Graft Copolymers Research Articles

Redox-Sensitive Delivery of Doxorubicin from Nanoparticles of Poly(ethylene glycol)-Chitosan Copolymer for Treatment of Drug-Resistant Oral Cancer Cells.

Reactive oxygen species (ROS)-sensitive polymer nanoparticles were synthesized for tumor targeting of an anticancer drug, doxorubicin (DOX). For this purpose, chitosan-methoxy poly(ethylene glycol) (mPEG) (ChitoPEG)-graft copolymer was synthesized and then DOX was conjugated to the backbone of chitosan using a thioketal linker. Subsequently, the chemical structure of the DOX-conjugated ChitoPEG copolymer (ChitoPEGthDOX) was confirmed via 1H nuclear magnetic resonance (NMR) spectra. Nanoparticles of the ChitoPEGthDOX conjugates have spherical shapes and a size of approximately 100 nm. Transmission electron microscopy (TEM) has shown that ChitoPEGthDOX nanoparticles disintegrate in the presence of hydrogen peroxide and the particle size distribution also changes from a monomodal/narrow distribution pattern to a multi-modal/wide distribution pattern. Furthermore, DOX is released faster in the presence of hydrogen peroxide. These results indicated that ChitoPEGthDOX nanoparticles have ROS sensitivity. The anticancer activity of the nanoparticles was evaluated using AT84 oral squamous carcinoma cells. Moreover, DOX-resistant AT84 cells were prepared in vitro. DOX and its nanoparticles showed dose-dependent cytotoxicity in both DOX-sensitive and DOX-resistant AT84 cells in vitro. However, DOX itself showed reduced cytotoxicity against DOX-resistant AT84 cells, while the nanoparticles showed almost similar cytotoxicity to DOX-sensitive and DOX-resistant AT84 cells. This result may be due to the inhibition of intracellular delivery of free DOX, while nanoparticles were efficiently internalized in DOX-resistant cells. The in vivo study of a DOX-resistant AT84 cell-bearing tumor xenograft model showed that nanoparticles have higher antitumor efficacy than those found in free DOX treatment. These results may be related to the efficient accumulation of nanoparticles in the tumor tissue, i.e., the fluorescence intensity in the tumor tissue was stronger than that of any other organs. Our findings suggest that ChitoPEGthDOX nanoparticles may be a promising candidate for ROS-sensitive anticancer delivery against DOX-resistant oral cancer cells.

Preparation, characterization and swelling studies of bio-waste-derived absorbent hydrogels

A class of polymeric materials known as “hydrogel products” have a hydrophobic structure that enables them to hold significant volumes of water in their three-dimensional networks. It is thought that it is of utmost importance that they can be used extensively in a variety of industrial, biomedical and environmental applications. In this view, I have synthesized a uniuqe hydrogel made from cellulose extracted from banana pseudostem (BPC). This hydrogel exhibits superabsorbent properties. The synthesis was achieved by free-radical graft copolymerization of poly 2-(acryloyloxy) ethyl trimethylammonium chloride copolymer N,N-dimethylacrylamide (AETAC- co-DMA) onto a BPC backbone using ammonium persulfate as the initiator and methylene bisacrylamide as the cross-linking agent. The graft copolymer was studied using FT-IR spectroscopy to confirm its structure. It was further characterized by field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis (TGA) to determine its morphological and thermal properties, respectively. The Effect of various parameters of free-radical graft copolymerization on the swelling behavior of the hydrogel was studied and the optimized copolymer was used to conduct pH and salt sensitivity tests on the hydrogel. The maximum water uptake of the hydrogel was found to be 427 g/g under optimum conditions of initiator, monomer and cross-linker concentrations of 0.0657 mol/L, 1.6 mol and 0.0972 mol/L correspondingly. The hydrogel was found to be pH and salt-sensitive and the salt uptake followed the order KCl>NaCl>CaCl>FeCl3. The excellent water absorbency, pH and salt responsiveness of the prepared hydrogel suggest its applicability not only in agriculture and wastewater treatment, but also in biomedicine for the controlled release of drugs.

The synthesis of multifunctional cellulose graft alternating copolymers of 3,4-dihydrocoumarin and epoxides in DBU/DMSO/CO2 solvent system

Cellulose graft copolymers having well-defined structures could incorporate the characteristics of both the cellulose skeleton and side chains, providing a new method for the preparation functionalised cellulose derivatives. Herein, a series of multifunctional cellulose grafted, alternating 3,4-dihydrocoumarin (DHC) and epoxide (EPO) copolymers (cell-g-P(DHC-alt-EPO)) were prepared in a metal-free DBU/DMSO/CO2 solvent system without adding additional catalyst. Four examples of cell-g-P(DHC-alt-EPO) with tunable thermal and optical properties were synthesized by copolymerization of DHC with styrene oxide (SO), propylene oxide (PO), cyclohexene oxide (CHO) or furfuryl glycidyl ether (FGE) onto cellulose. The nonconjugated cell-g-P(DHC-alt-EPO) showed UV absorption properties with the maximum absorption peak at 282 nm and 295 nm and photoluminescence performance. A clustering-triggered emission mechanism was confirmed and consistent with DFT theoretical calculations. In DMSO solution, the copolymer (DHCSO5) with DP of 11.64 showed ACQ behaviour as the concentration increased. In addition, DHCSO5 had good antioxidant capacity with an instantaneous radical scavenging activity of 2,2-diphenyl-1-picrylhydrazine (DPPH) up to 65 % at a concentration of 40 mg/ ml and increased to 100 % after 30 min. Thus, the multifunctional cell-g-P(DHC-alt-EPO) materials had a variety of potential applications in the fields of fluorescent printing, bio-imaging, UV- shielding and antioxidants.

Preparation and characterization of biocomposite from modified α-cellulose of Agave cantala leaf fiber by graft copolymerization with 2‑hydroxy ethyl methacrylate

In this study a prominent technique namely grafting of 2‑hydroxy ethyl methacrylate (known as HEMA) monomer onto modified bleached Agave cantala leaf fibers (ACLF) to fabricate bio-composite by using K2S2O8/FeSO4 as a redox initiator in aqueous media to develop mechanical tensile strength and also for sustainable environmental performances. Various investigated parameters like reaction time, monomer concentration, initiator concentration, grafting temperature have been optimized successfully to obtain maximum grafting yield. Noteworthy that the grafting percentage onto modified fibres has shown an increasing tendency while monomer concentration increases from (0.084–0.82)Mol/L and initiator concentration from (0.005–0.0074)Mol/L and thereafter it started to decrease. Meanwhile, the rate of reaction actually depends upon the reaction time and temperature. Whereas maximum graft yield was obtained exactly at 70 °C within 2 h in addition the obtained values were around 87.25% and 95.79% respectively. The modified and grafted polymeric samples were characterized by FTIR spectroscopy, SEM analysis and TGA techniques. The effect of external influences such as temperature, exposure to sunlight and biodegradability in sewage water on raw, modified fibers and HEMA-g-ACLF composites were also studied. The tensile properties and water resistance characteristics of grafted products were far better than that of extracted raw and modified α-cellulosic fibers.

Tailored PVDF Graft Copolymers via ATRP as High-Performance NCM811 Cathode Binders.

High-nickel layered oxides, e.g., LiNi0.8Co0.1Mn0.1O2 (NCM811), are promising candidates for cathode materials in high-energy-density lithium-ion batteries (LIBs). Complementing the notable developments of modification of active materials, this study focused on the polymer binder materials, and a new synthetic route was developed to engineer PVDF binders by covalently grafting copolymers from poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) with multiple functionalities using atom transfer radical polymerization (ATRP). The grafted random copolymer binder provided excellent flexibility (319% elongation), adhesion strength (50 times higher than PVDF), transition metal chelation capability, and efficient ionic conductivity pathways. The NCM811 half-cells using the designed binders exhibited a remarkable rate capability of 143.4 mA h g-1 at 4C and cycling stability with 70.1% capacity retention after 230 cycles at 0.5 C, which is much higher than the 52.3% capacity retention of nonmodified PVDF. The well-retained structure of NCM811 with the designed binder was systematically studied and confirmed by post-mortem analysis.

Effects of different modifying agents on the preparation and properties of coagulants derived from excess sludge.

The contents and kinds of oxygen-containing functional groups are very significant when preparing cationic hydrochar coagulants via graft copolymerization. Herein, the hydrothermal conditions to produce sludge-based hydrochar (SBC) precursors were optimized by introducing different kinds and amounts of modifying agents (i.e., HCOOH, citric acid (CA), H2SO4, and H2O2), then the surface properties and flocculation performance of derived cationic coagulants (SBC-g-DMC) were studied. Results showed that the utilization of four modifiers raised the acidic groups on the SBC surface; thereinto, the presence of CA could evidently increase the content of phenolic hydroxyl groups. After DMC monomer grafting, the formed coagulants possess positive zeta potentials over a wide pH range (i.e., 3.0 ~ 11.0), showing a typical cationic property. The grafting ratio and efficiency, as well as the cationic degree of coagulants prepared with different SBC precursors follow a descending order of SBCCA-g-DMC > [Formula: see text]-g-DMC > SBCHCOOH-g-DMC > [Formula: see text]-g-DMC; thus, SBCCA-g-DMC coagulant with the best grafting result shows a superior flocculation performance. When a dosage of 4mg/L was adopted, the average turbidity removal rate of SBCCA-g-DMC could reach up to 94.44%. Meanwhile, due to the possible and robust oxidation with the initiator, H2O2 seems not a perfect modifier for SBC preparation. This study could provide an essential reference for the optimal synthesis of SBC and its based coagulants for organic matter recovery and pollutant removal.

Cellulose-supported bioadsorbent from natural hemp fiber for removal of anionic dyes from aqueous solution

The aim of this study is to prepare an eco-friendly bioadsorbent by graft copolymerization and modification from hemp fiber including bio-macromolecules such as cellulose, hemicellulose and lignin for anionic dyes adsorption from aqueous solutions, and to investigate adsorptive properties. The prepared cellulose-supported bioadsorbent (TEPA-(GMA-g-HF)) was characterized in detail using SEM-EDX, STEM, FTIR, XRD, TGA and BET techniques and calculating the point of zero charge. It was used as an adsorbent to remove three different anionic dyes, Remazol Brilliant Blue R (RBBR), Reactive Red 120 (RR120) and Reactive yellow 160 (RY160) from the aqueous medium. The effects of adsorbent amount, pH, initial dye concentration, time and temperature on the adsorption were investigated. From the results, it was determined that the adsorption of all three dyes to the developed fibrous bioadsorbent was more compatible with the pseudo-second-order kinetic and the Langmuir isotherm model. It was found that the adsorption capacity increased with increasing temperature, and the adsorption capacity at 298 K was 91.70 mg/g for RBBR, 83.33 for RY160 and 76.34 mg/g for RR120, respectively. Dye removal efficiencies were provided as approximately 100 % at acidic pHs. This high removal efficiency has also achieved in the dense matrix medium, and even after five consecutive reused.

Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

Self-Assembled Graft Copolymer Nanofibers with an Adjustable Internal and External Structure

Influence of side chain lengths in mechanophore‐containing polyisobutylene‐graft‐polystyrene

AbstractPolymer architecture plays an important role in morphology and mechanochemical response. Here, graft copolymers containing mechanophores at the backbone‐arm junction are synthesized through a combination of post‐polymerization modification of butyl rubber and controlled radical polymerization. A series of graft copolymers with 70:30 or 50:50 polyisobutylene:polystyrene (PIB:PS) volume fractions were synthesized by changing the grafting density and arm length to keep the volume fractions constant. The morphologies for these polymers are disordered but show a decreasing domain size with shorter arm lengths, and the samples with a greater number of PS side chains show greater domain mixing. Using pulsed ultrasound experiments, we found greater backbone scission occurs for polymers with a greater number of short grafts per chain than the long grafts with fewer grafting points. Finally, mechanophore activation is greater for samples with arm molecular weights ≥13 kg/mol, attributed to exceeding the cutoff molecular weight for PS.

Radiation-Induced Graft Copolymerization of Methacrylonitrile onto Poly (Tetrafluoroethylene-co-ethylene) Film by Discontinuous Method

An attempt has been made to graft copolymerize the vinyl monomer methacrylonitrile onto poly tetrafluoroethylene-co-ethylene, known as Tefzel film, by the double-irradiation method in aqueous medium. Optimum conditions for attaining the maximum percentage of grafting were evaluated. The maximum percentage of grafting for methacrylonitrile was obtained 128.7 % at an optimum dose of 24.9 kGy using 2.98 mol L-1 of methacrylonitrile. Investigations on the effects of different chain-length aliphatic alcohols, methanol, ethanol, n-butanol, cyclohexanol and amyl alcohol on the grafting percentages of methacrylonitrile have been performed. Characterization of Tefzel and grafted Tefzel films have been performed by infrared spectroscopy and Thermogravimetric Analysis. Methacrylonitrile grafted Tefzel films showed better thermal stability.

Effects of salicylic acid-grafted bamboo hemicellulose on gray mold control in blueberry fruit: The phenylpropanoid pathway and peel microbial community composition

Bamboo hemicellulose (HC) is a natural plant polysaccharide with good biocompatibility and biodegradability. But its poor antibacterial activity limits its application in fruits preservation. In this study, based on the good inducer of salicylic acid (SA) for plant diseases resistance, a novel antibacterial coating material was synthesized by grafting SA onto HC. The study aimed to investigate the synergistic effect of HC-g-SA on antibacterial ability, induces diseases resistance and microbial community composition of postharvest fruit. The graft copolymer treatment significantly reduced the incidence of gray mold caused by Botrytis cinerea in blueberries during storage (P < 0.05), and significantly stimulated the activity of key enzymes, including phenylalanine ammonia-lyase, chalcone isomerase, laccase, and polyphenol oxidase, leading to an increase in fungicidal compounds such as flavonoids, lignin, and total phenolics produced by the phenylpropanoid pathway in blueberries (P < 0.05). Moreover, the HC-g-SA coating altered bacterial and fungal community composition such that the abundance of postharvest fruit-peel pathogens was significantly reduced. After 8 days storage, the blueberry fruits treated by HC-g-SA had a weight loss rate of 12.42 ± 0.85 %. Therefore, the HC-g-SA graft copolymer had a positive impact on the control of gray mold in blueberry fruit during postharvest storage.

MORPHOLOGICAL AND THERMAL PROPERTIES OF BIODEGRADABLE GRAFT COPOLYMER LLDPE-G-MA/GEL COMPOSITES

In this work, a biodegradable graft copolymer based on linear low density polyethylene grafted maleic anhydride and gelatin (LLDPE-g-MA/Gel) was formed by reactive mixing of functionalized polyethylene with gelatin to achieve finely dispersed blend morphology. Using a selection of components of the mixture, we’d studied its morphology and thermal properties. It was found that thermal stability (initial temperature) of the composition decreases as the amount of gelatin increases due to degradation of gelatin. In the temperature range of 400-500 ºC, the maximum rate of destruction of the graft copolymer increases significantly with higher gelatin content. Samples having identical composition were selected using a Brabender plastograph and a mechanical mixer; and when taken at different rates, the morphological structure of the samples was determined to depend on their mixing rate. The morphological structure was found to show that increased speed leads to effective reaction of two components and crushing of particles into smaller ones.

Fabrication of PLGA Nanoparticles Using Combination of PCL-PVA-PEG Copolymer as Surfactant: In-Vitro Characterization and Cytotoxicity Study

Objective: The present study aimed to fabricate Poly lactic acid co-glycolic acid (PLGA) nanoparticles loaded with resveratrol using a novel graft co-polymer surfactant named Soluplus®. Methods: The PLGA nanoparticles were prepared in the present study using polyvinyl caprolactam polyvinyl acetate polyethylene glycol amphiphilic graft copolymer named Soluplus® as surfactant through double emulsification and single emulsification-solvent evaporation method. The formulations were prepared successfully to encapsulate the drug resveratrol, and then evaluated for their particle size, polydispersity index, zeta potential, drug loading and the degree of entrapment of the drug. A scanning electron microscope was used to examine the morphology of the nanoparticles. In vitro drug release was assessed and, mathematical pharmacokinetic modelling was done to assess the release pattern. A comparative cytotoxicity study between free drug and prepared nanoparticles using MTT assay was carried out for cell viability evaluation. Uptake and internalization of nanoparticles were also studied using confocal fluorescence microscopy. Results: The results demonstrated successful fabrication of the PLGA nanoparticles using the Soluplus as polymer surfactant. The drug, polymer and the all the excipients were found to be compatible and did not indicate any interaction. The results also indicated the prepared nanoparticles (SF2) as suitable resveratrol delivery vehicle in terms of the compliant particle size (344.6 ±6.63 nm), polydispersity index (0.962), zeta potential (- 18.5±1.21), drug loading (18.94± 0.27%), the entrapment efficiency (39.62±0.17%) and drug release (75.13±0.17%). The shape and surface morphology of the formulated nanoparticles were found to be spherical and smooth. Cytotoxicity study also demonstrated significant reduction of cell viability by the nanoparticle compared to free resveratrol. The highest cytotoxicity of SF2 against MCF7 cell was found in 2000 nM concentration with 3.03±0.05 percent of cell viability. It was found that the percentage of growth inhibition was increasing with increasing concentration of SF2 and IC50 value of this assay was 108.94 μg/ml. Conclusion: It has been found that the Resveratrol loaded PLGA nanoparticles were successfully formulated and found to perform better in terms of efficacy and cytotoxicity.

Ascorbic acid-loaded gellan-g-poly(ethylene glycol) methacrylate matrix as a wound-healing material

Ascorbic acid (AA) is one of the important biomolecules involved in all phases of wound healing. The aim of this study was to develop a new hydrogel system that offers topical delivery of ascorbic acid to wounds during wound care management. In this work, we grafted poly (ethylene glycol) methacrylate onto a renewable biopolymer gellan, and the graft copolymer (GPMA) formed was crosslinked covalently and ionically, and used as a matrix for delivering AA to the wounds. By the processes of grafting and crosslinking, the mechanical properties of the gellan increased several fold compared to mechanically weak native gellan. In vitro cytotoxicity evaluation showed that GPMA was non-cytotoxic to fibroblast cells. GPMA hydrogel matrix allowed the sustained release of AA. When AA was incorporated in GPMA, a significant improvement in wound closure was observed in scratch wound assay performed with keratinocytes. Since AA acts as a cofactor in collagen synthesis, the controlled delivery of AA to the wound microenvironment favors the up-regulation of colα1 gene expression. This study revealed that ascorbic acid, at a concentration of 150 μM, has a favorable impact on wound healing when tested in vitro. Overall results indicate that the GPMA matrix could be a promising material for wound healing applications.

Green Synthesized Silver Nanoparticles Loaded in Polysaccharide Hydrogel Applied to Chronic Wound Healing in Mice Models.

The prevalence of chronic wounds is increasing owing to the expanding population and the growing number of individuals suffering from diabetes. Such a chronic wound continues to be a significant healthcare burden for diabetic patients because it frequently carries a high chance of limb loss due to amputation and reduces survival as a result. Development of innovative wound dressing materials with the potential to stop bacterial infections and accelerate the process of tissue regeneration is needed to increase the effectiveness of diabetic wound healing. In the current study, a co-polymerization process based on a free radical reaction was used to create a hydrogel of polysaccharides blend graft acrylamide (PsB-g-Am). Starch, chitosan, and alginate make up the polysaccharides blend (PsB). The produced hydrogel's structure was characterized using FTIR spectroscopy. The antibacterial activities of silver nanoparticles synthesized through the green method using garlic bulb (Allium sativum) is reported. The silver nanoparticles' physical characteristics were examined using scanning electron microscopy, transmission electron microscopy analysis, and UV-visible spectroscopy and they were found to range in size from 50 to 100 nm. The agar well diffusion technique is used to investigate the antibacterial characteristics. Inclusion of silver nanoparticles in the hydrogels demonstrated concentration-dependent antibacterial behavior against Gram-negative Klebsiella pneumoniae and Gram-positive Staphylococcus aureus during antimicrobial testing of the hydrogels. When hydrogels were applied to diabetic mice, the system was examined for its healing abilities, and positive therapeutic results were obtained in as little as 14 days. Thus, it can be inferred that graft copolymer of chitosan-AgNPs hydrogels can promote healing in chronic wounds over time and can be utilized as an alternative to conventional therapies for chronic wounds (such as those brought on by diabetes) in mouse models.

Nanoparticles and polymers complexes as a harmless shale plugging inhibitor for ocean water-based drilling fluids

Due to the stringent environmental regulations that have been gradually proposed, the additives of WBDFs with low toxicity and degradability have become crucial. Clays and nano-micron fractures are the main causes of wellbore instability in ocean shale formations. In this paper, the plugging inhibitor was designed based on the skeletal structure of molecule, functional groups and molecular weight. Then the silane coupling agent was used to modify silica nanoparticles. And further the ZY-1 as a harmless plugging inhibitor was created by graft copolymerization of transition product and AA-AAK. These evaluation results demonstrated that ZY-1 not only was nontoxic and biodegradable, but also displayed a decent thermal stability (150 °C) and plugging inhibitive performance. What's more, this paper proposed the underlying inhibition and plugging mechanisms based on the structure and function of ZY-1.

Synthesis and characterization of lignin-graft-polyacrylamide copolymers: effect of type and concentration of initiator and co-initiator, monomer concentration, and reaction temperature and time on efficiency of graft copolymerization

Synthesis and characterization of lignin-graft-polyacrylamide copolymers: effect of type and concentration of initiator and co-initiator, monomer concentration, and reaction temperature and time on efficiency of graft copolymerization

Design and development of pH-responsive alginate-based nanogel carriers for etoposide delivery

Recently, pH-responsive nanogels are playing progressively important roles in cancer treatment. The present study focuses on designing and developing pH-responsive alginate-based nanogels to achieve a controlled release of etoposide (Et) while enhancing its hydrophilicity. Alginate (ALG) is grafted with 2-hydroxypropyl methacrylamide (HPMA) through a microwave-supported method, and the chemical structure of the graft copolymer (ALG-g-PHPMA) was verified by 1H/13C NMR and FTIR techniques. The ALG-g-PHPMA and anticancer drug-loaded ALG-g-PHPMA@Et nanogels were obtained using an emulsion method, and their structures were characterized through FTIR, TG/DSC, AFM/TEM, BET, and DLS analyses. The ALG-g-PHPMA nanogels demonstrated a good drug encapsulation efficiency (79.60 %), displaying a pH-dependent release profile and an in vitro accelerated release of Et compared to the ALG nanogels. Thermal and BET analyses revealed enhanced stability, surface area, and porosity volume of the alginate nanogels. The grafting of PHPMA chains onto alginate altered the surface topology of the ALG nanogels, resulting in lower surface roughness. Furthermore, cytotoxicity tests showed the high biocompatibility of the ALG-g-PHPMA copolymer and its nanogels. The ALG-g-PHPMA@Et nanogels exhibited a higher anticancer effect on lung cancer (H1299) cells than free etoposide. These results suggest that the ALG-g-PHPMA nanogels can be applied as a pH-dependent nanoplatform for delivering anticancer drugs.

Graft copolymerization of anion and cation onto silica and application in mixed-mode of reversed phase/ hydrophilic interaction/ ion exchange chromatography

Ionic liquids (ILs) have turned out to be one of the best choices to fabricate mixed-mode stationary phases, this work aimed to investigate the possibility and merit of copolymerizing cations and anions as modifications. We prepared two ILs stationary phases, one of which was constructed by copolymerizing cation and anion (p-vinylbenzene sulfonate). Two stationary phases were characterized and comprehensively evaluated. The stationary phases showed great repeatability (RSD <0.87%) and high efficiency (up to 83,810 plate/m). Both stationary phases can operate under a mixed mode of reversed phase/hydrophilic interaction/ion exchange chromatography (RPLC/HILIC/IEC). Chromatographic evaluation results revealed that copolymerized anions endow stationary phase superior selectivity under RPLC and HILIC modes, so hydrophobic terphenyls isomer (under ACN/H2O = 35/65) and hydrophilic nucleotides and bases (under ACN/100 mM NH4FA buffer = 90/10) are better separated. Organic and inorganic anions showed entirely different retention behaviors on two stationary phases, and the mechanism was investigated by linear solvation energy relationship (LSER) and thermodynamic analysis. This work proved that copolymerizing cations and anions of ILs could be a promising method to prepare stationary phases, the retention property and mechanism need further research.

Heterogeneous Radioinduced Graft Copolymerization of Caprolactone in Nanochitosan

This work focus on the chitosan-caprolactone graft copolymers’ (Ch-g-CL) synthesis through Radio Induced Grafting (RIG) of heterogeneous blends of solid chitosan polymers (particulated and nanoprecipitated) and liquid ε-caprolactone monomer, without the need of further reagents nor dissolution. The irradiation process was conducted at room temperature with gamma radiation from 60Co, followed in air and also under vacuum. Commonly applied sterilization doses of 25 and 45 kGy were used. The samples were analyzed, before and after irradiation, through FTIR-ATR, elemental analysis, scanning electron microscopy, 1H-NMR and size exclusion chromatography (SEC). It was found that copolymerization was successful on the blends with nanochitosan, due to a drastic increase in the active surface of the biopolymer. It was observed that the incorporation was better at higher doses and while irradiated on air, with up to 29% caprolactone incorporation. FTIR studies, along with elemental analysis and SEC, indicate that the most probable reaction is caprolactone grafting from/onto chitosan's amine groups. It was also observed that the incorporation increased in the higher molecular weight chitosan, which also has higher amine content. Practically, copolymers with 5–10% grafting sites with CL side chains of up to nine units, were obtained depending on the case. These RIG syntheses showed to lead to tunable Ch-g-CL structures of interest for biomedical applications as tissue scaffolds and drug delivery systems.