Search Results (199)

Interfacial polymerization (IP) has been widely utilized to synthesize composite membranes. However, precise control of this reaction remains a challenge due to the complexity of the IP process. Herein, an optical three-dimensional microscope was used to directly observe the IP process. To construct copolyesteramide containing phthalazine moiety films, rigid monomer 4-(4′-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ) and flexible monomer piperazine (PIP) were used as aqueous phase monomers, and trimesoyl chloride (TMC) served as the organic phase monomer. Multilayer cellular structures were observed for the copolyesteramide films during the IP process. The effects of multiple factors including the ratio between flexible and rigid monomers, co-solvents, and the addition of phase transfer catalysts on the film growth and the morphologies were investigated. This research aims to deepen our understanding of the IP process, especially for the principles which govern polymer film growth and morphology, to promote new methodologies for regulating interfacial polymerization in composite membrane preparation. Full article

The development of sustainable nanofiltration membranes requires alternatives to petroleum-derived polymer substrates. This study demonstrates the successful use of an eco-friendly cellulose acetate/cellulose nitrate (CA/CN) blend substrate for fabricating high-performance modified thin-film composite (mTFC) membranes. A dense, non-porous polyamide (PA) selective layer was formed via the interfacial polymerization method and modified with 0.05–0.1 wt.% HKUST-1 (Cu₃BTC₂, MOF-199). Characterization by FTIR, XPS, SEM, AFM, and contact angle measurements confirmed the CA/CN substrate’s suitability for TFC membrane fabrication. HKUST-1 incorporation created a distinctive ridge-and-valley morphology while significantly altering PA layer hydrophilicity and roughness. The mTFC membrane performance could be fine-tuned by the controlled incorporation of HKUST-1; incorporation through the aqueous phase slowed down the formation of the PA layer and significantly reduced its thickness, while the addition through the organic phase resulted in the formation of a denser layer due to HKUST-1 agglomeration. Thus, either enhanced permeability (123 LMH bar⁻¹ with 0.05 wt.% aqueous-phase incorporation) or rejection (>89% dye removal with 0.05 wt.% organic-phase incorporation) were achieved. Both mTFC membranes also exhibited improved heavy metal ion rejection (>91.7%), confirming their industrial potential. Higher HKUST-1 loading (0.1 wt.%) caused MOF agglomeration, reducing performance. This approach establishes a sustainable fabrication route for tunable TFC membranes targeting specific separation tasks. Full article

Amphiphilic block copolymers are essential for developing advanced polymer nanomaterials with applications in bioimaging, drug delivery, and nanoreactors. In this study, we successfully synthesized functional block copolymer assemblies at high concentrations through redox-initiated reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of 2-(acetoacetoxy)ethyl methacrylate (AEMA), a β-ketoester functional monomer. Utilizing a redox initiation system at 50 °C, we produced poly(poly(ethylene glycol) methyl ether methacrylate)-b-PAEMA (PPEGMA_n-PAEMA_m). Kinetic studies demonstrated rapid monomer conversion exceeding 95% within 30 min, with distinct polymerization phases driven by micelle formation and monomer depletion. Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS) revealed the formation of diverse morphologies, including worm-like, vesicular structures, and spherical micelles, depending on the macro-CTA molecular weight and monomer concentration. Additionally, post-polymerization modification with aggregation-induced emission (AIE) luminogens, such as 1-(4-aminophenyl)-1,2,2-tristyrene (TPE-NH₂), resulted in AIE-active polymer assemblies exhibiting strong fluorescence in aqueous dispersions. These AIE-active polymer assemblies also exhibited good biocompatibility. These findings demonstrate the efficacy of redox-initiated RAFT emulsion polymerization in fabricating functional, scalable block copolymer assemblies with potential applications in the field of life sciences. Full article

Porous polymer membranes with highly interconnected open-cellular structure and high toughness are crucial for various application fields. Polymerized high internal phase emulsions (polyHIPEs), which usually exist as monoliths, possess the advantages of high porosity and good connectivity. However, it is difficult to prepare membranes due to brittleness and easy pulverization. Copolymerizing acrylate soft monomers can effectively improve the toughness of polyHIPEs, but it is easy to cause emulsion instability and pore collapse. In this paper, stable HIPEs with a high content of butyl acrylate (41.7 mol% to 75 mol% based on monomers) can be obtained by using a composite emulsifier (30 wt.% based on monomers) consisting of Span80/DDBSS (9/2 in molar ratio) and adding 0.12 mol·L⁻¹ CaCl₂ according to aqueous phase concentration. On this basis, polyHIPE membranes with high open-cellular extent and high toughness are firstly prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization. The addition of the RAFT agent significantly improves the mechanical properties of polyHIPE membranes without affecting open-cellular structure. The toughness of polyHIPE membranes prepared by RAFT polymerization is significantly enhanced compared with conventional free radical polymerization. When the molar ratio of butyl acrylate/styrene/divinylbenzene is 7/4/1, the polyHIPE membrane prepared by RAFT polymerization presents plastic deformation during the tensile test. The toughness modulus reaches 93.04 ± 12.28 kJ·m⁻³ while the open-cellular extent reaches 92.35%, and it also has excellent thermal stability. Full article

Contact electrification (CE) spans from atomic to macroscopic scales, facilitating charge transfer between materials upon contact. This interfacial charge exchange, occurring in solid–solid (S–S) or solid–liquid (S–L) systems, initiates radical generation and chemical reactions, collectively termed contact-electro-chemistry (CE-Chemistry). As an emerging platform for green chemistry, CE-Chemistry facilitates redox, luminescent, synthetic, and catalytic reactions without the need for external power sources as in traditional electrochemistry with noble metal catalysts, significantly reducing energy consumption and environmental impact. Despite its broad applicability, the mechanistic understanding of CE-Chemistry remains incomplete. In S–S systems, CE-Chemistry is primarily driven by surface charges, whether electrons, ions, or radicals, on charged solid interfaces. However, a comprehensive theoretical framework is yet to be established. While S–S CE offers a promising platform for exploring the interplay between chemical reactions and triboelectric charge via surface charge modulation, it faces significant challenges in achieving scalability and optimizing chemical efficiency. In contrast, S–L CE-Chemistry focuses on interfacial electron transfer as a critical step in radical generation and subsequent reactions. This approach is notably versatile, enabling bulk-phase reactions in solutions and offering the flexibility to choose various solvents and/or dielectrics to optimize reaction pathways, such as the degradation of organic pollutants and polymerization, etc. The formation of an interfacial electrical double layer (EDL), driven by surface ion adsorption following electron transfer, plays a pivotal role in CE-Chemical processes within aqueous S–L systems. However, the EDL can exert a screening effect on further electron transfer, thereby inhibiting reaction progress. A comprehensive understanding and optimization of charge transfer mechanisms are pivotal for elucidating reaction pathways and enabling precise control over CE-Chemical processes. As the foundation of CE-Chemistry, charge transfer underpins the development of energy-efficient and environmentally sustainable methodologies, holding transformative potential for advancing green innovation. This review consolidates recent advancements, systematically classifying progress based on interfacial configurations in S–S and S–L systems and the underlying charge transfer dynamics. To unlock the full potential of CE-Chemistry, future research should prioritize the strategic tuning of material electronegativity, the engineering of sophisticated surface architectures, and the enhancement of charge transport mechanisms, paving the way for sustainable chemical innovations. Full article

Step emulsification (SE) is renowned for its robustness in generating monodisperse emulsion droplets at arrayed nozzles. However, few studies have explored poly(dimethylsiloxane) (PDMS)-based SE devices for producing monodisperse oil-in-water (O/W) droplets and polymeric microspheres with diameters below 20 µm—materials with broad applicability. In this study, we present a PDMS-based microfluidic SE device designed to achieve this goal. Two devices with 264 nozzles each were fabricated, featuring straight and triangular nozzle configurations, both with a height of 4 µm and a minimum width of 10 µm. The devices were rendered hydrophilic via oxygen plasma treatment. A photocurable acrylate monomer served as the dispersed phase, while an aqueous polyvinyl alcohol solution acted as the continuous phase. The straight nozzles produced polydisperse droplets with diameters exceeding 30 µm and coefficient-of-variation (CV) values above 10%. In contrast, the triangular nozzles, with an opening width of 38 µm, consistently generated monodisperse droplets with diameters below 20 µm, CVs below 4%, and a maximum throughput of 0.5 mL h⁻¹. Off-chip photopolymerization of these droplets yielded monodisperse acrylic microspheres. The low-cost, disposable, and scalable PDMS-based SE device offers significant potential for applications spanning from laboratory-scale research to industrial-scale particle manufacturing. Full article

Biodegradable and biocompatible polymeric materials and stimulus-responsive hydrogels are widely used in the pharmaceutical, agricultural, biomedical, and consumer sectors. The effectiveness of these formulations depends significantly on the appropriate selection of polymer support. Through chemical or enzymatic hydrolysis, these materials can gradually release bioactive agents, enabling controlled drug release. The objective of this work is to synthesize, characterize, and apply two controlled-release polymeric systems, focusing on the release of a phyto-pharmaceutical agent (herbicide) at varying pH levels. The copolymers were synthesized via free radical polymerization in solution, utilizing tetrahydrofuran (THF) as the organic solvent and benzoyl peroxide (BPO) as the initiator, without the use of a cross-linking agent. Initially, the herbicide was grafted onto the polymeric chains, and its release was subsequently tested across different pH environments in a heterogeneous phase using an ultrafiltration (UF) system. The development of these two controlled-release polymer systems aimed to measure the herbicide’s release across different pH levels. The goal is to adapt these materials for agricultural use, enhancing soil quality and promoting efficient water usage in farming practices. The results indicate that the release of the herbicide from the conjugate systems exceeded 90% of the bioactive compound after 8 days at pH 10 for both systems. Furthermore, the two polymeric systems demonstrated first-order kinetics for herbicide release in aqueous solutions at different pH levels. The kinetic constant was found to be higher at pH 7 and 10 compared to pH 3. These synthetic hydrogels are recognized as functional polymers suitable for the sustained release of herbicides in agricultural applications. Full article

This study investigates the stability and application of trithiocarbonate-based chain transfer agents (CTAs) in reversible addition–fragmentation chain transfer (RAFT) radical polymerization under harsh conditions. We evaluated the stability of 4-cyano-4-(2-carboxyethylthiothioxomethylthio) pentanoic acid (Rtt-17) and 4-cyano-4-(dodecylsulfanylthiocarbonyl) sulfanylpentanoic acid (Rtt-05) at 60 °C under basic conditions using ¹H NMR and UV–vis absorption spectra, showing that Rtt-05 is more stable than Rtt-17. The greater stability of Rtt-05 is attributed to the hydrophobic dodecyl group, which allows it to form micelles in water, thereby protecting the trithiocarbonate group from the surrounding aqueous phase. In contrast, hydrophilic Rtt-17, without long alkyl chains, cannot form micelles in water. Following the stability assessment, Rtt-17 and Rtt-05 were employed for RAFT polymerization of hydrophilic monomers, such as N,N-dimethylacrylamide (DMA) and 2-(methacryloyloxy)ethyl phosphorylcholine (MPC). DMA can dissolve in both water and organic solvents, and MPC can dissolve in water and polar solvents. Both CTAs successfully controlled the polymerization of DMA, producing polymers with narrow molecular weight distributions (M_w/M_n) less than 1.2. Also, Rtt-17 demonstrated effective control of MPC polymerization, yielding M_w/M_n values of around 1.2. However, during the polymerization of MPC, Rtt-05 failed to maintain control, resulting in a broad M_w/M_n (≥1.9). The inability of Rtt-05 to control MPC polymerization is due to the formation of micelles, which disrupts the interaction between the hydrophilic MPC propagating radicals and the trithiocarbonate group in the hydrophobic core of Rtt-05 micelles. The findings provide critical insights into designing CTAs for specific applications, particularly for biomedical and industrial uses of hydrophilic polymers, highlighting the potential for precise molecular weight control and tailored polymer properties. Full article

In order to solve the problems of long dissolution and preparation time, cumbersome preparation, and easy moisture absorption and deterioration during storage or transportation, acrylamide (AM), acrylic acid (AA), sodium p-styrene sulfonate (SSS), and cetyl dimethylallyl ammonium chloride (DMAAC-16) were selected as raw materials, and the emulsion thickener P(AM/AA/SSS), which can be instantly dissolved in water and rapidly thickened, was prepared by the reversed-phase emulsion polymerization method. DMAAC-16, the influence of emulsifier dosage, oil–water ratio, monomer molar ratio, monomer dosage, aqueous pH, initiator dosage, reaction temperature, reaction time, and other factors on the experiment was explored by a single-factor experiment, and the optimal process was determined as follows: the oil–water volume ratio was 0.4, the emulsifier dosage was 7% of the oil phase mass, the initiator dosage was 0.03% of the total mass of the reaction system, the reaction time was 4 h, the reaction temperature was 50 °C, the aqueous pH was 6.5, and the monomer dosage was 30% of the total mass of the reaction system (monomeric molar ratio n(AM):n(AA):n(SSS):n(DMAAC-16) = 79.2:20:0.5:0.3). X-ray diffraction analysis (XRD), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy analysis were carried out on the polymerization products. At the same time, a series of performance test experiments such as thickening performance, temperature and shear resistance, salt resistance, sand suspension performance, core damage performance, and fracturing fluid flowback fluid reuse were carried out to evaluate the comprehensive effect and efficiency of the synthetic products, and the results show that the P(AM/AA/SSS/DMAAC-16) polymer had excellent solubility and excellent properties such as temperature and shear resistance. Full article

Bead-foaming technology effectively addresses production cycles, polymerization control, and cellular structure defects in conventional bulk foaming, especially in high-performance PMI foams. In this work, highly expandable PMI beads were synthesized based on the aqueous suspension polymerization of methacrylic acid-methacrylonitrile-tert-butyl methacrylate (MAA-MAN-tBMA) copolymers. The suspension polymerization was stabilized by reducing the solubility of MAA by the salting-out effect and replacing formamide (a common PMI foaming agent) with tBMA. The polymerization process was optimized by varying salting-out agents, dispersants, water-to-oil ratio (WOR), and stirring speed to achieve uniform bead sizes (0.2–0.4 mm) and high bead yields (>70%). The expansion ratio of the beads can be easily tuned by adjusting tBMA content and foaming time and temperature. Beads with 10%tBMA can reach up to 64 times under a free-forming process at 240 °C, which serves as an excellent precursor toward high-performance in-mold foaming PMI. The beads exhibit excellent in-mold foaming capabilities, thermal stability (Td = 392 °C), and mechanical properties. This work provides a technical foundation for the bead-foaming technology of PMI foams, reducing the cost of PMI foam production and providing the possibility to expand the application of PMI foam in civilian use. Full article

MoS₂, a typical transition metal dichalcogenide, features a layered structure, multi-phase transition, and tunable band gap, which is a promising candidate for aqueous zinc-ion batteries (AZIBs). Recent studies have focused on the metastable 1T-MoS₂ phase, which exhibits superior electrical conductivity and electrochemical activity compared to the more stable 2H phase. Herein, a straightforward one-step hydrothermal method was used to synthesize three-dimensional MoS₂/polymer composites (H-MoS₂-PEDOT). Under acidic conditions, the polymerization and intercalation of EDOT molecules in the MoS₂ layers promote the phase transition from 2H to 1T, thereby enhancing its conductivity and electrochemical performance. Additionally, it was found that the intercalated PEDOT and small amounts of water molecules have contributed to enhancing Zn²⁺ ion diffusion and cycle stability. As a result, AZIBs based on the H-MoS₂-PEDOT composite deliver a high specific capacity of 173.6 mAh g⁻¹ at 1 A g⁻¹, maintaining a specific capacity of 116 mAh g⁻¹ and a capacity retention of 82.8% after 1000 cycles at 5 A g⁻¹. Full article

Forward osmosis (FO) technology, known for its minimal energy requirements, excellent resistance to fouling, and significant commercial potential, shows enormous promise in the development of sustainable technologies, especially with regard to seawater desalination and wastewater. In this study, we improved the performance of the FO membrane in terms of its mechanical strength and hydrophilic properties. Generally, the water flux (J_w) of polyisophenylbenzamide (PMIA) thin-film composite (TFC)-FO membranes is still inadequate for industrial applications. Here, hydrophilic polydopamine (PDA)@ zeolitic imidazolate frameworks-8 (ZIF-8) nanomaterials and their integration into PMIA membranes using the interfacial polymerization (IP) method were investigated. The impact of PDA@ZIF-8 on membrane performance in both pressure-retarded osmosis (PRO) and forward osmosis (FO) modes was analyzed. The durability and fouling resistance of these membranes were evaluated over the long term. When the amount of ZIF-8@PDA incorporated in the membrane reached 0.05 wt% in the aqueous phase in the IP reaction, the J_w values for the PRO mode and FO mode were 12.09 LMH and 11.10 LMH, respectively. The reverse salt flux (J_s)/J_w values for both modes decreased from 0.75 and 0.80 to 0.33 and 0.35, respectively. At the same time, the PRO and FO modes’ properties were stable in a 15 h test. The incorporation of PDA@ZIF-8 facilitated the formation of water channels within the nanoparticle pores. Furthermore, the J_s/J_w ratio decreased significantly, and the FO membranes containing PDA@ZIF-8 exhibited high flux recovery rates and superior resistance to membrane fouling. Therefore, PDA@ZIF-8-modified FO membranes have the potential for use in industrial applications in seawater desalination. Full article

A series of hydrophilic copolymers were prepared using 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) from free radical polymerization at different feed monomer ratios using ammonium persulfate (APS) initiators in water at 70 °C. The herbicide 2,4-dichlorophenoxy acetic acid (2,4-D) was grafted to Poly(HEMA-co-IA) by a condensation reaction. The hydrolysis of the polymeric release system, Poly(HEMA-co-IA)-2,4-D, demonstrated that the release of the herbicide in an aqueous phase depends on the polymeric system’s pH value and hydrophilic character. In addition, the swelling behavior (Wt%) was studied at different pH values using Liquid-phase Polymer Retention (LPR) in an ultrafiltration system. The acid hydrolysis of the herbicide from the conjugates follows a first-order kinetic, showing higher kinetic constants as the pH increases. The base-catalyzed hydrolysis reaction of the herbicide follows a zero-order kinetic, where the basic medium acts as a catalyst, accelerating the release rate of the herbicide and showing higher kinetic constants as the pH increases. The differences in the release rates found for the hydrogel herbicide at different pH values can be correlated with the difference in their swelling capacity, where the release rate generally increases with an increase in the swelling capacity from water solution at higher pH values. The study of the release process revealed that all samples in distilled water at a pH of 10 are representative of agricultural systems. It showed first-order swelling kinetics and an absorption capacity that conforms to the parameters for hydrogels for agricultural applications, which supports their potential for these purposes. Full article

Cellulose acetate butyrate is a biodegradable cellulose ester bioplastic produced from plentiful natural plant-based resources. Solvent-exchange-induced in situ gels are particularly promising for periodontitis therapy, as this dosage form allows for the direct delivery of high concentrations of antimicrobial agents to the localized periodontal pocket. This study developed an in situ gel for periodontitis treatment, incorporating a combination of metronidazole and doxycycline hyclate, with cellulose acetate butyrate serving as the matrix-forming agent. Consequently, assessments were conducted on the physicochemical properties, gel formation, drug permeation, drug release, morphological topography, and antimicrobial activities of the formulation. The formulation demonstrated an increased slope characteristic of Newtonian flow at higher bioplastic concentrations. The adequate polymer concentration facilitated swift phase inversion, resulting in robust, solid-like matrices. The mechanical characteristics of the transformed in situ gel typically exhibit an upward trend as the polymer concentration increased. The utilization of sodium fluorescein and Nile red as fluorescent probes effectively tracked the interfacial solvent–aqueous movement during the phase inversion of in situ gels, confirming that the cellulose acetate butyrate matrix delayed the solvent exchange process. The initial burst release of metronidazole and doxycycline hyclate was minimized, achieving a sustained release profile over 7 days in in situ gels containing 25% and 40% cellulose acetate butyrate, primarily governed by a diffusion-controlled release mechanism. Metronidazole showed higher permeation through the porcine buccal membrane, while doxycycline hyclate exhibited greater tissue accumulation, both influenced by polymer concentration. The more highly concentrated polymeric in situ gel formed a uniformly porous structure. Metronidazole and doxycycline hyclate-loaded in situ gels showed synergistic antibacterial effects against S. aureus and P. gingivalis. Over time, the more highly concentrated polymeric in situ gel showed superior retention of antibacterial efficacy due to its denser cellulose acetate butyrate matrix, which modulated drug release and enhanced synergistic effects, making it a promising injectable treatment for periodontitis, particularly against P. gingivalis. Full article

The cell immobilization technique, which restricts living cells to a certain space, has received widespread attention as an emerging biotechnology. In this study, a yeast (Saccharomyces cerevisiae)-loaded highly open-cell emulsion-templated polyethylene glycol (PEG-polyHIPE) was synthesized to be a reusable enzymatic catalyst. An emulsion was prepared with polyethylene glycol diacrylate (PEGDA) aqueous solution, cyclohexane, and polyethylene-polypropylene glycol (F127) as the continuous phase, dispersed phase, and surfactant, respectively. Then PEG-polyHIPE was obtained by polymerization of the PEGDA in emulsion. The highly porous materials obtained by the emulsion-templating method are suitable for use as carrier materials for yeast immobilization, due to their favorable structural designability. During the activation process, the yeast S. cerevisiae can readily gain access to the interior of the material via the interconnected pores and immobilize itself inside the voids. The yeast-loaded polyHIPE was then used to ferment glucose for ethanol production. The yeast immobilized inside the polyHIPE has high fermentation efficiency, good recoverability, and storage stability. After seven cycles, the yeast maintained 70% initial fermentation efficiency. The S. cerevisiae kept more than 90% of the initial cellular activity after one week of storage both in the dry state and in yeast extract peptone dextrose medium (YPD) at 4 °C. This study strongly demonstrates the feasibility of using high-throughput porous materials as cell immobilization carriers to efficiently osmotically immobilize cells in polyHIPEs for high-performance fermentation. Full article