confirmed the crosslinking of the chitosan chains and the incorporation of the carboxylic groups on the surface of the final chitosan beads. After the grafting copolymerization process, an additional peak at 1726 cm -1 corresponding to the carboxylic C=O groups of the grafted chains appeared, indicating the successful preparation of poly(IA)- g -chitosan. Thermal stability studies showed that the grafting copolymerization improved the thermal stability of the beads. X-ray and Scanning Electron Microscopy confirmed the successful grafting of the itaconic acid on the surface of the beads. The study revealed that the higher the initiator concentration, the greater the number of side chains, whereas the higher the monomeric concentration, the longer the length of these side chains. The adsorption mechanism involved hydrogen bonding to the carboxylic groups of the grafted chains along with n-π* stacking interaction between the amino group of the chitosan and the aromatic rings of diclofenac potassium. The adsorption efficiencies of diclofenac potassium onto the grafted beads were significantly improved compared to the unfunctionalized chitosan beads, reaching values above 90%. The removal efficiency of grafted chitosan increased with an increase in the concentration in the range of 10-30 ppm and then flattened out in the range of 30-50 ppm. The removal efficiencies of 1-50 ppm of DCF ranged between about 75% and 92% for the grafted chitosan and 30-45% for the crosslinked chitosan. Rapid adsorption occurred within 20 min for all grafted sample combinations, and the adsorption kinetics followed a pseudo-second-order model with q e values ranging from 28 to 44.25 g/mg and R 2 values greater than 0.9915. The results highlight the potential of grafted chitosan beads in removing emerging contaminants from contaminated water without harming the environment.

Waterborne polyurethane-acrylate (WPUA) grafted with polyurethane was prepared to improve the film-forming ability of hard-type acrylic latex. To balance the film-formation ability and hardness, the WPUA latex was designed with a hard core (polyacrylate) and soft shell (polyurethane). The grafting ratio was controlled through varying the content of 2-hydroxyethyl methacrylate (HEMA) used to cap the ends of the polyurethane prepolymer. The morphologies of the latex particles, film surface, and fracture surface of the film were characterized through transmission electron microscopy, atomic force microscopy, and scanning electron microscopy, respectively. An increase in the grafting ratio resulted in the enhanced miscibility of polyurethane and polyacrylate but reduced adhesion between particles and increased minimum film formation temperature. In addition, grafting was essential to obtain transparent WPUA films. Excessive grafting induced defects such as micropores within the film, leading to the decreased hardness and adhesive strength of the film. The optimal HEMA content for the preparation of a WPUA coating with excellent film-forming ability and high hardness in ambient conditions was noted to be 50%. The final WPUA film was prepared without coalescence agents that generate volatile organic compounds.

Maleic anhydride (MA) was grafted onto poly(lactic acid) (PLA) in the presence of styrene (St) by using a free-radical grafting methodology. The grafting degree (Dg) of MA was increased from 0.65 wt % to 1.1 wt % with the St/MA ratio up to 2/1, where the grafting efficiency (Eg) of MA was 27%. However, both Dg and Eg were decreased with further increasing of the St/MA ratio to 4/1. The Dg of MA increased with MA concentration and showed a maximum at 180 °C in the temperature range of 165 °C–190 °C. The grafting mechanisms of MA in the presence of St are analyzed based on titration, thermogravimetric analysis and infrared results, i.e., MA is grafted onto PLA chains via single monomers and a charge-transfer-complex (CTC) at St/MA ratios of ≤ 1/1, while dominantly via St-co-MA oligomers at St/MA ratios of around 2/1. Copolymerization rather than grafting of St and MA occurs at St/MA ratios of around 4/1. The thermal stability of PLA was compromised to a certain extent by the grafting of MA, resulting in reductions in the decomposition temperature (Td-5%) and molecular weight of the PLA. In addition, the crystallization and melting temperatures of the PLA were slightly reduced after the grafting.

The mechanical properties of composites are highly dependent on the interfacial interaction. In the present work, inspired by marine mussel, the adhesion between energetic crystals of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and polymer binders was improved. Three types of linear polymeric agents of glycidyl azide polymer (GAP), polyethylene glycol (PEG), and polytetramethylene ether glycol (PTMEG) were grafted onto TATB particles bridged through polydopamine (PDA) films. SEM images showed that 5% grafting contents could evidently form roughness shells on the surface. With a reinforcement at the interface produced by grafting shells, the mechanical properties of polymer-bonded explosives (PBXs) exhibited outstanding mechanical performance, especially for the PTMEG-grafting sample. Examined by the contact-angle test, the PTMEG-grafting sample possessed a value of polar component similar to that of fluoropolymer, leading to an excellent wettability of the two phases. Additionally, different contents of PTMEG were grafted to reveal that the mechanical properties could be improved even with content as little as 0.5 wt.% PTMEG. These results might highlight a correlation between interfacial interaction and macroscopic properties for mechanically energetic composites, while providing a versatile route of grafting on highly loaded composites.

The objective of this research was to verify the feasibility of the use of newly synthesized biopolymer materials for sizing cotton yarns based on the basic principles of chemical modification. Research included acid hydrolysis of potato starch up to controlled molar masses together with graft-polymerization and methacrylic acid onto hydrolyzed starch to improve hydrophilicity and solubility, to increase the capability of film forming, to increase adhesive potential and to avoid retrogradation phenomena. Research objectives were primarily focused on finding an appropriate, environmentally-friendly and productive sizing agent for cotton yarns via the analysis and systematization of a large number of synthesis methods in conjunction with the characterization and properties of graft-copolymers. The research results showed that potassium persulfate initiator was most efficient in grafting of methacrylic acid onto hydrolyzed starch, while azobisisobutyronitrile (AIBIN) initiator was most efficient in grafting of acrylic acid (AC). FTIR analysis confirmed that new and efficient products for sizing cotton yarns from synthetized potato starch were obtained. Research on rheological properties of copolymers shows a higher viscosity of grafted products indicating the good stability of potential starches. Ecological improvements have been established through high desizing degree as well as improvements in physical-mechanical properties of yarn, abrasion resistance and decrease in yarn surface hairiness were noticed. The use of new derivatives of potato starch, especially of hydrolyzed starch grafted with methacrylic acid (MAA), potassium persulfate (KPS) as initiator, was confirmed. Anova statistical analysis determined the influence of the entire sizing process on individual yarn parameters.

The goals of the paper were first the obtainment and characterization of sodium alginate-g-acrylamide polyelectrolytes by electron beam irradiation in the range of 0.5 to 2 kGy, and second, the evaluation of flocculation efficacy and heavy metal removal capacity from aqueous solutions of known concentrations. Based on sodium alginate concentration, two types of grafted polymers were obtained. Physical, chemical, and structural investigations were performed. Flocculation studies under different stirring conditions on 0.5, 0.1 and 0.2% kaolin suspension were done. The removal capacity of Cu2+ and Cr6+ ions was also investigated. The acrylamide grafting ratio on sodium alginate backbone was found up to 2000% for samples containing 1% sodium alginate and up to 500% for samples containing 2% sodium alginate. Transmittances between 98 and 100% were obtained using, in the flocculation studies, polyelectrolytes containing 2% sodium alginate in concentrations of 0.5 and 1 ppm on kaolin suspension of 0.1 wt %. The polymer concentration was found critical for kaolin suspension of 0.05 and 0.1 wt %. Polymers containing 1% sodium alginate were efficient in Cr6+ ion removal, while those containing 2% in Cu2+ ion removal.

Blend copolymers (PVA/S) were grafted with polyethylene glycol methyl methacrylate (PEGMA) with different ratios. Potassium persulfate was used as an initiator. The blend copolymer (PVA/S) was created by combining poly(vinyl alcohol) (PVA) with starch (S) in various ratios. The main idea was to study the effect of different ratios of the used raw materials on the biodegradability of plastic films. The resulting polymers (PVA/S/PEGMA) were analyzed using FTIR spectroscopy to investigate the hydrogen bond interaction between PVA, S, and PEGMA in the mixtures. TGA and SEM analyses were used to characterize the polymers (PVA/S/AA). The biodegradability and mechanical properties of the PVA/S/PEGMA blend films were evaluated. The findings revealed that the mechanical properties of the blend films are highly influenced by PEGMA. The time of degradation of the films immersed in soil and Coca-Cola increases as the contents of PVA and S and the molecular weight (MW) of PEGMA increase in the terpolymer. The M8 sample (PVA/S/PEGMA in the ratio of 3:1:2, respectively) with a MW of 950 g/mol produced the lowest elongation at break (67.5%), whereas M1 (PVA/S/PEGMA in the ratio of 1:1:1, respectively) with a MW of 300 g/mol produced the most (150%). The film's tensile strength and elongation at break were improved by grafting PEGMA onto the blending polymer (PAV-b-S). T g and T m increased when the PEGMA MW increased from 300 to 950. T g (48.4 °C) and T m (190.9 °C) were the lowest in M1 (300), while T g (84.8 °C) and T m (190.9 °C) were greatest in M1 (950) at 209.3 °C. The increased chain and molecular weight of PEGMA account for the increase in T g and T m of the copolymers.

Environmentally responsive poly(N-isopropylacrylamide) brushes were grafted from the surface of polymer particles or flat surfaces in order to generate reversible hydrophilic and hydrophobic surfaces. The use of atom transfer radical polymerization was demonstrated for the grafting of polymer brushes as it allows efficient control on the amount of grafted polymer. The polymer particles were generated with or without surfactant in the emulsion polymerization and their surface could be modified with the atom transfer radical polymerization (ATRP) initiator. The uniform functionalization of the surface with ATRP initiator was responsible for the uniform grafting of polymer brushes. The grafted brushes responded reversibly with changes in temperature indicating that the reversible responsive behavior could be translated to the particle surfaces. The particles were observed to adsorb and desorb protein and virus molecules by changing the temperatures below or higher than 32 °C. The initiator functionalized particles could also be adsorbed on the flat surfaces. The adsorption process also required optimization of the heat treatment conditions to form a uniform layer of the particles on the substrate. The grafted polymer brushes also responded to the changes in temperatures similar to the spherical particles studied through water droplets placed on the flat substrates.

Two different series of biobased polyethylene (BioPE) were used for the manufacturing of biocomposites, complemented with thermomechanical pulp (TMP) fibers. The intrinsic hydrophilic character of the TMP fibers was previously modified by grafting hydrophobic compounds (octyl gallate and lauryl gallate) by means of an enzymatic-assisted treatment. BioPE with low melt flow index (MFI) yielded filaments with low void fraction and relatively low thickness variation. The water absorption of the biocomposites was remarkably improved when the enzymatically-hydrophobized TMP fibers were used. Importantly, the 3D printing of BioPE was improved by adding 10% and 20% TMP fibers to the composition. Thus, 3D printable biocomposites with low water uptake can be manufactured by using fully biobased materials and environmentally-friendly processes.

Alkali-soluble resins (ASRs) are a type of electrosteric emulsifiers of high interest because they can profitably improve the features of waterborne dispersions. In this work, they have been synthesized in-situ through a one-pot approach and they have been used as polymeric surfactants for a second emulsion polymerization step in the same reactor. This strategy provides some advantages compared to other polymerization techniques, like the intensification of the process and the absence of organic solvents. Their use can also further reduce the environmental impact of formulations for film-forming applications, since grafting reactions with the particles have been observed and quantified in relation with the synthetic parameters. These chemical linkages with the particles may reduce the leaching and the release of surfactants from polymeric films, for example in water-based coatings or adhesives. The systems have been also studied from the kinetics point of view, finding relevant differences with other electrosterically stabilized processes from the literature, as well as concerns the nucleation mechanism.

As the only renewable resource among the four basic materials (steel, cement, plastic, wood), wood itself and wood products have a "low carbon" value and play an important role in storing carbon. The moisture absorption and expansion properties of wood limit its application scope and shorten its service life. To enhance the mechanical and physical properties of fast-growing poplars, an eco-friendly modification procedure has been used. This was accomplished by the in situ modification of wood cell walls by vacuum pressure impregnation with a reaction of water-soluble 2-hydroxyethyl methacrylate (HEMA) and N,N'-methylenebis(acrylamide) (MBA). The anti-swelling efficiency of HEMA/MBA-treated wood was improved (up to 61.13%), whereas HEMA/MBA-treated wood presented a lower weight-gain rate (WG) and water-absorption rate (WAR). It was observed that the modulus of elasticity, hardness, density, and other properties of modified wood had improved significantly, as indicated by XRD analysis. Modifiers diffuse primarily within cell walls and cell interstices of wood, causing crosslinks between the modifiers and the cell walls, reducing its hydroxyl content and blocking the channels for water movement, thereby enhancing its physical properties. This result can be obtained by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDX), Nitrogen adsorption test imaging ATR-FTIR (Attenuated total reflection-Fourier-Transform Infrared) Spectroscopy, and nuclear magnetic resonance (NMR) and Nitrogen adsorption test. Overall, this straightforward, high-performance modification method is crucial for maximizing wood's efficiency and the sustainable development of human society.

Chitosan is a polysaccharide extracted from animal sources such as crab and shrimp shells. In this work, chitosan films were modified by grafting them with a thermoresponsive polymer, poly(di(ethylene glycol) methyl ether methacrylate) (PMEO 2 MA). The films were modified to introduce functional groups useful as reversible addition-fragmentation chain transfer (RAFT) agents. PMEO 2 MA chains were then grown from the films via RAFT polymerization, making the chitosan films thermoresponsive. The degree of substitution of the chitosan-based RAFT agent and the amount of monomer added in the grafting reaction were varied to control the length of the grafted PMEO 2 MA chain segments. The chains were cleaved from the film substrates for characterization using 1 H NMR and a gel permeation chromatography analysis. Temperature-dependent contact angle measurements were used to demonstrate that the hydrophilic-hydrophobic nature of the film surface varied with temperature. Due to the enhanced hydrophobic character of PMEO 2 MA above its lower critical solution temperature (LCST), the ability of PMEO 2 MA-grafted chitosan films to serve as a substrate for cell growth at 37 °C (incubation temperature) was tested. Interactions with cells (fibroblasts, macrophages, and corneal epithelial cells) were assessed. The modified chitosan films supported cell viability and proliferation. As the temperature is lowered to 4 °C (refrigeration temperature, below the LCST), the grafted chitosan films become less hydrophobic, and cell adhesion should decrease, facilitating their removal from the surface. Our results indicated that the cells were detached from the films following a short incubation period at 4 °C, were viable, and retained their ability to proliferate.