Methyl Ether Methacrylate Research Articles

Closely Packed Core-Shell Micelle Structures of Double Hydrophilic Miktoarm Star Copolymers at the Air-Water Interface.

The aggregation behavior of amphiphilic block copolymers at the air-water interface has been extensively studied, but less attention was given to that of star copolymers. In this work, we studied the interfacial aggregation behavior of two double hydrophilic pH- and temperature-responsive miktoarm star copolymers of poly[di(ethylene glycol) methyl ether methacrylate]-poly[2-(dimethylamino)ethyl methacrylate] (PDEGMA3-PDMAEMA3 and PDEGMA4-PDMAEMA7, the subscripts denote arm numbers) with different molecular weights. The effects of subphase pH and temperature on the monolayer isotherms and hysteresis curves of the two star copolymers and the morphologies of their Langmuir-Blodgett (LB) films were studied by the Langmuir film balance technique and atomic force microscopy, respectively. At the air-water interface, the two star copolymers tend to form closely packed micelles. These micelles exhibit a core-shell structure, where the small hydrophobic core consists of cross-linker of ethylene glycol dimethacrylate (EGDMA) and the carbon backbones of PDEGMA and PDMAEMA arms and the short hydrophilic shell is composed of di(ethylene glycol) and tertiary amine side groups. With increasing subphase pH, the surface pressure versus molecular area isotherms shift toward larger mean molecular areas as a result of the enhanced interface adsorption of nonprotonated tertiary amine groups. The isotherm shift of PDEGMA3-PDMAEMA3 monolayers is primarily attributed to high density of tertiary amine groups in the shells, while that of PDEGMA4-PDMAEMA7 is mainly attributed to high density of di(ethylene glycol) groups in the shells. The hysteresis degrees in the monolayers of the two copolymers under alkaline and neutral conditions are greater than those under acidic conditions due to the decreased protonation degree of the tertiary amine groups. At 10 °C, the mobility of the shells is poor and the isotherms are located on the right. Above the lower critical solution temperature, di(ethylene glycol) groups contract, which causes a slight shift of the isotherms toward smaller mean molecular areas.

Anthrapyrazolone functionalized Oligo(ethylene glycol)methyl ether methacrylates based fluorescent polymeric hydrogel for selective detection of Tetracycline drug

Tetracycline (TC) antibiotics are essential for treating bacterial infections; however, overuse and improper disposal place the environment in danger and promote the growth of drug-resistant microorganisms. Monitoring their impact on living organisms is vital. Polymeric-based hydrogels offer promise in antibiotic detection due to their versatility and biocompatibility, despite their uncommon use for this purpose. In this study, we have synthesized a fluorescent polymeric hydrogel, P(OEGMA-co-DIMA) utilizing oligo(ethylene glycol)methyl ether methacrylates (OEGMA) and laboratory-synthesized fluorescent anthrapyrazolone containing monomer, 2-(benzo[1,2,3-cd:4,5,6-c’d]bis(indazole)-2(7H)-yl)ethyl methacrylate (DIMA) for the fluorometric detection of TC in the aqueous medium. The P(OEGMA-co-DIMA) hydrogel exhibited exceptional affinity towards TC while exhibiting high selectivity. The chemosensing behavior of the hydrogel was also compared with the DIMA monomer. Upon adding TC, emission analysis revealed a notable quenching in the emission intensity of the P(OEGMA-co-DIMA) hydrogel as well as the DIMA monomer. The Stern Volmer rate constants (Ksv) of the hydrogel (Ksv = 9.99 x 103 M−1) in water and DIMA (Ksv = 25.63 x 103 M−1) in acetonitrile showed a higher quenching rate constant with a limit of detections (LODs) of 1.3 nM and 0.11 nM. Turn-off fluorescence behavior occurs via a static quenching mechanism through a photoinduced electron transfer process and intermolecular hydrogen bonding. To validate the selectivity, the interference analyses in an aqueous medium with different antibiotics are provided. To rationalize the real-time applicability of the hydrogel, studies were extended to water samples obtained from deionized water, tap water, lake water, and also in milk samples. The recovery rate and LOD for real samples ranged from 83.8 % to 111 % and 0.83 to 3.6 nM, respectively.

Constructing the Polymer Molecules to Regulate the Electrode/Electrolyte Interface to Enhance Lithium-Metal Battery Performance.

Lithium-ion batteries, with high energy density and long cycle life, have become the battery of choice for most vehicles and portable electronic devices; however, energy density, safety and cycle life require further improvements. Single-functional group electrolyte additives are very limited in practical applications, a ternary polymer bifunctional electrolyte additive copolymer (acrylonitrile-butyl hexafluoro methacrylate- poly (ethylene glycol) methacrylate- methyl ether) (PMANHF) was synthesized by free radical polymerization of acrylonitrile, 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate and poly (ethylene glycol) methyl ether methacrylate. A series of characterizations show that in Li metal anodes, the preferential reduction of PMANHF is conducive to the formation of a uniform and stable solid electrolyte interphase layer, and Li deposition is uniform and dense. At the NCM811 cathode, a film composed of LiF- and Li3N-rich is formed at the cathode-electrolyte interface, mitigating the side reaction at the interface. At 1.0 mA cm-2, the Li/Li cell can be stabilized for 1000 cycles. In addition, the Li/NCM811 cell can stabilize 200 cycles with a cathode capacity of 153.7 mAh g-1, with the capacity retention of 89.93 %, at a negative/positive capacity ratio of 2.5. This study brings to light essential ideas for the fabrication of additives for lithium-metal batteries.

High toughness, ultra-sensitive, and extreme environment resistant fabric temperature sensors based on supramolecular-polymer dual network ionic conductive elastomers

Liquid-free ionic conductive elastomers (ICEs) show great potential for next-gen wearable electronics, free from issues like solvent evaporation and freezing. However, crafting ICEs with both strength and temperature sensitivity remains a significant challenge. In this study, a supramolecular gel based on 1,3:2,4-bis (3,4-dimethylbenzene methylene) sorbitol (DMBS) is selected as the first network, and poly(ethylene glycol) methyl ether methacrylate (PEGMA) copolymerized with diallyl dimethyl bis (trifluoromethyl sulfonyl)imide (DADMATFSI) is added as the second network, with the addition of lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI). The supramolecular-polymer dual network ion-conductive elastomer SP-DN-LiTFSI is created. The elastomer exhibits exceptional mechanical characteristics, including a maximum tensile stress of 1591.1 kPa and an impressive strain of 2361 %. Additionally, it demonstrates an extraordinarily high toughness of 33.121 MJ m−3. Moreover, this elastomer-based temperature sensor is responsive to external stimuli, such as blowing, and boasts an outstanding temperature sensing coefficient (S) of 0.114 °C−1 within the range of 30–60 °C. Remarkably, it can discern even the slightest temperature variations as low as 0.5 °C within the typical human body temperature range. This work represents an innovative integration of a dual network structure and two strategies for elastomer fabrication. It provides a novel approach for developing highly sensitive wearable temperature measurement devices that exhibit exceptional resistance to mechanical wear.

Dendritic Polymer-Based Nanomedicines Remodel the Tumor Stroma: Improve Drug Penetration and Enhance Antitumor Immune Response.

The dense extracellular matrix (ECM)insolidtumors, contributed by cancer-associated fibroblasts (CAFs), hinders penetration of drugs and diminishes their therapeutic outcomes. A sequential treatment strategy of remodeling the ECM via a CAF modifier (dasatinib, DAS) is proposed to promote penetration of an immunogenic cell death (ICD) inducer (epirubicin, Epi) via apoptotic vesicles, ultimately enhancing the treatment efficacy against breast cancer. Dendritic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA)-based nanomedicines (poly[OEGMA-Dendron(G2)-Gly-Phe-Leu-Gly-DAS] (P-DAS) and poly[OEGMA-Dendron(G2)-hydrazone-Epi] (P-Epi)) are developed for sequential delivery of DAS and Epi, respectively. P-DAS reprograms CAFs to reduce collagen by downregulating collagen anabolism and energy metabolism, thereby reducing the ECM deposition. The regulated ECM can enhance tumor penetration of P-Epi to strengthen its ICD effect, leading to an amplified antitumor immune response. In breast cancer-bearing mice, this approach alleviates the ECM barrier, resulting in reduced tumor burden and increased cytotoxic T lymphocyte infiltration, and more encouragingly, synergizes effectively with anti-programmed cell death 1 (PD-1) therapy, significantly inhibiting tumor growth and preventing lung metastasis. Furthermore, systemic toxicity is barely detectable after sequential treatment with P-DAS and P-Epi. This approach opens a new avenue for treating desmoplastic tumors by metabolically targeting CAFs to overcome the ECM barrier.

Flowmicro In-Line Analysis-Driven Design of Reactions Mediated by Unstable Intermediates: Flash Monitoring Approach.

The direct observation of reactive intermediates is an important issue for organic synthesis. However, intermediates with an extreme instability are hard to be monitored by common spectroscopic methods such as FTIR. We have developed synthetic method utilizing flow microreactors, which enables a generation and reactions of unstable intermediates. Herein we report that, based on our flowmicro techniques, we developed an in-line analysis method for reactive intermediates in increments of milliseconds. We demonstrated the direct observation of the living and dead species of the anionic polymerization of alkyl methacrylates. The direct information of the living species enabled the anionic polymerization and copolymerization of oligo(ethylene glycol) methyl ether methacrylates, which is the important but difficult reaction in the conventional method.

Correlation between Ionic Conductivity and Mechanical Properties of Solid-like PEO-based Polymer Electrolyte.

Poly(ethylene glycol) methyl ether methacrylate polymer networks (PEO-based networks), with or without anionic bis(trifluoromethanesulfonyl)imide (TFSI)-grafted groups, are promising electrolytes for Li-metal all solid-state batteries. Nevertheless, there is a need to enhance our current understanding of the physicochemical characteristics of these polymer networks to meet the mechanical and ionic conductivity property requirements for Li battery electrolyte materials. To address this challenge, our goal is to investigate the impact of the cross-linking density of the PEO-based network and the ethylene oxide/lithium ratio on mechanical properties (such as glass transition temperature and storage modulus) and ionic conductivity. We have synthesized a series of cross-linked PEO-based polymers (si-SPE for single ion solid polymer electrolyte) via solvent-free radical copolymerization. These polymers are synthesized by using commercially available lithium 3-[(trifluoromethane)sulfonamidosulfonyl]propyl methacrylate (LiMTFSI), poly(ethylene glycol)methyl ether methacrylate (PEGM), and [poly(ethylene glycol) dimethacrylate] (PEGDM). In addition, we have synthesized a series of cross-linked PEO-based polymers (SPE for solid polymer electrolyte) using LiTFSI as the ionic species. Most of the resulting polymer films are amorphous, self-standing, flexible, homogeneous, and thermally stable. Interestingly, our research has revealed a correlation between ionic conductivity and mechanical properties in both the SPE and si-SPE series. Ionic conductivity increases as glass transition temperature, α relaxation temperature, and storage modulus decrease, suggesting that Li+ transport is influenced by polymer chain flexibility and Li+/EO interaction.

Location of a Hydrophobic Load in Poly(oligo(ethylene glycol) methyl ether methacrylate)s (PEGMAs) Dissolved in Water and Probed by Fluorescence.

Two series of pyrene-labeled poly(oligo(ethylene glycol) methyl ether methacrylate)s referred to as PyEG5-PEGnMA and PyC4-PEGnMA were prepared to probe the region surrounding the polymethacrylate backbone by using the fluorescence of the dye pyrene. PyEG5-PEGnMA and PyC4-PEGnMA were prepared by copolymerizing the EGnMA methacrylate monomers with penta(ethylene glycol) 1-pyrenemethyl ether methacrylate or 1-pyrenebutyl methacrylate, respectively. In organic solvents, the much longer 18 non-hydrogen atom linker connecting the pyrene moieties to the polymethacrylate backbone in the PyEG5-PEGnMA samples enabled the deployment of the pyrenyl labels into the solution. In water, however, an excited pyrene for PyEG5-PEGnMA was found to probe a same volume as for the PyC4-PEGnMA samples where a much shorter 6 non-hydrogen atom spacer connected pyrene to the backbone. Another surprising observation, considering that the hydrophobicity of pyrene induces strong pyrene aggregation for many pyrene-labeled water-soluble polymers (Py-WSPs) in water, was the little pyrene aggregation found for the PyEG5-PEGnMA and PyC4-PEGnMA samples in water. These effects could be related to the organic-like domain (OLD) generated by the oligo(ethylene glycol) side chains densely arranged around the polymethacrylate backbone of the polymeric bottlebrush (PBB). Additional fluorescence experiments conducted with the penta(ethylene glycol) 1-pyrenemethyl ether derivative indicated that the cylindrical OLD surrounding the polymethacrylate backbone had a chemical composition similar to that of ethylene glycol. Binding of hydrophobic pyrene molecules to unlabeled PEGnMA bottlebrushes in water further supported the existence of the OLD. The demonstration, that PEGnMA samples form an OLD in water, which can host and protect hydrophobic cargoes like pyrene, should lead to the development of improved PEGnMA-based drug delivery systems.

Hybrid Dynamic Covalent Network-Based Protecting Layer for Stable Li-Metal Batteries.

Metallic lithium (Li) is considered as the "Holy Grail" anode material for next-generation energy storage systems due to its extremely high theoretical capacity and low electrochemical potential. Before the commercialization of the Li electrode, dendritic Li growth and the unstable solid electrolyte interphase layer should be conquered. Herein, a hybrid covalent adaptable polymer network (HCAPN) is prepared via the random copolymerization of poly(ethylene glycol) methyl ether methacrylate and -acetoacetoxyethyl methacrylate, followed by chemical cross-linking with polyethylenimine (PEI) and amine-modified silicon dioxide (SiO2). Such a hybrid network, where PEI and amine-modified SiO2 formed a vinylogous urethane-based dynamic covalent bond with the copolymer, respectively, shows improved mechanical properties, solvent resistance, and excellent healability/recyclability. As the protecting layer on the Li electrode, the assembled HCAPN@Li||HCAPN@Li symmetric cell shows a long cycle life of 800 h with low overpotential at a current density of 1 mA cm-2, and superior electrochemical performance can be achieved in the HCAPN@Li||LiFePO4 full cell (capacity retention of 77% over 400 cycles at 1.5 C) and HCAPN@Li||NCM811 cell (capacity retention of 79% after 300 cycles). Surface morphology analysis is also performed for physical insight into their role as protecting layer. This work provides a new perspective for constructing a hybrid dynamic covalent network-based polymer protecting layer for inhibiting Li dendrite growth.

Ionogel hybrid polymer electrolytes encompassing room-temperature ionic liquids for 4V-class Li-metal batteries operating at ambient temperature

ABSTRACT In this study, we prepare ionogels composed of bisphenol A ethoxylate dimethacrylate, poly(ethylene glycol) methyl ether methacrylate, lithium bis(trifluoromethanesulfonyl)imide, and 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide or 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ionic liquids via rapid, scalable, solvent-free UV-induced polymerization. The various hybrid polymer electrolyte formulations are thoroughly characterized using a comprehensive set of physico-chemical and electrochemical methods, including gel content, FTIR, rheology, DTMA, TGA, SEM, cycling voltammetry, impedance spectroscopy, and galvanostatic cycling in laboratory-scale Li-metal cells. We particularly focus on the influence of using two different ionic liquids as reaction medium on the properties of the resulting materials and their electrochemical behaviors. Our results indicate that viscosity affects the polymerization kinetics of the ionogels, which in turn might affect their thermal stability and galvanostatic cycling behavior. In the purpose of promoting overall performance of solid-state batteries, we also present the results of composite electrolytes obtained by introducing Li7La3Zr2O12 (LLZO) into ionogels and following in-situ UV-polymerisation. The addition of LLZO ceramic results in more porous solid networks, leading to enhanced charge/discharge stability at ambient temperature and higher C-rates featuring 4V-class NMC cathodes, enlightening the promising prospects of the developed materials to be successfully implemented as stable, durable, and efficient electrolytes in next-generation Li-metal cells.

A Nanocomposite Dynamic Covalent Cross-Linked Hydrogel Loaded with Fusidic Acid for Treating Antibiotic-Resistant Infected Wounds.

Methicillin-resistant Staphylococcus aureus (MRSA) is associated with high levels of morbidity and is considered a difficult-to-treat infection, often requiring nonstandard treatment regimens and antibiotics. Since over 40% of the emerging antibiotic compounds have insufficient solubility that limits their bioavailability and thus efficacy through oral or intravenous administration, it is crucial that alternative drug delivery products be developed for wound care applications. Existing effective treatments for soft tissue MRSA infections, such as fusidic acid (FA), which is typically administered orally, could also benefit from alternative routes of administration to improve local efficacy and bioavailability while reducing the required therapeutic dose. Herein, we report an antimicrobial poly(oligoethylene glycol methacrylate) (POEGMA)-based composite hydrogel loaded with fusidic acid-encapsulating self-assembled polylactic acid-b-poly(oligo(ethylene glycol) methyl ether methacrylate) (PLA-POEGMA) nanoparticles for the treatment of MRSA-infected skin wounds. The inclusion of the self-assembled nanoparticles (380 nm diameter when loaded with fusidic acid) does not alter the favorable mechanical properties and stability of the hydrogel in the context of its use as a wound dressing, while fusidic acid (FA) can be released from the hydrogel over ∼10 h via a diffusion-controlled mechanism. The antimicrobial studies demonstrate a clear zone of inhibition in vitro and a 1-2 order of magnitude inhibition of bacterial growth in vivo in an MRSA-infected full-thickness excisional murine wound model even at very low antibiotic doses. Our approach thus can both circumvent challenges in the local delivery of hydrophobic antimicrobial compounds and directly deliver antimicrobials into the wound to effectively combat methicillin-resistant infections using a fraction of the drug dose required using other clinically relevant strategies.

Block sequence dependent self-assembly and optoelectronic behavior of thermo- and pH-sensitive Polythiophene-graft-[Poly(diethylene glycol methyl ether methacrylate)-block-Poly(dimethyl amino ethyl methacrylate)] copolymers

To overcome the difficulty of using multistep process we report an one pot synthesis of polythiophene (PT)-graft block copolymers with thermo-sensitive poly(diethyleneglycol methyl ether methacrylate)(PDEGMEM) and pH-sensitive poly(dimethyl amino ethyl methacrylate)(PDMAEMA) using ATRP technique. The polymers PT-g-(PDEGMEM10-b-PDMAEMA3) (P1), PT-g-(PDMAEMA10-b-PDEGMEM3) (P2) and PT-g-(PDMAEMA6-ran-PDEGMEM8) (P3) are characterized by 1H NMR and SEC techniques. HRTEM study shows that P1 and P3 exhibit micellar morphology but P2 shows vesicular morphology, all sizes increase with increasing pH and temperature. UV–vis absorption spectra show pH, temperature and sequence dependent absorbance peak, and dc-conductivity (P2 > P3 > P1) indicates semi-conducting nature. Current-Voltage (I-V) property shows pH dependent memory and OMEIC property following above order. At pH3, on irradiation with white light the photocurrent gains of P2, P3 and P1 are 7.9, 6.6 and 3.5, respectively. Thus PT-graft block copolymers exhibit tunable self-assembly, optoelectronic, transport and photocurrent properties depending on proximity and preponderance of block sequence from PT backbone and also for their pH and thermo-responsivity.

Phase Behavior and Conformational Asymmetry near the Comb-to-Bottlebrush Transition in Linear-Brush Block Copolymers.

This study explores how conformational asymmetry influences the bulk phase behavior of linear-brush block copolymers. We synthesized 60 diblock copolymers composed of poly(trifluoroethyl methacrylate) as the linear block and poly[oligo(ethylene glycol) methyl ether methacrylate] as the brush block, varying the molecular weight, composition, and side-chain length to introduce different degrees of conformational asymmetry. Using small-angle X-ray scattering, we determined the morphology and phase diagrams for three different side-chain length systems, mainly observing lamellar and cylindrical phases. Increasing the side-chain length of the brush block from three to nine ethylene oxide units introduces sufficient asymmetry between the blocks to alter the phase behavior, shifting the lamellar-to-cylindrical transitions toward lower brush block compositions and transitioning the brush block from the dense comb-like regime to the bottlebrush regime. Coarse-grained simulations support our experimental observations and provide a mapping between the composition and conformational asymmetry. A comparison of our findings to strong stretching theory across multiple phase boundary predictions confirms the transition between the dense comb-like regime and the bottlebrush regime.

Helical Superstructures from the Hierarchical Self-Assembly of Coil-Coil Block Copolymer Guided by Side Chain Amyloid-β(17-19) LVF Peptide.

The rational design of precisely controlled hierarchical chiral nanostructures from synthetic polymers garnered inspiration from sophisticated biological materials. Since chiral peptide motifs induce helix formation in macromolecules, herein we report the synthesis of a novel type of hybrid polymer consisting of a β-sheet forming a LVF [L = leucine, V = valine, and F = phenylalanine] tripeptide pendant polymethacrylate block and a poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) block. The designed block copolymer self-organized into helical superstructures with a left-handed twisting sense, as visualized by field emission scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. This intriguing hierarchical self-assembly is driven by the minimalistic peptide motif that itself has a high propensity to adopt an antiparallel β-sheet conformation. We also report the generation of a diverse array of nanostructures, including spherical micelles, spindle micelles, rod-like micelles, vesicles, helical supramolecular fibers, and helical toroids via self-assembly of the designed block copolymer in tetrahydrofuran/water mixed solvents. To realize the observable helical superstructure, a twisted two-dimensional core-shell tape is proposed as a structure model in which the peptide segments form an antiparallel β-sheet with a polymer shell. The findings contribute to the advancement of a helical polymer or the superhelical self-assembly of polymers, paving the way for diverse applications in materials science and related fields.

Thermo-responsive poly(di(ethylene glycol) methyl ether methacrylate) brushes as substrate-independent release coatings for cell culture and selective cell separation and purification

Abstract A systematic study on the surface-initiated polymerization of di(ethylene glycol) methyl ether methacrylate (DEGMA) by atom transfer radical polymerization (ATRP) from glass, silicon, titanium as well as tissue culture polystyrene (TCPS) is reported in an attempt to expand the known thermoresponsive poly(di(ethylene glycol) methyl ether methacrylate) (PDEGMA) cell release layers on gold to other substrates. The use of these substrate materials requires an altered immobilization chemistry to couple a bromide containing ATRP initiator to the surfaces. Using aminosilanes or polydopamine as coupling layers for the attachment of α-bromoisobutyryl bromide (BiBB) and the direct functionalization of surface hydroxyl groups with trichlorosilane-functionalized ATRP initiators all surfaces studied were shown to facilitate the growth of PDEGMA brushes using the same conditions that were reported previously for polymerization on gold. The brush layers obtained were characterized systematically using wetting, ellipsometry, X-ray photoelectron spectroscopy (XPS) as well as atomic force microscopy (AFM) analyses. Selective cell release and separation of PaTu 8988t and NIH 3T3 cells, which are known to exhibit different behavior after temperature drop-induced brush swelling, was observed for all substrates, albeit for different brush thicknesses, implying variations in initiator and also PDEGMA grafting density. The successful modification of biomedically relevant materials (Ti and TCPS) implies that the previously reported stem cell purification and selective cell release of various cell types, which is facilitated by PDEGMA brushes, can be realized and consequently scaled up in the future.

Superior antibacterial surfaces using hydrophilic, poly(MPC) and poly(mOEGMA) free chains of amphiphilic block copolymer for sustainable use

Surface modification of electrically neutral hydrophilic polymers is one of the most promising methods for preventing biofouling and biological contamination by proteins and bacteria. Surface modification of inorganic materials such as silica-based glass can render them more durable and thus help in achieving the sustainable development goals. This study reports a novel method for the simple and effective surface modification of glass surfaces with amphiphilic block copolymers possessing the silane coupling segment composed of 3-(methacryloyloxy)propyltris (trimethylsilyloxy) silane and 3-methacryloxypropyltrimethoxysilane. The ability of hydrophilic segments composed of either 2-methacryloyloxyethyl phosphorylcholine (MPC) or poly(ethylene glycol) methyl ether methacrylate (mOEGMA) to prevent bacterial adhesion was investigated. The target block copolymers were prepared by reversible addition-fragmentation chain transfer polymerization and the monomer units of the hydrophilic segments were controlled to be either 120 or 160. The polymers were modified on the substrate by dip-coating. Contact angle measurements indicated that the block copolymer with the PMPC hydrophilic segment formed a hydrophilic surface without pre-hydration, while those with the PmOEGMA hydrophilic segment-coated surface became hydrophilic upon immersion in water. The block copolymer-coated surfaces decreased S. aureus adhesion, and a significant reduction was observed with the MPC-type block copolymer. The following surface design guidelines were thus concluded: (1) the block copolymer is superior to the random copolymer and (2) increasing the hydrophilic segment length further decreases bacterial adhesion.

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.

Oligo(ethylene glycol) methyl ether methacrylate based hydrogel with intrinsic antibacterial activity against Pseudomonas aeruginosa as a model of a major wound infecting human pathogen

Wound dressings represent the first important defense line against potentially life-threatening infections. Successful materials should unify efficiency, simplicity of production with the ease of application. Cationic polymers based on quaternary ammonium salt moieties along the polymer chain promise high efficacy against growth of relevant pathogens including drug-resistant strains. We present a novel and easy-to-handle wound dressing material based on the well-defined copolymers of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA), using quaternization with 1,6-dibromohexane for hydrogel formation. The material obtained from this robust approach was perfectly biocompatible with human dermal fibroblasts and revealed an auspicious degree of intrinsic antibacterial activity against P. aeruginosa as a model pathogen for hospital-acquired infections. Formation of bacterial biofilms was prevented in early- and late-stages and even planktonic cells were killed upon gel contact. The rheological properties of the hydrogel materials were comprehensively characterized in both dry and swollen states. Excellent biological performance and appropriate viscoelastic properties qualify the hydrogels from our production approach as truly promising novel wound dressing materials with long-lasting and contact-active bactericidal activities. We believe that this charmingly simple procedure and the mechanical properties of the hydrogel may open new avenues towards cost-effective next-generation first-line wound-care materials.

Fabrication of antimicrobial cationic hydrogels driven by physically and chemically crosslinking for wound healing

The wound therapy based on antibiotic delivery inevitably leads to the emergence of drug resistance. Hydrogel biomaterials with inherent antibacterial activities have emerged as promising candidates for addressing this issue. However, developing an inherently antibacterial hydrogel through simple and facile strategies to promote localized wound infection healing remains a challenge. In this study, we successfully constructed antimicrobial cationic hydrogels with self-healing and injectable properties through physically and chemically dual-crosslinked networks. The networks were formed by the copolymers poly[(di(ethylene glycol) methyl ether methacrylate)-co-(4-formylphenyl methacrylate)-co-(2-(methacryloyloxy)ethyl]trimethylammonium chloride solution)] (PDFM) and poly[(di(ethylene glycol) methyl ether methacrylate)-co-(2-aminoethyl methacrylate hydrochloride)-co-(2-(((6-(6-methyl-4[1H]pyrimidionylureido) hexyl)carbamoyl)oxy)ethyl methacrylate)] (PDAU). The hydrogel systems effectively facilitate the regeneration and healing of infected wounds through the contact bactericidal feature of quaternary ammonium cations. The presence of Schiff base bonds in the injectable hydrogels imparts remarkable pH responsiveness and self-healing properties. In vitro experiments verified their intrinsic antibacterial activities along with their favorable cytocompatibility and hemocompatibility in both in vitro and in vivo. In addition, the hydrogel significantly accelerated the healing of bacterially infected in a full-thickness skin wound. This facilely prepared dual-crosslinked hydrogel, without antibiotics loading, holds significant prospects for treating infected wounds.

Harnessing disulfide and transesterification bond exchange reactions for recyclable and reprocessable 3D-printed vitrimers

Two new vitrimeric materials have been studied for potential additive manufacturing applications such as 3D-printing. A monomer containing disulfide bonds and β-hydroxyesters was easily synthesized from two low-cost and commercially available reagents. Another disulfide-containing monomer was synthesized for comparison purposes. Materials were prepared through a UV-light radical polymerization of methacrylates. The addition of two reactive diluents such as poly(ethylene glycol) methyl ether methacrylate (PEGMA) and ethylene glycol phenyl ether methacrylate (EGPMA) was necessary to achieve a suitable viscosity for the curing as well as for their printability. The curing process was controlled by FTIR. Thermomechanical properties were investigated by means of DMTA analysis revealing near-ambient Tg values. Stress relaxation tests revealed that both materials were capable to relax the 63% of the initial stress in less than 10 min at 110 °C. The recyclability of the materials was achieved, and the mechanical and thermomechanical properties of the recycled samples were compared to the virgin ones revealing a great recovery of the initial properties. Finally, Digital Light Processing (DLP) technique was used to print complex structures with high resolution highlighting the great potential of these vitrimeric materials in 3D printing.