Glycol Methyl Ether Methacrylate Research Articles

A Total Internal Reflection Microscopy (TIRM)-Based Approach for Direct Characterization of Polymer Brush Conformational Change in Aqueous Solution.

This study presents a novel approach utilizing total internal reflection microscopy (TIRM) to effectively characterize the swelling and collapse of polymer brushes in aqueous solutions. Zwitterionic poly(carboxybetaine methacrylate) (PCBMA) and nonionic poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) brushes are chosen as model systems. By investigation of an intriguing theory-experiment discrepancy observed during the measurement of near-wall hindered diffusion, valuable insights into the compressibility of polymer brushes are obtained, revealing their conformational information in aqueous solution. The results demonstrate that zwitterionic PCBMA brushes exhibit minimal antipolyelectrolyte effects in 0.1-10 mM NaCl solution but undergo significant swelling with increasing pH. On the other hand, nonionic POEGMA brushes exhibit similar responses to ionic strength as weak polyelectrolyte brushes. These unexpected findings enhance our understanding of polymer brushes beyond classical theories. The TIRM-based approach proves to be effective for characterizing polymer brushes and other soft nanomaterials.

Co-Assembled Nanosystems Exhibiting Intrinsic Fluorescence by Complexation of Amino Terpolymer and Its Quaternized Analog with Aggregation-Induced Emission (AIE) Dye.

Aggregation-induced emission dyes (AIEs) have gained significant interest due to their unique optical properties. Upon aggregation, AIEs can exhibit remarkable fluorescence enhancement. These systems are ideal candidates for applications in bioimaging, such as image-guided drug delivery or surgery. Encapsulation of AIEs in polymeric nanocarriers can result in biocompatible and efficient nanosystems. Herein, we report the fabrication of novel nanoaggregates formulated by amino terpolymer and tetraphenylethylene (TPE) AIE in aqueous media. Poly(di(ethylene glycol) methyl ether methacrylate-co-2-(dimethylamino)ethylmethacrylate-co-oligoethylene glycol methyl ether methacrylate), P(DEGMA-co-DMAEMA-co-OEGMA) hydrophilic terpolymer was utilized for the complexation of the sodium tetraphenylethylene 4,4',4″,4‴-tetrasulfonate AIE dye. Fluorescence spectroscopy, physicochemical studies, and self-assembly in aqueous and fetal bovine serum media were carried out. The finely dispersed nanoparticles exhibited enhanced fluorescence compared to the pure dye. To investigate the role of tertiary amino groups in the aggregation phenomenon, the polymer was quaternized, and quaternized polymer nanocarriers were fabricated. The increase in fluorescence intensity indicated stronger interaction between the cationic polymer analog and the dye. A stronger interaction between the nanoparticles and fetal bovine serum was observed in the case of the quaternized polymer. Thus, P(DEGMA-co-DMAEMA-co-OEGMA) formulations are better candidates for bioimaging applications than the quaternized ones, presenting both aggregation-induced emission and less interaction with fetal bovine serum.

Fungal Attachment-Resistant Polymers for the Additive Manufacture of Medical Devices.

This study reports the development of the first copolymer material that (i) is resistant to fungal attachment and hence biofilm formation, (ii) operates via a nonkilling mechanism, i.e., avoids the use of antifungal actives and the emergence of fungal resistance, (iii) exhibits sufficient elasticity for use in flexible medical devices, and (iv) is suitable for 3D printing (3DP), enabling the production of safer, personalized medical devices. Candida albicans (C. albicans) can form biofilms on in-dwelling medical devices, leading to potentially fatal fungal infections in the human host. Poly(dimethylsiloxane) (PDMS) is a common material used for the manufacture of medical devices, such as voice prostheses, but it is prone to microbial attachment. Therefore, to deliver a fungal-resistant polymer with key physical properties similar to PDMS (e.g., flexibility), eight homopolymers and 30 subsequent copolymers with varying glass transition temperatures (Tg) and fungal antiattachment properties were synthesized and their materials/processing properties studied. Of the copolymers produced, triethylene glycol methyl ether methacrylate (TEGMA) copolymerized with (r)-α-acryloyloxy-β,β-dimethyl-γ-butyrolactone (AODMBA) at a 40:60 copolymer ratio was found to be the most promising candidate by meeting all of the above criteria. This included demonstrating the capability to successfully undergo 3DP by material jetting, via the printing of a voice prosthesis valve-flap using the selected copolymer.

Organotin(IV) compounds loaded in thermo- and pH-responsive smart polymeric nanocarriers based on poly(DEGMA-co-OEGMA)-b-poly(DEAEM) a drug releasing system and in vitro anticancer activity

Nanocarriers in cancer treatment are important for transport and release of insoluble drugs. In this work, block thermo- and pH-responsive copolymers based on poly(di(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate) (PDO) and poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEA) were tested. At pH 7.4 and 37 °C, the title polymers formed micelles which were used for the loading and release of diorganotin(IV) complexes (LSnR2), where L is a Schiff base ligand and R = n-butyl (LSnBu2) or cyclohexyl (LSnCy2). Results revealed that the PDO-b-PDE block copolymers could enhance the solubility of LSnR2(IV) compounds in PBS at pH = 7.4, resulting in good loading capacity (%DLC) and loading efficiency (%DLE), and better release performance (pH-dependent and T-dependent) than the free compound. In vitro cytotoxic activity was evaluated by the sulforhodamine B (SRB) assay against a normal cell line, African green monkey kidney fibroblast (COS-7) and seven human cancer cell lines prostate (PC-3), leukemia (K-562), colon (HCT-15), lung (SKLU-1), central nervous system glia (U-251), breast Strogen receptor-positive (MCF-7) and breast hormone-independent (MDA-MB-231). The non-loaded block copolymers were non-cytotoxic, but the loaded ones showed high cell growth inhibition against human cancer cell lines. Results confirmed that these temperature and pH-sensitive polymeric systems are excellent candidates for the loading and release of potential metallodrugs, such as LSnR2, against diverse types of cancers.

A pH-Responsive Hydrogel for the Oral Delivery of Ursolic Acid: A Pentacyclic Triterpenoid Phytochemical.

In this study, poly(HEMA-PEGxMEM-IA) hydrogels were prepared by radical copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGxMEM), 2-hydroxyethyl methacrylate (HEMA), and itaconic acid (IA). The reaction was carried out in ethanolic solution using N,N'-methylenebisacrylamide (MBA) as a crosslinking agent and 1-hydroxycyclohexyl phenyl ketone (HCPK) as a photo-initiator. The poly(HEMA-PEGxMEM-IA) hydrogels (HGx) were evaluated as a delivery system for ursolic acid (UA), a phytochemical extracted from the plant Clinopodium revolutum, "flor de arena". The hydrogels were characterized by Fourier-transform infrared spectroscopy (FTIR-ATR), Raman spectroscopy, X-Ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The swelling behavior was studied in buffer solutions from pH 2 to 10, specifically at pH 2.2 (gastric environment) and 7.4 (intestinal environment). It was found that the hydrogels studied showed sensitivity to pH. At pH 2.2, the degree of swelling for HG5 and HG9 hydrogels was 0.45 and 0.93 (g water/g hydrogel), respectively. At pH 7.4, the degree of swelling for HG5 and HG9 hydrogels was 1.97 and 2.64 (g water/g hydrogel), respectively. The SEM images show the variation in pore size as a function of pH, and the UA crystals in the pores of the hydrogels can also be observed. The in vitro UA release data best fit the Korsmeyer-Peppas kinetic model and the diffusion exponent indicates that the release mechanism is governed by Fickian diffusion.

Micelles of poly[oligo(ethylene glycol) methacrylate] as delivery vehicles for zinc phthalocyanine photosensitizers

Drug-loaded polymeric micelles have proven to be highly effective carrier systems for the efficient delivery of hydrophobic photosensitizers (PSs) in photodynamic therapy (PDT). This study introduces the micellization potential of poly(oligoethylene glycol methyl ether methacrylate) (pOEGMA) as a novel approach, utilizing the hydrophobic methacrylate segments of pOEGMA to interact with highly hydrophobic zinc phthalocyanine (ZnPc), thereby forming a potential micellar drug carrier system. The ZnPc molecule was synthesized from phthalonitrile derivatives and its fluorescence, photodegradation, and singlet oxygen quantum yields were determined in various solvents. In solvents such as tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide, the ZnPc compound exhibited the requisite photophysical and photochemical properties for PDT applications. The pOEGMA homopolymer was synthesized via reversible addition-fragmentation chain-transfer polymerization, while ZnPc-loaded pOEGMA micelles were prepared using the nanoprecipitation method. Characterization of the pOEGMA, ZnPc, and micelles was conducted using FTIR,1H-NMR, dynamic light scattering, matrix-assisted laser desorption/ionization time-of-flight mass spectrometries, gel permeation chromatography, and transmission electron microscopy. The critical micelle concentration was determined to be 0.027 mg ml-1using fluorescence spectrometry. The drug loading and encapsulation efficiencies of the ZnPc-loaded micelles were calculated to be 0.67% and 0.47%, respectively. Additionally, the release performance of ZnPc from pOEGMA micelles was monitored over a period of nearly 10 d, while the lyophilized micelles exhibited stability for 3 months. Lastly, the ZnPc-loaded micelles were more biocompatible than ZnPc on L929 cell line. The results suggest that the pOEGMA homopolymer possesses the capability to micellize through its methacrylate segments when interacting with highly hydrophobic molecules, presenting a promising avenue for enhancing the delivery efficiency of hydrophobic PSs in PDT. Moreover, it was also deciphered that obtained formulations were highly biocompatible according to cytotoxicity results and could be safely employed as drug delivery systems in further applications.

A green bulk modification for imparting a green VIPS membrane with antifouling properties

BackgroundMembrane preparation and membrane modification processes have long involved the use of toxic solvents. The present work proposes to only use envrionmentally-friendly solvents for both the fabrication and the surface modification of hydrophobic microfiltration membranes. In addition, coating processes for membrane modification are essentially surface modification processes. However, spray-coating may be a suitable method for both surface and bulk modification. MethodsAfter dissolving poly(vinylidene fluoride) in dimethylsulfoxide, membranes were formed by the vapor-induced phase separation process, and then modified using an aqeous solution of an amphiphilic copolymer containing poly(ethylene glycol) methyl ether methacrylate units. Then, a variety of physicochemical techniques were employed to characterize the membrane structure and prove the effectiveness of the surface/bulk modification. Antifouling tests in static and dynamic conditions were conducted. Significant findingsIt is possible to reduce the water contact angle of the top surface of the membrane from 135° to 0° and that of the bottom surface from 126° to 0° within <10 s, indicating successful hydrophilization of the membrane on the one hand, and top-to-bottom modification, despite solely exposing the top surface to the spray, on the other hand. This conclusion was confirmed by deidcated surface chemistry analyses. Besides, the membranes maintained their original highly porous and symmetric structure with light effects on surface porosity and pore size following the spray-coating process. The drasting improvement of hydrophilicity resulted in effective mitigation of fibrinogen adsorption (reduced by 85 %) and Escherichia coli adhesion (reduced by 86 %). Fouling during cyclic filtration involving a bacterial suspension was also effectively reduced with a flux recovery ratio of 53 % (against 37 % for a commercial hydrophilic membrane) and an irreversible flux decline ratio of 47 % (against 63 % for a commercial hydrophilic membrane) in the conditions of the test.

Essential Oil Components Incorporated Emulsion Hydrogels for Eradicating Dermatophytosis Caused by Pathogenic Fungi Trichophyton mentagrophytes and Microsporum canis.

Dermatophytosis is a prevalent fungal infection and public health burden, majorly caused by the attack of zoophilic fungi genera of Trichophyton and Microsporum. Among them, T. mentagrophytes and M. canis are the dominating pathogens that cause dermatophytosis in humans. Though anti-fungal treatments are available, the widespread drug resistance and minimal efficacy of conventional therapies cause recurring infections. In addition, prolonged anti-fungal medications induce several systemic side effects, including hepatotoxicity and leucopenia. The anti-dermatophytic formulation of biocompatible essential oil components (EOCs) is attractive due to their highly potent anti-dermatophytic action. Herein, two EOCs, Eugenol (EU) and Isoeugenol (IU), incorporated emulsion hydrogel (EOCs-EHG) synthesized from hydroxypropylmethyl cellulose and poly(ethylene glycol) methyl ether methacrylate. The cytocompatibility of the hydrogels is confirmed by treating them with fibroblast and keratinocyte cell lines. The EOCs-EHG demonstrated pH and temperature-responsive sustained release of entrapped EOCs and inhibited fungal spore germination. T. mentagrophytes and M. canis biofilms are eradicated at a minimal inhibitory concentration of 2µg mL-1 each of EU and IU. The in vivo anti-dermatophytic activity of EOCs-EHG is confirmed in dermatophyte-infected Wistar albino rat models. The topical application of EOCs-EHG demonstrated complete infection eradication and facilitated skin regeneration, emphasizing the therapeutic potential of EOCs-EHG against dermatophytosis.

RAFT copolymerization of methyl methacrylate and di(ethylene glycol) methyl ether methacrylate in a hexylpyridinium ionic liquid

AbstractSmart polymers undergo significant physical or chemical changes in response to stimuli like temperature and pH. Achieving a narrow molecular weight distribution is crucial for their sensitivity. Reversible addition–fragmentation chain transfer (RAFT) in ionic liquids is an effective method for synthesizing such polymers due to its favorable kinetics and environmental benefits. Most studies use imidazolium ionic liquids, while pyridinium ionic liquids are less common despite their easy synthesis. This study reports the first successful RAFT copolymerization of di(ethylene glycol) methyl ether methacrylate (DEGMEMA) and methyl methacrylate in N‐hexylpyridinium hexafluorophosphate ([HPY][PF6]). Both linear and hyperbranched copolymers (Mn &gt; 25,000) with narrow molecular weight distribution were synthesized, showing observable temperature responses and biocompatibility. The linear copolymers had a desirable dispersity (Ð) of less than 1.10, while the hyperbranched copolymer had a Ð of 2.034. The lower critical solution temperatures (LCSTs) of the copolymers were close to or below the LCST of PDEGMEMA (26°C). This study indicates that pyridinium ionic liquids can be explored as a suitable solvent for synthesizing methacrylate‐based smart polymers.

Porphyrin encapsulated in organic polymers: Electropolymerization and preliminary investigations on electrocatalytic activity

AbstractIn the present work, the incorporation of hydrophobic porphyrins in organic polymers through electrochemically induced polymerization of monomers on conventional electrodes and the preliminary investigations on the electrocatalytic activity of these modified electrodes are explained. Electropolymerized porphyrins show better activity than organic polymers of N‐isopropylacrylamide, triethylene glycol methyl ether methacrylate, and glycerol 1,3‐diglycerolate diacrylate for nitrite oxidation due to the presence of cobalt metal ion. Among the porphyrins investigated, electropolymerized cobalt tetra‐2‐thienylporphyrin requires the least overpotential, due to ease of polymerization and better coating on glassy carbon electrode compared with that of cobalt tetraphenylporphyrin and cobalt tetra‐3‐thienylporphyrin. On encapsulating these porphyrins in organic polymers, improved current and lower overpotential are noticed.

In-Situ Observation of Ice-Adhesion Interface Under Tangential Loading: Anti-Icing Mechanism of Hydrophilic PPEGMA Polymer Brush

Techniques preventing icing and ice accumulation on surfaces are required to solve snow- and ice-induced accidents and disasters. Recently, hydrophilic polymers have attracted attention as a passive anti-icing method. This study examined the ice-adhesion properties of the hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) concentrated polymer brush (CPB). A custom-built apparatus was developed to obtain the ice-adhesion strength and visualize the dynamics of the ice-adhesion interface under tangential loading. The ice-adhesion interface for a PPEGMA-CPB-coated glass substrate was investigated by comparing it with the bare glass substrate. As a result, the CPB exhibited a low ice-adhesion strength of less than 100 kPa, the dependencies of which on the drive speed and temperature indicate a high-viscous liquid-like layer at the interface, even below the melting point of water, leading to the smooth onset of sliding due to its self-lubricity without any rupture events (including precursory events) observed for the bare glass.

Flexibility of Poly(alkyl methacrylate)s Characterized by Their Persistence Length Determined through Pyrene Excimer Formation.

A series of poly(alkyl methacrylate)s and poly(oligo(ethylene glycol) methyl ether methacrylate)s labeled with 1-pyrenebutanol were referred to as the PyC4-PCnMA samples with n = 1, 4, 6, 8, 12, and 18 and the PyC4-PEGnMA samples with n = 0-5, 9, 16, and 19, respectively. Pyrene excimer formation (PEF) upon the encounter between an excited and a ground-state pyrenyl labels was employed to determine their persistence length (lp) in o-xylene. The fluorescence decays of the PyC4-PCnMA and PyC4-PEGnMA samples were acquired and analyzed with the fluorescence blob model to yield the number (Nblob) of structural units in the volume probed by an excited pyrenyl label. Nblob was found to decrease with an increasing number (NS) of non-hydrogen atoms in the side chain, reaching a plateau for the PyC4-PEGnMA samples with a longer side chain (n = 16 and 19). The Nblob values were used to determine lp. The lp values for the PyC4-PCnMA and PyC4-PEGnMA samples increased linearly with increasing NS2 as predicted theoretically, which agreed with the lp values obtained by viscometry for a series of PCnMA samples. The good agreement between the lp values retrieved by PEF and viscometry served to validate the PEF-based methodology for determining lp for linear polymers.

Boosting the Cell Harvesting Performance of Poly(di(ethylene glycol)methyl ether methacrylate) Cell Release Layers via Copolymerization of Photo- and Thermoresponsive Monomers.

The performance of the cell-selective thermoresponsive poly(di(ethylene glycol)methyl ether methacrylate) (PDEGMA) cell harvest system is shown to be drastically enhanced by exploiting the combination of photoresponsive spiropyran derivates and PDEGMA in copolymerized brushes. The analysis of copolymerized 1'-(2-methacryloxyethyl)-3',3'-dimethyl-6-nitrospiro(2H-1-benzopyran-2,2'-indoline) (SPMA) (DEMGA) di(ethylene glycol)methyl ether methacrylate brushes revealed that a minor adjustment of the SPMA/DEGMA ratios results in a significant alternation of wettability as well as protein adsorption, when switching the temperature from 37 to 22°C and alternately irradiating using different light wavelengths (from 530 to 365nm). Thin P(SPMA-co-DEGMA) layers supported pancreatic tumor PaTu 8988t cells with high cell viability. Copolymer layers with 2.5% SPMA/DEGMA led to the highest efficiency of enzyme-free cell release with very good cell viability. The release is induced by cooling the cell culture medium to 22°C and irradiating the surface with 365nm light. Compared to neat PDEGMA, the P(SPMA-co-DEGMA) layers showed a threefold increase in the speed of the change of cell morphology of the attached cells and a >5 times increased fraction of detached cells, which underlines the potential of these dual responsive PDEGMA systems for optimized performance in the facile capture, culture, and release of different cell lines.

Terpyridine-Decorated Polymer Nanosphere Latex: Template Nanocarriers for the Synthesis of Cu-CeO2 Hollow Spheres.

Water-soluble polymers with the ability to complex metal ions through complexing ligands have attracted significant interest in diverse domains, such as optical or catalyst applications. In this paper, we successfully synthesized, through a one-pot process combining polymerization-induced self-assembly and reversible addition-fragmentation chain transfer polymerization, aqueous dispersions of terpyridine-decorated poly[poly(ethylene glycol)methyl ether methacrylate]-b-poly(methyl methacrylate) (tpy-PPEGMA-b-PMMA) amphiphilic block copolymers. The in-situ formation of well-defined amphiphilic block copolymers and their self-assembly led to nanosphere latex with the hydrodynamic diameters increasing from 17 to 52 nm and the length of the copolymers increasing from 21,000 to 51,000 g·mol-1. These aqueous dispersed tpy-PPEGMA-b-PMMA nanospheres effectively complex metal ions, such as Cu2+, in a stoichiometric ratio of 2:1. Subsequently, these metal-complexed nanospheres were employed as soft template nanocarriers to control, on the nanometer scale, the dispersion of metal on a nanostructured support. This is exemplified by the synthesis of copper supported on cerium oxide hollow spheres (Cu-CeO2) using Cu2+-tpy-PPEGMA-b-PMMA as template nanocarriers and CeO2 nanoparticles. This novel assembly engineering strategy for the preparation of atomically dispersed metal on a nanostructured support was highlighted through the utilization of Cu-CeO2 hollow spheres as an electrocatalyst for the nitrate reduction reaction (NO3RR) to NH3. These encouraging outcomes emphasize the potential of metal-metal oxide-nanostructured materials to treat contaminated water sources with nitrate while allowing the green production of ammonia.

Surface-Grafted Biocompatible Polymer Conductors for Stable and Compliant Electrodes for Brain Interfaces.

Durable and conductive interfaces that enable chronic and high-resolution recording of neural activity are essential for understanding and treating neurodegenerative disorders. These chronic implants require long-term stability and small contact areas. Consequently, they are often coated with a blend of conductive polymers and are crosslinked to enhance durability despite the potentially deleterious effect of crosslinking on the mechanical and electrical properties. Here the grafting of the poly(3,4 ethylenedioxythiophene) scaffold, poly(styrenesulfonate)-b-poly(poly(ethylene glycol) methyl ether methacrylate block copolymer brush to gold, in a controlled and tunable manner, by surface-initiated atom-transfer radical polymerization (SI-ATRP) is described. This "block-brush" provides high volumetric capacitance (120 F cm─3), strong adhesion to the metal (4h ultrasonication), improved surface hydrophilicity, and stability against 10000 charge-discharge voltage sweeps on a multiarray neural electrode. In addition, the block-brush film showed 33% improved stability against current pulsing. This approach can open numerous avenues for exploring specialized polymer brushes for bioelectronics research and application.

Supramolecularly-Cross-Linked Nanogel Assemblies for On-Demand, Ultrasound-Triggered Chemotherapy.

Stimulating the release of small nanoparticles (NPs) from a larger NP via the application of an exogenous stimulus offers the potential to address the different size requirements for circulation versus penetration that hinder chemotherapeutic drug delivery. Herein, we report a size-switching nanoassembly-based drug delivery system comprised of ultrasmall starch nanoparticles (SNPs, ∼20-50 nm major size fraction) encapsulated in a poly(oligo(ethylene glycol) methyl ether methacrylate) nanogel (POEGMA, ∼150 nm major size fraction) cross-linked via supramolecular PEG/α-cyclodextrin (α-CD) interactions. Upon heating the nanogel using a non-invasive, high-intensity focused ultrasound (HIFU) trigger, the thermoresponsive POEGMA-CD nanoassemblies are locally de-cross-linked, inducing in situ release of the highly penetrative drug-loaded SNPs. HIFU triggering increased the release of nanoassembly-loaded DOX from 17 to 37% after 3 h, a result correlated with significantly more effective tumor killing relative to nanoassemblies in the absence of HIFU or drug alone. Furthermore, 1.5× more total fluorescence was observed inside a tumor spheroid when nanoassemblies prepared with fluorophore-labeled SNPs were triggered with HIFU relative to the absence of HIFU. We anticipate this strategy holds promise for delivering tunable doses of chemotherapeutic drugs both at and within a tumor site using a non-invasive triggering approach.

Biocompatibility of mussel-inspired water-soluble tissue adhesives.

Wound closure in surgeries is traditionally achieved using invasive methods such as sutures and staples. Adhesion-based wound closure methods such as tissue adhesives, sealants, and hemostats are slowly replacing these methods due to their ease of application. Although several chemistries have been developed and used commercially for wound closure, there is still a need for better tissue adhesives from the point of view of toxicity, wet-adhesion strength, and long-term bonding. Catechol chemistry has shown great promise in developing wet-set adhesives that meet these criteria. Herein, we have studied the biocompatibility of a catechol-based copolymer adhesive, poly([dopamine methacrylamide]-co-[methyl methacrylate]-co-[poly(ethylene glycol) methyl ether methacrylate]) or poly(catechol-MMA-OEG), which is soluble in water. The adhesive was injected subcutaneously in a mouse model on its own and in combination with a sodium periodate crosslinker. After 72 h, 4 weeks, and 12 weeks, the mice were euthanized and subjected to histopathological analysis. Both adhesives were present and still palpable at the end of 12 weeks. The moderate inflammation observed for the poly(catechol-MMA-OEG) cohort at 72 h had reduced to mild inflammation at the end of 12 weeks. However, the moderate inflammatory response observed for the poly(catechol-MMA-OEG) + crosslinker cohort at 72 h had not subsided at 12 weeks.

Effect of Embedded g-C3N4 Nanosheets on the Hydration and Thermal Response Behavior of Cross-Linked Thermoresponsive Copolymer Films.

The effect of embedded graphitic carbon nitride (g-C3N4) nanosheets on hydration and thermal response behavior of cross-linked thermoresponsive poly(di(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate), abbreviated as P(MA-co-MA300), thin films is probed by white light interferometry. Compared with that of the cross-linked pure P(MA-co-MA300) films, the surface roughness of the cross-linked hybrid films is slightly increased, which is caused by the minor aggregation of g-C3N4 nanosheets during the spin-coating process. After exposure to a water vapor atmosphere, both cross-linked pure and hybrid films can absorb water and swell. However, the introduction of g-C3N4 not only induces a larger hydration extent but also triggers a nonlinear transition behavior upon heating. This prominent difference might be related to the residual hydrophilic groups (-NH2 and N-H) on the surface of g-C3N4 nanosheets, which enhance the interaction and absorption capability for water molecules in the hybrid films. Upon further increasing the amount of embedded g-C3N4 nanosheets in films, more hydrogen bonds are formed and a larger hydration extent of films is observed. To break all of the hydrogen bonds in films, a higher transition temperature (TT) is required. The observed hydration and transition behaviors of hybrid films can be used to design hydrogel-based films for hydrogen evolution or wastewater treatment.

Investigating oligo(ethylene glycol) methacrylate thermoresponsive copolymers

Methacrylate-based polymers are frequently used in the development of thermoresponsive smart materials for biomedical applications. Among all the routes to such polymers, reversible addition fragmentation chain transfer (RAFT) copolymerisation is one of the most widely used. This paper reports the synthesis of thermoresponsive copolymers comprising oligo(ethylene glycol) methyl ether methacrylate with Mn of 300 (OEGMA300) and di(ethylene glycol) methyl ether methacrylate (DiEGMA). Polymers of molecular weight up to 100 kDA were obtained via RAFT polymerisation, mediated by a dithiobenzoate chain transfer agent (CTA) at 70 °C. An appropriate solvent, ratio of initiator to monomers, and minimum reaction polymerisation time were essential to provide optimum polymers. The synthesis of homogenous p(OEGMA300-co-DIEGMA) polymers with PDI of 1.1–1.2 was achieved in toluene with ≥10 h of reaction. Increasing the molecular weight of the p(OEGMA300-co-DiEGMA) polymers decreases the polydispersity index. p(OEGMA300-co-DiEGMA) polymers with Mw of 50,000 Da were successfully synthesised with lower critical solution temperatures (LCSTs) of 41.3 °C, 43.0 °C and >45 °C for OEGMA300:DiEGMA molar ratios of 2:8, 3:7 and 4:6, respectively. Further, the LCST was not found to be affected by the polymer molecular weight. The p(OEGMA300-co-DiEGMA) polymers showed no cytotoxicity to Caco-2 cells at a concentration of 1 mg mL−1, whereas a decrease of HDF cell viability by up to 26.5 % was seen. These polymers could be beneficial for several biomedical applications, such as developing formulations for temperature-triggered drug delivery.

Realization of Enhanced Interfacial Lithium-Ion Transfer in Composite Polymer Electrolytes via Grafting Oligo-PEG Molecular Brushes on Silica-Coated Nanofibers for All-Solid-State Lithium Metal Batteries.

Polyether-based polymer electrolytes are attractive but still challenging for high-energy-density solid-state lithium metal batteries due to their limited Li-ion conductivity at room temperature. Herein, an oligomeric polyethylene glycol methyl ether methacrylate (PEGMEM)-modified silica-coated polyimide fibrous scaffold (PINF@PEGMEM-SiO2) was introduced in polyethylene glycol dimethyl ether (PEGDME) to enhance the Li-ion transportation at room temperature. PINF@PEGMEM-SiO2 was developed to build a continuous and interconnected interface for continuous Li-ion transportation in bulk. The carbonyl groups (C═O) of PEGMEM on SiO2 can promote the dissociation of lithium salts and enhance the migration of free Li ions at the interface. The same -C-C-O- unit contained in both PEGMEM and PEGDME ensures the compatibility of PEGMEM at the interface and PEGDME in the bulk. The prepared PEGDME-based polymer electrolyte exhibits a high ionic conductivity of 1.14 × 10-4 S cm-1 at 25 °C and an improved Li-ion transference number of 0.41. Furthermore, LiFePO4/Li and LiNi0.8Co0.1Mn0.1O2/Li cells with excellent cyclability and rate capability at ambient temperature are obtained.