Search Results (266)

Hybrid fluorinated copolymers containing POSS moieties along with fluorinated homopolymers were synthesized via organocatalyzed atom transfer radical (co)polymerization (O-ATRP) of fluoroalkyl methacrylate (FMA) and a POSS-based monomer (IBSS) using perylene as a photocatalyst. Linear and four- and eight-armed star-shaped (co)polymers in a wide range of molecular weights with M_n(SEC) up to 53,100 g/mol for poly(FMA), 22,700 g/mol for poly(IBSS) and 87,300 g/mol for poly(FMA-co-IBSS) were successfully prepared. During polymerization, C–F activation was found to induce chain transfer and branching reactions, contributing to structural diversity. A mechanism for chain transfer to the polymer resulting in branching was proposed, applying density functional theory (DFT). Films based on the obtained (co)polymers showed tunable morphology, high thermal stability (up to 306 °C) and hydrophobicity, with water contact angles reaching 98°. Full article

Atom transfer radical polymerization (ATRP) is a leading reversible deactivation radical polymerization method. It has become an emerging technology to synthesize well-defined, tailor-made polymers, promoting the development of advanced materials (e.g., bioconjugates and nanocomposites) with precisely designed and controlled macromolecular architectures. ATRP-produced polymers or polymeric materials have been successfully applied in the fields of drug delivery, tissue engineering, sample separation, environmental monitoring, bioimaging, clinical diagnostics, etc. In this review, we systematically summarize the progress of ATRP-based chemical and biological sensors in different application fields, including ion sensing, small-molecule detection, bioimaging, and signal amplification for biosensors. Finally, we briefly outline the prospects and future directions of ATRP. This review is expected to provide a fundamental and timely understanding of ATRP-based sensors and guide the design of novel materials and methods for sensing applications. Full article

In this study, patch-structured C₈/CHO template microspheres were successfully synthesized through in situ reduction and sol–gel reactions, providing a reusable platform for subsequent modifications. Based on these templates, temperature-responsive PW₁₂O₄₀³⁻-PILs/PNIPAM Janus nanosheets were prepared via sequential Schiff-base coupling and ATRP. Structural characterizations (XRD, SEM, TEM, FTIR, and TGA) confirmed successful functionalization and nanosheet formation. The PNIPAM moiety endowed the nanosheets with temperature responsiveness, while the incorporation of polymerized ionic liquids and phosphotungstate anions further enhanced amphiphilicity and dispersion stability. When applied as particulate emulsifiers in water/toluene systems, the Janus nanosheets formed stable Pickering emulsions at elevated temperatures and underwent reversible emulsification–demulsification upon temperature cycling. These findings demonstrate the potential of PW₁₂O₄₀³⁻-PILs/PNIPAM Janus nanosheets as smart emulsifiers for responsive separation and formulation technologies. Full article

The application of microsphere molecularly imprinted materials for the targeted extraction and purification of flavonoids derived from agricultural waste has emerged as a prominent area of investigation. An innovative boronate affinity imprinted microsphere (MC-CD@BA-MIP) was successfully synthesized using the Pickering emulsion interfacial assembly strategy for the selective separation of naringin (NRG). The double-bond functionalized covalent organic framework (COF)-based microspheres were synthesized through Schiff–base reaction and secondary interfacial emulsion polymerization. Then, the synthetic mono-(6-mercapto-6-deoxy)-β-cyclodextrin (SH-β-CD) was grafted onto the surface of the microspheres (MC) using click chemistry. The 1-allylpyridine-3-boronic acid (APBA) as a functional monomer was grafted onto the initiator (ABIB) through atom transfer radical polymerization (ATRP). Ultimately, the synthesized boronic acid-imprinted ABIB-BA-MIPs were immobilized onto the COFs microsphere surface through host–guest interactions. As expected, under neutral conditions, the MC-CD@BA-MIPs still exhibited a significant adsorption capacity (38.78 μmol g⁻¹ at 308 K) for NRG. The regenerated MC-CD@BA-MIPs maintained 92.56% of their initial adsorption capacity through six consecutive cycles. Full article

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

To address the growing demand for environmentally friendly flexible sensors, here, a composite hydrogel of nanocellulose (NC) and polyvinyl alcohol (PVA) was designed and fabricated using Camellia oleifera shells as a sustainable alternative to petroleum-based raw materials. Firstly, NC was extracted from Camellia oleifera shells and modified with 2-chloropropyl chloride to obtain a nanocellulose-based initiator (Init-NC) for atomic transfer radical polymerization (ATRP). Subsequently, sulfonyl betaine methacrylate (SBMA) was polymerized by Init-NC initiating to yield zwitterion-functionalized nanocellulose (NC-PSBMA). Finally, the NC-PSBMA/PVA hydrogel was fabricated by blending NC-PSBMA with PVA. A Fourier transform infrared spectrometer (FT-IR), proton nuclear magnetic resonance spectrometer (¹H-NMR), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), universal mechanical testing machine, and digital source-meter were used to characterize the chemical structure, surface microstructure, and sensing performance. The results indicated that: (1) FT-IR and ¹H NMR confirmed the successful synthesis of NC-PSBMA; (2) SEM, TEM, and alternating current (AC) impedance spectroscopy verified that the NC-PSBMA/PVA hydrogel exhibits a uniform porous structure (pore diameter was 1.1737 μm), resulting in significantly better porosity (15.75%) and ionic conductivity (2.652 S·m⁻¹) compared to the pure PVA hydrogel; and (3) mechanical testing combined with source meter testing showed that the tensile strength of the composite hydrogel increased by 6.4 times compared to the pure PVA hydrogel; meanwhile, it showed a high sensitivity (GF = 1.40, strain range 0–5%; GF = 1.67, strain range 5–20%) and rapid response time (<0.05 s). This study presents a novel approach to developing bio-based, flexible sensing materials. Full article

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

Polymer brushes (PBs) are transformative surface-modifying nanostructures, yet their synthesis via controlled methods like copper-mediated surface-initiated atom-transfer radical polymerization (Cu⁰-SI-ATRP) faces reproducibility challenges due to a lack of understanding of parameter interdependencies. This study systematically evaluates the Cu⁰-SI-ATRP process for polyacrylamide brushes (PAM-PBs), aiming to clarify key parameters that influence the synthesis process. This evaluation followed a step-by-step characterization that tracked molecular changes through infrared spectroscopy (IR) and surface development by contact angle (CA) through two different mixing methods: ultrasonic mixing and process simplification (Method A) and following literature-based parameters (Method B). Both methods, consisting of surface activation, 3-aminopropyltriethoxysilane (APTES) deposition, bromoisobutyryl bromide (BiBB) anchoring, and polymerization, were analyzed by varying parameters like concentration, temperature, and time. Results showed ultrasonication during surface activation enhanced siloxane (1139→1115 cm⁻¹) and amine (1531 cm⁻¹) group availability while reducing APTES concentration to 1 Vol% without drying sufficed for BiBB anchoring. BiBB exhibited insensitivity to concentration but benefited from premixing, evidenced by sharp C–Br (~1170 cm⁻¹) and methyl (3000–2800 cm⁻¹) bands. Additionally, it was observed that PAM-PBs improved with Method A, which had reduced variance in polymer fingerprint regions compared to Method B. Adding to the above, CA measurements gave complementary step-by-step information along the modifications of the surface, revealing distinct wettability behaviors between bulk PAM and synthesized PAM-PBs (from 51° to 37°). As such, this work identifies key parameter influence (e.g., mixing, BiBB concentration), simplifies steps (drying omission, lower APTES concentration), and demonstrates a step-by-step, systematic parameter decoupling that reduces variability. In essence, this detailed parameter analysis addresses the PAM-PBs synthesis process with better reproducibility than the previously reported synthesis method and achieves the identification of characteristic behaviors across the step-by-step process without the imperative need for higher-cost characterizations. Full article

Star polymers—macromolecules featuring multiple arms radiating from a central core—offer unique potential for biomedical applications due to their tunable architecture, multifunctionality and ability to incorporate stimuli-responsive and biocompatible components. In this study, functional star polymers with oligo (ethylene glycol) methyl ether methacrylate (OEOMA) arms and 2-(dimethylamino)ethyl methacrylate (DMAEMA) core units were synthesized via atom transfer radical polymerization (ATRP) using the “arm-first” strategy. The star polymers were used as nanoreactors for the in situ reduction of silver nitrate to form silver nanoparticles (AgNPs) without additional reducing agents. UV–Vis spectroscopy confirmed the formation of spherical AgNPs with absorption maxima around 430 nm, and transmission electron microscopy revealed uniform particle morphology. These hybrid nanomaterials (STR-AgNPs) were incorporated into polymethyl methacrylate (PMMA)-based bone cement to impart antibacterial properties. Mechanical testing showed that the compressive strength remained within acceptable limits, while antibacterial assays against E. coli demonstrated a significant inhibition of bacterial growth. These findings suggest that STR-AgNPs serve as promising candidates for infection-resistant bone implants, providing localized antibacterial effects while maintaining mechanical integrity and biocompatibility. Full article

Thread-based analytical devices are low-cost, portable, and easy to use, making them ideal for detecting various biomolecules like glucose and DNA with minimal sample requirements, while also offering environmental benefits through their biodegradability. This study explores the potential of zwitterionic poly(sulfobetaine methacrylate) brushes modified cotton thread (PSBMA@threads) as an innovative substitute for DNA solid-phase extraction. The PSBMA polymer brushes were synthesized on cotton threads via surface-initiated atom transfer radical polymerization (SI-ATRP). The usability of the PSBMA@threads for DNA extraction from cell lysates containing cell debris, proteins, and detergents was evaluated. Characterization using SEM, FTIR, and EDS confirmed the successful functionalization with PSBMA polymer brushes. The antifouling properties of PSBMA@threads, including resistance to non-specific protein adsorption and underwater oil repellency, were assessed. The results demonstrated selective DNA capture from protein and lipid-rich lysates. Optimized extraction parameters improved DNA yield, enabling efficient extraction from tumor cells, which successfully underwent PCR amplification. Comparative experiments with commercial silica membrane-based columns revealed that PSBMA@threads exhibited comparable DNA extraction capability. The PSBMA@threads maintained extraction capability after six months of ambient storage, highlighting its stability and cost-effectiveness for nucleic acid isolation in analytical applications. Full article

Medical titanium alloy Ti-6Al-4V (TC4) is widely used as a surgical implant material in biomedical fields owing to its superior biocompatibility, corrosion resistance, and mechanical performance, particularly for osseous integration applications. However, long-term contact of medical titanium-based implants with human soft tissues may induce infection and inflammation. To address these limitations, a drug-loading gel was designed to be synthesized on a TC4 surface to improve biointegration. Considering the critical regulatory roles of temperature and pH in physiological environments, this study synthesized a dual-responsive hydrogel using the temperature-sensitive monomers 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and oligoethylene glycol methacrylate (OEGMA) and the pH-sensitive monomer diethylaminoethyl methacrylate (DEAEMA), employing stereocomplexed polylactic acid as a physical crosslinker and N,N′-methylenebisacrylamide (MBA) as a chemical crosslinker. A polydopamine-based initiator was synthesized via dopamine functionalization with 2-bromoisobutyryl bromide (BIBB). The amphiphilic co-network hydrogel was grafted onto a modified TC4 surface through atom transfer radical polymerization (ATRP). Integration of the drug-loading gel and TC4 gives the implant an “active therapeutic” function by localized drug release. The results demonstrated that the energy storage modulus of the double-crosslinked gel matched that of human soft tissues. The gels exhibited efficient drug release. Full article

CO₂-responsive polymers have emerged as a significant class of smart materials, distinguished by their ability to reversibly alter their properties upon exposure to CO₂. Due to CO₂’s abundant availability, low cost, non-toxicity, energy efficiency, and excellent biocompatibility, these polymers offer remarkable environmental and practical advantages. This review succinctly explores recent advancements in the synthesis, mechanisms, and applications of CO₂-responsive polymers, emphasizing the pivotal roles of specific acidic and basic functional groups such as carboxylic acids, phenolic groups, amines, amidines, guanidines, and imidazoles. Advanced polymerization techniques including free radical polymerization (FRP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), and nitroxide-mediated polymerization (NMP) are critically evaluated for their precision and flexibility in polymer design. Significant applications in smart separation, carbon capture, drug delivery, desalination, emulsions, tissue engineering, and sensing technologies are discussed comprehensively. Although substantial progress has been made, ongoing challenges include enhancing response speed, durability, sustainability, and economic viability. Future research is recommended to focus on innovative polymer structures, computational modeling, hybrid materials, and greener synthesis methods. This review aims to inspire continued exploration and practical utilization of CO₂-responsive polymers to address pressing environmental and technological needs. Full article

The preparation of stable dispersions of MoS₂ by ultrasonic aqueous and/or organic media containing amphiphilic molecules is an attractive and widely applicable method to form MoS₂ fine particles while suppressing its aggregation. In this study, we developed a series of polymers with pendant sulfide moieties as a new dispersant, under the hypothesis that it would interact with sulfur atoms on MoS₂ surfaces. First, we designed a sulfide group-substituted methacrylate derivative (ESMA) with the hypothesis that it would interact with the MoS₂ surface through sulfur-sulfur interactions. Then, we synthesized well-defined polymers with pendant sulfide groups by living radical polymerization (ATRP). Next, 0.5 wt% MoS₂ was added to a DMSO solution containing 1 wt% of the obtained polymer (polyESMA), and the mixture was treated with a bath-type ultrasonicator for 3 h to obtain a MoS₂ dispersion. We found that stable dispersions of MoS₂ in a fine particle state, although not in the form of single-layer or few-layer nanosheets, could be readily formed in DMSO using polyESMA as a polymeric dispersant. Furthermore, we synthesized polymeric dispersants with different molecular weights and investigated the relationship between the structure of the dispersant and the dispersion stability. Full article

In recent years, the disposal of agricultural lignocellulosic residues has been accompanied by problems such as resource waste and environmental pollution. Therefore, the development of valorization technologies has emerged as a strategic priority in sustainable materials science. This study pioneered the use of corncob cellulose as the substrate (a representative agricultural lignocellulosic residue) and transformed it into ionized cellulose by grafting methacryloxyethyl trimethyl ammonium chloride (DMC) via atom transfer radical polymerization (ATRP) and UV-initiated polymerization. Characterizations demonstrated exceptional properties: robust mechanical strength (1.28 MPa tensile strength with 573% elongation); outstanding thermal stability (stable to 278 °C); cryogenic tolerance (retaining flexibility at −25 °C); and universal adhesion capability (4.23 MPa to glass substrates, with adequate interfacial bonding across diverse surfaces). Meanwhile, the ionogel exhibited exceptional sensing sensitivity (gauge factor, GF = 1.23–2.08), demonstrating versatile application potential in wearable electronics. It achieved the precise detection of subtle strains (1–5% strain range) and the high-fidelity acquisition of electrocardiogram (ECG) signals. This study broadens the design paradigm of agricultural lignocellulosic residue-based functional materials. It also provides a novel technical pathway to develop eco-friendly intelligent sensors. Full article

This study explored the formation of soft colloidal particles from a diblock ionomer (DI) with the monomeric composition (acrylonitrile)_x-co-(glycidyl methacrylate)_y-b-(3-sulfopropyl methacrylate potassium)_z—abbreviated as (A_xG_y)S_z, where x >> z > y. A colloidal dispersion was generated by introducing water into the pre-prepared DMSO solutions of DI, which led to micelle formation and subsequent coagulation. The assembly of the hydrophobic (A_xG_y) blocks was influenced by water content and chain conformational flexibility (the ability to adopt various forms of conformation). The resulting microgel structure (in particle form) consists of coagulated micelles characterized by discrete internal hydrophobic gel domains and continuous external hydrophilic gel layers. Characterization methods included light scattering, zeta potential analysis, and particle size distribution measurements. In contrast, the copolymer (A_xG_y) chains form random coil aggregates in DMSO–H₂O mixtures, displaying a chain packing state distinct from the hydrophobic gel domains as aforementioned. Additionally, the amphiphilic glycidyl methacrylate (G) units within the (A_xG_y) block were found to modulate the microgel dimensions. Notably, the nanoscale hydrogel corona exhibits high accessibility to reactive species in aqueous media. The typical microgel has a spherical shape with a diameter ranging from 50 to 120 nm. It exhibits a zeta potential of −65 mV in a neutral aqueous medium; however, it may precipitate if the metastable colloidal dispersion state cannot be maintained. Its properties could be tailored through adjusting the internal chain conformation, highlighting its potential for diverse applications. Full article