Hydrophilic Monomers Research Articles

The effects of synthetic and physical factors on the properties of poly(acrylic acid)-based hydrogels synthesized by precipitation polymerization technique: a review

Abstract The polymer obtained from hydrophilic monomers can be transformed into a hydrogel via cross-linking by different cross-linkers. Hydrogels are three-dimensional networks that can absorb several times their weight and swell in water/swelling media, improving the media’s viscosity as a thickener. The cross-linked poly(acrylic acid) microparticles prepared via precipitation polymerization technique are often synthesized by radical polymerization and have carboxylic functional groups in their structure, which make the hydrogel properties such as swelling capacity, particle morphology, and viscosity be controlled by physical factors such as solvent, neutralizer, pH, pK a , zeta potential, and ionic strength of the swelling media, as well as synthetic factors including comonomer, cross-linker, and network type. In this paper, the effects of crucial factors on the synthetic and swelling steps are elaborated to facilitate the achievement of poly(acrylic acid)-based xerogels having desirable rheological properties, such as swelling/viscosity optimization, which is the primary purpose of a thickener in any swelling media.

3D micro/nano hydrogel structures fabricated by two-photon polymerization for biomedical applications.

Hydrogels are three-dimensional natural or synthetic cross-linked networks composed of polymer chains formed by hydrophilic monomers. Due to the ability to simulate many properties of natural extracellular matrix, hydrogels have been widely used in the biomedical field. Hydrogels can be obtained through a variety of polymerization strategies such as heating and redox. However, photochemistry is one of the most interesting methods for researchers in this field. Gelatin-methacryloyl (GelMA) inherits the biological activity of gelatin and has become one of the gold standards in the field of biomaterials. GelMA, as a photopolymerizable hydrogel precursor, can be used to fabricate 3D porous structures for biomedical applications through two-photon polymerization. We report a new formulation of GelMA-based photoresist and used it to manufacture a series of two-photon polymerization structures, with a maximum resolution less than 120nm. The influence of process parameters on 3D structures manufacturing is studied by adjusting the scanning speed, laser power, and layer spacing values in two-photon polymerization processing. In vitro biological tests show that the 3D hydrogel produced by two-photon polymerization in this paper is biocompatible and suitable for MC3T3-E1 cell.

Free radical graft polymerization of hydroxyethyl methacrylate and acrylic acid on polyetherimide membrane surface via redox system to improve anti-fouling and oil resistance performance

In this paper, a new scheme of graft polymerization of acrylic acid (AA) and hydroxyethyl methacrylate (HEMA) initiated by the generation of free radicals in a redox system was used to modify the surface of polyetherimide (PEI) membranes and to improve the antifouling and oil resistance properties. Various physicochemical characterization techniques (ATR-FTIR, XPS, TG, SEM, AFM, etc.) confirmed the successful grafting of hydrophilic monomers onto the PEI membrane surface. Further, the effects of different monomer concentrations on graft density, permeation separation, contamination resistance, and mechanical properties were investigated. Both PEI-g-PAA and PEI-g-PHEMA showed better hydrophilicity (WCA decreased from 60° in PEI to 33° and 45°, respectively), efficient separation (75–84%) in oil-containing wastewater filtration tests with methyl tert-butyl ether (MTBE) and petroleum ether with a slight decrease in mechanical strength. In addition, bovine serum albumin (BSA) and MTBE were selected as contaminants to examine the antifouling properties. Compared to the flux recovery rate (FRR) of 75% for the original PEI membranes, the grafted membranes almost wholly recovered the permeate flux with a simple backwash of ultrapure water. In summary, the results of the above study suggest the development of a novel and simple preparation strategy for surface grafting modification of PEI membranes, which will facilitate the subsequent research of PEI materials in membrane development, and the resulting grafted membranes will be of developmental and exploratory value in the field of oil and water treatment.

Supramolecular copolymerization of hydrophobic and hydrophilic monomers in liquid crystalline media.

In the case of covalent polymers, immiscible polymers can be integrated by covalently linking them together, but such a strategy is not possible in supramolecular polymers. Here we report the supramolecular copolymerization of two porphyrin-based monomers, C10P2H and TEGPCu with side chains bearing cyanobiphenyl (CB) groups at the ends of hydrophobic alkyl or hydrophilic tetraethylene glycol chains, respectively. These monomers undergo self-sorting supramolecular polymerization in highly diluted solutions ([monomer] = 3.4 × 10-9 mol% (2.0 × 10-8 mol L-1)) in nonpolar media due to the incompatibility of the side chains. Surprisingly, these monomers undergo supramolecular copolymerization under high concentration conditions ([monomer] = 7.7 mol%) in the medium of 4-cyano-4'-pentyloxybiphenyl (5OCB) to form a columnar liquid crystalline phase under thermodynamic conditions, where the individual columns are composed of supramolecular block copolymers. The combination of CB ends of both monomers and the 5OCB medium is essential for the two monomers to form an integrated structure in a condensed system without phase separation.

Intelligent Hydrogel-Assisted Hepatocellular Carcinoma Therapy

Given the high malignancy of liver cancer and the liver’s unique role in immune and metabolic regulation, current treatments have limited efficacy, resulting in a poor prognosis. Hydrogels, soft 3-dimensional network materials comprising numerous hydrophilic monomers, have considerable potential as intelligent drug delivery systems for liver cancer treatment. The advantages of hydrogels include their versatile delivery modalities, precision targeting, intelligent stimulus response, controlled drug release, high drug loading capacity, excellent slow-release capabilities, and substantial potential as carriers of bioactive molecules. This review presents an in-depth examination of hydrogel-assisted advanced therapies for hepatocellular carcinoma, encompassing small-molecule drug therapy, immunotherapy, gene therapy, and the utilization of other biologics. Furthermore, it examines the integration of hydrogels with conventional liver cancer therapies, including radiation, interventional therapy, and ultrasound. This review provides a comprehensive overview of the numerous advantages of hydrogels and their potential to enhance therapeutic efficacy, targeting, and drug delivery safety. In conclusion, this review addresses the clinical implementation of hydrogels in liver cancer therapy and future challenges and design principles for hydrogel-based systems, and proposes novel research directions and strategies.

Triazine-structured covalent organic framework nanosheets with inherent hydrophilicity for the highly efficient and selective enrichment of glycosylated peptides.

Protein glycosylation plays a crucial role in various biological processes and is related to various diseases. Highly specific enrichment of glycopeptides before mass spectrometry detection is crucial for comprehensive glycoproteomic analysis. However, it still remains a great challenge due to the absence of affinity materials with excellent enrichment efficiency. In this work, a triazine structure linked by a -NH- bond of two-dimensional (2-D) covalent organic framework (COF) nanosheets was synthesized as an affinity adsorbent for the selective capture of glycopeptides. In particular, by introducing hydrophilic monomers via a bottom-up approach, the 2-D COF (denoted as NENP-1) nanosheets were provided with abundant amino groups and inherent hydrophilicity. Owing to the specific surface area and excessive accessible sites for hydrophilicity, the resulting NENP-1 nanosheets exhibited an outstanding glycopeptide enrichment efficiency from standard samples with a superior detection sensitivity (1 × 10-10 M), good enrichment selectivity (1 : 800, HRP tryptic digest to BSA protein), excellent binding capacity (100 mg g-1), great reusability, and recovery (60.2%). Furthermore, using the NENP-1 nanosheet adsorbent, twenty-four endogenous glycopeptides in the serum of patients with gastric cancer were successfully identified by LC-MS/MS technology, which illustrates a promising prospective of hydrophilic COF nanosheets in glycoproteomics research.

Itaconic Acid-Based Organic-Polymer Monolithic Column for Hydrophilic Capillary Electrochromatography and Its Application in Pharmaceutical Analysis.

Itaconic acid is an excellent hydrophilic monomer owing to the dicarboxylic group possessing strong polarity. This study reports on the preparation of a new organic-polymer monolithic column poly(itaconic acid-co-3-(acryloyloxy)-2-hydroxypropyl methacrylate) (poly(IA-co-AHM)) featuring excellent hydrophilic chromatography ability and its application in pharmaceutical analysis. The monolithic column was successfully synthesized by using the monomer itaconic acid and the cross-linker AHM through an in situ copolymerization method. Optical microscopy, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) were employed for the characterization of the poly(IA-co-AHM) monolithic column, and all of these demonstrated that the prepared itaconic acid-based monolithic column exhibited satisfactory permeability and a homogeneous porous structure. Owing to the carboxylic groups of itaconic acid, a cathodic electroosmotic flow (EOF) was generated on the itaconic acid-based monolithic column among the pH ranges of the mobile phase from 4.0 to 9.0. Depending on the powerful hydrophilic interactions, different kinds of polar substances, including thioureas, nucleoside drugs, sulfonamides, and polypeptides, were separated efficiently by the itaconic acid-based monoliths poly(IA-co-AHM). The separations of polar compounds were successfully realized, even at a lower level of 50% acetonitrile content on this monolithic column. The highest column efficiencies corresponding to N,N'-dimethylthiourea and idoxuridine were 102 720 and 124 267 N/m, respectively. The poly(IA-co-AHM) monolithic column displayed excellent repeatability, whose relative standard deviations (RSDs) of the retention time and peak area were both lower than 5.0%. All experimental results demonstrated that the new itaconic acid-functionalized monolithic column was greatly appropriate to separate the polar compounds under the HILIC mode.

Cationic amphiphilic acrylic copolymer retanning agent for metal-free eco-leather production

Producing metal-free leather is an effective approach to eliminate Cr pollution and achieve sustainable development of the leather industry. However, the high water sorption of the metal-free leather and the mismatching of the charge properties between the metal-free tanned leather and anionic post-tanning chemicals result in the unsatisfactory properties of the leather products, thereby restricting the industrial application of metal-free tanning technologies. Herein, a series of cationic amphiphilic acrylic copolymers (PSD) with different molar ratios of hydrophobic monomer to cationic hydrophilic monomer were synthesized and applied in the retanning of a metal-free tanned leather. PSD can effectively penetrate to the hierarchy of collagen fibril of leather and firmly bind to collagen carboxyls to form a thin hydrophobic coating on the fibril surface due to their small particle size (< 70 nm), excellent surface activity and cationic amine groups (3–27 μmol/g). Molecular dynamics (MD) simulations confirm that the primary driving force between PSD and collagen is electrostatic interaction. MD simulations and water resistance tests demonstrate that the amphiphilic PSD provides the metal-free leather with moderate hydrophobicity, which indicates the upgrade of the comprehensive properties of leather. PSD retanning enhances the uptake rate of anionic dyes and fatliquors (> 90 %) and endows the metal-free leather with excellent filling effect and bright color. The molar ratio of hydrophilic monomer and hydrophobic monomer plays an important role in the performance of PSD. The hydrophobic segments contribute to the hydrophobicity enhancement of leather, and the cationic hydrophilic segments in PSD contribute to the charge regulation of leather and robust binding of post-tanning chemicals. Hence, the multifunctional PSD retanning agents can fulfill the demands for versatile metal-free leather types and promise to boost the sustainable development of the leather industry.

Construction of a Biomimetic Receptor Based on Hydrophilic Multifunctional Monomer Covalent Organic Framework Molecularly Imprinted Polymers for Molecular Recognition of Cyanidin-3-O-Glucoside.

Anthocyanins (AOCs) are phenols that are readily soluble in water and are commonly present in plants. The chemical instability of AOC, however, causes it to be severely limited in terms of extraction and purification. Hence, in order to obtain efficient and stable extraction of AOC, we designed hydrophilic multifunctional monomer covalent organic framework molecularly imprinted polymers (HMCMIPs) as adsorbents. The functional reagent, p-aminobenzenesulfonic acid (ASA), was added to this material during synthesis to facilitate the sulfonation modification of covalent organic frameworks (COFs), which enhanced its affinity for hydrophilic guests (cyanidin-3-O-glucoside, the representative nutritional and functional ingredient in AOC). With ASA serving as a terminator, overextension of the material to form micron-level cross-linked structures is prevented, thereby increasing its surface area and mass transfer efficiency. The biomimetic receptors were then created by integrating MIPs into sulfonated COFs in order to create multiple binding sites specific for C3G recognition. HMCMIPs exhibited excellent adsorption capacity (1566 mg/g) and superior selectivity (selectivity coefficient >12) for C3G. It has been demonstrated that high purity (93.72%) C3G can be obtained rapidly and efficiently by utilizing HMCMIPs. There may be a potential benefit to the synthesis strategy of HMCMIPs for the extraction of specific active ingredients in the future.

A highly antifouling and eco-friendly hydrogel coating based on capsaicin derivative -functionalized polymer

Antifouling hydrogels have received extensive attention in the field of marine antifouling due to their excellent hydrophilicity and environmental friendliness. However, the antifouling applications of traditional hydrogels are limited by their poor antibacterial properties, and capsaicin derivatives, as nontoxic and environmentally friendly antifoulants, can be used to improve the antibacterial properties of hydrogels. From the perspective of practical application, hydrogels were obtained by crosslinking the copolymer of the capsaicin derivative N,N'-((4,5,6-trihydroxy-1,3-phenylene) bis (methylene)) diacrylamide (TPA), lipophilic monomers and hydrophilic monomers. This hydrogel exhibited anti-protein performance due to its hydrophilicity, and the capsaicin derivative caused the hydrogel coating to exhibit excellent algae inhibition performance (the minimum adhesion density of diatoms on the surface of the hydrogel coating was less than 440 cells/mm2), better algae anti-adhesion abilities than hydrogel reported in the other paper, and antibacterial effects (the antibacterial rate was more than 95%). After 73 d of panel testing in a real marine environment, there was still a good antifouling effect in the hydrogel coating. Hence, the antifouling performance was improved significantly by capsaicin derivative (TPA)-functionalized hydrogel coating. A new strategy is provided in this study for the preparation of hydrogels with superior marine antifouling properties.

Fabrication and evaluation of novel amphiphilic star block copolymers for increasing free water content in lignite to make coal water slurries

In order to reduce the apparent viscosity of lignite coal water slurries (CWSs) and improve its static stability, a series of three-arm amphiphilic block copolymers have been prepared through RAFT polymerization by using poly(ethylene glycol) methyl ether acrylate (PEGMA) and sodium 4-vinylbenzenesulfonate (SSNa) as hydrophilic monomers and styrene (St) as hydrophobic monomer. The chemical structure of the copolymers has been investigated, and the impact of relative molecular weight, hydrophilic/hydrophobic ratio, and ionic group content on the pulping performance of three-arm amphiphilic block copolymers has been examined. The lignite coal water slurries (CWSs) prepared from the block copolymer tri-P(St50-s-SSNa50)10K-b-PPEGMA10K exhibit a remarkably low apparent viscosity of 395 mPa·s and excellent static stability when the coal content is at 55 wt% and dispersant content is at 0.5 wt%. Moreover, these CWSs can achieve a maximum pulping concentration of up to 59 wt%. Additionally, the thermogravimetric test reveals insights into the water occurrence in CWSs, indicating that higher levels of free water content correspond to lower apparent viscosities. Suitable hydrophobicity facilitates the removal of internal water from lignite by dispersants, disrupting its flocculation structure and promoting CWSs formation. Meanwhile, the presence of ionic groups enhances the static stability of the resulting CWSs. Furthermore, the adsorption behavior of the three-arm amphiphilic block copolymer dispersant in lignite has been analyzed through XPS testing to elucidate its dispersion mechanism. The use of three-arm amphiphilic block copolymers in preparing lignite CWSs results in lower apparent viscosity and improved static stability, attributed to the amphiphilic and steric hindrance effects of dispersants. This not only expands the application range of lignite CWSs but also highlights the significant potential of this type of dispersant.

Synthesis of well‐defined methacrylate copolymers and their use for stabilizing membrane proteins

AbstractWe describe the synthesis of a novel series of amphiphilic methacrylate copolymers composed of one hydrophobic monomer carrying a cyclohexyl group and one hydrophilic monomer carrying a short poly(ethylene glycol) chain comprising 6, 9, or 19 units. RAFT polymerization was used to yield well‐defined polymers. First, we studied the kinetic of this copolymerization and calculated the reactivity ratios according to different linear least‐squares (LLS) methods. We thus could demonstrate the statistical copolymerization of the two monomers. Then, by varying the ratio of each monomer in the copolymerization, we developed a series of polymers that were tested for their abilities to extract membrane proteins from Escherichia coli cells overexpressing the Bacillus subtilis multidrug resistance ABC transporter (BmrA) and to stabilize the light‐driven proton transporter bacteriorhodopsin (bR). While our copolymers failed to directly extract significant amounts of proteins, they were found to provide stabilizing environments for extracted membrane proteins, suggesting they could be used as non‐ionic stabilizing polymers.

Tunable backbone-degradable robust tissue adhesives via in situ radical ring-opening polymerization

Adhesives with both robust adhesion and tunable degradability are clinically and ecologically vital, but their fabrication remains a formidable challenge. Here we propose an in situ radical ring-opening polymerization (rROP) strategy to design a backbone-degradable robust adhesive (BDRA) in physiological environment. The hydrophobic cyclic ketene acetal and hydrophilic acrylate monomer mixture of the BDRA precursor allows it to effectively wet and penetrate substrates, subsequently forming a deep covalently interpenetrating network with a degradable backbone via redox-initiated in situ rROP. The resulting BDRAs show good adhesion strength on diverse materials and tissues (e.g., wet bone >16 MPa, and porcine skin >150 kPa), higher than that of commercial cyanoacrylate superglue (~4 MPa and 56 kPa). Moreover, the BDRAs have enhanced tunable degradability, mechanical modulus (100 kPa-10 GPa) and setting time (seconds-hours), and have good biocompatibility in vitro and in vivo. This family of BDRAs expands the scope of medical adhesive applications and offers an easy and environmentally friendly approach for engineering.

Poly(dibenzofuran-p-terphenyl piperidinium)-based anion exchange membranes with enhanced phase separation for water electrolysis

Anion exchange membranes (AEMs) based on non-aryl ether–type poly(aryl piperidinium) have recently drawn significant attention because of their excellent ion exchange capacity (IEC), chemical stability, and ionic conductivity. However, the reactivity of poly(aryl piperidinium) varies significantly depending on the type of monomer used and is also accompanied by very rapid polymerization. These limitations have hindered the development of an AEM with controllable morphology. In the present study, AEMs with the desired morphology were obtained using hydrophilic and hydrophobic monomers; indeed, a well-controlled morphology was achieved even though they were random copolymers. Specifically, hydrophilic dibenzofuran and hydrophobic p-terphenyl were used as raw materials to develop the novel AEM material p(BF-TP)-Pip-x, i.e., a poly(dibenzofuran-p-terphenyl-piperidinium)-based copolymer. The dibenzofuran content relative to p-terphenyl was 5%, 10%, and 30%, resulting in three types of p(BF-TP)-Pip-x-based membranes. Their properties were compared with a poly(p-terphenyl-piperidinium)(pTP-Pip)-based AEM, a homopolymer composed solely of p-terphenyl. p(BF-TP)-Pip-10, a membrane with a dibenzofuran content of 10%, exhibited excellent mechanical properties with a tensile strength of 42 MPa and an elongation of break of 9.7%, along with high ionic conductivity at 144 mS cm−1 at 80 °C, owing to its well-developed, phase-separated morphology. Furthermore, its conductivity retention was 93% after treatment in a 2 M KOH solution at 80 °C for 960 h. For a given IEC, excellent alkaline stability was achieved compared to existing poly(aryl piperidinium)-based AEMs. p(BF-TP)-Pip-10 also exhibited excellent thermal and oxidative stability. In AEM water electrolysis tests, the membrane showed a very high current density of 1309 mA cm−2 at 1.8 V, a 120% improvement over pTP-Pip.

Water-Content-Dependent Switching of the Bending Behavior of Photoresponsive Hydrogels Composed of Hydrophilic Acrylamide-Based Main Chains and Hydrophobic Azobenzene.

Photoresponsiveness is a promising characteristic of stimulus-responsive materials. Photoresponsiveness can be achieved by incorporating photoresponsive molecules into polymeric materials. In addition, multiple-stimuli-responsive materials have attracted scientists' interest. Among the numerous multiple-stimuli-responsive materials, moisture- and photoresponsive materials are the focus of this report. These stimuli-responsive materials responded to the stimuli synergistically or orthogonally. Unlike most stimulus-responsive materials utilizing moisture and light as stimuli, the materials studied herein switch their photoresponsiveness in the presence of moisture. Appropriate copolymers consisting of hydrophilic acrylamide-based monomers for the main chain and hydrophobic azobenzene moieties switched their bending behaviors at 6-9 wt% water contents. At water contents lower than 6 wt%, the polymeric materials bent away from the light source, while they bent toward the light source at water contents higher than 10 wt%. At a low water content, the bending behaviors can be described on the molecular scale. At a high water content, the bending behavior requires consideration of the phase scale, not only the molecular scale. By controlling the balance between hydrophilicity and hydrophobicity, the switching behavior was achieved. This switching behavior may inspire additional strategies for the application of polymeric material as actuators.

A novel star polymer for regulating fluid loss in oil-based mud under high temperature conditions

Oil-Based Mud (OBM) is a highly effective drilling fluid system for challenging wellbore conditions such as water-sensitive and high-temperature drilling operations. To minimize filtration loss and achieve thin filter cake, fluid loss control additives are essential. This study introduces a star polymer as an alternative to traditional additives like gilsonite or linear polymer. The star polymer was synthesized using Reversible Addition Fragmentation Chain Transfer polymerization (RAFT) with hydrophilic and lipophilic monomers and crosslinkers. Mud properties such as rheology, fluid loss, mud cake thickness, and emulsion stability were evaluated for OBM and compared with commercially available fluid loss control additives at simulated downhole pressure and temperatures. Spectroscopy and thermogravimetric analysis were used to determine the chemical architecture and thermal stability of the star polymer. The results showed that the star polymer demonstrated thermal stability up to 225 °C, resulting in a small amount of fluid loss volume and ultra-thin filter cake for OBM systems with mud weight at 10.5 ppg and 13.4 ppg. Furthermore, the star polymer improved emulsion stability without significantly affecting plastic viscosity (PV), unlike commercially available fluid loss control additives. The results were consistent for both diesel and synthetic oil-based mud systems.

Altering the bio-inert properties of surfaces by fluorinated copolymers of mPEGMA

Hydrophilic materials display “bio-inert properties”, meaning that they are less recognized as foreign substances by proteins and cells. Such materials are often water soluble; therefore, one general approach to enable the use of these materials in various applications deals with copolymerizing hydrophilic monomers with hydrophobic ones to facilitate such resulting copolymers water insoluble. However, reducing the hydrophilic monomer amount may reduce the bio-inert properties of the material. The decrease in bio-inert properties can be avoided when small amounts of fluorine are used in copolymers with hydrophilic monomers, as presented in this article. Even in small quantities (7.9 wt%), the fluorinated monomer, 1,1,1,3,3,3-hexafluoropropan-2-yl 2-fluoroacrylate (FAHFiP), contributed to the improved hydrophobicity of the polymers of the long side-chain poly(ethylene glycol) methyl ether methacrylate (mPEGMA) bearing nine ethylene glycol units turning them water insoluble. As evidenced by the AFM deformation image, a phase separation between the FAHFiP and mPEGMA domains was observed. The copolymer with the highest amount of the fluorinated monomer (66.2 wt%) displayed also high (82 %) FAHFiP amount at the polymer–water interface. In contrast, the hydrated sample with the lowest FAHFiP/highest mPEGMA amount was enriched of three times more hydrophilic domains at the polymer–water interface compared to that of the sample with the highest FAHFiP content. Thus, by adding a small FAHFiP amount to mPEGMA copolymers, water insoluble in the bulk too, could be turned highly hydrophilic at the water interface. The high content of intermediate water contributed to their excellent bio-inert properties. Platelet adhesion and fibrinogen adsorption on their surfaces were even more decreased as compared to those on poly(2-methoxyethyl acrylate), which is typically used in medical devices.

Mediator Monomer Regulated Emulsion Interfacial Polymerization to Synthesize Nanofractal Magnetic Particles for Nucleic Acid Separation.

Polymer-based magnetic particles have been widely used for the separation of biological samples including nucleic acids, proteins, virus, and cells. Existing magnetic particles are almost prepared by coating polymers on magnetic nanoparticles (NPs). However, this strategy usually encounters the problem of poor magnetic NPs loading capacity. Here, a series of nanofractal magnetic particles (nanoFMPs) synthesized by a strategy of mediator monomer regulated emulsion interfacial polymerization is presented, which allows effective magnetic NPs loading and show efficient nucleic acid separation performance. The mediator monomers facilitate the dispersion of magnetic NPs in internal phase to achieve higher loading, and the hydrophilic monomers use electrostatic interactions to form surface nanofractal structures with functional groups. Compared with magnetic particles without nanofractal structure, nanoFMPs exhibit a higher nucleic acid extraction capability. This strategy offers an effective and versatile way for the synthesis of nanoFMPs toward efficient separation in various fields from clinical diagnosis to food safety and environmental monitoring.

Synthesis of bio‐based modified amphoteric acrylate epoxy emulsion surface sizing agent via RAFT polymerization

AbstractThe synthesis of bio‐based modified amphoteric epoxy modified acrylate sizing emulsion based on reversible addition fragmentation chain transfer (RAFT) polymerization and its application in paper sizing were studied. A macromolecular chain transfer agent for RAFT polymerization was synthesized by the esterification of epoxy resin E‐51 with RAFT agent to eliminate the active groups on RAFT agent. Amphoteric polymer emulsifiers with good emulsification and dispersion effects in acidic and alkaline media were successfully prepared by RAFT polymerization. After neutralization, other monomers were polymerized to access cationic sizing emulsion (acid neutralization) and anionic sizing emulsion (alkali neutralization). The effects of bio‐based monomer content, hydrophilic monomer dimethylaminoethyl methacrylate (DM) content and degree of quaternization on the properties of sizing emulsion and sizing paper were further explored. In addition to the particle size and polymer dispersion index (PDI) of latex particles in different experimental groups, the water resistance, folding resistance, bursting strength, tensile strength and surface roughness of sized paper were analyzed and evaluated. Based on these results, a better sizing emulsion formulation was established. It was confirmed that the addition of bio‐based monomers can improve the sizing performance of paper.

Synthesis of water-soluble NIR macro-photocatalysts from polymerizable zinc phthalocyanine

To improve the solubility and recyclability of the NIR photocatalyst, two synthetic strategies, namely “living” polymers with permanent NIR photocatalyst by reversible addition-fragmentation chain transfer (RAFT) polymerization and “non-living” polymers with recyclable NIR macro-photocatalyst (macro-PC) by conventional radical polymerization, were developed by copolymerization of hydrophilic and polymerizable zinc phthalocyanine (ZnTAPc-MAm or ZnTAPc-Am) monomers. The resultant macro-PCs from RAFT polymerization were endowed with permanent NIR photocatalysis due to the attachment of zinc phthalocyanine moieties, and the features of both “living” and permanent NIR photocatalyst of the “living” macro-PCs were verified by much simple multiple chain extensions via RAFT polymerization in water (only involved in “living” polymers and fresh monomer) under irradiation with NIR LED light (λmax = 730 nm) at room temperature. In addition, the resultant water-soluble “non-living” macro-PCs from conventional radical polymerization were endowed with only NIR photocatalysis property but they could be easily recycled just by centrifugation, which facilitates to synthesize tailored polymers by recyclable PCs under NIR irradiation.