Radical Polymerization Research Articles

Dielectric parameters of polymers and monomers of the vinyl series in the microwave range

The production of polymeric materials is one of the fast-growing sectors in the chemical industry. Improving methods for synthesizing high-molecular compounds and studying their physicochemical characteristics are important tasks of synthetic chemistry. Radical polymerization is currently the main method for producing polymeric materials. Its advantages involve simplicity and low cost, along with the possibility of obtaining a wide range of polymeric materials. The results of measuring the dielectric parameters of various high-molecular compounds (polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, poly(glycidyl methacrylate)) in the frequency range of 100–200 GHz (refractive index and dielectric loss tangent tgδ) are presented. The compounds under study were both those synthesized by radical polymerization with the participation of the conventional initiator, i.e., azobisisobutyric acid dinitrile, and commercial products. The absorption capacity of polymers at room temperature was compared. Polymers with the highest and lowest absorption capacity were determined. The dependence of tgδ on frequency for all the polymers under study is linear, with absorption in the polymers increasing with frequency. Poly(glycidyl methacrylate) exhibits the highest absorption among the studied macromolecules with tgδ being equal to 0.043 at 200 GHz. The minimum tgδ value of 0.0068 was found for polystyrene. For the polymers under study, the refractive index value varies in the range from 1.09 to 1.39. In addition, dielectric properties of the original vinyl monomers (styrene, vinyl acetate, glycidyl methacrylate) were studied. The results are of interest when developing approaches to obtaining polymeric materials with specified characteristics based on vinyl monomers by the method of radical polymerization.

Dual-Responsive Alginate/PNIPAM Microspheres Fabricated by Microemulsion-Based Electrospray.

Smart materials for drug delivery are designed to offer a precise and controlled release of therapeutic agents. By responding to specific physiological stimuli, such as changes in temperature and pH, these materials improve treatment efficacy and minimize side effects, paving the way for personalized therapeutic solutions. In this study, we present the fabrication of dual-responsive alginate/poly(N-isopropylacrylamide) (PNIPAM) microspheres, having the ability to respond to both pH and temperature variations and embedding the lipophilic bioactive compound Ozoile. Ozoile® Stable Ozonides is obtained from extra virgin olive oil and acts as an inducer, interacting with major biological pathways by means of modulating the systemic redox balance. The dual-responsive microspheres are prepared by electrospray technique without the use of organic solvents. PNIPAM is synthesized by radical polymerization using the APS/TEMED redox initiators. The microspheres are further optimized with a chitosan coating to enhance their stability and modulate the degradation kinetics of the gel matrix. A comprehensive morphological analysis, Fourier transform infrared (FTIR) spectroscopy, and degradation assays are conducted to confirm the structural stability and pH-responsive behavior of the hydrogel microspheres. A study of the volume phase transition temperature (VPTT) by differential scanning calorimetry (DSC) is used to assess the microsphere thermal response. This research introduces a promising methodology for the development of targeted drug delivery systems, which are particularly useful in the context of oxidative stress modulation and inflammation management.

Oral delivery of Sunitinib malate using carboxymethyl cellulose/poly(acrylic acid-itaconic acid)/Cloisite 30B nanocomposite hydrogel as a pH-responsive carrier.

This work aimed to fabricate a Cloisite 30B-incorporated carboxymethyl cellulose graft copolymer of acrylic acid and itaconic acid hydrogel (Hyd) via a free radical polymerization method for controlled release of Sunitinib malate anticancer drug. The synthesized samples were characterized by FTIR, XRD, TEM, and SEM-dot mapping analyses. The encapsulation efficiency of Hyd and Hyd/Cloisite 30B (6 wt%) was 81 and 93%, respectively, showing the effectiveness of Cloisite 30B in drug loading. An in vitro drug release study showed that drug release from all samples in a buffer solution with pH 7.4 was higher than in a buffer solution with pH 5.5. During 240min, the cumulative drug release from Hyd/Cloisite 30B (94.97% at pH 7.4) is lower than Hyd (53.71% at pH 7.4). Also, drug-loaded Hyd/Cloisite 30B (6 wt%) demonstrated better antibacterial activity towards S. Aureus bacteria and E. Coli. High anticancer activity of Hyd/Cloisite 30B against MCF-7 human breast cancer cells was shown by the MTT assay, with a MCF-7 cell viability of 23.82 ± 1.23% after 72-hour incubation. Our results suggest that Hyd/Cloisite 30B could be used as a pH-controlled carrier to deliver anticancer Sunitinib malate.

Effect of the Size of the Molecular Mass of Some Amine Groups Modified to Maleic anhydride-alt-1-Octadecene Copolymer on Thermal Stability

In this study, 1-octadecene-alt-maleic anhydride (OC-MA) copolymer was synthesized by radical polymerization method. The synthesized copolymer was first time modified with ammonia, methylamine, aniline and hexamethylenediamine reagents in acetone environment. The modified amidic acid derivatives were divided into two parts as quantity. One of these amounts was dried as an amidic acid derivative, and the other was imidized in dimethylformamide environment with constant stirring at 150 °C for 5 hours. Structural characterizations of the obtained samples were determined from the FTIR spectra. Thermal stability was compared from Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) curves. It was established that the modified copolymers were thermally more stable than that of the original OC-MA copolymer. However, it was observed that the size of the molar masses of the reagents participating in the modification reactions showed linear or parabolic increases according to thermal parameter temperature of the decomposition reaction obtained from the TGA and DSC curves.

Nucleobase‐Driven Wearable Ionogel Electronics for Long‐Term Human Motion Detection and Electrophysiological Signal Monitoring

AbstractIonogels are considered as ideal candidates for constructing flexible electronics due to their superior electrical conductivity, flexibility, high thermal and electrochemical stability. However, it remains a great challenge to simultaneously achieve high sensitivity, repeated adhesion, good self‐healing, and biocompatibility through a straightforward strategy. Herein, inspired by nucleobase‐tackified strategy, a multifunctional adhesive ionogel is developed through one‐step radical polymerization of acrylated adenine/uracil (Aa/Ua) and acrylic acid (AA) monomers in sodium caseinate (SC) stabilized liquid metal dispersions. As a soft conductive filler, the incorporating of liquid metal not only improves the electrical conductivity, but also enhances the mechanical strength, satisfying the stretchable sensing application. The large amount of noncovalent interactions (hydrogen bonding, metal coordination, and ion‐dipole interactions) within the networks enable the ionogels to possess excellent stretchability, skin‐like softness, good self‐healing, and strong adhesion. Based on these desirable characteristics, the ionogel is suitable for wearable strain sensors to precisely detect diverse human movements under extreme environments. Moreover, the seamless adhesion with human skin allows the ionogel to function as bioelectrode patch for long‐term and high‐quality electrophysiological signal acquisition. This research provides a promising strategy for designing ionogels with tailored functionalities for wearable electronics that satisfy diverse application requirements.

Adsorption and detection of praseodymium ion by ion-imprinted polymer with ultra-low sensitivity.

A novel kind of carbon dot (CD) was prepared by one-step hydrothermal microwave assisted method using L-tryptophan and L-tartaric acid as raw materials. Monodisperse poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres were utilized as the matrix, with praseodymium (Pr) ion (Pr3+) as the template, methacrylic acid as the functional monomer, and 5-amino-8-hydroxyquinoline (5-AHQ) acts as the ligand. A composite microsphere of ion-imprinted polymer (IIP) and CD (noted CD@IIP) was prepared by surface-initiated atom transfer radical polymerization (SI-ATRP). For comparison, IIP without CD (Pr-IIP) and non-imprinted polymer (NIP) were also prepared. Through static adsorption experiments, it was determined that the saturated adsorption amount of CD@IIP is 47.19mgg-1, that of Pr-IIP is 54.49mgg-1, while that of NIP is only 24.32mgg-1. Dynamic adsorption experiments showed that the equilibrium of three kinds of materials wasreached within 30min. Particularly, CD@IIP could emit two fluorescence peaks at 325nm and 421nm under ultraviolet irradiation, and exhibited excellent selectivity and fluorescence quenching effect on Pr3+. The fluorescence response of Pr3+ in the range 0-400μmol L-1 was determined by ratiometric fluorescence method, offering a two-stage model and robust linear regression coefficient. These results demonstrated that CD@IIP exhibited selective adsorption ability for Pr3+, and a sensitive, rapid and simple method for detection of Pr3+ was successfully developed.

Heterogeneous Catalysts Catalyzed Photo‐Atom Transfer Radical Polymerization (Photo‐ATRP)

Heterogeneous Catalysts Catalyzed Photo‐Atom Transfer Radical Polymerization (Photo‐ATRP)

Exploring the impact of poly(sodium styrene sulfonate) dispersants’ architecture on their performance in coal water slurry preparation

In this work, the architecture of poly(sodium styrene sulfonate) (PSSNa) dispersants were flexibly tailored by various strategies. Three categories of PSSNa dispersants with different topologies were obtained, namely, linear structured PSSNa (1-A-PSSNa), three-arm star PSSNa (3-AS-PSSNa) and six-arm star PSSNa (6-AS-PSSNa). The molecular weights (Mn) of these dispersants were adjusted in the range of 3200–26,200 g/mol by varying the feeding ratio of monomer to initiator. In addition, the polydispersity index (PDI) of resultant dispersants were also varied by using different polymerization technologies, such as atom transfer radical polymerization (ATRP) and conventional free radical polymerization technique (RP). Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) verified these architecture parameters of resultant PSSNa dispersants. Afterwards, the impact of these architectural factors on the performance of PSSNa dispersants in coal water slurry (CWS) preparation were evaluated. The results revealed that with the Mn of dispersants increased from 9800 to 26,200 g/mol, the apparent viscosity of CWS increased by around 11 %. The comparison between dispersants with approximate Mn (26,200 and 26,900 g/mol) and very different PDI (1.27 and 2.25) indicated that wide PDI are favourable for the performance. This work also confirmed that the topology of dispersants has a significant impact on their performance. The maximum coal loaded can increase from 63.9 % to 64.3 % when 1-A-PSSNa dispersant was replaced by 6-AS-PSSNa. Meanwhile, these architectural factors have a limited impact on the fluid type of CWSs, as all CWSs obtained in this work were pseudoplastic fluids regardless of the used dispersants. The potential mechanism was investigated using various technologies, such as the measurements of zeta potentials, contact angles, and low-field nuclear magnetic resonance spectra. The results revealed that topologizing did not alter the interaction between dispersant and coal surface. However, due to the special features of topological polymers, they can grant adsorbed coal particles with enhanced electrostatic repulsion and steric hindrance, which facilitated the dispersion of coal particles.

Group transfer radical polymerization for the preparation of carbon-chain poly(α-olefins).

Radical polymerization is a powerful technique for producing a variety of polymeric materials. However, the chain transfer reaction impedes the formation of polymers from many common α-olefins such as propene and 1-butene using this method. Consequently, poly(α-olefins) are predominantly produced via coordination polymerization. To address this limitation, we have devised a strategy involving group transfer radical polymerization (GTRP) to facilitate the radical homopolymerization to access carbon-chain poly(α-olefins). This approach enables the precise construction of a diverse array of carbon-chain poly(α-olefins) with high molecular weights. Furthermore, by using nonconventional monomers, we extend the applicability of this technique to the copolymerization of α-olefins with acrylonitrile, paving the way for the synthesis of copolymers with different monomers. To investigate the properties of the polymers obtained by this method, one of the poly(α-olefins) is studied as an interphase layer material in anode-free Li metal batteries, and the results indicate the potential of the polymer in energy storage applications.

Synthesis of bifunctional copolymeric nanofibers with selective extracting U(VI) from the solution and antibacterial property

Facing the problem of future nuclear fuel shortage, developing high-performance adsorbent materials is key. In this work, the amidoxime group/imidazole functionalized ionic liquid copolymer fibers containing bromide salts, and fluoroborate salts (namely P(AO/VEIMBr)8 and P(AO/VEIMBF4)6) were prepared by a one-pot method and free radical polymerization, hydroxyl amination reaction and electrostatic spinning, and characterized by SEM, FT-IR, and 1 H NMR. The influence of solid-liquid ratio, ionic strength, and adsorption time on the adsorption performance was investigated by batch adsorption experiments. In the meanwhile, the adsorption kinetics and thermodynamic processes of U(VI) on the copolymer fibers was also studied. Adsorption mechanism of U (VI) on polymer fibers was explored by XPS spectroscopic analysis combined with DFT method. Finally, the antimicrobial properties of the copolymer fibers were tested. The experimental results showed that the polymer nanofibers synthesized for U(VI) has a fast adsorption, high adsorption capacity at ionic strength close to seawater, and excellent reusability. The adsorption process conformed to the pseudo-second-order kinetic model and Langmuir model, which indicated that chemical adsorption and monolayer adsorption are dominant for adsorption U(VI) on the polymer nanofibers, and exhibits the highest Uranium adsorption capacity (76.92 mg/g and 81.96 mg/g at pH=8.1+0.1, respectively). XPS result showed the amine nitrogen and oxime oxygen in the amidoxime functional group were coordinated with uranyl(VI) ions. The antibacterial experiments showed that the copolymer fibers have antimicrobial properties and the antibacterial rate is over 90 %. Therefore, the nanofibers may be a promising material for extracting uranium from the weak alkaline wastewater or seawater.

Investigating on the Performance and Mechanism of Poly(styrene-methyl methacrylate-ethyl methacrylate-butyl acrylate) as Nano Sealing Agent in Oil-Based Drilling Fluids.

Conventional micron sealants are unable to effectively seal nanopores and fractures in shale formations, and the development of new nanomaterials has now become a major research focus to address the instability of shale gas wells. In this paper, oil-based drilling fluids (ODFs) sealants named SMEB (poly(styrene-methyl methacrylate-ethyl methacrylate-butyl acrylate)) were synthesized by free radical polymerization. The SMEB has been characterized by Fourier transform infrared spectroscopy (FTIR), laser scattering analysis (LSA), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The effect of SMEB on the rheological properties of drilling fluids was evaluated by assessing the changes in the rheological parameters of ODFs before and after aging. In addition, the sealing performance of SMEB in ODFs was investigated by high-temperature, high-pressure (HTHP) fluid loss tests and HTHP dense core permeability tests. The results indicated that the particle size of SMEB ranged from 60.68 to 157.39 nm, with a median size of 89.62 nm. The initial decomposition temperature of SMEB was 334 °C, which was in line with the requirement of high-temperature resistance for materials used in shale gas wells. The addition of SMEB has minimal effect on the rheological properties of the drilling fluids and did not adversely affect its performance. At 150 °C and 3.5 MPa, the sealing efficiency of the simulated mud cake was 59.69% with a measured permeability of 0.77 × 10-4 mD at a concentration of 0.5 wt % SMEB. Additionally, when 0.5 wt % SMEB was applied to artificial cores at 105 °C and 3.5 MPa, the sealing efficiency was as high as 86.70%, and the corresponding permeability was 0.48 × 10-3 mD. SMEB demonstrated excellent sealing capabilities in both simulated mud cake and artificial cores, reducing and preventing drilling fluids filtrate flow into the formation. Therefore, SMEB can be applied to drilling fluids as a novel sealing agent and make a significant contribution to maintaining wellbore stability.

Al(SO4)(OH)·5H2O Stemming from Complexation of Aluminum Sulfate with Water-Soluble Ternary Copolymer and further Stabilized by Silica Gel as Effective Admixtures for Enhanced Mortar Cementing.

A water-soluble ternary copolymer bearing carboxyl, sulfonic, and amide functional groups was synthesized using ammonium persulfate-catalyzed free radical polymerization in water, resulting in high monomer conversion. This copolymer was then complexed with aluminum sulfate, forming an admixture containing Al(SO4)(OH)·5H2O, which was subsequently combined with silica gel. Characterization revealed that the synthesized copolymer formed a large, thin membrane that covered both the aluminum compounds and the silica gel blocks. The introduction of this complex admixture, combining the copolymer and aluminum sulfate, not only reduced the setting times of the cement paste but also enhanced the mechanical strengths of the mortar compared to using aluminum sulfate alone. The complex admixture led to the formation of katoite, metajennite, and C3A (tricalcium aluminate) in the mortar, demonstrating significant linking effects, whereas pure aluminum sulfate could not completely transform C3S within 24 h. Further addition of silica gel to the complex admixture further shortened the setting times of the paste, slightly reduced compressive strength, but improved flexural strength compared to the initial complex admixture. The silicon components appeared to fill the micropores and mesopores of the mortar, accelerating cement setting and enhancing flexural strength, while slightly decreasing compressive strength. This study contributed to the development of new cementing accelerators with improved hardening properties.

Transforming watermelon (Citrullus lanatus) rind into durable superabsorbent hydrogels for enhanced soil water retention properties and adsorbs dye in water

Innovative superabsorbent hydrogels were synthesized from watermelon rind (WR), an abundant agricultural waste. The process involved free radical polymerization of acrylic acid (AA) and acrylamide (AAm) with WR particles activated by ammonium persulfate (APS), resulting in (AA-co-AAm)/WR hydrogels with high equilibrium swelling capacities of 749 ± 32 g/g. Notably, after eight cycles, the WR hydrogel maintained 94.88 % of its initial swelling capacity, significantly outperforming the (AA-co-AAm) hydrogel without WR (13.80 % retention). This durability, combined with excellent water retention across various soil textures and high adsorption capacity for methylene blue (MB), underscores the WR hydrogel as a superior soil moisture conservation agent. This study marks a significant advance in recycling organic waste and enhancing water management in agricultural soils, demonstrating the potential for sustainable hydrogel development.

Preparation and evaluation of polymeric ionic liquid functionalized microparticles as the efficient adsorbent for pipette tip solid phase extraction of sulfonamides

Sulfonamides (SAs) residues are commonly found in environmental samples, which is highly concerning for public safety and environmental protection. The detection of SAs is quite important but challenging. In this work, a kind of polymeric ionic liquid functionalized microparticles (PIL-FM) was synthesized via a simple free radical polymerization reaction, and applied as the adsorbent for pipette tip solid phase extraction (PT-SPE) of three SAs from river water, milk powder and honey samples. The adsorption performance of PIL-FM on SAs were evaluated using adsorption kinetics and adsorption isotherms, and the results showed that PIL-FM had the best selectivity for SMZ with the maximum adsorption capacity was as high as 45.05 mg·g−1. The extraction process was optimized and the adsorption mechanism was preliminarily discussed. PIL-FM has the excellent selectivity for SAs mainly because of the strong π-π interaction, and the electrostatic repulsion between them in the elution step also has a positive impact. Under optimal conditions, combined with HPLC, this PT-SPE method had wide linearity (0.2–100 μg·L−1, R2 ≥ 0.9998) and low limits of detection (0.06–0.08 μg·L−1). The intra-day and inter-day repeatability were found to be 3.7 %–4.6 % and 4.5 %–6.2 %, respectively. The suggested PT-SPE method is simple, low cost, rapid, and efficient to extract SAs, and can be applied for the monitoring of SAs residues in the aquatic environment and in food.

Nitrogen-doped amorphous monolayer carbon.

Monoatomic-layered carbon materials, such as graphene1 and amorphous monolayer carbon2,3, have stimulated intense fundamental and applied research owing to their unprecedented physical properties and a wide range of promising applications4,5. So far, such materials have mainly been produced by chemical vapour deposition, which typically requires stringent reaction conditions compared to solution-phase synthesis. Herein, we demonstrate the solution preparation of free-standing nitrogen-doped amorphous monolayer carbon with mixed five-, six- and seven-membered (5-6-7-membered) rings through the polymerization of pyrrole within the confined interlayer cavity of a removable layered-double-hydroxide template. Structural characterizations and first-principles calculations suggest that the nitrogen-doped amorphous monolayer carbon was formed by radical polymerization of pyrrole at the α, β and N sites subjected to confinement of the reaction space, which enables bond rearrangements through the Stone-Wales transformation. The spatial confinement inhibits the C-C bond rotation and chain entanglement during polymerization, resulting in an atom-thick continuous amorphous layer with an in-plane π-conjugation electronic structure. The spatially confined radical polymerization using solid templates and ion exchange strategy demonstrates potential as a universal synthesis approach for obtaining two-dimensional covalent networks, as exemplified by the successful synthesis of monolayers of polythiophene and polycarbazole.

The Coordination of Aluminum Sulfate with a Water-Soluble Block Copolymer Containing Carboxyl, Amide, Sulfonic and Anhydride Groups Providing Both Accelerating and Hardening Effects in Cement Setting

Two water-soluble block copolymers composed of acrylic acid (AA), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), and optionally maleic anhydride (MAH) were synthesized through ammonium persulfate-catalyzed free radical polymerization in water. The introduction of aluminum sulfate (AS) into the resulting mixtures significantly reduced the setting times of the paste and enhanced the mechanical strength of the mortar compared to both the additive-free control and experiments facilitated solely by pure AS. This improvement was primarily attributed to the inhibition of rapid Al3+ hydrolysis, which was achieved through coordination of the synthesized block copolymers, along with the formation of newly identified hydrolytic intermediates. Notably, the ternary copolymer (AA–AMPS–MAH) exhibited superior performance compared to that of the binary copolymer (AA–AMPS). In the early stages of cement setting, clusters of ettringite (AFt) were found to be immobilized over newly detected linkage phases, including unusual calcium silicate hydrate and epistilbite. In contrast to the well-documented role of polymers in retarding cement hydration, this study presents a novel approach by providing both accelerating and hardening agents for cement setting, which has significant implications for the future design of cement additives.

Self-Polymerized Tough and High-Entanglement Zwitterionic Functional Hydrogels.

Zwitterionic hydrogels exhibit great potential in biomedical applications due to their antifouling properties and biocompatibility. However, the single-network structure of pure zwitterionic hydrogels leads to a low toughness and strength, limiting their application in biomedical fields. In this work, a high entanglement sulfobetaine methacrylate-dopamine hydrogel (SBMA-DA-PE) with low cross-linker content and high monomer concentration is prepared by using a dopamine oxidative radical polymerization method. Compared to a regular zwitterionic hydrogel, the SBMA-DA-PE hydrogel exhibits a 5-fold increase in tensile fracture stress and a 10-fold increase in compressive fracture stress. The SBMA-DA-PE hydrogel possesses excellent mechanical properties (the maximum compressive stress ≥4.85MPa, the maximum compressive strain ≥90%). Besides, the non-covalent interactions between catechol or ortho-quinones within the SBMA-DA-PE hydrogel, combined with strong intermolecular electrostatic interactions, endow the SBMA-DA-PE hydrogel with great self-healing capabilities and fatigue resistance. The SBMA-DA-PE hydrogel demonstrates low swellability and possesses good antifouling properties. Furthermore, the good printability and conductivity of the tough SBMA-DA-PE hydrogel endows it with new possibilities for developing biological 3D scaffolds and electronic devices. Overall, this work provides new insights into the preparation of zwitterionic hydrogels with high mechanical strength and multi-functionality for biomedical applications.

Installing a Trigger to Upcycle High-Density Polyethylene.

Creating C═C bonds as "weak" sites in the stable C-C chains of polyethylene (PE) is an appealing strategy to promote sustainable development of the polyolefin industry. Compared to methods, such as dehydrogenation and postpolymerization modification, the copolymerization of ethylene (E) and butadiene (BD) should be a convenient and direct approach to introduce C═C bonds in PE, whereas it encounters problems in controlling the composition and regularity of the copolymer due to the mismatched activities and mechanisms between the two monomers. Herein, we report by employing the amidinate gadolinium complex, controllable E/BD copolymerization was achieved, where BD was incorporated in the uniformly discrete 1,4 mode. The obtained copolymer possesses the same physical, mechanical, processing, and antioxygen (aging at 100 °C for 28 days) properties as commercial high-density-PE, which, strikingly, were degraded by C═C bonds into α,ω-telechelic oligomers with narrow distribution. These degraded functional products were transferred to compatibilizers via atom-transfer radical polymerization or immortal ring-opening polymerization, achieving upcycling.

Synthesis and properties of biomass‐based polymethacrylate comprising chitin‐derived 2‐acetamide‐2‐deoxyisosorbide as a repeat unit

AbstractSynthesis and applications of biobased polymers have been extensively studied in order to reduce the use of petroleum‐based polymers and likewise environmental load. Several biobased polymers have been produced on a commercial large scale to date. However, the lineup of biobased high‐performance polymers with transparency and high glass transition temperature is inadequate and their development is a critical issue. In this article, we design a new biobased polymethacrylate comprising rigid cis‐fused bicyclic 2‐acetamide‐2‐deoxyisosorbide (ADI) as a repeat unit. We have recently invented catalytic transformation systems from chitin as a marine biomass to ADI as a new nitrogen‐containing platform chemical. The ADI‐based polymethacrylate is synthesized via free radical polymerization of the methacrylic acid ester of ADI initiated by (NH4)2S2O8 and N,N,N′,N′‐tetramethylethylenediamine in dimethylsulfoxide–H2O mixed solvent. The molecular weight and its dispersity are estimated by size exclusion chromatography on the basis of polymethylmethacrylate standards. UV–visible spectroscopy demonstrates the high transparency of the polymer in the visible wavelength region. Differential scanning calorimetry analysis of the polymer clarifies the remarkably high glass transition temperature, compared with that of polymethylmethacrylate. The thermal decomposition temperature of the polymer is also evaluated by thermogravimetric analysis. On the basis of the favorable properties of the ADI‐based polymer, the present study proposes it as a nitrogen‐containing biobased polymer useful for real‐world applications. © 2024 Society of Chemical Industry.

PH‐responsive bionanocomposite pectin grafted with dimethylaminoethyl methacrylate and acrylic acid copolymer along with silver nanoparticles for breast cancer drug delivery

AbstractIn this study, we developed a pH‐responsive hydrogel membrane composed of pectin, dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA) through a free radical‐triggered graft copolymerization method. Freshly formed silver nanoparticles (AgNPs) produced from the reduction reaction were embedded in the produced hydrogel. Pectin‐grafted dimethylaminoethyl methacrylate and acrylic acid copolymer [poly (DMAEMA‐co‐AA)‐g‐pectin] and its bionanocomposite with AgNPs were confirmed by Fourier‐transform infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The swelling behavior of poly (DMAEMA‐co‐AA)‐g‐pectin in solutions with diverse pH values was assessed. For use as a controlled drug delivery agent, the hydrogel was loaded with 5‐fluorouracil (5‐FU). The incorporation of AgNPs had a great impact on the entrapment efficiency of 5‐FU. At pH 7.4, nearly 48% of the 5‐FU was released in vitro from the polymeric nanocomposite within 24 h. Moreover, poly (DMAEMA‐co‐AA)‐g‐pectin and poly (DMAEMA‐co‐AA)‐g‐pectin/AgNPs presented high cytocompatibility toward normal skin fibroblast cells (BJ1), and the drug delivery system strongly inhibited human Caucasian breast adenocarcinoma cells (MCF‐7). These results demonstrated that these poly (DMAEMA‐co‐AA)‐g‐pectin/AgNPs are an excellent candidate for use in anticancer drug delivery systems.Highlights Free radical polymerization of nanocomposites incorporated with nanoparticles. Nanoparticles improve the bionanocomposites' drug loading. The developed bionanocomposites exhibit control drug release. The novel bionanocomposites acts as an excellent anticancer drug carrier.