Poly Oligo Ethylene Glycol Methacrylate Research Articles

Architectural Modification of Conformal PEG-Bottlebrush Coatings Minimizes Anti-PEG Antigenicity While Preserving Stealth Properties.

Poly(ethylene glycol) (PEG), a linear polymer known for its "stealth" properties, is commonly used to passivate the surface of biomedical implants and devices, and it is conjugated to biologic drugs to improve their pharmacokinetics. However, its antigenicity is a growing concern. Here, the antigenicity of PEG is investigated when assembled in a poly(oligoethylene glycol) methacrylate (POEGMA) "bottlebrush" configuration on a planar surface. Using ethylene glycol (EG) repeat lengths of the POEGMA sidechains as a tunable parameter for optimization, POEGMA brushes with sidechain lengths of two and three EG repeats are identified as the optimal polymer architecture to minimize binding of anti-PEG antibodies (APAs), while retaining resistance to nonspecific binding by bovine serum albumin and cultured cells. Binding of backbone- versus endgroup-selective APAs to POEGMA brushes is further investigated, and finally the antigenicity of POEGMA coatings is assessed against APA-positive clinical plasma samples. These results are applied toward fabricating immunoassays on POEGMA surfaces with minimal reactivity toward APAs while retaining a low limit-of-detection for the analyte. Taken together, these results offer useful design concepts to reduce the antigenicity of polymer brush-based surface coatings used in applications involving human or animal matrices.

Targeting to the Bone: Alendronate-Directed Combretastatin A-4 Bearing Antiangiogenic Polymer-Drug Conjugates.

Selective targeting of tumor site with chemotherapeutic agents appears to be one of the most effective methods to address many of the problems encountered with conventional chemotherapy. In this work, poly(oligoethylene glycol)methacrylate (POEGMA) based bone-targeting polymers bearing an antiangiogenic drug combretastatin A4 (CA4) were synthesized using free radical polymerization. Targeted and nontargeting copolymers were evaluated for their bone targeting efficiency, cytotoxicities against endothelial cells, namely, HUVECs and U2-OS and Saos-2 cancerous cell lines, as well as their antiangiogenic activity against endothelial cell tube formation by HUVECs. It is observed that the drug conjugated polymers conjugated with the bisphosphonate groups containing drug alendronate (ALN) have remarkably high affinity for bone mineral when compared to the polymer-drug conjugates devoid of the bisphosphonate groups. Both targeted and nontargeted polymer-drug conjugates show a sustained drug release in rat plasma with an overall release of 80-93% over 5 days. In vitro studies revealed high levels of cytotoxicity of the polymer-drug conjugates against HUVECs and U2-OS, and moderate cytotoxicity toward Saos-2. Importantly, the CA4 conjugated copolymers displayed excellent level of antiangiogenic activity as deduced from in vitro endothelial cell tube formation assay using HUVECs. Overall, a novel bone-targeting antiangiogenic polymer-drug conjugate that can be further elaborated to carry additional anticancer drugs is disclosed.

Hydrophilic Polymer Brush Layers on Stainless Steel Using Multilayered ATRP Initiator Layer.

Thin polymer coatings (in tens of nanometers to a micron thick) are desired on industrial surfaces such as stainless steel. In this thickness range coatings are difficult to produce using conventional methods. In this context, surface-initiated controlled polymerization method can offer a promising tool to produce thin polymer coatings via bottom-up approach. Furthermore, the industrial surfaces are chemically heterogeneous and exhibit surface features in the form of grain boundaries and grain surfaces. Therefore, the thin coatings must be equally effective on both the grain surfaces and the grain boundary regions. This study illustrates a novel "periodic rejuvenation of surface initiation" process using surface-initiated ATRP technique to amplify the graft density of poly(oligoethylene glycol)methacrylate (POEGMA) brush layers on stainless steel 316L surface. The optimized conditions demonstrate a controlled, macroscopically homogeneous, and stable POEGMA brush layer covering both the grain surface and the grain boundary region. Various relevant parameters-surface cleaning methods, controllability of thickness, graft density, homogeneity and stability-were studied using techniques such as ellipsometer, X-ray photoelectron spectroscopy, scanning electron microscopy-energy-dispersive X-ray, surface zeta potential, and infrared reflection-adsorption spectroscopy.

Stimuli-Responsive Cellulose Nanocrystals for Surfactant-Free Oil Harvesting.

Cellulose nanocrystals with grafted binary polymer brushes (CNC-BPB), poly(oligoethylene glycol) methacrylate (POEGMA) and poly(methacrylic acid) (PMAA), were prepared by cerium-mediated polymerization in aqueous solution. The physical properties of CNC-BPB can be controlled by external triggers, such as temperature and pH, which can be utilized to stabilize and destabilize oil-water emulsions. By virtue of the modifications, these bifunctionalized CNCs diffused to the oil-water interface and stabilized the oil droplets at high pHs. When the pH was lowered to 2, strong hydrogen bonding between POEGMA and PMAA chains grafted on the CNC induced the coalescence of the emulsion droplets, resulting in the phase separation of oil and water. For emulsions stabilized by CNC-POEGMA and free PMAA mixtures, instantaneous coalescence was not observed at low pHs. Successive stabilization-destabilization over 5 cycles was demonstrated by modulating the pH with the addition of acid or base without any loss in efficiency. This work demonstrates that functional sustainable nanomaterials can be used for small scale oil-water separations, particularly for oil droplet transportation and harvesting of lipophilic compounds.

A facile method towards rough morphology polymer brush for increased mobility of embedded nanoparticles

The control of polymer brush morphology is important in determining its performance for various applications such as for anti-fouling coatings or as a host for polymer brush-nanoparticle nanocomposites. Herein we introduce a novel method to vary the surface roughness of polymer brushes by sequential growth in different solvent qualities. Poly(oligo ethylene glycol) methacrylate (POEGMA) was first grown homogeneously using a solvent of 20% water in methanol. A second round of synthesis was then performed with varying ratio of methanol-to-water and ethanol-to-water. We found that roughness generally increased with higher water content during the second round synthesis. Finally we observed, through incorporating as-prepared gold nanoparticles into POEGMA, that nanoparticle distribution and mobility could be improved by having a rougher surface morphology. These findings could be beneficial in designing localized surface plasmon resonance (LSPR)-based solid phase sensing platforms that rely on gold nanoparticle re-organization in polymer brushes.