Methacrylate-based Copolymers Research Articles

Verification of the Self-Healing Ability of PP-co-HUPy Copolymers in Epoxy Systems.

This work concerns the verification of the self-healing ability of PP-co-HUPy copolymers dispersed in epoxy systems. PP is the acronym for the Poly-PEGMA polymer, and HUPy refers to the HEMA-UPy copolymers based on ureidopyrimidinone (UPy) moieties. In particular, this work aims to verify whether this elastomer characterized by an intrinsic self-healing ability can activate supramolecular interactions among polymer chains of an epoxy resin, as in the elastomer alone. The elastomer includes a class of polyethylene glycol monomethyl ether methacrylate-based copolymers, with different percentages of urea-N-2-amino-4-hydroxy-6-methyl pyrimidine-N'-(hexamethylene-n-carboxyethyl methacrylate) (HEMA-UPy) co-monomers. The self-healing capability of these copolymers based on possible quadruple hydrogen bond interactions between polymer chains has been verified. The formulated epoxy samples did not show self-healing efficiency. This can be attributed to the formation of phase segregation that originates during the curing process of the samples, although the PP-co-HUPy copolymers are completely soluble in the liquid epoxy matrix EP. The morphological investigation highlighted the presence of crystals of PP-co-HUPy copolymers, which are in greater quantity in the sample containing the highest weight percentage (7.8 wt%) of HUPy units. Furthermore, the crystals act as promotors for increasing the curing degree (DC) of the epoxy systems containing HUPy units. DC goes from 91.6% for EP to 96.1% and 95.4% for the samples containing weight percentages of 2.5 and 7.8 wt% of HUPy units, respectively. Dynamic mechanical analysis (DMA) shows storage modulus values for epoxy systems containing PP-co-HUPy units lower than that of the unfilled resin EP. The values of maximum in Tan δ (Tg), representing the temperature at which the glass transition occurs, are 220 for the unfilled resin EP, 228 for the sample containing 2.5 wt% of HEMA-UPy units, and 211 for the sample containing 7.8 wt% of HEMA-UPy units.

Four-Component Statistical Copolymers by RAFT Polymerization.

This manuscript serves as the starting point for in-depth research of multicomponent, statistical, methacrylate-based copolymers that potentially mimic the behavior of proteins in aqueous solutions. These synthetic macromolecules are composed of specially chosen comonomers: methacrylic acid (MAA), oligoethylene glycol methyl ether methacrylate (OEGMA475), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA). Monomer choice was based on factors such as the chemical nature of pendant functional groups, the polyelectrolyte/polyampholyte and amphiphilic character and the overall hydrophobic-hydrophilic balance (HLB) of the obtained quaterpolymers. Their synthesis was achieved via a one-pot reversible addition fragmentation chain transfer (RAFT) polymerization in two distinct compositions and molecular architectures, linear and hyperbranched, respectively, in order to explore the effects of macromolecular topology. The resulting statistical quaterpolymers were characterized via 1H-NMR and ATR-FTIR spectroscopies. Their behavior in aqueous solutions was studied by dynamic (DLS) and electrophoretic light scattering (ELS) and fluorescence spectroscopy (FS), producing vital information concerning their self-assembly and the structure of the formed aggregates. The physicochemical studies were extended by tuning parameters such as the solution pH and ionic strength. Finally, the quaterpolymer behavior in FBS/PBS solutions was investigated to test their colloid stability and biocompatibility in an in vivo-mimicking, biological fluid environment.

Exploration of the thermal and mechanical characteristics of polymethyl methacrylate-based copolymers: implications for wind turbine blades applications

Abstract Wind turbine (WT) blade fabrication typically employs thermosetting resins, whose recycling challenges post-retirement have resulted in environmental pressures. Thus, there is an urgent need to develop a low-viscosity, high-performance, and recyclable material with excellent mechanical properties that is compatible with WT fabrication processes, serving as a viable alternative to traditional epoxy resins. Poly(methyl methacrylate) (PMMA) resin is considered a promising candidate for replacing epoxy resins. However, the mechanical properties of PMMA still require improvement. In this study, we investigated the effects of introducing copolymerized monomers on the comprehensive performance of PMMA resin without affecting its viscosity, examining the influence of these copolymerized monomers on the material’s thermal and mechanical properties. Meanwhile, the mechanical properties of the synthesized PMMA-based copolymers were compared with those of blade-specific epoxy resin (WD0135). The results revealed that compared to WD0135, the flexural strength and modulus of the prepared PMMA copolymers significantly increased to 96.6 and 3158.6 MPa, respectively, with a tensile strength reaching 74.2 MPa. Consequently, this series of PMMA-based resins demonstrates immense potential for large-scale material part fabrication via casting techniques.

Exploring Functional Polymers in the Synthesis of Luminescent ZnO Quantum Dots for the Detection of Cr6+, Fe2+, and Cu2.

The main aim of this work is to demonstrate that well-defined methacrylate-based copolymers with oligoethylene glycol side chains and functional groups such as thiol and glycidyl, obtained by photo-initiated reversible addition-fragmentation chain transfer (RAFT) in ethanol, are highly suitable as templates in the synthesis and protection of ZnO quantum dots (ZnO QDs) with remarkable photoluminescent properties. While the affinity of thiol groups to metallic surfaces is well established, their interaction with metal oxides has received less scrutiny. Furthermore, under basic conditions, glycidyl groups could react with hydroxyl groups on the surface of ZnO, representing another strategy for hybrid synthesis. The size and crystalline morphology of the resulting hybrids were assessed using DLS, TEM, and XRD, indicating that both polymers, even with a low proportion of functional groups (5% mol) are appropriate as templates and ligands for ZnO QDs synthesis. Notably, thiol-containing polymers yield hybrids with ZnO featuring excellent quantum yield (up to 52%), while polymers with glycidyl groups require combination with the organosilane aminopropyl triethoxysilane (APTES) to achieve optimal results. In both cases, these hybrids exhibited robust stability in both ethanol and aqueous environments. Beyond fundamental research, due to the remarkable photoluminescent properties and affordability, these hybrid ZnO QDs are expected to have potential applications in biotechnology and green science; in particular, in this study, we examined their use in the detection of environmental contaminants like Fe2+, Cr6+, and Cu2+. Specifically, the limit of detection achieved at 1.13 µM for the highly toxic Cr6+ underscores the significant sensing capabilities of the hybrids.

Preparation of Protein A Membranes Using Propargyl Methacrylate-Based Copolymers and Copper-Catalyzed Alkyne-Azide Click Chemistry.

The development of convective technologies for antibody purification is of interest to the bioprocessing industries. This study developed a Protein A membrane using a combination of graft polymerization and copper(I)-catalyzed alkyne-azide click chemistry. Regenerated cellulose supports were functionalized via surface-initiated copolymerization of propargyl methacrylate (PgMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA300), followed by a reaction with azide-functionalized Protein A ligand. The polymer-modified membranes were characterized using attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), gravimetric analysis, and permeability measurements. Copolymer composition was determined using the Mayo-Lewis equation. Membranes clicked with azide-conjugated Protein A were evaluated by measuring static and dynamic binding (DBC10) capacities for human immunoglobulin G (hIgG). Copolymer composition and degree of grafting were found to affect maximum static binding capacities, with values ranging from 5 to 16 mg/mL. DBC10 values did not vary with flow rate, as expected of membrane adsorbers.

NIR-triggered upconversion and sensitized NIR-emission in Yb-based Eosin Y lake doped latex nanoparticles.

Here, Yb-based Eosin Y lakes (EOS-Yb) have been encapsulated in organic nanoparticles (NPs) by microemulsion radical polymerization of methacrylate-based copolymers. These photoactive EOS-Yb NPs emit in the visible and near infrared (NIR) upon excitation at 530 nm and can also display NIR-to-visible upconversion emission upon excitation at 980 nm.

Fast Gold Recovery from Aqueous Solutions and Assessment of Antimicrobial Activities of Novel Gold Composite

A novel porous gold polymer composite was prepared by the functionalization of a glycidyl methacrylate-based copolymer (pGME) with ethylene diamine (pGME-en), and activation by gold (pGME-en/Au), in a simple batch adsorption procedure in an acid solution, at room temperature. Detailed characterization of the pGME-en before and after activation was performed. The main focuses of this research were the design of a method that can enable the recovery of gold and the reuse of this multipurpose sorbent as an antimicrobial agent. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis pointed out amine groups as the primary binding sites for Au activation, while hydroxyl groups also contributed to the chelation reaction. pGME-en exhibited fast gold adsorption with an adsorption half-time of 5 min and an equilibrium time of 30 min. The maximal adsorption capacity was about 187 mg/g. The analysis of sorption experimental data with a non-linear surface reaction and diffusion-based kinetic models revealed the pseudo-second-order and Avrami model as the best fit, with unambiguous control by liquid film and intra-particle diffusion. The biological activity studies against Staphylococcus aureus, Listeria monocytogenes, Escherichia coli, and Candida albicans revealed moderate activity of pGME-en/Au against different bacterial and fungal species. pGME-en/Au was stable in a saline solution, with a release of approximately 2.3 mg/g after 24 h.

Quantifying elasticity maps of methacrylate-based copolymers using atomic force microscopy

Quantifying elasticity maps of methacrylate-based copolymers using atomic force microscopy

L-Lysine-Modified pNIPAm-co-GMA Copolymer Hydrogel for pH- and Temperature-Responsive Drug Delivery and Fluorescence Imaging Applications.

The development of dual-stimuli-responsive hydrogels attracts much research interest owing to its unique stimuli-responsive characteristics. In this study, a poly-N-isopropyl acrylamide-co-glycidyl methacrylate-based copolymer was synthesized by incorporating N-isopropyl acrylamide (NIPAm) and a glycidyl methacrylate (GMA) monomer. The synthesized copolymer, pNIPAm-co-GMA was further modified with L-lysine (Lys) functional units and further conjugated with fluorescent isothiocyanate (FITC) to produce a fluorescent copolymer pNIPAAm-co-GMA-Lys hydrogel (HG). The in vitro drug loading and dual pH- and temperature-stimuli-responsive drug release behavior of the pNIPAAm-co-GMA-Lys HG was investigated at different pH (pH 7.4, 6.2, and 4.0) and temperature (25 °C, 37 °C, and 45 °C) conditions, respectively, using curcumin (Cur) as a model anticancer drug. The Cur drug-loaded pNIPAAm-co-GMA-Lys/Cur HG showed a relatively slow drug release behavior at a physiological pH (pH 7.4) and low temperature (25 °C) condition, whereas enhanced drug release was achieved at acidic pH (pH 6.2 and 4.0) and higher temperature (37 °C and 45 °C) conditions. Furthermore, the in vitro biocompatibility and intracellular fluorescence imaging were examined using the MDA-MB-231 cell line. Therefore, we demonstrate that the synthesized pNIPAAm-co-GMA-Lys HG system with temperature- and pH-stimuli-responsive features could be promising for various applications in biomedical fields, including drug delivery, gene delivery, tissue engineering, diagnosis, antibacterial/antifouling material, and implantable devices.

Evaluation of the Efficiency of Random and Diblock Methacrylate-Based Amphiphilic Cationic Polymers against Major Bacterial Pathogens Associated with Cystic Fibrosis.

Cystic fibrosis (CF) is associated with repeated lung bacterial infection, mainly by Pseudomonas aeruginosa, Staphylococcus aureus, and Mycobacterium abscessus, all known to be or becoming resistant to several antibiotics, often leading to therapeutic failure and death. In this context, antimicrobial peptides and antimicrobial polymers active against resistant strains and less prompt to cause resistance, appear as a good alternative to conventional antibiotics. In the present study, methacrylate-based copolymers obtained by radical chemistry were evaluated against CF-associated bacterial strains. Results showed that the type (Random versus Diblock) and the size of the copolymers affected their antibacterial activity and toxicity. Among the different copolymers tested, four (i.e., Random10200, Random15000, Random23900, and Diblock9500) were identified as the most active and the safest molecules and were further investigated. Data showed that they inserted into bacterial lipids, leading to a rapid membranolytic effect and killing of the bacterial. In relation with their fast bactericidal action and conversely to conventional antibiotics, those copolymers did not induce a resistance and remained active against antibiotic-resistant strains. Finally, the selected copolymers possessed a preventive effect on biofilm formation, although not exhibiting disruptive activity. Overall, the present study demonstrates that methacrylate-based copolymers are an interesting alternative to conventional antibiotics in the treatment of CF-associated bacterial infection.

Methyl Methacrylate-Based Copolymers: Recent Developments in the Areas of Transparent and Stretchable Active Matrices.

The recent advancements of poly(methyl methacrylate) (PMMA) as a transparent flexible polymer material have been utilized in numerous areas of engineering and materials science. PMMA-based copolymers demonstrate outstanding mechanical and optical properties owing to high transparency, lightweight nature, high impact resistance, and stress relaxation across glass transition temperature. These copolymers have unique characteristics of retaining optical and microstructural integrities during successive bending or elongations which make them an attractive choice for materials of stretchable electronics. In particular, there has been an escalated rise in the use of methyl methacrylate (MMA)-based transparent and stretchable copolymer films during the recent decades. Therefore, we have highlighted these recent developments into a comprehensive review in order to aid the future progress in these diverse fields. Herein, we have highlighted the scope of MMA as an important building block for the synthesis of highly transparent and flexible materials. The synthetic pathways of these copolymer materials and the resulting mechanical properties have been discussed. Moreover, the immense scope of these copolymer films has been highlighted by virtue of their applications in various industries.

Glycerol methacrylate-based copolymers: Reactivity ratios, physicochemical characterization and cytotoxicity

Understanding the chemical composition of biocompatible copolymers is crucial for diverse biomedical applications such as the conjugation of polymers to drugs, peptides or proteins. Here, we report the Reversible Addition-Fragmentation Chain Transfer (RAFT) copolymerizations and reactivity ratios (r) of the less explored biocompatible copolymer systems based on glycerol mono-methacrylate (GMMA) monomer. Hence, we investigated the copolymerization of GMMA with the comonomers N-hydroxy succinimide methacrylate (NHSMA), N-isopropylacrylamide (NIPAM) and butyl acrylate (BuA). The estimated r values and sequence length distributions suggest that a chain radical of GMMA monomer prefers cross propagation in the system GMMA/NHSMA (rGMMA = 0.32 rNHSMA = 1.01). In the case of GMMA/NIPAM (rGMMA = 2.55 rNIPAM = 0.11) and GMMA/BuA (rGMMA = 3.31 rBuA = 0.66) systems, as shown by the relatively high rGMMA values in both copolymerizations, the formation of gradient copolymers might be favored. To understand the role of the comonomer composition in the thermal and solution properties of the final materials, the glass transition temperature (Tg) values of the copolymers, as determined by differential scanning calorimetry (DSC), were compared to build Tgvs. composition plots generated with the Fox, Brostow and Kwei equations. DSC investigations also revealed an interesting effect of molecular interactions between the polymer chains possibly formed via hydrogen bonding conveyed by the GMMA groups in the copolymers. Furthermore, light transmittance measurements of the poly(GMMA-stat-NIPAM) copolymer system in aqueous solutions revealed that the cloud point temperature (Tcp) of the solutions increases with the content of GMMA groups in the copolymer; however, this behavior was limited by the NIPAM composition (>0.74 mol fraction). Interestingly, a copolymer material with a GMMA/NIPAM composition (FGMMA/FNIPAM) of 26/74 exhibited a TCP = 38 °C, which is close to the human body temperature. Finally, cytotoxicity assays indicated the excellent biocompatibility of the obtained copolymers, which suggests that these copolymer systems might be suitable alternatives for bioconjugated systems in biomedical applications.

Glycidyl Methacrylate-Based Copolymers as Healing Agents of Waterborne Polyurethanes.

Self-healing materials and self-healing mechanisms are two topics that have attracted huge scientific interest in recent decades. Macromolecular chemistry can provide appropriately tailored functional polymers with desired healing properties. Herein, we report the incorporation of glycidyl methacrylate-based (GMA) copolymers in waterborne polyurethanes (WPUs) and the study of their potential healing ability. Two types of copolymers were synthesized, namely the hydrophobic P(BA-co-GMAy) copolymers of GMA with n-butyl acrylate (BA) and the amphiphilic copolymers P(PEGMA-co-GMAy) of GMA with a poly(ethylene glycol) methyl ether methacrylate (PEGMA) macromonomer. We demonstrate that the blending of these types of copolymers with two WPUs leads to homogenous composites. While the addition of P(BA-co-GMAy) in the WPUs leads to amorphous materials, the addition of P(PEGMA-co-GMAy) copolymers leads to hybrid composite systems varying from amorphous to semi-crystalline, depending on copolymer or blend composition. The healing efficiency of these copolymers was explored upon application of two external triggers (addition of water or heating). Promising healing results were exhibited by the final composites when water was used as a healing trigger.

Electrokinetic and surface properties of some methacrylate-based copolymers

Electrokinetic and surface properties of some methacrylate-based copolymers

Affinity-based isolation of extracellular vesicles by means of single-domain antibodies bound to macroporous methacrylate-based copolymer

Correct elucidation of physiological and pathological processes mediated by extracellular vesicles (EV) is highly dependent on the reliability of the method used for their purification. Currently available chemical/physical protocols for sample fractionation are time-consuming, often scarcely reproducible and their yields are low. Immuno-capture based approaches could represent an effective purification alternative to obtain homogeneous EV samples. An easy-to-operate chromatography system was set-up for the purification of intact EVs based on a single domain (VHH) antibodies-copolymer matrix suitable for biological samples as different as conditioned cell culture medium and human plasma. Methacrylate-based copolymer is a porous solid support, the chemical versatility of which enables its efficient functionalization with VHHs. The combined analyses of morphological features and biomarker (CD9, CD63 and CD81) presence indicated that the recovered EVs were exosomes. The lipoprotein markers APO-A1 and APO-B were both negative in tested samples. This is the first report demonstrating the successful application of spherical porous methacrylate-based copolymer coupled with VHHs for the exosome isolation from biological fluids. This inexpensive immunoaffinity method has the potential to be applied for the isolation of EVs belonging to different morphological and physiological classes.

Kinetic parameters, thermal stability, biological activity, and dielectric properties of new methacrylate-based copolymers functionalized with methylparaben

Kinetic parameters, thermal stability, biological activity, and dielectric properties of new methacrylate-based copolymers functionalized with methylparaben

Water and Oil Repellency of Methacrylate-based Copolymer with Fluoroalkyl Group Side Chain

In the present paper, we report the mechanism of water and oil repellency (both static and dynamic) of methacrylate-based polymers with fluoroalkyl group side chains. Surface rearrangement has the greatest effect on dynamic water repellency, although surface composition mainly affects static water repellency. However, both static and dynamic oil repellences are influenced significantly by the surface composition and the molecular aggregation states.

Concentration Polarization Enabled Reactive Coating of Nanofiltration Membranes with Zwitterionic Hydrogel.

In this study, the bottleneck challenge of membrane fouling is addressed via establishing a scalable concentration polarization (CP) enabled and surface-selective hydrogel coating using zwitterionic cross-linkable macromolecules as building blocks. First, a novel methacrylate-based copolymer with sulfobetain and methacrylate side groups was prepared in a simple three-step synthesis. Polymer gelation initiated by a redox initiator system (ammonium persulfate and tetramethylethylenediamine) for radical cross-linking was studied in bulk in order to identify minimum (“critical”) concentrations to obtain a hydrogel. In situ reactive coating of a polyamide nanofiltration membrane was achieved via filtration of a mixture of the reactive compounds, utilizing CP to meet critical gelation conditions solely within the boundary layer. Because the feasibility was studied and demonstrated in dead-end filtration mode, the variable extent of CP was estimated in the frame of the film model, with an iterative calculation using experimental data as input. This allowed to discuss the influence of parameters such as solution composition or filtration rate on the actual polymer concentration and resulting hydrogel formation at the membrane surface. The zwitterionic hydrogel-coated membranes exhibited lower surface charge and higher flux during protein filtration, both compared to pristine membranes. Salt rejection was found to remain unchanged. Results further reveal that the hydrogel coating thickness and consequently the reduction in membrane permeance due to the coating can be tuned by variation of filtration time and polymer feed concentration, illustrating the novel modification method’s promising potential for scale-up to real applications.

Influence of Salt Concentration on Hydrated Polymer Relative Permittivity and State of Water Properties

Little is known about how aqueous electrolyte exposure affects hydrated polymer relative permittivity and state of water properties. Increasing NaCl solution concentration (0.01, 0.1, and 1.0 mol/L) caused a cross-linked glycidyl and glycerol methacrylate-based copolymer to osmotically deswell and caused ion sorption to increase opposite to electrostatic theory and Maxwell Garnett equation predictions. The presence, due to salt solution equilibration, of ions in the polymer drove an increase in static permittivity compared to that of pure water-equilibrated equivalent water content samples. The influence of salt concentration on hydrated polymer dielectric permittivity properties was fundamentally different from its influence on aqueous electrolyte solutions where dielectric permittivity decreases as salt concentration increases. Generally, the amount of bulk-like water in the polymers decreased as salt concentration increased, but a maximum was observed in low water content (<7% by mass) polymers, suggesting that ions and water may compete for interactions with the polymer.

Gel Polymer Electrolyte Based on Methyl Methacrylate and Ethyl Methacrylate for Lithium-Ion Batteries

This article deals with gel polymer electrolytes (GPEs) composed of methacrylate-based copolymers. The experiment is based on the preparation of GPE with copolymers, measurement of their electrochemical properties, and following measurements with negative electrode LTO (Li4Ti5O12) and positive electrode NMC (LiNi0.33Mn0.33Co0.33O2). The functionality of electrolyte was verified by cyclic voltammetry and measurement of capacity.