Radical Polymerization Research Articles

Intrinsically Thermally Degradable Microstructures Fabricated by Photodimerization in Rapid 3D Laser Printing

AbstractClassical photoresists utilized in direct laser writing (DLW) rely on photoinitiators and radical polymerization mechanisms to induce the cross‐linking process. Herein, a simple initiator‐free photoresist is introduced that enables the rapid fabrication of intrinsically thermally degradable 3D microstructures via DLW. The reported photoresist exploits the [2 + 2] photo‐dimerization reaction of a multifunctional monosubstituted thiomaleimide compound while harvesting on‐demand microstructure degradation through the intrinsic thermally reversible nature of the photocrosslinks. The photoresist exceeds attainable DLW printing speeds for non‐chain growth resins, readily attaining 1500 µm s−1 and up to 5000 µm s−1, making it a promising system to compete with traditional photo‐initiator containing resists while introducing on‐demand post‐printing degradability.

Intercalation of Polyacrylonitrile Nanoparticles in Ti3C2Tx MXene Layers for Improved Supercapacitance.

We report the intercalation of polyacrylonitrile nanoparticles in Ti3C2Tx MXene layers through simple sonication. The use of polyacrylonitrile, which was synthesized via radical polymerization, offered dual benefits: (1) It increased the interlayer spacing of MXene, thereby exposing more surface area and enhancing ion transport channels during charge and discharge cycles, and (2) Integrating MXene with polyacrylonitrile enables the creation of a composite with conductive properties, following percolation principle. X-ray diffraction analysis showed an increase in the c-lattice parameter, indicative of the interlayer spacing, from 22.31 Å for the pristine MXene to 37.73 Å for the MXene-polyacrylonitrile composite. The intercalated polyacrylonitrile nanoparticles facilitated the delamination by weakening the interlayer interactions, especially during sonication. Electrochemical assessments revealed significant improvement in the properties of the MXene-polyacrylonitrile composite compared to the pristine MXene. The assembled asymmetric device achieved a good specific capacitance of 32.1 F/g, an energy density of 11.42 W h/kg, and 82.2% capacitance retention after 10,000 cycles, highlighting the practical potential of the MXene-polyacrylonitrile composite.

Bayesian optimization of radical polymerization reactions in a flow synthesis system

Bayesian optimization of radical polymerization reactions in a flow synthesis system

Antimicrobial Peptide SAAP-148-Functionalized Hydrogels from Photocrosslinkable Polymers with Broad Antibacterial Activity.

Antimicrobial peptides (AMPs) are promising alternatives to traditional antibiotics for treating skin wound infections. Nonetheless, their short half-life in biological environments restricts clinical applicability. Covalent immobilization of AMPs onto suitable substrates offers a comprehensive solution, creating contact-killing surfaces with long-term functionality. Here, a copolymer of poly[(hydroxy ethyl acrylamide)-co-(4-benzophenone acrylamide)-co-(pentafluorophenyl acrylate)-co-(ECOSURF EH-3 acrylate)], in short poly(HEAAm-co-BPAAm-co-PFPA-co-EH3A), is synthesized by free radical polymerization. Subsequent modification of active ester groups with the amine groups of SAAP-148, results in a copolymer, that is non-cytotoxic to human lung fibroblasts. UV photocrosslinking of the benzophenone units yields a polymer network that forms a hydrogel after swelling with aqueous medium. Both the SAAP-148-modified polymer in solution and the photocrosslinked hydrogels show good antimicrobial activity against strains of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii, including multidrug-resistant strains, frequently found in wound infections. The covalent attachment of SAAP-148 prevents leaching, ensuring sustained antimicrobial activity for at least 48 h in diluted human blood plasma and 14 days in PBS. This prolonged retention of antimicrobial activity in human blood plasma significantly enhances its clinical potential. Overall, this study shows the potential of the AMP-functionalized photocrosslinkable polymer as antimicrobial wound dressings, providing an effective alternative to antibiotics.

Preparation of viscosity-reducing polycarboxylate superplasticizer (PCE) and its role in low water-to-cement ratio system

Owing to the low water-cement ratio (less than 0.25) of ultra-high-performance concrete (UHPC) materials, the system exhibits increased viscosity, diminished slurry flow, and challenges in pouring during the construction process, which compromise its workability. Consequently, the development of highly efficient viscosity-reducing polycarboxylate superplasticizer (PCE) is of paramount importance. In this study, we synthesized a series of viscosity-reducing polycarboxylate superplasticizers(JN-PCE) utilizing allyl polyethylene glycol ether (APEG), acrylic acid (AA), and sodium methallyl sulfonate (SMAS) as raw materials through the process of free radical polymerization. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and energy-dispersive X-ray spectroscopy were employed to characterize the materials. Subsequent evaluations of surface tension, fluidity, adsorption performance, and Marsh time demonstrated that these superplasticizers exhibited commendable dispersion and remarkable viscosity-reducing properties within a low water-cement ratio system. At a water-cement ratio of 0.18, the Marsh time of the JN-type PCE was reduced by 40% while maintaining the same fluidity, thereby underscoring the effective viscosity-reducing capabilities of the synthesized polycarboxylate superplasticizer.

Study on the mechanical properties of Polyacrylic Acid/Chitosan double network hydrogels in dynamic water content

Abstract Hydrogels have demonstrated significant potential in wound dressings, owing to their adjustable water content, excellent biocompatibility, and other advantages. An ideal wound dressing requires absorbing exudate while maintaining mechanical properties to prevent secondary damage to the wound under external pressure. In this study, Polyacrylic Acid (PAA)/Chitosan (CS) double network hydrogels were prepared via radical polymerization, and the swelling ratio, compressive modulus, and other parameters were experimentally measured. A hyperelastic finite element model of the hydrogel was then established, and its rationality was validated by experiments. Based on the model, the impacts of CS content and dynamic water content on the compressive properties of PAA/CS hydrogels were analyzed. Tetracycline hydrochloride was loaded into PAA/CS hydrogels, the drug release performance and adhesion experiments were carried out. The results indicated that, compared with the hydrogels with 2.5% and 5% CS content, the hydrogel with 1% CS content had the highest swelling ratio, which was 1774%. Meanwhile, its equilibrium water content could attain 94.6%. When the water content varied within the range from 45% to 75%, the compressive strength of the hydrogel with 5% CS content ranged from 0.33 MPa to 1.22 MPa, similar to that of skin tissue. Additionally, the prepared drug-loaded PAA/CS hydrogels exhibited a drug release pattern approximately following the Korsmeyer-Peppas model within 7 days. They also exhibited remarkable adhesion to porcine skin and different substrate surfaces. This study provides a basis for the clinical application of PAA/CS double network hydrogels as wound dressings in the repair of infected wounds.

Localized Thermoresponsive Behavior in P(NIPAm‐co‐AAc) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering

ABSTRACTStimuli‐responsive polymers stand out for their ability to respond to small environmental changes. One of the most representative thermo‐sensitive materials is poly(N‐isopropyl acrylamide) (PNIPAm), which presents reversible phase transitions close to the human body temperature. However, previous studies observed that the copolymerization of NIPAm with small quantities of different monomers like acrylic acid (AAc) results in copolymers with reduced or lost thermo‐responsivity. In this study, thermo‐sensitive PNIPAm, pH‐sensitive poly(acrylic acid) (PAAc), and various proportions of their copolymers P(NIPAm‐co‐AAc) were obtained by free radical polymerization and thoroughly characterized. Rheological and structural studies reveal the remaining thermosensitivity of the copolymers manifested at short molecular ranges. These alterations in short‐range interactions are observed in all samples containing NIPAm, and they are evidenced by changes in the fractality of their structure and flow index behavior of the Viscosity Ostwald–de Waele Model. Particularly, when the copolymer proportion of NIPAm/AAc is about 40/60, the Beaucage model reveals two structural levels, ~200 and ~10 nm. Furthermore, the model exhibits a thermal response of the lower‐size substructures, indicating possible segregation of NIPAm‐rich regions from copolymer chains. The evidence found in this work could contribute to the development of nanosystems, in which local thermoresponsive effects are sought, such as for active drug targeting.

Quantitative Examination and Mechanistic Insights of Polymer Chain Conformation Confined in Nanopores by Time-Resolved Fluorescence Resonance Energy Transfer.

The conformational studies of polymers confined at the nanoscale remain challenging and controversial due to the limitations of characterization techniques. In this study, we utilized the high sensitivity of time-resolved fluorescence resonance energy transfer (trFRET) and a site-specific dye-labeling strategy to characterize the conformation of polymer chains confined in anodic aluminum oxide (AAO) nanopores. This strategy introduced a fluorescent donor (carbazole) and acceptor (anthracene) at the center of poly(butyl methacrylate) (PBMA) chains grown by atom transfer radical polymerization (ATRP). By quantitatively analyzing fluorescence decay through the Förster mechanism and the Drake-Klafter-Levitz (DKL) formalism, we can determine both the energy transfer efficiency and the spatial distribution of the dyes. This analysis revealed that the PBMA chains, with a molecular weight of 40 kDa, maintained their bulk-like conformation even when confined within nanopores as small as 10 nm in diameter. This study is the first to demonstrate the use of trFRET for investigating chain conformation in confined polymer systems, which can be generalized to other polymer types and polymer topologies in different confined geometries.

Mechanism of Inhibiting Spontaneous Coal Combustion by Dopa Hydrosol

ABSTRACT A new type of biomass environmentally friendly hydrosol (DEP) was proposed to inhibit coal spontaneous combustion (CSC). The DEP consists of two parts, the PDopa side chain solution formed by the redox reaction of Dopa and EGCG and the main chain sol solution formed by the free radical polymerization of AA under the action of APS initiator. The −COOH, −NH2, and −OH in Dopa can be grafted onto the skeleton of the main chain via double strong hydrogen bonding interactions with the −COOH group in PAA to form a stable three-dimensional cross-linked network structure. DEP can inhibit CSC through three aspects: oxygen isolation, increasing the activation energy of coal oxidation, scavenging active groups and free radicals. The calculation simulation results show that EGCG in DEP can remove various active free radicals with lower activation energy at room temperature, breaking the chain cycle reaction of coal spontaneous combustion, which proves its high efficiency. This study provides a new way to apply mussel-inspired adhesion mechanisms to the prevention of CSC.

The influence of cavitation radicals on the suspension polymerization of n‐butyl methacrylate during ultrasonic emulsification

AbstractThe influence of cavitation‐generated free radicals on the suspension polymerization of n‐butyl methacrylate under ultrasonic irradiation was investigated experimentally and by kinetic modeling. A kinetic model of radical polymerization was proposed, considering the interaction of free radicals generated in cavitation bubbles with both monomer molecules and free radicals formed within the monomer droplets. It was found that the primary contribution to the polymerization acceleration come from cavitation radicals generated inside the monomer droplets, whereas the impact of cavitation radicals formed in the dispersion medium decreases as the fraction of monomer in the mixture decreases. Increasing the concentration of cavitation radicals was shown to lead to a reduction in the average chain length and the dispersity of terminated chains. It was demonstrated that the computational results are in good agreement with experimental data.Highlights Kinetic model for suspension polymerization in ultrasonic field is proposed. Impact of cavitation radicals on suspension polymerization kinetics is studied. Chain length and dispersity decrease with increasing amount of cavitation radicals.

RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials.

Control of the morphology of polymer systems is achieved through reversible-deactivation radical polymerization techniques such as Reversible Addition-Fragmentation chain Transfer (RAFT). Advanced RAFT techniques offer much more than just "living" polymerization - the RAFT toolkit now enables morphological control of polymer systems across many decades of length-scale. Morphological control is explored at the molecular-level in the context of syntheses where individual monomer unit insertion provides sequence-defined polymers (single unit monomer insertion, SUMI). By being able to define polymer architectures, the synthesis of bespoke shapes and sizes of nanostructures becomes possible by leveraging self-assembly (polymerization induced self-assembly, PISA). Finally, it is seen that macroscopic materials can be produced with nanoscale detail, based on phase-separated nanostructures (polymerization induced microphase separation, PIMS) and microscale detail based on 3D-printing technologies. RAFT control of morphology is seen to cross from molecular level to additive manufacturing length-scales, with complete morphological control over all length-scales.

α-Trifluoromethylated Quinolines as Safe and Storable PET-Donor for Radical Polymerizations.

In the quest for powerful, safe, and storable photoinduced-electron transfer (PET) donors, the attention is turned to the α-trihalomethylated amine moiety that is not studied in the context of PET-reductants. The thermal and photophysical properties of α-trifluoromethylated quinolines are thus studied and their reducing abilities evaluated as initiators of polymerization reactions. Polymers of high molecular weights are obtained through a radical polymerization process and the PET-donor can be stored within the monomer for several months without losing its efficiency. Mechanistic investigations, combining spectroscopic analysis and theoretical calculations, confirm the mode of activation of these electron donors and the generation of radical intermediates through single electron transfer.

Uniform Polymer Microspheres by Photoinduced Metal-Free Atom Transfer Radical Precipitation Polymerization.

Herein, a photoinduced method is introduced for the synthesis of highly cross-linked and uniform polymer microspheres by atom transfer radical polymerization (ATRP) at room temperature and in the absence of stabilizers or surfactants. Uniform particles are obtained at monomer concentrations as high as 10% (by volume), with polymers being exempt from contamination by residual transition metal catalysts, thereby overcoming the two major longstanding problems associated with thermally initiated ATRP-mediated precipitation polymerization. Moreover, the obtained particles have also immobilized ATRP initiators on their surface, which directly enables the controlled growth of densely grafted polymer layers with adjustable thickness and a well-defined chemical composition. The method is then employed successfully for the synthesis of molecularly imprinted polymer microspheres.

A Multi-Enzyme Nanocascade to Target Disease-Relevant Metabolites.

Metabolic processes in living organisms depend on the synergistic actions of enzymes working in proximity and in concert, catalyzing reactions effectively while regulating the formation of metabolites. This enzyme synergy offers promising therapeutic application for diseases such as alcohol intoxication, cancer, and hyperinflammation. Despite their potential, the clinical translation of enzyme cascades is restricted by challenges including poor enzyme stability, short half-life, and a lack of delivery strategies that maintain enzyme proximity. In this study, multi-enzyme nanocascades synthesized are developed through in situ atom transfer radical polymerization using a zwitterionic monomer. This method markedly enhances enzyme stability and proximity, thereby prolonging their circulation half-life after systemic administration. It is demonstrated that the nanocascades of uricase and catalase effectively reduce uric acid levels without excessive hydrogen peroxide production, providing a potential antidote for hyperuricemia. Moreover, in a murine breast cancer model, the nanocascades of glucose oxidase and catalase inhibited tumor progression and enhanced the therapeutic efficacy of doxorubicin. The prolonged circulation and promoted reaction efficacy of these nanocascades underscore their substantial potential in enzyme replacement therapy and the treatment of various diseases.

Synthesis of Oil-Soluble Polymer-Grafted Carbon Dots with Outstanding Colloidal Stability and Tribological Properties in Polyalphaolefin.

Herein, a series of polylauryl methacrylate-grafted CDs (CDs-PLMA-m, m denotes the reaction time in hours) with core-shell structure were synthesized via surface-initiated atom-transfer radical polymerization (SI-ATRP). Due to the good solubility of PLMA in hydrocarbons, all of the CDs-PLMA-m can be facilely dispersed in polyalphaolefin (PAO) to form pellucid colloidal dispersions. The reciprocating ball-on-plate sliding friction tests proved that the addition of 3.0 wt % CDs-PLMA-1 markedly lessened the wear and friction of PAO by 53.0 and 40.0%, respectively. The tribological performances of the CDs-PLMA-1 (3.0 wt %)/PAO dispersion did not attenuate sharply when the friction duration extended from 20 to 200 min or the applied load increased from 20 to 100 N, revealing the long lifetime and desirable load-carrying effect of CDs-PLMA-1. Based on the friction tests, the antifriction behavior of CDs-PLMA-1 was related to the synergies between the molecular lubrication of PLMA-1 brushes and the nanolubrication of CDs. Furthermore, the wear analyses disclosed the deposition of tribofilm composed of a lot of CDs-PLMA-1 and a spot of iron oxides, which provided oxidation resistance and an antiwear function. This study established a reliable route to the synthesis of oil-soluble polymer-grafted CDs, enabling high-efficiency lubrication of CDs in PAO.

Synthesis and Binding Properties of High-Affinity Histidine-Bearing Polymers for Wood Lignin.

The pursuit of molecules capable of binding to wood lignin is pivotal for advancing lignin degradation technology, particularly when combined with lignin degradation catalysts. In this study, synthetic polymers bearing histidine moieties, demonstrating remarkable affinity for wood lignin are reported. These polymers, featuring varying degrees of histidine substitution in the form of histidine methyl esters, are synthesized through controlled radical polymerization of an activated ester-bearing monomer, employing a fluorescein-labeled chain transfer agent and subsequent postpolymerization amidation with histidine methyl ester. The binding properties of these histidine-bearing polymers with milled wood lignin under aqueous conditions are investigated. Qualitative assessment of lignin-binding capabilities involve spectroscopic analysis of changes in absorbance of visible light and fluorescence intensity. Furthermore, quantitative evaluation is conducted through surface plasmon resonance measurements to determine the binding parameters of the polymers with wood lignin. Notably, polymers with higher histidine substitution exhibit enhanced binding affinity compared to those with lower histidine substitution levels.

Novel carboxymethyl cellulose-based hydrogel embedded with metal organic framework for efficient cationic dye removal from water

The rGO/CMC/β-CD (RCβ) hydrogel was synthesized from reduced graphene oxide (rGO), β-cyclodextrin (β-CD) and sodium carboxymethyl cellulose (CMC) by radical polymerization. A novel hydrogel adsorbent was created by growing the metal-organic framework (Cu-BTC) in-situ on RCβ hydrogel, which has excellent adsorption capacities for cationic dyes in wastewater. The adsorption parameters such as the amount of adsorbent, pH of solution and adsorption time were optimized through batch adsorption experiments. Under the optimal conditions of pH 6.0, adsorbent dosage of 0.01 g and experimental temperature of 25 °C, Langmuir isothermal model was used to fit the maximum adsorption capacities of methylene blue (MB), crystal violet (CV) and malachite green (MG), which were 892.66, 842.75 and 633.77 mg g−1, respectively. The fitting results of adsorption kinetics revealed that the pseudo-second-order model can describe the adsorption process better. Based on proposed studies, the dye molecules were adsorbed onto RCβ@Cu-BTC hydrogel mainly through electrostatic interaction, hydrogen bonding and π–π interactions. After five cycles, the adsorption efficiency of the RCβ@Cu-BTC hydrogel for MB, CV and MG can still reach 80 %, 77 % and 72 %, which shows that the adsorbent has good adsorption performance. Various adsorption experiments shows that RCβ@Cu-BTC hydrogel has great potential in treating dye wastewater.

CO2 hydrate formation in superabsorbent hydrogels for carbon capture—A comparison of water-confined framework vs non-water framework

This study investigates the kinetics of CO2 hydrate formation in saturated hydrogel particles—water-confined frameworks—through both experimental and numerical methods, and compares the results with those obtained in silica gels, silicon-based frameworks. Three hydrogel materials with varying swelling ratios were synthesized via radical polymerization. An advanced shrinking core model was developed, incorporating factors of CO2 solubility, gas diffusion, gas–water reaction, capillary effects, and hydrogel functional groups. Results showed rapid CO2 hydrate growth within the first 100 min, with CO2 uptake reaching 78%–82% of the final amount by 600 min. The highest percent water conversion achieved was 96.6%. Simulations indicated a significant decrease in CO2 diffusion coefficient through the hydrate shell over time, especially in hydrogels with higher methacrylic acid content. Capillary effects diminished as the reaction proceeded, with final water consumption via capillaries accounting for 14.4%–26.7% of the total. Hydrogels with higher swelling ratios and higher agglomeration degree formed more porous hydrate shells, enhancing CO2 diffusion but resulting in lower overall CO2 uptake due to their lower water content. Comparisons with hydrophilic porous silica gel revealed that, although hydrogels initially posed greater mass transfer resistance, they ultimately exhibited superior CO2 absorption capacity and rate.

A new Rose Bengal glycopolymer: Photosensitization in two stages

Antimicrobial photodynamic therapy is a promising alternative to deal with antimicrobial resistance. However, both the low specificity and low local oxygen molecular concentrations decrease the antimicrobial efficiency limiting its use. An interesting approach to the problem is the use of molecules that can react reversibly with singlet oxygen by the formation of reversible endoperoxides, such as naphthalene, anthracene and pyridone derivatives. Particularly, the use of these molecules with mannosyl derivatives allow the interaction with adhesins presented on pili and fimbriae improving the localization near to bacteria. In this work, we synthesized polymeric nanoparticles able to generate singlet oxygen (under both irradiation and dark conditions) in the vicinity of a center capable of recognizing mannose and oxidize nearby biomolecules. Rose Bengal was used as photosensitizer due to its attractive photophysical properties (vis absorption, high singlet oxygen generation) and biocompatibility. The polymeric nanoparticles were obtained by radical polymerization using polyvinyl alcohol as a template, showing sizes around 300 nm with negative zeta potential by dynamic light scattering. The singlet oxygen generation was monitored following DPBF consumption and showed to be dependent on the amount of pyridone in the feed of polymers. In addition, the release of singlet oxygen was also dependent on pyridone concentration showing a slower rate constant at 40 % pyridone, while for contents of 10 % and 60 % higher rate constants were observed. The specific interaction of glycopolymers with Concanavalin A was demonstrated by successful agglutination assays, but also a low participation of unspecific interactions for polymers without mannosyl derivatives was observed. On the other hand, the oxidation of amino acids of Concanavalin A was monitored by acrylamide gel electrophoresis. Type I and Type II photosensitization were observed with the formation of dimers and fragments with lower molecular weight, while in dark conditions only products with lower molecular weight were observed, result consistent with singlet oxygen released by pyridone endoperoxides.

Enhancing strength and toughness simultaneously: Diblock-grafted cellulose nanofiber one-component nanocomposites

To overcome the drawbacks of homopolymer-grafted CNF one-component nanocomposites, a range of diblock-grafted cellulose nanofiber (CNF), CNF-g-(polybutyl acrylate-b-polymethyl methacrylate)s were synthesized through reversible-deactivation radical polymerization (RDRP) methods. The chemical structures and ratios between the two blocks were confirmed, with surface-grafted CNF observed as submicron particles. Both thermal and thermodynamic analysis revealed two glass transition temperatures (Tg) in the diblock-grafted CNF, and phase-separated morphology was observed in the nanocomposites. The densely grafted CNF displayed island structures, while sparsely grafted samples transitioned into continuous structure. Thermodynamic analysis showed that the diblock-grafted CNF nanocomposites maintained mechanical properties at high temperatures. These nanocomposites demonstrated robust strength and toughnes, with tensile strength reaching as high as 43.7 ± 1.6 MPa and elongation at break of 70.3 ± 16.2 %. Moreover, while densely grafted CNF exhibited higher modulus and strength, whereas sparsely grafted CNF displayed behavior more reminiscent of thermoplastic elastomers, indicated by lower modulus and higher elongation.