Oligo Ethylene Glycol Methacrylate Research Articles

Poly[oligo(ethylene glycol) methacrylate]-b-poly[(vinyl benzyl trimethylammonium chloride)] Based Multifunctional Hybrid Nanostructures Encapsulating Magnetic Nanoparticles and DNA.

We report on the preparation of novel and multifunctional hybrid spherical-shaped nanostructures involving a double-hydrophilic block copolymer, namely the neutral cationic poly[oligo(ethylene glycol) methacrylate]-b-poly[(vinyl benzyl trimethylammonium chloride)] (POEGMA-b-PVBTMAC) diblock copolymer, initially complexed with hydrophilic anionic magnetic nanoparticles (MNPs), and subsequently, with short deoxyribonucleic acid (113 bases DNA). The POEGMA-b-PVBTMAC copolymer, the copolymer/MNPs and the copolymer/MNPs/DNA tricomponent hybrid electrostatic complexes were studied by dynamic/electrophoretic light scattering (DLS/ELS) and cryogenic transmission electron microscopy (cryo-TEM) techniques for the determination of their structure and solution properties. The MNPs were complexed efficiently with the oppositely charged diblock chains, leading to well-defined hybrid organic–inorganic spherical-shaped nanostructures. A significant aggregation tendency of the MNPs is noticed in cryo-TEM measurements after the electrostatic complexation of DNA, implying an accumulation of the DNA macromolecules on the surface of the hybrid tricomponent complexes. Magnetophoretic experiments verified that the MNPs maintain their magnetic properties after the complexation initially with the copolymer, and subsequently, within the block polyelectrolyte/MNPs/DNA nanostructures.

Tricomponent Amphiphilic Poly(oligo(ethylene glycol) methacrylate) Brush-Grafted Poly(lactic acid): Synthesis, Nanoparticle Formation, and In Vitro Uptake and Release of Hydrophobic Dyes

Tricomponent amphiphilic brush-grafted copolymers of poly(lactic acid)-graft-poly(oligo(ethylene glycol) methacrylate) (PLA-g-POEGMA) were prepared by atom-transfer radical polymerization (ATRP) of...

Functionalization of Cellulose Nanocrystals with POEGMA Copolymers via Copper-Catalyzed Azide-Alkyne Cycloaddition for Potential Drug-Delivery Applications.

Elongated colloidal nanoparticles (NPs) have significant potential for drug delivery and imaging applications in cancer therapy, but progress depends on developing a deeper understanding of how their physicochemical properties affect their interactions with cells and with tumors. Cellulose nanocrystals (CNCs) are biocompatible, rodlike colloids that are broadly surface-functionalizable, making them interesting as modular drug carriers. In this report, we describe the attachment of a statistical copolymer containing oligoethylene glycol methacrylate (OEGMA; Mn ≈ 500 Da) and small amounts of aminopropylmethacrylamide (APMA) to CNCs. Here, the copolymer is designed to serve as a "stealth" corona to minimize protein adsorption, and the amino groups provide functionality for the attachment of diagnostic or therapeutic moieties. The corona polymer with a terminal azide group was synthesized by atom transfer radical polymerization using tert-butyloxycarbonyl (tBoc)-protected APMA as the comonomer. A key step in this synthesis was the grafting of acetylene groups to the CNC surface via a reaction with NaOH plus propargyl bromide in aqueous dimethyl sulfoxide. The copolymer was attached to the CNCs using copper-catalyzed azide-alkyne cycloaddition (CuAAC) "click" chemistry. By determining the mean number of amino groups per copolymer and amino group content of the CNC sample, we were able to infer that there were on average ca. 300 polymer molecules per CNC. Preliminary evaluation in a human ovarian cancer cell line (HEYA8) and a human breast cancer cell line (MDA-MB-436) demonstrated that these CNCs are nontoxic. We also assessed the cellular uptake of these CNC NPs in the same two cell lines using flow cytometry and distinguished between NPs being internalized by the cell or surface-bound using a trypan blue quenching experiment. These results provide support for applications of polymer-coated CNCs in medicine and are encouraging for further studies in vitro and in vivo to evaluate their potential as drug-delivery vehicles.

Antifouling Polymer Brushes via Oxygen-Tolerant Surface-Initiated PET-RAFT.

This work presents a new method for the synthesis of antifouling polymer brushes using surface-initiated photoinduced electron transfer-reversible addition–fragmentation chain-transfer polymerization with eosin Y and triethanolamine as catalysts. This method proceeds in an aqueous environment under atmospheric conditions without any prior degassing and without the use of heavy metal catalysts. The versatility of the method is shown by using three chemically different monomers: oligo(ethylene glycol) methacrylate, N-(2-hydroxypropyl)methacrylamide, and carboxybetaine methacrylamide. In addition, the light-triggered nature of the polymerization allows the creation of complex three-dimensional structures. The composition and topological structuring of the brushes are confirmed by X-ray photoelectron spectroscopy and atomic force microscopy. The kinetics of the polymerizations are followed by measuring the layer thickness with ellipsometry. The polymer brushes demonstrate excellent antifouling properties when exposed to single-protein solutions and complex biological matrices such as diluted bovine serum. This method thus presents a new simple approach for the manufacturing of antifouling coatings for biomedical and biotechnological applications.

Polymer Membrane with Glycosylated Surface by a Chemo-Enzymatic Strategy for Protein Affinity Adsorption

Membranes with glycosylated surfaces are naturally biomimetic and not only have excellent surface hydrophilicity and biocompatibility, but have a specific recognition to target biomacromolecules due to the unique chemo-biological properties of their surface carbohydrates; however, they cannot be easily chemically produced on large scales due to the complex preparation process. This manuscript describes the fabrication of a polypropylene membrane with a glycosylated surface by a chemo-enzymatic strategy. First, hydroxyl (OH) groups were introduced onto the surface of microporous polypropylene membrane (MPPM) by UV-induced grafting polymerization of oligo(ethylene glycol) methacrylate (OEGMA). Then, glycosylation of the OH groups with galactose moieties was achieved via an enzymatic transglycosylation by β-galactosidase (Gal) recombinanted from E. coli. The fabricated glycosylated membrane showed surprisingly specific affinity adsorption to lectin ricinus communis agglutinin (RCA120). The chemo-enzymatic route is easy and green, and it would be expected to have wide applications for large-scale preparation of polymer membranes with glycosylated surfaces.

Temperature and Redox‐Responsive Hydrogels Based on Nitroxide Radicals and Oligoethyleneglycol Methacrylate

AbstractA temperature and redox‐responsive polymer hydrogel is constructed by randomly incorporating 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐methacrylate (TEMPO) stable nitroxide radicals and oligoethyleneglycol methacrylate (OEGMA) groups in a polymer network. TEMPO can be reversibly oxidized into an oxoammonium cation (TEMPO+) providing the redox‐responsive properties while the lower critical solubility temperature (LCST) of OEGMA results in temperature‐responsive properties. Since a rather low amount of di(ethylene glycol) dimethacrylate (OEGMA2) is used to chemically crosslink the polymer network, the accordingly formed hydrogels obtained after swelling with water consist of microgel particles with entangled polymer chains that are not chemically crosslinked. By varying the amount of TEMPO in the polymer network, it is demonstrated that the radical form of TEMPO aggregates into hydrophobic domains acting as physical crosslinking nodes in the hydrogels and further increasing the cohesion between microgel particles. Increasing the temperature results in two opposite effects on the solubility of TEMPO and OEGMA units. The oxidation of TEMPO into TEMPO+ also results in a deep change in the hydrogel properties since TEMPO+ units are essentially hydrophilic and do not aggregate into physical crosslinking nodes.

Physicochemical Evaluation of Insulin Complexes with QPDMAEMA-b-PLMA-b-POEGMA Cationic Amphiphlic Triblock Terpolymer Micelles.

Herein, poly[quaternized 2-(dimethylamino)ethyl methacrylate-b-lauryl methacrylate-b-(oligo ethylene glycol)methacrylate] (QPDMAEMA-b-PLMA-b-POEGMA) cationic amphiphilic triblock terpolymers were used as vehicles for the complexation/encapsulation of insulin (INS). The terpolymers self-assemble in spherical micelles with PLMA cores and mixed QPDMAEMA/POEGMA coronas in aqueous solutions. The cationic micelles were complexed via electrostatic interactions with INS, which contains anionic charges at pH 7. The solutions were colloidally stable in all INS ratios used. Light-scattering techniques were used for investigation of the complexation ability and the size and surface charge of the terpolymer/INS complexes. The results showed that the size of the complexes increases as INS ratio increases, while at the same time the surface charge remains positive, indicating the formation of clusters of micelles/INS complexes in the solution. Fluorescence spectroscopy measurements revealed that the conformation of the protein is not affected after the complexation with the terpolymer micellar aggregates. It was observed that as the solution ionic strength increases, the size of the QPDMAEMA-b-PLMA-b-POEGMA/INS complexes initially decreases and then remains practically constant at higher ionic strength, indicating further aggregation of the complexes. atomic force microscopy (AFM) measurements showed the existence of both clusters and isolated nanoparticulate terpolymer/protein complexes.

Well-Defined Dual Light- and Thermo-Responsive Rod-Coil Block Copolymers Containing an Azobenzene, MEO2MA and OEGMA.

Here we report the dual light- and thermo-responsive behavior of well-defined rod-coil block copolymers composed of an azobenzene unit, 2-(2-methoxyethoxy)ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methacrylate (OEGMA). Azobenzene-containing rigid rod blocks prepared by chain growth condensation polymerization of the azobenzene containing monomer were used as a macroinitiator of atom transfer radical polymerization (ATRP) after attaching an α-bromoisobutyryl group as an end group. Synthesis of well-defined rod-coil block copolymers with different coil block lengths was achieved by copolymerization of MEO2MA and OEGMA monomers. The synthesized polymers exhibited amphiphilic properties and polymeric micelles were formed in aqueous solution. The light-responsive behaviors of azobenzene moieties, photoisomerization by irradiation of light, and thermo-responsive behaviors of P(MEO2MA-co-OEGMA) coil blocks, aggregation by increment of temperature over lower critical solution temperature, were investigated. A dual stimuli-responsive behavior of the rod-coil block copolymers was observed when exposed to light and heat.

Functional star polymers as reagents for efficient nucleic acids delivery into HT-1080 cells

Star polymers of N,N′-dimethylaminoethyl methacrylate (DMAEMA) and hydroxyl-bearing oligo(ethylene glycol) methacrylate (OEGMA-OH) were used as pDNA and mRNA carriers. To the best of our knowledge, this is the first report of stars in the formation of polyplexes with mRNA. Polyplexes efficiently delivered nucleic acids into HT-1080 cells, while their cytotoxicity was kept significantly low due to the presence of OEGMA-OH units in the star. Hydroxyl functionalities were used for the introduction of fluorophore moieties for monitoring of the complex location after the cell uptake. Thus, versatile gene delivery vectors based upon functional star polymers were developed.

Binding Capability and Non–biofouling Efficacy of Poly[2‐(methacryloyloxy)ethyl‐4‐pentynoate‐co‐oligo(ethylene Glycol) Methacrylate] Films on Gold Surfaces

We demonstrated the binding capability and non-biofouling efficacy of biotinylated, poly(MAEP-co-OEGMA) films using streptavidin and fibrinogen. The copolymeric films were synthesized on gold substrates without activation or passivation via the surface initiated-controlled radical polymerization of MAEP and OEGMA in five different molar ratios, followed by biotinylation using “click” chemistry. The copolymeric film synthesized with MAEP at a mole fraction of 0.2 exhibited the best performance of surface plasmon resonance.

Nanostructured degradable macroporous hydrogel scaffolds with controllable internal morphologies via reactive electrospinning

Creating micro/nanostructured hydrogels with tunable morphologies under cell-friendly processing conditions would enable rational engineering of hydrogel scaffolds for targeted biomedical applications. Herein, an all-aqueous single-step reactive electrospinning method is applied to prepare hydrogel networks with controlled morphologies on both the nanoscale and the microscale. Hydrazide and aldehyde-functionalized poly(oligo ethylene glycol methacrylate) (POEGMA) are co-spun from a double barrel syringe together with poly(ethylene oxide) (PEO) as an electrospinning aid. By varying the concentrations and molecular weights of PEO and/or POEGMA, various morphologies from pure fibers to beaded fibers to bead network morphologies with tunable bead sizes can be fabricated, all of which remain monolithically stable in water due to the dynamic covalent crosslinks formed within the gel structure. The rates and magnitudes of swelling, degradation, and mechanics of the resulting scaffolds can be tuned by independently controlling gel morphologies on the nanoscale (i.e. crosslink density within the gel) and the microscale (i.e. the network structure formed), with an atypical independence of swelling relative to the mechanics and degradation rate observed. Furthermore, the internal morphology of the networks is demonstrated to systematically alter both the cell responses within the scaffolds and the rate of protein release from the scaffolds, with small fibers showing optimal cell proliferation, bead networks exhibiting the slowest protein release kinetics and very high maintained cell viabilities post-electrospinning, and beaded fibers showing intermediate properties. Statement of SignificanceControlling the internal structure of hydrogels is critical to successfully applying hydrogels in biomedical applications such as tissue engineering or cell/drug delivery. However, current techniques to fabricate hydrogel scaffolds typically require additives or gelation processes that are poorly compatible with cells and/or require multi-step processes. In this paper, we describe the fabrication of hydrogel scaffolds with tunable feature sizes (from nanometer to micrometer scale) and structures (from all fibers to bead/fiber mixtures to a new “bead network” morphology) using a reactive electrospinning strategy leveraging dynamic hydrazone crosslinking. We show single-step cell/protein loading and systematic control over cell proliferation and protein release kinetics by systematically manipulating the scaffold morphologies and feature sizes, allowing facile customization of scaffold properties for targeted applications.

PH-Responsive benzaldehyde-functionalized PEG-based polymeric nanoparticles for drug delivery: Effect of preparation method on morphology, dye encapsulation and attachment

Functionalized, pH-responsive and biocompatible polymeric nanoparticles have attracted the interest of many researchers working on novel pharmaceutical formulations. Here, in an effort to develop an efficient drug delivery formulation, all these properties are combined in one polymeric nanoparticle system. More specifically, benzaldehyde-functionalized amphiphilic block copolymers based on PEG-based oligo(ethylene glycol) methacrylate (OEGMA), benzaldehyde-containing para-formyl phenyl methacrylate (pFPMA) and pH-responsive 2-(diisopropyl)aminoethyl methacrylate (DPA) monomers are readily prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. pH-Switch and single emulsion-solvent evaporation post-polymerization processing methods are used to prepare benzaldehyde-functionalized PEGylated pH-responsive nanoparticles with diameters of 180–230 nm. After nanoparticle formation, the benzaldehyde groups on the surface are shown to react with an Alexa Fluor 488 hydroxylamine dye through oxime bond formation, illustrating the potential for these particles to be surface-functionalized with biologically important molecules, such as fluorescent dyes for tracking their intracellular fate or antibodies for targeted therapy. Encapsulation of Nile Red and rhodamine 6G dyes is performed during the post-polymerization processing step for nanoparticle formation. Nanoparticles with a fluorescent cargo were shown to be successfully internalized in both A2780 ovarian cancer and A549 lung epithelial human cells in vitro, further illustrating the potential for these formulations to be used as triggered release therapeutic drug delivery vehicles.

Stimuli-responsive hydrogel consisting of hydrazide-functionalized poly(oligo(ethylene glycol)methacrylate) and dialdehyde cellulose nanocrystals

This graphical abstract depicts our hydrogel consisting of hydrazide-functionalized poly(oligo(ethylene glycol) methacrylate) and dialdehyde cellulose nanocrystals and its thermoresponsive and self-healing properties.

Effect of the side ethylene glycol and hydroxyl groups on the polymerization kinetics of oligo(ethylene glycol methacrylates). An experimental and modeling investigation

Polymerization of oligo(ethylene glycol) methyl ether methacrylate (POEGMMA300) and oligo(ethylene glycol) hydroxyethyl methacrylate (POEGHEMA).

Mucus-responsive functionalized emulsions: design, synthesis and study of novel branched polymers as functional emulsifiers.

Mucus lines the moist cavities throughout the body, acting as barrier by protecting the underlying cells against the external environment, but it also hinders the permeation of drugs and drug delivery systems. As the rate of diffusion is low, the development of a system which could increase retention time at the mucosal surface would prove beneficial. Here, we have designed a range of branched copolymers to act as functional mucus-responsive oil-in-water emulsifiers comprising the hydrophilic monomer oligo(ethylene glycol) methacrylate and a hydrophobic dodecyl initiator. The study aimed to investigate the importance of chain end functionality on successful emulsion formation, by systematically replacing a fraction of the hydrophobic chain ends with a secondary poly(ethylene glycol) based hydrophilic initiator in a mixed-initiation strategy; a decrease of up to 75 mole percent of hydrophobic chain ends within the branched polymer emulsifiers was shown to maintain comparative emulsion stability. These redundant chain ends allowed for functionality to be incorporated into the polymers via a xanthate based initiator containing a masked thiol group; thiol groups are known to have mucoadhesive character, due to their ability to form disulfide bonds with the cysteine rich areas of mucus. The mucoadhesive nature of emulsions stabilised by thiol-containing branched copolymers was compared to non-functional emulsions in the presence of a biosimilar mucosal substrate and enhanced adherence to the mucosal surface was observed. Importantly, droplet rupture and mucus triggered release of dye-containing oil was seen from previously highly-stable thiol-functional emulsions; this observation was not mirrored by non-functional emulsions where droplet integrity was maintained even in the presence of mucus.

Short oligo(ethylene glycol) chain incorporated thermoresponsive microgels: from structural analysis to modulation of solution properties.

Herein, we report synthesis of thermoresponsive poly(N-isopropylaccrylamide) (PNIPAM) microgels with short oligo(ethylene glycol) (OEG) chain comonomers (1 to 4/5 repeating unit) by surfactant-free precipitation copolymerization. The efficient incorporation of the comonomers was confirmed by a complete set of characterization methods viz., FTIR, 1H NMR, TEM, DLS, and viscometry. The structural heterogeneity and the distribution of the comonomers within the microgels were determined by means of 1H high-resolution transverse relaxation magnetization measurements. Interestingly, the incorporation of these short OEG chain comonomers led to the formation of a core-corona structure, in which the comonomers were mainly located in the core of the polymeric network with PNIPAM dangling chains at the microgel periphery. The experimental investigations of deswelling behaviours revealed that the OEG chains allowed precise control over the colloidal properties, including phase transition, particles size, swelling degree and polydispersity of the microgels. The tuneability of these properties that was interpreted in terms of polymeric hydrophobic/hydrophilic balance as well as structural diversity, could be achieved by changing the OEG chain length, comonomer feed and crosslinking density. Further, we found that the microgels with more hydrophilic OEG chains were able to show a higher relative swelling, and the same solid content thus led to a higher viscosity at all temperatures. The OEG chains remarkably improved the colloidal stability of the microgels in electrolyte solutions even at higher temperatures, thereby paving the way for the use of these microgels in a range of applications.

Conductive Self-Healing Nanocomposite Hydrogel Skin Sensors with Antifreezing and Thermoresponsive Properties.

With growing interest in flexible and wearable devices, the demand for nature-inspired soft smart materials, especially intelligent hydrogels with multiple perceptions toward external strain and temperatures to mimic the human skin, is on the rise. However, simultaneous achievement of intelligent hydrogels with skin-compatible performances, including good transparency, appropriate mechanical properties, autonomous self-healing ability, multiple mechanical/thermoresponsiveness, and retaining flexibility at subzero temperatures, is still challenging and thus limits their application as skinlike devices. Here, conductive nanocomposite hydrogels (NC gels) were delicately designed and prepared via gelation of oligo(ethylene glycol) methacrylate (OEGMA)-based monomers in a glycerol-water cosolvent, where inorganic clay served as the physical cross-linker and provided conductive ions. The resultant NC gels exhibited good conductivity (∼3.32 × 10-4 S cm-1, akin to biological muscle tissue) and an autonomously self-healing capacity (healing efficiency reached 84.8%). Additionally, such NC gels displayed excellent flexibility and responded well to multiple strain/temperature external stimuli and subtle human motions in a wide temperature range (from -20 to 45 °C). These distinguished properties would endow such NC gels significant applications in fields of biosensors, human-machine interfaces, and soft robotics.

Stabilization of Fibronectin by Random Copolymer Brushes Inhibits Macrophage Activation.

We show that protein unfolding on biomaterials may be dramatically reduced via tuning the chemical heterogeneity of the protein-material interface. Specifically, using dynamic single-molecule methods, we confirmed that the transient structure and dynamics of fibronectin (FN) may be mediated through varying the composition of random copolymer brushes. The brushes, which themselves represent an intriguing biomaterial, were composed of oligoethylene glycol and sulfobetaine methacrylate and presumably stabilized FN through partitioning and/or segregation of the copolymers. We further showed that, by controlling the transient structure and dynamics of FN, the secretion of TNF-α and IL-6 by RAW 264.7 was markedly diminished.

Investigation of off-chip and on-chip self-assembly of amphiphilic diblock copolymers based on poly(dimethylsiloxane) and poly(oligo(ethylene glycol)methacrylate)

This study aims to optimize the molecular architecture of poly(dimethylsiloxane)-b-poly(oligo (ethylene glycol) methacrylate) (PDMS-b-POEGMA) amphiphilic copolymers and investigate the phase behavior in solutions via alteration of chemical composition, initial concentrations of copolymers, none-solvent entry rates in the dialysis method, and also alterations in the micelle preparation methodology. To this end, PDMS-b-POEGMA copolymers are synthesized with different compositions and sequence lengths. Careful monitoring of the morphological permutations of polymeric nanoparticles in aqueous solution is performed through the dialysis method as an off-chip approach. Spherical and rod morphologies with different sizes are acquired due to variations in the properties of copolymer solutions such as chemical composition, concentration and the rate of water as non-solvent. For the on-chip process, a suitable microfluidic reactor is designed via a Shrinky-Dink method to produce micelles and compare them with micelles prepared by the dialysis method. Applying the on-chip method decreases the particle size from 500 to 50 nm, and reduces the particle size distribution from about 0.8 to 0.4. Hence, the particles reached from the microfluidic technique are smaller with a narrower particle size distribution, compared to those obtained from the off-chip method.

Synthesis and thickening properties of copolymers of acrylic acid and alkoxy(С12-С14)oligoethylene glycol methacrylates

Samples of hydrophobically modifi ed polyacrylic acid containing 1% of alkoxy(С12-С14)oligoethylene glycol methacrylate units have been synthesized by free radical precipitation polymerization. The infl uence of the length of ethoxylated spacer of macromonomers and neutralization degree of carboxylic groups on thickening properties of obtained polymers in water and waterpropylene glycol mixtures at diff erent temperatures has been determined.