Radiation-induced Graft Research Articles

Breaking of Supercooling of Water Using Silver Iodide Immobilized on Fiber Prepared by Radiation-induced Graft Polymerization

Breaking of Supercooling of Water Using Silver Iodide Immobilized on Fiber Prepared by Radiation-induced Graft Polymerization

PE/PP fibrous adsorbents with bifunctional groups of tertiary amine and phosphate prepared by electron beam induced co-grafting for heavy metal adsorption of both cationic and anionic forms in acidic conditions.

A novel fabric adsorbent having bifunctional groups of tertiary amine and phosphate was prepared by co-graft polymerization of 2-diethylaminoethyl methacrylate (NMA) and 2-hydroxyethyl methacrylate phosphate (PMA) onto a polyethylene/polypropylene nonwoven fabric (PE/PP NF) under low-energy electron beam acceleration. The process involved pre-irradiating the fabric and immersing it in the comonomer solution for grafting. The kinetics of radiation-induced graft polymerization at a total dose of 100 kGy was investigated. For pre-irradiation at 100 kGy, the optimum condition offering highest degree of grafting was at 12 wt% of NMA, 8 wt% of PMA and 4 h of reaction time. The adsorption of anions using hydrogen chromate (HCrO4−) or Cr(VI) and cations using lead (Pb(II)), cadmium (Cd(II)) and copper (Cu(II)) in aqueous solution was carried out. The results demonstrated that the bifunctional adsorbent was able to adsorb both heavy metal anionic and cationic ions from water. The co-grafted adsorbents with tertiary amine and phosphate were able to adsorb 85% Cr(VI) anion and 29% Pb(II) cations from mixed Cr(VI) and Pb(II) solution at pH 3.0 and 71% Pb(II), 13% Cd(II) and 31 % Cu(II) from mixed Pb(II), Cd(II) and Cu(II) solution at pH 5.0. The unique achievement of this study is its hypothesis that a bifunctional adsorbent can be prepared from radiation-induced graft polymerization of two different monomers onto NF, along with proof that the prepared bifunctional adsorbent can actually absorb both cationic or anionic heavy metals forms. Additionally, the adsorbent's preparation offers a rapid and straightforward one-step grafting technique. Therefore, the new bifunctional adsorbents can remove heavy metal ions in aqueous solution, either in the cation or anion form, thus offering highly promising applications in industrial wastewater treatment.

Gamma radiation induced optimized synthesis of amine functionalised poly-glycidyl methacrylate grafted poly-propylene non-woven fabric and its adsorption behaviour towards aqueous Pb(II)

Comprehensive optimization of the functionalization of polypropylene (PP) non-woven fabric through gamma irradiation-induced graft polymerization of glycidyl methacrylate (GMA), results in a material having high grafting yield. The technique, utilizing a mutual irradiation method, produced poly-GMA (PGMA) grafted PP fabric with a remarkable grafting yield of 125 % in a 1:1 acetone–water mixture, subjected to 25 kGy of total dose at a dose rate of 5 kGyh−1. The enhancement of the amination process utilizing PGMA-grafted PP was investigated with polyamines. Under the optimized conditions, the diethylene triamine (DETA) functionalized variant was identified as an effective adsorbent for aqueous Pb2+ ions. The optimized adsorbent exhibited a high saturation capacity of approximately 230 mgg−1 for Pb2+ ions, demonstrating rapid kinetics at near-neutral pH and 25 °C. This low cost innovative material holds significant promise for effective lead removal from drinking water and industrial wastewater, offering a sustainable economical solution for environmental remediation.

Effect of radiation-induced graft polymerization onto pineapple nonwoven fabric reinforced polymer composite

Natural fiber-reinforced polymer composites are gaining attention for their environmental benefits, such as biodegradability and reduced carbon footprint, as well as the potential of the natural fibers to replace or partially substitute synthetic fibers in various applications. However, challenges, such as poor interfacial adhesion and moisture absorption, limit the effectiveness of natural fibers, such as pineapple nonwoven fabric (PNWF) as reinforcement materials in polymer composites. To address these challenges, this study aims to enhance the properties of PNWF through glycidyl methacrylate grafting via radiation-induced graft polymerization. A 22 factorial design was employed to assess the effects of absorbed dosage and monomer concentration on the properties of the grafted PNWF. Infrared spectroscopy and electron microscopy analyses confirmed successful grafting. The grafted PNWF exhibited improved thermal stability and mechanical properties. The resulting composites showed significant enhancements in tensile and flexural strength, specifically, with tensile strength increase ranging from 23.32 to 34.49 MPa and flexural strength from 39.14 to 54.59 MPa. Additionally, the tensile modulus ranged from 0.77 to 1.29 GPa, while the flexural modulus varied from 1.17 to 2.06 GPa. These findings highlight the potential of PNWF grafted with polyglycidyl methacrylate (PNWF-g-PGMA) as an effective reinforcement material for various applications.

Superhydrophobic melamine sponge prepared by radiation-induced grafting technology for efficient oil–water separation

Superhydrophobic melamine sponge prepared by radiation-induced grafting technology for efficient oil–water separation

Engineered loose nanofiltration membrane for efficient dye/salt separation by starting from poly(ether sulfone) powder modification

Loose nanofiltration (LNF) is increasingly considered as the powerful technique for dye desalination due to its clear advantages at energy efficiency, selectivity and low pollution. But the membrane materials for loose nanofiltration process still suffer from the low permeance, unsatisfactory selectivity, membrane fouling and high cost. Herein, we propose a new three-step route to fabricate efficient poly(ether sulfone) (PES) LNF membrane, which starts from PES powder modification via mutual radiation-induced grafting polymerization and ensues immersion precipitation phase inversion and amination processes. The obtained PES-based LNF membrane possessed a thinner skin layer and an unusual irregular vesicular pore structure in sublayer instead of the finger-like macrovoids of conventional PES membrane. Thus, it achieved larger filtration permeance (35.5 L m–2 h−1 bar−1), high dye rejection (93.7 % to Congo Red) but low salt rejection (2.9 % to NaCl) during the filtration process of Congo red-containing saline water. It also showed excellent separation stability at high operation pressure and tolerance to acidic, alkaline and chlorine-oxidative conditions. Therefore, such a three-step strategy could endow the PES membrane with both loose and thinner skin layer in a reliable and scalable way, enlightening the development of high-performance LNF membrane for wastewater treatment and resource recovery.

Antimicrobial silver loading onto reused high-density polyethylene matrices grafted with poly(4-vinylpyridine)

High-density polyethylene HDPE is a highly polluting plastic, and its reuse, reprocessing and modification are subjects of current research to mitigate environmental pollution. In recent times, it has been modified for specialized purposes as a harmless and resistant polymer. The present work details the modification of HDPE (obtained from Bonafont, Coke, and Gatorade caps) with the monomer 4-vinylpyridine (4VP) via radiation-induced grafting copolymerization initiated by gamma rays from a Co-60 source and with the subsequent Ag(I) loading using the reagent AgNO3 in aqueous medium. Poly(4VP) is widely used to retain metals and manufacture pH-responsive polymers, while Ag(I) is a recognized bactericide harmless to humans at therapeutic concentrations; therefore, both poly4VP and Ag(I) can work in a synergistic system against pathologic bacteria as is here proposed. We advance a favorable antimicrobial activity of the Ag-loaded graft copolymers evaluated in vitro with Kirby-Bauer tests against Pseudomonas aeruginosa and Staphylococcus aureus. Additionally, FTIR-ATR, TGA, contact angle, swelling, and pH response were carried out to complete the characterization.

Current Status and Applications of Gamma Radiation-induced Graft Copolymerized Chitosan

Chitosan (CS) is a natural polymer obtained by removing acetyl groups from chitin through alkaline hydrolysis. It possesses biodegradable properties and exhibits immunological, antibacterial, and wound-healing activities. This polysaccharide has undergone modification through radiation-induced graft copolymerization to broaden its application scope. The potential applications of CS can be expanded by introducing side chains through grafting. This article aims to review the innovative alternatives of gamma-graft-copolymerized CS and, for the first time, comprehensively examines the current applications of CS derivatives in dye removal, metal adsorption, antibacterial interventions, biomedical practices, drug delivery systems, and tissue engineering.

Towards the preparation of sustainable superplasticizers for geopolymeric pastes via radiation-induced grafting of sulfonic group-bearing monomers onto corn starch

To address escalating environmental and sustainability concerns of petroleum-based superplasticizers (SPs), this work aims to develop sustainable and eco-friendly starch-based SPs using gamma radiation for maintaining the desired workability of geopolymeric pastes. Specifically, two green SPs were prepared from starch via radiation-induced grafting of two sulfonic group-bearing monomers, namely 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and 4-styrene sulfonic acid sodium salt (Na4SS). The grafting reaction was improved by initial modification of starch with glycidyl methacrylate to insert vinyl groups into the starch backbone. The modified starch samples were characterized by a variety of analytical techniques such as FTIR, 1H NMR, EDX, SLS, and viscometry. The prepared SPs exhibited high stability in aqueous 5 % NaOH. The effect of the prepared SPs on the fresh properties of GGBFS/MK geopolymer was studied using the mini slump test, zeta potential, adsorption capacity, and setting time. They significantly improved the paste flowability and dispersion compared to the control. Notably, the aromatic Na4SS-grafted starch displayed a comparable enhancement to the commercial PNS, while outperforming the aliphatic AMPS-grafted sample. This emphasizes the potential of these green SPs to address the challenges posed by the petroleum-based SPs and maximize the benefit of using starch as a green renewable resource.

Radiation-Induced Grafting of Styrene onto Polyvinylfluoride (PVF) Films: Impact of Grafting Conditions on Grafted Film Properties

Radiation-Induced Grafting of Styrene onto Polyvinylfluoride (PVF) Films: Impact of Grafting Conditions on Grafted Film Properties

Radiation-induced grafting of polyethyleneimine onto cellulose triacetate membrane for separation of cesium ions from aqueous solution

Radiation grafting of polyethyleneimine (PEI) onto the surface of cellulose triacetate (CTA) membrane was successfully performed. Pre-radiation and co-radiation were applied by gamma rays at the dose of 12 kGy. FT-IR, SEM, XPS, contact angle, zeta-potential, grafting ratio, etc. Were used to characterize the PEI-CTA membranes before and after grafting. The FT-IR spectrum showed that a notable discernible shoulder peak of N–H appeared for amide at co-radiation and pre-radiation, and XPS analysis indicated that co-radiation achieved the highest N percent of 9.75%, suggesting that PEI was introduced into the membrane surface. In a forward osmosis (FO) process, the PEI-CTA membrane obtained higher cesium, Cs(I), retention (95–97%) than the CTA membrane with Cs(I) retention of 92%. Cs(I) fluxes significantly decreased from 0.09 to 0.02–0.03 mmol m−2h−1 after PEI modification. Effective Cs(I) retention was attributed to increase of the positive charges on CTA membrane when PEI was added, which exerted a repulsive effect on Cs(I), preventing them from moving towards the membrane direction. In the FO process, the PEI-CTA membrane featured the water flux of 23 L m−2 h−1 a little lower than that of CTA membrane (24 L m−2 h−1). Although modified PEI increased the hydrophilicity, the increase of water flux did not occur with the co-irradiated membrane, which was related to the high graft, higher thickness and resistance of the membrane.

Radiation-induced graft copolymerization of a phosphonate monomer onto short flax fibers and Miscanthus x giganteus stem fragments: Influence of substrate composition

The functionalization of Miscanthus x giganteus stems fragments (R-MSF) by dimethyl(methacryloyloxy)methyl phosphonate (MAPC1) using pre-irradiation was studied. The influence of the composition and the structure of the substrate on the grafting efficiency was investigated by comparing the results with short flax fibers (SFF) and bleached Miscanthus x giganteus stems fragments (B-MSF). The lignocellulosic substrates were irradiated at several target doses ranging from 11 to 108.1 kGy using e-Beam. Electron Paramagnetic Resonance spectroscopy (EPR) highlighted major differences in terms of radical nature between R-MSF, SFF, and B-MSF samples. Following the polymerization reactions, washing, and drying steps, the phosphorus contents were measured by X-ray fluorescence spectrometry (XRF). Unlike Flax, pre-irradiation grafting was not efficient on R-MSF. The role of lignin content on grafting reactions was then evaluated by comparing R-MSF with SFFand B-MSF), showing only a minor impact. Using a reducing agent, it was possible to reach a phosphorus content of about 1.4 wt% for R-MSF and up to 4.0 wt% for B-MSF for a 100 kGy dose. Furthermore, phosphorus mapping using scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDX) highlighted a homogeneous dispersion of the grafted macromolecules. This demonstrates the possibility of conducting pre-irradiation grafting on lignin-rich substrates without bleaching. Efforts were then made to optimize the operating conditions in terms of storage temperature, reaction temperature and Fe2+ concentration. Finally, the fire behavior of treated Miscanthus x giganteus stem fragments was evaluated by pyrolysis-combustion flow calorimetry (PCFC).

Porous Microspheres as Pathogen Traps for Sepsis Therapy: Capturing Active Pathogens and Alleviating Inflammatory Reactions.

Sepsis is a systemic inflammatory response syndrome caused by pathogen infection, while the current antibiotics mainly utilized in clinical practice to combat infection result in the release of pathogen-associated molecular patterns (PAMPs) in the body. Herein, we provide an innovative strategy for controlling sepsis, namely, capturing active pathogens by means of extracorporeal blood purification. Carbon nanotubes (CNTs) were modified with dimethyldiallylammonium chloride (DDA) through γ-ray irradiation-induced graft polymerization to confer a positive charge. Then, CNT-DDAs are blended with polyurethane (PU) to prepare porous microspheres using the electro-spraying method. The obtained microspheres with a pore diameter of 2 μm served as pathogen traps and are termed as PU-CNT-DDA microspheres. Even at a high flow rate of 50 mL·min-1, the capture efficiencies of the PU-CNT-DDAs for Escherichia coli and Staphylococcus aureus remained 94.7% and 98.8%, respectively. This approach circumvents pathogen lysis and mortality, significantly curtails the release of PAMPs, and hampers the production of pro-inflammatory cytokines. Therefore, hemoperfusion using porous PU-CNT-DDAs as pathogen traps to capture active pathogens and alleviate inflammation opens a new route for sepsis therapy.

Gamma radiation-induced grafting of poly(butyl acrylate) onto ethylene vinyl acetate copolymer for improved crude oil flowability

Ethylene vinyl acetate (EVA) copolymers are widely employed as pour point depressants to enhance the flow properties of crude oil. However, EVA copolymers have limitations that necessitate their development. This work investigated the modification of EVA via gamma radiation-induced grafting of butyl acrylate (BuA) monomers and the evaluation of grafted EVA as a pour point depressant for crude oil. The successful grafting of poly(butyl acrylate) p(BuA) onto EVA was verified through grafting parameters, FTIR spectroscopy, and 1H NMR spectroscopy. Treating crude oil with 3000 ppm of (EVA)0kGy, (EVA)50kGy, and (1EVA:3BuA)50kGy yielded substantial reductions in pour point of 24, 21, and 21 °C, respectively. Also, rheological characterization demonstrated improving evidenced by a viscosity reduction of 76.20%, 67.70%, and 71.94% at 25 °C, and 83.16%, 74.98%, and 81.53% at 12 °C. At low dosages of 1000 ppm, the EVA-g-p(BuA) exhibited superior pour point reductions compared to unmodified EVA, highlighting the benefit of incorporating p(BuA) side chains. The grafted EVA copolymers with p(BuA) side chains showed excellent potential as crude oil flow improvers by promoting more effective adsorption and co-crystallization with paraffin wax molecules.

Gamma radiation-induced grafting of C5 aliphatic petroleum resin onto ethylene-co-vinyl acetate copolymer for improving crude oil flowability

At present, ethylene-co-vinyl acetate (EVA) copolymers are the predominant choice among pour point depressants (PPDS) for enhancing the flowability of waxy crude oil. Still, they have shortcomings. Thus, this work aims to investigate the irradiation modification of a commercial EVA copolymer using C5 aliphatic petroleum resin (C5 PR) and its potential for utilization as a flow improver for crude oil. Results conclusively demonstrate the successful grafting of (C5 PR) onto EVA copolymer through gamma radiation, confirmed via grafting parameter characterization, FTIR, and 1H NMR spectroscopy. This modification significantly improved pour point results (ΔPPD = 24, 21, and 24 °C) for (EVA)0kGy, (EVA)50kGy, and (1EVA:1C5 PR)50kGy when treated with 3000 ppm of additives. Notably, the grafted EVA copolymers with C5 PR (1EVA:1C5 PR)50kGy outperformed non-modified EVA at a lower dosage of 1000 ppm. Also, irradiating EVA copolymer without insertion C5 PR resulted in EVA copolymer crosslinking, leading to a decrease in efficiency that could attributed to its accumulation. Furthermore, the crude oil’s rheological properties were substantially enhanced, evidenced by viscosity reductions of 60.8%, 51.3%, and 64.1% at 25 °C, and 55.2%, 18.7%, and 59.4% at 12 °C with the addition of 1000 ppm. Increasing the dosage to 3000 ppm led to even more remarkable viscosity decreases: 76.2%, 67.7%, and 78.2% at 25 °C, and 83.2%, 74.9%, and 84.7% at 12 °C for (EVA)0kGy, (EVA)50kGy, and (1EVA:1C5 PR)50kGy, respectively.

Preparation of xyloglucan-grafted poly(N-hydroxyethyl acrylamide) copolymer by free-radical polymerization for in vitro evaluation of human dermal fibroblasts

Xyloglucan is a rigid polysaccharide that belongs to the carbohydrate family. This hemicellulose compound has been widely used in biomedical research because of its pseudoplastic, mucoadhesive, mucomimetic, and biocompatibility properties. Xyloglucan is a polyose with no amino groups in its structure, which also limits its range of applications. It is still unknown whether grafting hydrophilic monomers onto xyloglucan can produce derivatives that overcome these shortcomings. This work aimed to prepare the first copolymers in which N-hydroxyethyl acrylamide is grafted onto tamarind xyloglucan by free-radical polymerization. The biocompatibility of these structures in vitro was evaluated using human dermal fibroblasts. Gamma radiation-induced graft polymerization was employed as an initiator by varying the radiation dose from 5–25 kGy. The structure of the graft copolymer, Xy-g-poly(N-hydroxyethyl acrylamide), was verified by thermal analysis, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The findings indicate that the degree of grafting and the cytotoxicity/viability of the xyloglucan-based copolymer were independent of dose. Notably, the grafted galactoxyloglucan exhibited efficient support for human dermal fibroblasts, showing heightened proliferative capacity and superior migration capabilities compared to the unmodified polymer. This copolymer might have the potential to be used in skin tissue engineering.

Flame Retardancy of Short Flax Fibers Modified by Radiation-Induced Grafting of Phosphonated Monomers: Comparison between Pre- and Simultaneous Irradiation Grafting.

Short flax fibers have been modified by radiation-induced grafting using methacrylate monomers containing phosphorus to give them a flame-retardant character. Two methodologies, namely pre-irradiation and simultaneous irradiation grafting, were examined. Certain parameters, notably the dose and the irradiation source (e-Beam and γ rays), were evaluated. The grafting efficiency, in terms of phosphorus content (mass percentage), was measured by X-ray fluorescence spectrometry (XRF). Using simultaneous irradiation, 2.39 wt% phosphorus could be obtained from 10 kGy, compared to 100 kGy in pre-irradiation. Furthermore, for similar phosphorus levels, the location of the grafted polymer chains was different for the two methodologies. The effect of phosphorus content on thermal properties and fire behavior was evaluated on a microscopic scale using a pyrolytic flow combustion calorimeter (PCFC) and on a laboratory scale using a cone calorimeter. It was then pointed out that flammability was linked to the phosphorus content and likely its location, which is associated with the radiation-induced grafting methodology, showing that the grafting conditions influence the final fire properties. Simultaneous irradiation, thus, proved to be more interesting in terms of efficiency and final properties.

Lignocellulosic Membranes Grafted with N-Vinylcaprolactam Using Radiation Chemistry: Load and Release Capacity of Vancomycin.

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.

Drug delivery in thermo-responsive silicone catheters by grafting of N-vinylcaprolactam using gamma radiation

Radiation-induced graft polymerization of poly(N-vinylcaprolactam) onto silicone catheters by direct irradiation method was studied. The effects of the irradiation dose, as well as the monomer concentration, on the grafting efficiency were studied. The conditions for achieving maximum grafting yield were observed at 30% of monomer concentration in toluene at 50 kGy. The graft polymerization was examined by different characterization methods, including measurements such as thermogravimetric analysis, infrared, water contact angle, and swelling. The temperature-responsive behavior of smart grafted copolymer was studied by swelling at different temperatures. Differently from pristine silicone catheter, the N-vinylcaprolactam-grafted catheters were able to load vancomycin and sustain the release for 30 h.Graphical abstract

GFN-xTB-Based Computations Provide Comprehensive Insights into Emulsion Radiation-Induced Graft Polymerization.

Invited for this month's cover are the collaborating groups of Dr. Ryohei Kakuchi and Ms. Kiho Matsubara at Gunma University, Japan, Prof. Kei Takahashi at Fukuoka Institute of Technology and The Institute of Statistical Mathematics, Japan, Prof. Takeshi Matsuda at Hannan University, Japan, Dr. Noriaki Seko and Dr. Yuji Ueki at National Institutes for Quantum Science and Technology, Japan. The cover picture shows the machine learning-based optimization and interpretation of radiation-induced graft polymerizations under emulsion conditions based on realistic information for monomers calculated by the state-of-the-art semiempirical method. More information can be found in the Research Article by Kiho Matsubara, Kei Takahashi, Ryohei Kakuchi, and co-workers.