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Search Results (826)

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Keywords = graft polymerization

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39 pages, 27477 KB  
Review
Three-Dimensional Printing and Bioprinting Strategies for Cardiovascular Constructs: From Printing Inks to Vascularization
by Min Suk Kim, Yuri Choi and Keel Yong Lee
Polymers 2025, 17(17), 2337; https://doi.org/10.3390/polym17172337 - 28 Aug 2025
Viewed by 750
Abstract
Advancements in bioinks and three-dimensional (3D) printing and bioprinting have significantly advanced cardiovascular tissue engineering by enabling the fabrication of biomimetic cardiac and vascular constructs. Traditional 3D printing has contributed to the development of acellular scaffolds, vascular grafts, and patient-specific cardiovascular models that [...] Read more.
Advancements in bioinks and three-dimensional (3D) printing and bioprinting have significantly advanced cardiovascular tissue engineering by enabling the fabrication of biomimetic cardiac and vascular constructs. Traditional 3D printing has contributed to the development of acellular scaffolds, vascular grafts, and patient-specific cardiovascular models that support surgical planning and biomedical applications. In contrast, 3D bioprinting has emerged as a transformative biofabrication technology that allows for the spatially controlled deposition of living cells and biomaterials to construct functional tissues in vitro. Bioinks—derived from natural biomaterials such as collagen and decellularized matrix, synthetic polymers such as polyethylene glycol (PEG) and polycaprolactone (PCL), or hybrid combinations—have been engineered to replicate extracellular environments while offering tunable mechanical properties. These formulations ensure biocompatibility, appropriate mechanical strength, and high printing fidelity, thereby maintaining cell viability, structural integrity, and precise architectural resolution in the printed constructs. Advanced bioprinting modalities, including extrusion-based bioprinting (such as the FRESH technique), droplet/inkjet bioprinting, digital light processing (DLP), two-photon polymerization (TPP), and melt electrowriting (MEW), enable the fabrication of complex cardiovascular structures such as vascular patches, ventricle-like heart pumps, and perfusable vascular networks, demonstrating the feasibility of constructing functional cardiac tissues in vitro. This review highlights the respective strengths of these technologies—for example, extrusion’s ability to print high-cell-density bioinks and MEW’s ultrafine fiber resolution—as well as their limitations, including shear-induced cell stress in extrusion and limited throughput in TPP. The integration of optimized bioink formulations with appropriate printing and bioprinting platforms has significantly enhanced the replication of native cardiac and vascular architectures, thereby advancing the functional maturation of engineered cardiovascular constructs. Full article
(This article belongs to the Section Innovation of Polymer Science and Technology)
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53 pages, 14385 KB  
Review
Stimuli-Responsive Starch-Based Biopolymer Coatings for Smart and Sustainable Fertilizers
by Babar Azeem
Gels 2025, 11(9), 681; https://doi.org/10.3390/gels11090681 - 26 Aug 2025
Viewed by 722
Abstract
The quest for sustainable agriculture demands nutrient delivery systems that align productivity with environmental responsibility. This review critically evaluates stimuli-responsive starch-based biopolymer coatings for controlled-release fertilizers (CRFs), highlighting their structure, functionality, and agronomic relevance. Starch, an abundant and biodegradable polysaccharide, offers intrinsic advantages [...] Read more.
The quest for sustainable agriculture demands nutrient delivery systems that align productivity with environmental responsibility. This review critically evaluates stimuli-responsive starch-based biopolymer coatings for controlled-release fertilizers (CRFs), highlighting their structure, functionality, and agronomic relevance. Starch, an abundant and biodegradable polysaccharide, offers intrinsic advantages such as modifiability, film-forming ability, and compatibility with green chemistry. The paper discusses starch’s physicochemical characteristics, its functionalization to achieve responsiveness to environmental triggers (pH, moisture, temperature, ionic strength), and coating strategies like in situ polymerization, grafting, and nanocomposite integration. A comprehensive analysis of release kinetics, swelling behavior, biodegradability, and water retention is provided, followed by evaluations under simulated field conditions, encompassing various soil types, environmental stressors, and crop responses. Comparative insights with other smart biopolymers such as chitosan, alginate, and cellulose underscore starch’s unique position in CRF technology. Despite promising developments, the review identifies critical research gaps, including limitations in scalability, coordination of multi-stimuli responses, and the need for extensive field validation. This work serves as a consolidated platform for researchers, policy makers, and agro-industrial stakeholders aiming to design smart, eco-friendly fertilizers that address global food security while minimizing ecological footprints. Full article
(This article belongs to the Section Gel Processing and Engineering)
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43 pages, 71331 KB  
Review
Polymeric and Polymer-Functionalized Drug Delivery Vectors: From Molecular Architecture and Elasticity to Cellular Uptake
by Thorsten Auth
Polymers 2025, 17(16), 2243; https://doi.org/10.3390/polym17162243 - 19 Aug 2025
Viewed by 647
Abstract
Polymers and polymer composites offer versatile possibilities for engineering the physico-chemical properties of materials on micro- and macroscopic scales. This review provides an overview of polymeric and polymer-decorated particles that can serve as drug-delivery vectors: linear polymers, star polymers, diblock-copolymer micelles, polymer-grafted nanoparticles, [...] Read more.
Polymers and polymer composites offer versatile possibilities for engineering the physico-chemical properties of materials on micro- and macroscopic scales. This review provides an overview of polymeric and polymer-decorated particles that can serve as drug-delivery vectors: linear polymers, star polymers, diblock-copolymer micelles, polymer-grafted nanoparticles, polymersomes, stealth liposomes, microgels, and biomolecular condensates. The physico-chemical interactions between the delivery vectors and biological cells range from chemical interactions on the molecular scale to deformation energies on the particle scale. The focus of this review is on the structure and elastic properties of these particles, as well as their circulation in blood and cellular uptake. Furthermore, the effects of polymer decoration in vivo (e.g., of glycosylated plasma membranes, cortical cytoskeletal networks, and naturally occurring condensates) on drug delivery are discussed. Full article
(This article belongs to the Special Issue Advanced Polymeric Composite for Drug Delivery Application)
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22 pages, 1661 KB  
Article
Biliary Injuries Repair Using Copolymeric Scaffold: A Systematic Review and In Vivo Experimental Study
by Salvatore Buscemi, Giulia Bonventre, Andrea Gottardo, Mariano Licciardi, Fabio Salvatore Palumbo, Giovanni Cassata, Luca Cicero, Giulia Lo Monte, Roberto Puleio and Attilio Ignazio Lo Monte
J. Funct. Biomater. 2025, 16(8), 297; https://doi.org/10.3390/jfb16080297 - 18 Aug 2025
Viewed by 481
Abstract
Background: Common bile duct (CBD) treatments are often associated with complications, limiting long-term efficacy. To overcome these issues, polymeric grafts have been suggested as promising alternatives, since they are highly customizable, biocompatible, and may reduce side effects frequency. Methods: A systematic review was [...] Read more.
Background: Common bile duct (CBD) treatments are often associated with complications, limiting long-term efficacy. To overcome these issues, polymeric grafts have been suggested as promising alternatives, since they are highly customizable, biocompatible, and may reduce side effects frequency. Methods: A systematic review was conducted, interrogating MEDLINE and Cochrane Library. Next, an in vivo study involved 20 pigs, which underwent a former controlled biliary injury. To repair the defect, a α,β-Poly(N-2-hydroxyethyl)-DL-Aspartamide (PHEA)–Polylactic-acid (PLA)–Polycaprolactone (PCL) scaffold was implanted. The animals were sacrificed at one and three months for gross and histological examinations, to assess tissue integration and healing outcomes. Results: The systematic review highlighted that such scaffolds have shown promising results in CBD regeneration, both in single and joined applications. These findings were confirmed by the in vivo study, where the use of such scaffolds—particularly, the planar ones—led to safe and complete bile duct regeneration. Histological analysis revealed lymphomonocytic infiltrates and neovascularization, while microscopic examination showed progressive scaffold degradation accompanied by biliary tissue regeneration. Conclusions: Experimental results are consistent with the literature, confirming the potential of such polymeric scaffolds in aiding complete CBD regeneration and being reabsorbed shortly after. Still, further studies are needed to fully validate their translational application. PROSPERO ID: CRD420251115056. Full article
(This article belongs to the Special Issue Polymers Materials Used in Biomedical Engineering)
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16 pages, 2076 KB  
Article
Amberlite XAD-4 Functionalized with 4-(2-Pyridylazo) Resorcinol via Aryldiazonium Chemistry for Efficient Solid-Phase Extraction of Trace Metals from Groundwater Samples
by Awadh O. AlSuhaimi
Appl. Sci. 2025, 15(16), 9044; https://doi.org/10.3390/app15169044 - 16 Aug 2025
Viewed by 471
Abstract
Aryl diazonium salt chemistry offers a robust and versatile approach for the modification of material surfaces via the covalent immobilization of reactive functional groups under mild conditions. In this study, this strategy was successfully applied to graft the chelating agent 4-(2-pyridylazo)resorcinol (PAR) onto [...] Read more.
Aryl diazonium salt chemistry offers a robust and versatile approach for the modification of material surfaces via the covalent immobilization of reactive functional groups under mild conditions. In this study, this strategy was successfully applied to graft the chelating agent 4-(2-pyridylazo)resorcinol (PAR) onto Amberlite XAD-4 resin. Initially, 4-nitrobenzenediazonium tetrafluoroborate (NBDT) was covalently anchored onto the resin surface using hypophosphorous acid as a reducing catalyst to introduce aryl nitro groups. These nitro groups were subsequently reduced to aniline functionalities, enabling diazo coupling with PAR. The successful modification of the resin was confirmed by ATR-FTIR spectroscopy, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The synthesized chelating resin exhibited sorption capacities of 0.152, 0.167, and 0.172 mM g−1 for Co(II), Ni(II), and Cu(II), respectively. The functionalized resin was packed into standard SPE cartridges and employed as a selective sorbent for the extraction and preconcentration of trace metals from groundwater samples collected from Dhalamah Valley, Al-Madinah Al-Munawwarah, prior to quantification by inductively coupled plasma mass spectrometry (ICP-MS). These results demonstrate the effectiveness of rapid diazonium-based surface functionalization for the preparation of selective polymeric metal chelators suitable for the extraction of trace metals from complex groundwater matrices. Full article
(This article belongs to the Section Chemical and Molecular Sciences)
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32 pages, 3378 KB  
Review
Thermoresponsive and Fluorescent Polymers: From Nanothermometers to Smart Drug Delivery Systems for Theranostics Against Cancer
by Mirian A. González-Ayón, Jesús E. Márquez-Castro, Diana V. Félix-Alcalá and Angel Licea-Claverie
Pharmaceutics 2025, 17(8), 1062; https://doi.org/10.3390/pharmaceutics17081062 - 15 Aug 2025
Viewed by 813
Abstract
This mini-review article is focused on polymeric materials that comprise thermoresponsive and fluorescent organic units. The combination of fluorescent clusters/dots embedded in or grafted with polymers is not considered in this article. Here we review the preparation, characterization, and application of thermoresponsive polymers [...] Read more.
This mini-review article is focused on polymeric materials that comprise thermoresponsive and fluorescent organic units. The combination of fluorescent clusters/dots embedded in or grafted with polymers is not considered in this article. Here we review the preparation, characterization, and application of thermoresponsive polymers functionalized covalently with organic fluorescent compounds either compartmentalized or randomly distributed: block-copolymers, self-assembled micelles or vesicles, core–shell nanogels, and their temperature driven self-assembly/shrinkage/expansion and resulting effect in fluorescence: quenching, enhancing, shifting. The applications suggested for these smart-materials are reviewed in the last ten years and range from nanothermometers, drug delivery systems, agents for bioimaging, sensors, and advanced materials for theranostics focused on cancer treatment. This article is organized reviewing the preparation methods, the main characterization techniques, and the application, depending on polymer architecture and the emission wavelength of the fluorophores. Finally, comments, suggestions, and problems to be solved for the advancement of these materials in the future prior to real-life applications are given. Full article
(This article belongs to the Special Issue Functionalized Polymers for Anticancer Applications)
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20 pages, 4874 KB  
Article
Preparation of pH-Responsive PET TeMs by Controlled Graft Block Copolymerisation of Styrene and Methacrylic Acid for the Separation of Water–Oil Emulsions
by Indira B. Muslimova, Dias D. Omertassov, Nurdaulet Zhumanazar, Nazerke Assan, Zhanna K. Zhatkanbayeva and Ilya V. Korolkov
Polymers 2025, 17(16), 2221; https://doi.org/10.3390/polym17162221 - 14 Aug 2025
Viewed by 536
Abstract
To develop membranes capable of efficient and switchable emulsion separation under variable pH conditions, pH-responsive surfaces were engineered on poly(ethylene terephthalate) track-etched membranes (PET TeMs) via a two-step UV-initiated RAFT graft polymerization process. Initially, polystyrene (PS) was grafted to render the surface hydrophobic, [...] Read more.
To develop membranes capable of efficient and switchable emulsion separation under variable pH conditions, pH-responsive surfaces were engineered on poly(ethylene terephthalate) track-etched membranes (PET TeMs) via a two-step UV-initiated RAFT graft polymerization process. Initially, polystyrene (PS) was grafted to render the surface hydrophobic, followed by the grafting of poly(methacrylic acid) (PMAA) to introduce pH-responsive carboxyl groups. Optimized conditions (117 mM MAA, RAFT:initiator 1:10, 60 min UV exposure at 10 cm) resulted in PET TeMs-g-PS-g-PMAA surfaces exhibiting tunable wettability, with contact angles shifting from 90° at pH 2 to 65° at pH 9. Successful grafting was confirmed by FTIR, AFM, SEM, TGA, and TB dye sorption. The membranes showed high degree of rejection (up to 98%) for both direct and reverse emulsions. In direct emulsions, stable flux values (70 ± 2.8 to 60 ± 2.9 L m−2 h−1 for cetane-in-water and 195 ± 8.2 to 120 ± 6.9 L m−2 h−1 for o-xylene-in-water) were maintained over five cycles at 900 mbar, indicating excellent antifouling performance. Reverse emulsions initially exhibited higher flux, but stronger fouling; however, flux recovery reached 91% after cleaning. These findings demonstrate the potential of PET TeMs-g-PS-g-PMAA as switchable, pH-responsive membranes for robust emulsion separation. Full article
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15 pages, 3565 KB  
Article
Controlled PolyDMAEMA Functionalization of Titanium Surfaces via Graft-To and Graft-From Strategies
by Chiara Frezza, Susanna Romano, Daniele Rocco, Giancarlo Masci, Giovanni Sotgiu, Monica Orsini and Serena De Santis
Micromachines 2025, 16(8), 899; https://doi.org/10.3390/mi16080899 - 31 Jul 2025
Viewed by 381
Abstract
Titanium is widely recognized as an interesting material for electrodes due to its excellent corrosion resistance, mechanical strength, and biocompatibility. However, further functionalization is often necessary to impart advanced interfacial properties, such as selective ion transport or stimuli responsiveness. In this context, the [...] Read more.
Titanium is widely recognized as an interesting material for electrodes due to its excellent corrosion resistance, mechanical strength, and biocompatibility. However, further functionalization is often necessary to impart advanced interfacial properties, such as selective ion transport or stimuli responsiveness. In this context, the integration of smart polymers, such as poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)—noted for its dual pH- and thermo-responsive behavior—has emerged as a promising approach to tailor surface properties for next-generation devices. This work compares two covalent immobilization strategies for PDMAEMA on titanium: the “graft-to” method, involving the attachment of pre-synthesized polymer chains, and the “graft-from” method, based on surface-initiated polymerization. The resulting materials were characterized with size exclusion chromatography (SEC) for molecular weight, Fourier-transform infrared spectroscopy (FTIR) for chemical structure, scanning electron microscopy (SEM) for surface morphology, and contact angle measurements for wettability. Electrochemical impedance spectroscopy and polarization studies were used to assess electrochemical performance. Both strategies yielded uniform and stable coatings, with the mode of grafting influencing both surface morphology and functional stability. These findings provide valuable insights into the development of adaptive, stimuli-responsive titanium-based interfaces in advanced electrochemical systems. Full article
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29 pages, 42729 KB  
Article
Sustainable and Functional Polymeric Coating for Wood Preservation
by Ramona Marina Grigorescu, Rodica-Mariana Ion, Lorena Iancu, Sofia Slamnoiu-Teodorescu, Anca Irina Gheboianu, Elvira Alexandrescu, Madalina Elena David, Mariana Constantin, Iuliana Raut, Celina Maria Damian, Cristian-Andi Nicolae and Bogdan Trica
Coatings 2025, 15(8), 875; https://doi.org/10.3390/coatings15080875 - 25 Jul 2025
Viewed by 714
Abstract
The development of sustainable and functional nanocomposites has attracted considerable attention in recent years due to their broad spectrum of potential applications, including wood preservation. Also, a global goal is to reuse the large volumes of waste for environmental issues. In this context, [...] Read more.
The development of sustainable and functional nanocomposites has attracted considerable attention in recent years due to their broad spectrum of potential applications, including wood preservation. Also, a global goal is to reuse the large volumes of waste for environmental issues. In this context, the aim of the study was to obtain soda lignin particles, to graft ZnO nanoparticles onto their surface and to apply these hybrids, embedded into a biodegradable polymer matrix, as protection/preservation coating for oak wood. The organic–inorganic hybrids were characterized in terms of compositional, structural, thermal, and morphological properties that confirm the efficacy of soda lignin extraction and ZnO grafting by physical adsorption onto the decorating support and by weak interactions and coordination bonding between the components. The developed solution based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and lignin-ZnO was applied to oak wood specimens by brushing, and the improvement in hydrophobicity (evaluated by water absorption that decreased by 48.8% more than wood, humidity tests where the treated sample had a humidity of 4.734% in comparison with 34.911% for control, and contact angle of 97.8° vs. 80.5° for untreated wood) and UV and fungal attack protection, while maintaining the color and aspect of specimens, was sustained. L.ZnO are well dispersed into the polymer matrix, ensuring a smooth and less porous wood surface. According to the results, the obtained wood coating using both a biodegradable polymeric matrix and a waste-based preservative can be applied for protection against weathering degradation factors, with limited water uptake and swelling of the wood, UV shielding, reduced wood discoloration and photo-degradation, effective protection against fungi, and esthetic quality. Full article
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11 pages, 2151 KB  
Article
Fabrication of Antibacterial Poly(ethylene terephthalate)/Graphene Nanocomposite Fibers by In Situ Polymerization for Fruit Preservation
by Jiarui Wu, Qinhan Chen, Aobin Han, Min Liu, Wenhuan Zhong, Xiaojue Shao, Yan Jiang, Jing Lin, Zhenyang Luo, Jie Yang and Gefei Li
Molecules 2025, 30(15), 3109; https://doi.org/10.3390/molecules30153109 - 24 Jul 2025
Viewed by 329
Abstract
A novel polyester/graphene nanocomposite fiber was produced using the in situ polymerization protocol with carboxylated graphene and melt spinning technology. The resulting nanocomposite fibers were characterized by X-ray diffraction (XRD), Raman spectroscopy, differential scanning calorimeter (DSC), and scanning electron microscope (SEM). The fibers [...] Read more.
A novel polyester/graphene nanocomposite fiber was produced using the in situ polymerization protocol with carboxylated graphene and melt spinning technology. The resulting nanocomposite fibers were characterized by X-ray diffraction (XRD), Raman spectroscopy, differential scanning calorimeter (DSC), and scanning electron microscope (SEM). The fibers containing 0.2 wt% graphene fraction showed an excellent dispersity of graphene nanosheets in polymeric matrix. DSC test showed that the efficient polymer-chain grafting depresses the crystallization of PET chains. This graphene-contained PET fabric exhibited attractive antibacterial properties that can be employed in fruit preservation to ensure food safety. Full article
(This article belongs to the Special Issue Design and Application of Functional Supramolecular Materials)
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16 pages, 2948 KB  
Article
Antifouling Polymer-Coated Anthocyanin-Loaded Cellulose Nanocrystals Demonstrate Reduced Bacterial Detection Capabilities
by Catherine Doyle, Diego Combita, Matthew J. Dunlop and Marya Ahmed
Polymers 2025, 17(15), 2007; https://doi.org/10.3390/polym17152007 - 22 Jul 2025
Viewed by 504
Abstract
Microbial contamination is a global concern with impacts on a variety of industries ranging from marine to biomedical applications. Recent research on hydrophilic polymer-based coatings is focused on combining antifouling polymers with nanomaterials to enhance mechanical, optical, and stimuli-responsive properties, yielding colour changing, [...] Read more.
Microbial contamination is a global concern with impacts on a variety of industries ranging from marine to biomedical applications. Recent research on hydrophilic polymer-based coatings is focused on combining antifouling polymers with nanomaterials to enhance mechanical, optical, and stimuli-responsive properties, yielding colour changing, self-healing, and super hydrophilic materials. This study combines the hydrophilic and antifouling properties of vitamin B5 analogous methacrylamide (B5AMA)-based polymers with stimuli-responsive anthocyanin-dye-loaded cellulose nanocrystals (CNCs) to develop antifouling materials with colour changing capabilities upon bacterial contamination. Poly(B5AMA)-grafted CNCs were prepared through surface-initiated photoiniferter reversible addition fragmentation chain transfer (SP-RAFT) polymerization and characterized through proton nuclear magnetic resonance (1H-NMR), transmission electron microscopy (SEM/TEM), and X-ray photon spectroscopy (XPS) to confirm the formation of surface-grafted polymer chains. The bare CNCs and poly(B5AMA)-grafted CNCs were loaded with anthocyanin dye and evaluated for pH-dependent colour changing capabilities. Interestingly, anthocyanin-loaded CNCs demonstrated vibrant colour changes in both solution and dried film form upon bacterial contamination; however, limited colour changing capabilities of the composites, specifically in dried film form, were attributed to the enhanced dispersibility and antifouling capabilities of the polymer-coated CNCs. Full article
(This article belongs to the Section Biobased and Biodegradable Polymers)
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12 pages, 11599 KB  
Article
Dual pH- and Temperature-Responsive Fluorescent Hybrid Materials Based on Carbon Dot-Grafted Triamino-Tetraphenylethylene/N-Isopropylacrylamide Copolymers
by Huan Liu, Yuxin Ding, Longping Zhou, Shirui Xu and Bo Liao
C 2025, 11(3), 53; https://doi.org/10.3390/c11030053 - 22 Jul 2025
Viewed by 552
Abstract
Carbon dots (CDs), a class of carbon-based fluorescent nanomaterials, have garnered significant attention due to their tunable optical properties and functional versatility. In this study, we developed a hybrid material by grafting pH- and temperature-responsive copolymers onto CDs via reversible addition-fragmentation chain-transfer (RAFT) [...] Read more.
Carbon dots (CDs), a class of carbon-based fluorescent nanomaterials, have garnered significant attention due to their tunable optical properties and functional versatility. In this study, we developed a hybrid material by grafting pH- and temperature-responsive copolymers onto CDs via reversible addition-fragmentation chain-transfer (RAFT) polymerization. Triamino-tetraphenylethylene (ATPE) and N-isopropylacrylamide (NIPAM) were copolymerized at varying ratios and covalently linked to CDs, forming a dual-responsive system. Structural characterization using FTIR, 1H NMR, and TEM confirmed the successful grafting of the copolymers onto CDs. The hybrid material exhibited pH-dependent fluorescence changes in acidic aqueous solutions, with emission shifting from 450 nm (attributed to CDs) to 500 nm (aggregation-induced emission, AIE, from ATPE) above a critical pH threshold. Solid films of the hybrid material demonstrated reversible fluorescence quenching under HCl vapor and recovery/enhancement under NH3 vapor, showing excellent fatigue resistance over multiple cycles. Temperature responsiveness was attributed to the thermosensitive poly(NIPAM) segments, with fluorescence intensity increasing above 35 °C due to polymer chain collapse and ATPE aggregation. This work provides a strategy for designing multifunctional hybrid materials with potential applications in recyclable optical pH/temperature sensors. Full article
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13 pages, 3561 KB  
Article
Preparing Surface-Functionalized Polymer Films with Hierarchically Ordered Structure by a Combination of Nanoimprinting and Controlled Graft Polymerization
by Masahiko Minoda, Daichi Shimizu, Tatsuya Nohara and Jin Motoyanagi
Surfaces 2025, 8(3), 48; https://doi.org/10.3390/surfaces8030048 - 11 Jul 2025
Viewed by 446
Abstract
It is widely recognized that fine surface structures found in nature contribute to surface functionality, and studies on the design of functional materials based on biomimetics have been actively conducted. In this study, polymer thin films with hierarchically ordered surface structure were prepared [...] Read more.
It is widely recognized that fine surface structures found in nature contribute to surface functionality, and studies on the design of functional materials based on biomimetics have been actively conducted. In this study, polymer thin films with hierarchically ordered surface structure were prepared by combining both nanoimprinting using anodically oxidized porous alumina (AAO) as a template and surface-initiated atom transfer radical polymerization (SI-ATRP). To prepare such polymer films, we designed a new copolymer (poly{[2-(4-methyl-2-oxo-2H-chromen-7-yloxy)ethyl methacrylate]-co-[2-(2-bromo-2-methylpropionyloxy)ethyl methacrylate]}; poly(MCMA-co-HEMABr)) with coumarin moieties and α-haloester moieties in the pendants. The MCMA repeating units function to fix the pillar structure by photodimerization, and the HEMABr ones act as the polymerization initiation sites for SI-ATRP on the pillar surfaces. Surface structures consisting of vertically oriented multiple pillars were fabricated on the spin-coated poly(MCMA-co-HEMABr) thin films by nanoimprinting using an AAO template. Then, the coumarin moieties inside each pillar were crosslinked by UV light irradiation to fix the pillar structure. SEM observation confirmed that the internally crosslinked pillar structures were maintained even when immersed in organic solvents such as 1,2-dichloroethane and anisole, which are employed as solvents under SI-ATRP conditions. Finally, poly(2,2,2-trifluoroethyl methacrylate) and poly(N-isopropylacrylamide) chains were grafted onto the thin film by SI-ATRP, respectively, to prepare the hierarchically ordered surface structure. Furthermore, in this study, the surface properties as well as the thermoresponsive hydrophilic/hydrophobic switching of the obtained polymer films were investigated. The surface morphology and chemistry of the films with and without pillar structures were compared, especially the interfacial properties expressed as wettability. Grafting poly(TFEMA) increased the static contact angle for both flat and pillar films, and the con-tact angle of the pillar film surface increased from 104° for the flat film sample to 112°, suggesting the contribution of the pillar structure. Meanwhile, the pillar film surface grafted with poly(NIPAM) brought about a significant change in wettability when changing the temperature between 22 °C and 38 °C. Full article
(This article belongs to the Special Issue Surface Science: Polymer Thin Films, Coatings and Adhesives)
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23 pages, 1189 KB  
Article
Hyaluronic Acid-Graft-Poly(L-Lysine): Synthesis and Evaluation as a Gene Delivery System
by Viktor Korzhikov-Vlakh, Polina Teterina, Nina Gubina, Apollinariia Dzhuzha, Tatiana Tennikova and Evgenia Korzhikova-Vlakh
Polysaccharides 2025, 6(3), 60; https://doi.org/10.3390/polysaccharides6030060 - 5 Jul 2025
Viewed by 898
Abstract
The synthesis of novel biodegradable polymers as non-viral vectors remains one of the challenging tasks in the field of gene delivery. In this study, the synthesis of the polysaccharide-g-polypeptide copolymers, namely, hyaluronic acid-g-polylysine (HA-g-PLys), using a copper-free [...] Read more.
The synthesis of novel biodegradable polymers as non-viral vectors remains one of the challenging tasks in the field of gene delivery. In this study, the synthesis of the polysaccharide-g-polypeptide copolymers, namely, hyaluronic acid-g-polylysine (HA-g-PLys), using a copper-free strain-promoted azide-alkyne cycloaddition reaction was proposed. For this purpose, hyaluronic acid was modified with dibenzocyclooctyne moieties, and poly-L-lysine with a terminal azido group was obtained using ring-opening polymerization of N-carboxyanhydride of the corresponding protected amino acid, initiated with the amino group azido-PEG3-amine. Two HA-g-PLys samples with different degrees of grafting were synthesized, and the structures of all modified and synthesized polymers were confirmed using 1H NMR and FTIR spectroscopy. The HA-g-PLys samples obtained were able to form nanoparticles in aqueous media due to self-assembly driven by electrostatic interactions. The binding of DNA and model siRNA by copolymers to form polyplexes was analyzed using ethidium bromide, agarose gel electrophoresis, and SybrGreen I assays. The hydrodynamic diameter of polyplexes was ˂300 nm (polydispersity index, PDI ˂ 0.3). The release of a model fluorescently-labeled oligonucleotide in the complex biological medium was significantly higher in the case of HA-g-PLys as compared to that in the case of PLys-based polyplexes. In addition, the cytotoxicity in normal and cancer cells, as well as the ability of HA-g-PLys to facilitate intracellular delivery of anti-GFP siRNA to NIH-3T3/GFP+ cells, were evaluated. Full article
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15 pages, 1555 KB  
Article
Synthesis and Characterization of Temperature- and pH-Responsive PIA-b-PNIPAM@Fe3O4 Nanocomposites
by Swati Kumari, Cayla Cook, Fatema Tarannum, Erick S. Vasquez-Guardado, Olufemi Ogunjimi and Keisha B. Walters
Nanomaterials 2025, 15(13), 1041; https://doi.org/10.3390/nano15131041 - 4 Jul 2025
Viewed by 661
Abstract
Stimuli-responsive polymers (SRPs) have garnered significant attention in recent decades due to their immense potential in biomedical and environmental applications. When these SRPs are grafted onto magnetic nanoparticles, they form multifunctional nanocomposites capable of various complex applications, such as targeted drug delivery, advanced [...] Read more.
Stimuli-responsive polymers (SRPs) have garnered significant attention in recent decades due to their immense potential in biomedical and environmental applications. When these SRPs are grafted onto magnetic nanoparticles, they form multifunctional nanocomposites capable of various complex applications, such as targeted drug delivery, advanced separations, and magnetic resonance imaging. In this study, we employed a one-step hydrothermal method using 3-aminopropyltrimethoxysilane (APTES) to synthesize APTES-modified Fe3O4 nanoparticles (APTES@Fe3O4) featuring reactive terminal amine groups. Subsequently, via two consecutive surface-initiated atom transfer radical polymerizations (SI-ATRP), pH- and temperature-responsive polymer blocks were grown from the Fe3O4 surface, resulting in the formation of poly(itaconic acid)-block-poly(N-isopropyl acrylamide) (PIA-b-PNIPAM)-grafted nanomagnetic particles (PIA-b-PNIPAM@Fe3O4). To confirm the chemical composition and assess how the particle morphology and size distribution of these SRP-based nanocomposites change in response to ambient pH and temperature stimuli, various characterization techniques were employed, including transmission electron microscopy, differential light scattering, and Fourier transform infrared spectroscopy. The results indicated successful synthesis, with PIA-b-PNIPAM@Fe3O4 demonstrating sensitivity to both temperature and pH. Full article
(This article belongs to the Section Nanocomposite Materials)
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