Glycol Methyl Ether Methacrylate Research Articles

Smart Self-Cleaning Membrane via the Blending of an Upper Critical Solution Temperature Diblock Copolymer with PVDF.

Poly(2,2,2-trifluoroethyl methacrylate)-b-poly(imidazoled glycidyl methacrylate-co-diethylene glycol methyl ether methacrylate) (PTFEMA-b-P(iGMA-co-MEO2MA)) containing an upper critical solution temperature (UCST) polymer chain was prepared and blended with poly(vinylidene fluoride) (PVDF) to produce a thermoresponsive membrane with smart self-cleaning performance. The successful preparation of the membrane was demonstrated by attenuated total reflection-Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy characterization. The membrane shows UCST performance, and its flux changes with the filtrate temperature as the UCST polymer chain stretches out and contracts in response to various temperatures. In addition, the UCST polymer chain can disrupt the foulant and push it away from the membrane when the temperature is above the UCST and thus enables membranes to exhibit a smart self-cleaning behavior. To the best of our knowledge, this work is the first report of a smart self-cleaning membrane based on the blending of a diblock copolymer containing a UCST polymer chain with PVDF.

ThermosensitivePMMAcore/oligo(ethylene glycol)‐based shell microgels as drug carriers in detoxification treatment

AbstractThe core‐shell structured polymer microgels were synthesized by coating the hydrophobic poly(methyl methacrylate) (PMMA) sphere cores with hydrophilic nonlinear poly(ethylene glycol)‐based gel shell layer. The uniqueness of these core‐shell microgels lies in the integration of the PMMA core microsphere with strong hydrophobicity and the novel oligo(ethylene glycol)‐based gel layer with well‐defined thermosensitivity for improving loading/release efficacy of two detoxification drugs (chlorpromazine and diltiazem). The hydrophilic shell is composed of hydrophilic copolymer of 2‐(2‐methoxyethoxy)ethyl methacrylate (MEO2MA) with oligo(ethylene glycol) methyl ether methacrylates (MEO5MA). It was found that the molar ratio of two shell monomersn(MEO2MA)/n(MEO5MA) of 1:6 was an ideal matching value for production of the P(MEO2MA)/P(MEO2MA‐co‐MEO5MA) core‐shell microgels with tunable volume phase transition temperature and excellent colloidal stability across the physiologically important temperature range. Moreover, chlorpromazine‐ and diltiazem‐loaded microgels can show an obvious thermosensitive release and in vitro sustained‐release characteristic up to 80 h.

PEGylation of Guanidinium and Indole Bearing Poly(methacrylamide)s - Biocompatible Terpolymers for pDNA Delivery.

This study describes the first example for shielding of a high performing terpolymer that consists of N-(2-hydroxypropyl)methacrylamide (HPMA), N-(3-guanidinopropyl)methacrylamide (GPMA), and N-(2-indolethyl)methacrylamide monomers (IEMA) by block copolymerization of a polyethylene glycol derivative - poly(nona(ethylene glycol)methyl ether methacrylate) (P(MEO9 MA)) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The molecular weight of P(MEO9 MA) is varied from 3 to 40 kg mol-1 while the comonomer content of HPMA, GPMA, and IEMA is kept comparable. The influence of P(MEO9 MA) block with various molecular weights is investigated over cytotoxicity, plasmid DNA (pDNA) binding, and transfection efficiency of the resulting polyplexes. Overall, the increase in molecular weight of P(MEO9 MA) block demonstrates excellent biocompatibility with higher cell viability in L-929 cells and an efficient binding to pDNA at N/P ratio of 2. The significant transfection efficiency in CHO-K1 cells at N/P ratio 20 is obtained for block copolymers with molecular weight of P(MEO9 MA) up to 10 kg mol-1 . Moreover, a fluorescently labeled analogue of P(MEO9 MA), bearing perylene monoimide methacrylamide (PMIM), is introduced as a comonomer in RAFT polymerization. Polyplexes consisting of labeled block copolymer with 20 kg mol-1 of P(MEO9 MA) and pDNA are incubated in Hela cells and investigated through structured illumination microscopy (SIM).

Unique Carbonate-Based Single Ion Conducting Block Copolymers Enabling High-Voltage, All-Solid-State Lithium Metal Batteries.

Safety and high-voltage operation are key metrics for advanced, solid-state energy storage devices to power low- or zero-emission HEV or EV vehicles. In this study, we propose the modification of single-ion conducting polyelectrolytes by designing novel block copolymers, which combine one block responsible for high ionic conductivity and the second block for improved mechanical properties and outstanding electrochemical stability. To synthesize such block copolymers, the ring opening polymerization (ROP) of trimethylene carbonate (TMC) monomer by the RAFT-agent having a terminal hydroxyl group is used. It allows for the preparation of a poly(carbonate) macro-RAFT precursor that is subsequently applied in RAFT copolymerization of lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide and poly(ethylene glycol) methyl ether methacrylate. The resulting single-ion conducting block copolymers show improved viscoelastic properties, good thermal stability (Tonset up to 155 °C), sufficient ionic conductivity (up to 3.7 × 10–6 S cm–1 at 70 °C), and high lithium-ion transference number (0.91) to enable high power. Excellent plating/stripping ability with resistance to dendrite growth and outstanding electrochemical stability window (exceeding 4.8 V vs Li+/Li at 70 °C) are also achieved, along with enhanced compatibility with composite cathodes, both LiNiMnCoO2 – NMC and LiFePO4 – LFP, as well as the lithium metal anode. Lab-scale truly solid-state Li/LFP and Li/NMC lithium-metal cells assembled with the single-ion copolymer electrolyte demonstrate reversible and very stable cycling at 70 °C delivering high specific capacity (up to 145 and 118 mAh g–1, respectively, at a C/20 rate) and proper operation even at a higher current regime. Remarkably, the addition of a little amount of propylene carbonate (∼8 wt %) allows for stable, highly reversible cycling at a higher C-rate. These results represent an excellent achievement for a truly single-ion conducting solid-state polymer electrolyte, placing the obtained ionic block copolymers on top of polyelectrolytes with highest electrochemical stability and potentially enabling safe, practical Li-metal cells operating at high-voltage.

RAFT Synthesis of Reactive Multifunctional Triblock‐Copolymers for Polyplex Formation

AbstractReversible addition–fragmentation chain transfer polymerization with a low‐temperature initiator can be used to synthesize multifunctional block copolymers for polyplex formation. Utilizing three methacrylate monomers (triethylene glycol methyl ether methacrylate (MEO3MA), pyridyldisulfideethyl methacrylate (PDSM), N,N‐dimethylethylenediamine methacrylate (DMAEMA)) and an azide bearing chain transfer agent for polymerization, the resulting triblock‐copolymers possess two orthogonally reactive functionalities (a block with reactive disulfide side chains and an azide end‐group) and two additional functional blocks for i) solubilization and ii) polyplex formation. Thereby, the MEO3MA block provides solubility in aqueous media and the DMAEMA block, having a tertiary amine in the side chain, allows polyplex formation with polyanionic biomacromolecules like DNA or RNA. Due to the reactive disulfide block the polyplexes can be (reversibly) crosslinked with dithiols. Because of the manifold of possibilities to modify the pDNApolyplexes, this polymers system is an interesting candidate for active‐targeting and codelivery approaches.

Ionic Liquid Containing Block Copolymer Dielectrics: Designing for High-Frequency Capacitance, Low-Voltage Operation, and Fast Switching Speeds.

Polymerized ionic liquids (PILs) are a potential solution to the large-scale production of low-power consuming organic thin-film transistors (OTFTs). When used as the device gating medium in OTFTs, PILs experience a double-layer capacitance that enables thickness independent, low-voltage operation. PIL microstructure, polymer composition, and choice of anion have all been reported to have an effect on device performance, but a better structure property relationship is still required. A library of 27 well-defined, poly(styrene)-b-poly(1-(4-vinylbenzyl)-3-butylimidazolium-random-poly(ethylene glycol) methyl ether methacrylate) (poly(S)-b-poly(VBBI+[X]-r-PEGMA)) block copolymers, with varying PEGMA/VBBI+ ratios and three different mobile anions (where X = TFSI–, PF6– or BF4–), were synthesized, characterized and integrated into OTFTs. The fraction of VBBI+ in the poly(VBBI+[X]-r-PEGMA) block ranged from to 100 mol % and led to glass transition temperatures (Tg) between −7 and 55 °C for that block. When VBBI+ composition was equal or above 50 mol %, the block copolymer self-assembled into well-ordered domains with sizes between 22 and 52 nm, depending on the composition and choice of anion. The block copolymers double-layer capacitance (CDL) and ionic conductivity (σ) were found to correlate to the polymer self-assembly and the Tg of the poly(VBBI+[X]-r-PEGMA) block. Finally, the block copolymers were integrated into OTFTs as the gating medium that led to n-type devices with threshold voltages of 0.5–1.5 V while maintaining good electron mobilities. We also found that the greater the σ of the PIL, the greater the OTFT operating frequency could reach. However, we also found that CDL is not strictly proportional to OTFT output currents.

Polymer-Grafted Porous Silica Nanoparticles with Enhanced CO2 Permeability and Mechanical Performance.

Three different types of polymer ligands, poly(methyl methacrylate) (PMMA), poly(methyl methacrylate-random-poly(ethylene glycol)methyl ether methacrylate) (PMMA-r-PEGMEMA), and poly(ionic liquid)s (PIL), were grafted onto the surface of 15 nm solid and large hollow porous silica nanoparticles (average particle size ∼60 nm) by surface-initiated atom transfer radical polymerization (SI-ATRP) to demonstrate the enhanced carbon dioxide (CO2) permeability as well as mechanical properties. After characterizing the purified products, free-standing bulk films were fabricated by the solvent-casting method. The poly(ionic liquid) nanocomposite films exhibited a much higher carbon dioxide permeance than PMMA and PMMA-r-PEGMEMA systems with a similar silica content. Also, the hollow silica-mixed matrix membranes showed a significant enhancement in CO2 permeability compared to the 15 nm solid silica films because of the pore structure. Despite the transparency loss due to the scattering of larger particle sizes, the hollow silica particle brush films exhibited the same mechanical properties as the 15 nm solid silica-derived ones.

Synergistic Stain Removal Achieved by Controlling the Fractions of Light and Thermo Responsive Components in the Dual-Responsive Copolymer Immobilized on Cotton Fabrics by Cross-Linker.

Enhanced synergistic stain removal is realized by tailoring the comonomer fractions of a light- and thermo-dual responsive copolymer, which is immobilized on cotton fabrics by a cross-linker. The copolymer poly(acrylamide azobenzene-co-ethylene glycol methacrylate-co-triethylene glycol methyl ether methacrylate), denoted P(AAAB1-co-EGMA2-co-MEO3MA17), is prepared by the ATRP polymerization method. The present molar ratio for these monomers is 1:2:17. Because of the existence of the light-responsive AAAB unit, the transition temperature of its aqueous solution under UV radiation is shifted to 39 °C, which is 2 °C higher than that in ambient conditions. This increase is caused by the trans-cis isomerization from the azobenzene groups, indicating an increased hydrophilicity of P(AAAB1-co-EGMA2-co-MEO3MA17) under UV radiation. After being immobilized onto cotton fabrics by a cross-linker, they are also dual-responsive. The equilibrium swelling ratio (ESR) of the cotton fabrics is further increased after UV radiation. Compared to our former investigation, the reduction of the AAAB molar fraction from 0.1 to 0.05 causes an increase of the ESR value by 10%. Moreover, the stain removal efficiency of the cotton fabrics immobilized with P(AAAB1-co-EGMA2-co-MEO3MA17) by cross-linker is also significantly improved under UV radiation. The hydrophilicity of the copolymer mainly from the MEO3MA units is crucial to the cleaning capability. Additionally lowering the attachment between stain and the copolymer coating on the cotton fabrics by trans-cis isomerization in those AAAB units also favors the cleaning. Hence, the stain removal is strongly improved by optimizing the fraction of light- versus thermo-responsive components in the copolymer, which can profoundly reduce the consumption of chemical detergents and energy during laundry.

Functional polymethacrylate composite elastomer filled with multilayer graphene and silica particles

In this work, a three-component composite elastomer consisting of poly(di(ethylene glycol)methyl ether methacrylate) (PMEO2MA), 110 nm spherical silica particles and multilayer graphene (MLG) is fabricated and its various functions brought about by the characteristic morphology formed by silica particles and MLG are clarified. The presence of silica particles greatly improved the dispersibility of MLG in PMEO2MA, allowing more MLG to be filled. The relative dielectric constant (ε) of the composite elastomers can be increased by increasing the amount of MLG while suppressing the increase in dielectric loss tangent (tanδ). The thermal conductivity of the composite elastomer peak in the middle of the increase in MLGs when the silica particles are not filled, whereas the silica particle-filled system is able to fill the MLGs up to a higher volume fraction and shows higher thermal conductivity. The dynamic viscoelasticity analysis of the composite elastomers shows that the filling effect of MLG is more remarkable in the composite elastomer containing 40 vol% silica particles. The loss factor of vibration damping is found to be larger in the 40 vol% SiO2 - 2.8 vol% MLG composite elastomer over a wider frequency range than in the non-MLG samples.

Ethyl methacrylate diblock copolymers as polymeric surfactants: Effect of molar mass and composition

Well-defined amphiphilic diblock copolymers and statistical copolymers were synthesised and investigated as polymeric surfactants. Specifically, two series of linear diblock copolymers-totaling 21 copolymers-were studied. In both series, the same hydrophobic monomer (ethyl methacrylate, EtMA) was used, whereas the hydrophilic monomer was changed. The first series was based on the non-ionic hydrophilic monomer, poly(ethylene glycol) methyl ether methacrylate (PEGMA, 300 g/mol), while the second series was based on the ionic, hydrophilic monomer, 2-(dimethylamino)ethyl methyl methacrylate (DMAEMA). The molar mass (MM) and compositions were systematically varied to investigate their effect on the final properties of the polymer. The aqueous solution properties of the copolymers, such as their cloud points, effective pKa values, hydrodynamic diameters, critical micelle concentrations and hydrophile-lipophile balances were determined. The hydrophobic content affected the thermoresponsive ability and the pKa of the polymer solutions significantly. Finally, the emulsifying properties of block copolymers were studied by preparing emulsions containing 1 w/w% of the polymer at the same water to methyl laurate ratio and observing their stability for 1 month. The stability of the emulsions was affected by both the MM and composition of the polymers, but to different extents for the non-ionic compared to the ionic series of polymeric macrosurfactants.

Hydration and Thermal Response Kinetics of a Cross-Linked Thermoresponsive Copolymer Film on a Hydrophobic PAN Substrate Coating Probed by In Situ Neutron Reflectivity.

The hydration and thermal response kinetics of the cross-linked thermoresponsive copolymer poly((diethylene glycol monomethyl ether methacrylate)-co-poly(ethylene glycol) methyl ether methacrylate), abbreviated as P(MEO2MA-co-OEGMA300), thin film on a hydrophobic polyacrylonitrile (PAN) substrate coating, which resembles a synthetic fabric, is probed by in situ neutron reflectivity (NR). The PAN and monomer (MEO2MA and OEGMA300) solutions are sequentially spin-coated onto a silicon (Si) substrate. Afterward, plasma treatment is applied to realize the cross-linking of PAN and monomers. The as-prepared cross-linked P(MEO2MA-co-OEGMA300) film on the hydrophobic PAN substrate coating presents a two-layer structure: a substrate-near layer, which is a mixture of PAN and P(MEO2MA-co-OEGMA300), and a main layer, which is composed of pure hydrophilic P(MEO2MA-co-OEGMA300). During hydration in D2O vapor atmosphere, the hydrophobic PAN component prevents the formation of D2O enrichment in the substrate-near layer. However, an additional vapor-near layer is observed on top of the main layer, which is enriched with D2O. The hydration process is constrained by the cross-linking points in the film, inducing the relaxation time to be longer than that in a spin-coated P(MEO2MA-co-OEGMA300) film. Because the as-prepared cross-linked film presents a transition temperature (TT) at 38 °C, the hydrated film switches to the collapsed state when the temperature is increased from 23 to 50 °C. The response to a thermal stimulus is also slower due to the existence of the internal cross-linking points as compared to the spin-coated film. Interestingly, no reswelling is observed at the end of the thermal stimulus, which can be also attributed to the presence of internal cross-linking points.

DLP 3D – printing of shape memory polymers stabilized by thermoreversible hydrogen bonding interactions

In this paper a simple three-components photopolymerizable system based on 2-hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol methyl ether methacrylate) (PEGMEMA) is used for the fabrication of thermoset H-bond stabilized shape memory polymers (SMPs) via digital light processing (DLP) three-dimensional (3D) printing. A bis(acyl)phosphane oxide derivative (BAPO-γ-CyD) was used as an all-in-one photoinitiator and crosslinking agent, so that no conventional multifunctional crosslinkers are needed. Due to the high elasticity ratio between the glassy and rubbery state and the presence of thermoreversibly associating hydrogen-bonding groups, the PHEMA-co-PEGMEMA polymers show an excellent thermally triggered shape memory response (strain recovery of 99%). A prototype of a thermoresponsive airflow diverter has been fabricated, demonstrating the potential integration of such SMPs to develop smart 3D – printed devices. Moreover, the possibility to easily design the glass transition temperature of the SMPs by varying the concentration of the two photopolymerizable ingredients allows to fine-tune the formulations such that materials can be printed showing shape memory behavior at different temperatures.

Photo/Thermal Dual Responses in Aqueous-Soluble Copolymers Containing 1-Naphthyl Methacrylate

Photoresponsive polymers capable of luminescence switching are attracting significant interest due to their potential application in fluorescence patterning, bioimaging, optical data storage, and anti-counterfeiting. In this work, we have developed aqueous-soluble copolymers of 1-naphthyl methacrylate and oligo(ethylene glycol) methyl ether methacrylate [P(1-NMA-co-OEGMA)] that undergo a significant shift in fluorescence emission wavelength after UV irradiation. Irradiation of the 1-naphthyl methacrylate moieties results in the photo-Fries rearrangement to form hydroxy aryl ketones, which exhibit strong emission at 475 nm through excited-state intramolecular proton transfer (ESIPT) and excited-state proton transfer (ESPT). The resultant shift in fluorescence emission maximum from 338 to 475 nm after rearrangement can potentially be exploited for fluorescence patterning. Furthermore, the copolymers are thermally sensitive in aqueous solutions. The lower critical solution temperature (LCST) of the copolymers depends on the content of hydrophobic 1-naphthyl methacrylate units; the photo-Fries rearrangement results in a more polar structure, shifting the LCST to a higher temperature. Of note, the temperature-triggered volume phase transition of copolymer hydrogels selectively ″switches off″ fluorescence arising from the ESPT mechanism, while the ESIPT emission is unaffected. We also demonstrate that films formed by coating the copolymers onto various substrates can be selectively patterned to form gradients in fluorescence intensity. These versatile P(1-NMA-co-OEGMA) copolymers are simple to prepare at low cost, demonstrate effective photoswitching, and have excellent water solubility, thus ensuring potential applications in a number of important areas.

Drug Release from Thermo-Responsive Polymer Brush Coatings to Control Bacterial Colonization and Biofilm Growth on Titanium Implants.

Despite decades of biomedical advances, the colonization of implant devices with bacterial biofilms is still a leading cause of implant failure. Clearly, new strategies and materials that suppress both initial and later stage bacterial colonization are required in this context. Ideal would be the implementation of a bactericidal functionality in the implants that is temporally and spatially triggered in an autonomous fashion at the infection site. Herein, the fabrication and validation of functional titanium-based implants with triggered antibiotic release function afforded via an intelligent polymer coating is reported. In particular, thermo-responsive poly(di(ethylene glycol) methyl ether methacrylate) (PDEGMA) brushes on titanium implants synthesized via a surface-initiated atom transfer radical polymerization with activators regenerated through the electron transfer technique (ARGET ATRP) allows for a controlled and thermally triggered release of the antibiotic levofloxacin at the wound site. Antibiotic loaded brushes are investigated as a function of thickness, loading capacity for antibiotics, and temperature. At temperatures of the infection site >37°Cthelower critical solution temperature behavior of the brushes afforded the triggered release. Hence, in addition to the known antifouling effects, the PDEGMA coating ensured enhanced bactericidal effects, as demonstrated in initial in vivo tests with rodents infected with Staphylococcus aureus.

Nonbiofouling Coatings Using Bottlebrushes with Concentrated Polymer Brush Architecture.

Concentrated polymer brushes (CPBs) are known to suppress biofouling phenomena, such as protein adsorption and cell adhesion. However, a cumbersome process is needed for their synthesis. Here, we report a simple and versatile method for fabricating nonbiofouling coatings that uses well-defined bottlebrushes instead of CPBs. First, a macroinitiator, poly[2-(2-bromoisobutyryloxy)ethyl methacrylate] (PBIEM), was synthesized by reversible addition-fragmentation chain transfer polymerization. Then, poly[poly(ethylene glycol) methyl ether methacrylate] was grafted from PBIEM through atom transfer radical polymerization to form well-defined bottlebrushes. By controlling the graft chain length, two types of bottlebrushes could be prepared, namely those with a semi-dilute polymer brush (SDPB) structure or a CPB structure on the surface of the outermost layer. Crosslinked films of the bottlebrushes were prepared on silicon wafers by spin-coating and subsequent radical coupling. Importantly, the CPB-type bottlebrush films showed significantly better nonbiofouling characteristics than those of the SDPB-type bottlebrush films.

ACID-LABILE CORE CROSS-LINKED MICELLES FOR pH-TRIGGERED RELEASE OF DOXORUBICIN

A acid-labile core cross-linked micelle system of amphiphilic triblock copolymer of poly(oligo(ethylene glycol) methyl ether methacrylate)-block-poly(styrene-alt-maleic anhydride)-block-poly(styrene) (POEGMA-b-PSMA-b-PS) was prepared. The POEGMA-b-PSMA-b-PS triblock copolymers were synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization. Doxorubincin (DOX) was entrapped into micellar structure with POEGMA block as a shell and PSMA-b-PS block as a core. Then, core cross-linking was carried out by amidation reaction between 2,2-bis(aminoethoxy)propane and maleic anhydride group inner core. DOX loading content and efficiency were calculated to be 18 and 90 (wt. %), respectively. Core cross-linked micelles illustrated good stability under physiological condition but disassociated rapidly under acidic pH. The DOX release experiments indicated a rapid DOX release at pH 5.0 compared to pH 7.4.

DPD simulations and experimental study on reduction-sensitive polymeric micelles self-assembled from PCL-SS-PPEGMA for doxorubicin controlled release

Delivery of anticancer drugs by amphiphilic polymeric micelles with disulfide bonds as the reduction-responsive groups has potential application in the field of drug-controlled release. In this study, three disulfide-linked polycaprolactone-b-polyethylene glycol methyl ether methacrylate (PCL-SS-PPEGMA) were synthesized and confirmed by 1H NMR and GPC, and then used for doxorubicin (DOX) delivery. The CMC values of the three PCL-SS-PPEGMA micelles were low (0.71–4.56 mg/L), indicative of the good stability of micelles in aqueous solution. The drug loading content (LC) and encapsulation efficiency (EE), together with the DOX accelerated release profiles were determined, with good drug loading capacity and well drug-controlled release performance. And to explore the mesoscopic behavior of reduction-responsive drug-loaded polymeric micelles, by using a dedicated disulfide bond-breaking model and script, dissipative particle dynamics (DPD) simulations were carried out on the three PCL-SS-PPEGMA polymers. Their self-assembled behavior, formation of DOX-loaded micelles, the disulfide bond-breaking process, as well as the DOX reduction-responsive release process were simulated and assessed. Comparing the DPD simulation results with the experimental data, we found that they were in good agreement, effectively demonstrating that the DPD simulation method developed can provide a practical mesoscopic approach for the reduction-responsive drug-loaded polymeric micelles that involved the cleavage of dynamic covalent bonds.

Stiffness-Dependent Intracellular Location of Cylindrical Polymer Brushes.

Cylindrical polymer brushes (CPBs) are macromolecules with nanoparticle proportions. Their modular synthesis enables tailoring of their chemical composition as well as the dialing-up of overall dimensions and physicochemical properties. In this study, two rod-like poly[(ethylene glycol) methyl ether methacrylate] (PEGMA)-based CPBs with varying stiffness but otherwise comparable features and functionality, are synthesized. Differences in particle stiffness are assessed using small angle neutron scattering (SANS). It is observed that the fate of the two CPBs within cells is distinctly different. Stiffer CPBs seem to gravitate toward the mitochondria, whereas CPBs with reduced stiffness are present in different intracellular vesicles.

P(MMA‐co‐HPMA)‐b‐POEGMA copolymers: synthesis, micelle formation in aqueous media and drug encapsulation

AbstractWe report the synthesis and the micellar self‐assembly in aqueous media of novel amphiphilic block copolymers. The copolymers consist of a poly[(methyl methacrylate)‐co‐(hydroxypropyl methacrylate)] statistical copolymer block and a poly[oligo(ethylene glycol) methyl ether methacrylate] block, and were synthesized by reversible addition–fragmentation chain transfer polymerization. The amphiphilic P(MMA‐co‐HPMA)‐b‐POEGMA block copolymers contain monomers of differing polarity and in varying ratios. Furthermore, HPMA segments are chosen in order to enhance hydrogen bonding interactions within the core of spherical micelles formed by the copolymers in aqueous media, as evidenced by light scattering and fluorescence spectroscopy studies. The amphiphilic copolymers are able to encapsulate the hydrophobic drugs curcumin and indomethacin as found using light scattering and spectroscopic methods. © 2021 Society of Industrial Chemistry.

Application of Redox-Responsive Hydrogels Based on 2,2,6,6-Tetramethyl-1-Piperidinyloxy Methacrylate and Oligo(Ethyleneglycol) Methacrylate in Controlled Release and Catalysis.

Hydrogels have reached momentum due to their potential application in a variety of fields including their ability to deliver active molecules upon application of a specific chemical or physical stimulus and to act as easily recyclable catalysts in a green chemistry approach. In this paper, we demonstrate that the same redox-responsive hydrogels based on polymer networks containing 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) stable nitroxide radicals and oligoethylene glycol methyl ether methacrylate (OEGMA) can be successfully used either for the electrochemically triggered release of aspirin or as catalysts for the oxidation of primary alcohols into aldehydes. For the first application, we take the opportunity of the positive charges present on the oxoammonium groups of oxidized TEMPO to encapsulate negatively charged aspirin molecules. The further electrochemical reduction of oxoammonium groups into nitroxide radicals triggers the release of aspirin molecules. For the second application, our hydrogels are swelled with benzylic alcohol and tert-butyl nitrite as co-catalyst and the temperature is raised to 50 °C to start the oxidation reaction. Interestingly enough, benzaldehyde is not miscible with our hydrogels and phase-separate on top of them allowing the easy recovery of the reaction product and the recyclability of the hydrogel catalyst.