Polymerization Of Allyl Glycidyl Ether Research Articles

Polymerization of Allyl Glycidyl Ether under the Action of the BF3–H2O Catalytic System

Polymerization of Allyl Glycidyl Ether under the Action of the BF3–H2O Catalytic System

Guanidinium-Incorporated Micelleplexes for Low Toxic and Efficient siRNA Delivery

Small interfering RNA (siRNA)-based therapy has emerged as a powerful therapeutic tool due to its target-specific gene silencing. However, the therapeutic efficacy has been limited by poor cellular uptake, and therefore delivery vehicles are required to improve the cellular uptake. Herein, guanidinium-incorporated polyether-based block copolyelectrolytes were developed for improved cellular uptake and consequently increased gene silencing efficiency. Guanidinium-functionalized poly(ethylene oxide-b-allyl glycidyl ether) (G-PEO-PAGE) were prepared by living anionic ring opening polymerization of allyl glycidyl ether and post-modification to introduce guanidinium groups. G-PEO-PAGE provides efficient complexation with siRNA due to highly cationic charges of the guanidinium groups at physiological pH, resulting in significantly improved cellular uptake of siRNA and consequently increased gene silencing efficiency. In addition, G-PEO-PAGE showed significantly lower cytotoxicity compared to branched polyethylenimine as a commercial counterpart. This study demonstrates that guanidinium-incorporated block copolyelectrolytes have a great potential for efficient and low toxic siRNA delivery.

Fabrication of functionalized magnetic microspheres based on monodispersed polystyrene for quantitation of allyl-benzodioxoles coupled with gas chromatography and mass spectrometry

Monodispersed magnetic microspheres were synthesized by the magnetization of the aminized polystyrene cores and the subsequent polymerization of allyl glycidyl ether, divinylbenzene and N-vinyl-2-pyrrolidone, which exhibited excellent monodispersity in aqueous solution and high efficiency for allyl-benzodioxoles extraction. Various techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR) and vibrating sample magnetometry (VSM) were employed to characterize the composites. Coupled with gas chromatography-mass spectrometry (GC–MS), a sensitive and simple magnetic solid phase extraction (MSPE) procedure based on the prepared microspheres was established for determination of allyl-benzodioxoles in cola-flavoured drinks. The factors affecting the extraction procedure, such as pH value, adsorbent amount, adsorption time, desorption solution and desorption time were optimized. The developed method was characterized by a high recovery (spiked at 5 μg L−1, 25 μg L−1 and 250 μg L−1), a low detection limit (0.05 μg L−1 for safrole and 0.08 μg L−1 for myristicin), a good linearity (correlation coefficients higher than 0.9990 for both) and a satisfactory repeatability (relative standard deviation below 3.7% for both, n = 3). The approach proposed here was confirmed to be fast and reliable for quantitative analysis of allyl-benzodioxoles in cola samples, especially at a trace level.

Analysis of epoxy functionalized layers synthesized by plasma polymerization of allyl glycidyl ether.

The deposition of epoxide groups by plasma polymerization opens new horizons for robust and quick immobilization of biomolecules on any type of substrate. However, as of now there are just very few papers dealing with the deposition of epoxy layers by plasma polymerization, probably due to the high reactivity of this group leading to a low functionalization efficiency. In this work we carried out an extensive experimental and theoretical investigation of plasma synthesis of epoxide groups from a low pressure allyl glycydyl ether (AGE) plasma. The influence of composite parameter W/F and the working pressure on the density of epoxide groups and the layer stability was thoroughly addressed. It was found that by increasing the working pressure it is possible to sufficiently raise the concentration of epoxide groups. The composite parameter W/F was shown to be a crucial parameter in affecting the density of epoxides. An optimal value of W/F of around 2.3 eV per molecule leading to the highest density of epoxides produced in the process at 15 Pa was revealed through FT-IR and XPS findings. This value correlates well with the ab initio calculations suggesting that the lowest bond dissociation energy belongs to the C-O bond of the epoxide ring. Therefore, in order to increase the density of epoxides deposited by plasma polymerization, a precursor molecule containing at least two epoxide rings is strongly advised to be employed.

Synthesis of allyl end‐block functionalized poly(ε‐caprolactone)s and their facile post‐functionalization via thiol–ene reaction

ABSTRACTA simple and facile strategy for the functionalization of commercial poly(ε‐caprolactone) diols (PCLs) with pendant functionalities at the polymer chain termini is described. Well‐defined allyl‐functionalized PCLs with varying numbers of allyl end‐block side‐groups were synthesized by cationic ring‐opening polymerization of allyl glycidyl ether using PCL diols as macroinitiators. Further functionalization of the allyl‐functionalized PCLs was realized via the UV‐initiated radical addition of a furan‐functionalized thiol to the pendant allyl functional groups, showing the suitability for post‐modification of the PCL materials. Changes in polymer structure as a result of varying the number of pendant functional units at the PCL chain termini were demonstrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 928–939

Synthesis and Aqueous Solution Properties of Block Copolyethers with Latent Chemical Functionality

Three series of polyglycidol-poly(allyl glycidyl ether)-polyglycidol (PG-PAGE-PG) triblock copolymers with ranging PG contents and fixed molar masses of the middle PAGE block are prepared. The copolymers are analogous to the Pluronic, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), block copolymers in which the chemically inert PEO and PPO are substituted by PG and PAGE, respectively, exhibiting latent chemical functionality. They are prepared by solvent-free sequential anionic polymerization of allyl glycidyl ether and ethoxyethyl glycidyl ether followed by cleavage of the protective groups. In aqueous solution the block copolymers self-associate. According to the thermodynamic data, the self-association is enthalpically favored with a small entropy contribution, which is fundamentally different from that of Pluronic block copolymers. The nanostructures are parameterized by dynamic and static light scattering and visualized by transmission electron microscopy. Data indicate formation of relatively large particles that are identified as compound particles held together by strong hydrogen bonding promoted by the numerous hydroxyl groups from the PG moieties.

Impact of Pendant Functional Groups and Method of Preparation on Aggregation Behaviour of Pegylated Copolymers

Block copolymer micelle-based drug formulation has emerged as a drug delivery system for clinical development. One of the major challenges is that these block copolymer micelles often only serve to solubilize the drug but have poor stability and limited drug retention. In the current study, anionic polymerization of oxirane derivatives on methoxy-polyethylene glycol (mPEG) was used to obtain amphiphilic and biocompatible block copolymer micelles. Polymerization of allyl glycidyl ether (AGE) enabled functionalization with pendant alkyl chains by thiol-ene click chemistry (mPEG-b- (AGE-C6, 12, 16, or 18)n) and polymerization of pheyl glycidyl ether (mPEG-b-(PheGE)n). In aqueous media, these block copolymers self-assemble to form aggregates that include a mobile hydrophobic core and a hydrophilic shell. These micelles were characterized using infrared spectroscopy, transmission electron microscopy, and atomic force microscopy. All block copolymer micelles have identical fingerprint at the mPEG region at around 1100 cm-1 and distinct fingerprint for the acyl chain region between 2800 and 3000 cm-1 that confirmed the chemical composition of each preparation. Depending on the core forming block and the method of preparation (dialysis and emulsion oil-in-water), the block copolymer micelles were found to have distinct morphologies. For instance, mPEG-b-(PheGE)n remain spherical shaped through both methods; while mPEG-b- (AGE-C6)n shaped in spheres through dialysis but short filomicelles through emulsion oil-in-water; and (mPEG-b- (AGE-C12)n) shaped as rod-like worms through dialysis but network of long worms through emulsion oil-in-water. In vitro study was also performed to demonstrate the biocompatibility of these block copolymer micelles supporting this series of materials exhibits great promise for future application in drug delivery.

Luteinizing-hormone-releasing-hormone-containing biodegradable polymer micelles for enhanced intracellular drug delivery

A biodegradable triblock copolymer, poly(ethylene oxide)-block-poly(allyl glycidyl ether)-block-poly(dl-lactide) (mPEG-b-PAGE-b-PLA), with allyl groups on its middle block was designed and synthesized through anionic polymerization of allyl glycidyl ether (AGE) with PEG monomethyl ether sodium salt as the macroinitiator and subsequent ring-opening polymerization of dl-lactide. Luteinizing hormone-releasing hormone (LHRH) was conjugated to the PAGE block through a linkage of -SCH2CH2C([double bond, length as m-dash]O)NH- between the allyl and LHRH residues. The LHRH content in the conjugate was ca. 25 wt%. Owing to the amphiphilic nature of the conjugate, it was self-assembled into micelles of 15-40 nm in diameter and with the LHRH moieties in the hydrophilic corona of the micelles. Cellular uptake experiments were carried out using flow cytometry and confocal laser scanning microscopy (CLSM) with HeLa cells as LHRH-receptor overexpressing cells and HepG-2 cells as normal cells. HeLa cells displayed more cellular uptake of the LHRH-micelles than the normal cells. In vivo biodistribution of the LHRH-containing micelles and LHRH-free micelles was studied using a CRI Maestro™ imaging system. Preferred accumulation in tumor sites of LHRH-containing micelles was observed at 24 hours post injection. Therefore, LHRH-conjugated amphiphilic copolymers might be used as a potential drug delivery system for the treatment of LHRH receptor overexpressing carcinoma.

Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks

AbstractPoly(allyl glycidyl ether) and poly(allyl glycidyl ether‐co‐epichlorohydrin) were prepared by monomer‐activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i‐Bu3Al]/[NOct4Br] = 2−4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living‐like manner gradient‐type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate‐free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Amphiphilic Linear-Hyperbranched Block Copolymers with Linear Poly(ethylene oxide) and Hyperbranched Poly(carbosilane) Block

The synthesis of amphiphilic linear-hyperbranched block copolymers with a linear poly(ethylene oxide) (PEO) segment and a hyperbranched poly(carbosilane)s (PCS) block in a rapid three-step strategy is described, combining oxyanionic polymerization with carbosilane chemistry. A linear precursor block copolymer was synthesized via anionic polymerization of allyl glycidyl ether onto a commercial hydroxyl-terminated PEO, using its cesium alkoxide as macro-initiator. The resulting linear AB or ABA-type di- or triblock copolymers serve as polymer cores for the subsequent hydrosilylation polyaddition of an AB2-type carbosilane monomer. Di(allyl)methylsilane or methyldi(undec-10-enylsilane) were employed, using Karstedt’s catalyst as Pt0-species. Due to the high reactivity of allyloxy groups in catalytic hydrosilylation reactions, the slow monomer addition technique, previously used for the controlled polyaddition of AB2-monomers, was not necessary in this case and complete conversion of all core allyl groups is ...

Reactive Epoxy-Functionalized Thin Films by a Pulsed Plasma Polymerization Process

A novel plasma functionalization process based on the pulsed plasma polymerization of allyl glycidyl ether is reported for the generation of robust and highly reactive epoxy-functionalized surfaces with well-defined chemical properties. Using a multitechnique approach including X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and ellipsometry, the effect of the plasma deposition parameters on the creation and retention of epoxy surface functionalities was characterized systematically. Under optimal plasma polymerization conditions (duty cycle: 1 ms/20 ms and 1 ms/200 ms), reactive uniform films with a high level of reproducibility were prepared and successfully used to covalently immobilize the model protein lysozyme. Surface derivatization was also carried out with ethanolamine to probe for epoxy groups. The ethanolamine blocked surface resisted nonspecific adsorption of lysozyme. Lysozyme immobilization was also done via microcontact printing. These results show that allyl glycidyl ether plasma polymer layers are an attractive strategy to produce a reactive epoxy functionalized surface on a wide range of substrate materials for biochip and other biotechnology applications.

Block Copolymers Containing Intrinsically Proton-Conducting Blocks Tethered with Benzimidazole Units

ABA triblock copolymers having benzimidazole-tethered end blocks have been prepared and characterized with respect to their intrinsically proton conducting properties. The copolymers were synthesized by using a linear poly(ethylene oxide) (PEO) as a difunctional macroinitiator for the anionic ring-opening polymerization of allyl glycidyl ether. The pendent allyl groups of the end blocks were subsequently linked with 2-(2-benzimidazolyl)ethanethiol via a free radical thiol-ene coupling reaction. Thermogravimetry showed that the final materials were stable up to 210 C under a nitrogen atmosphere. The benzimidazole units of the copolymers were found to crystallize from solution but not from the melt. After heating the materials above the melting point of benzimidazole units, the copolymers displayed single glass transitions temperatures (Tg's). Moreover, the crystallization of the PEO blocks was depressed which may indicate a high degree of interaction between the dissimilar blocks. The proton conductivity was found to be promoted by a high benzimidazole concentration and a high segmental mobility, that is, low Tg's of the copolymers. Increased concentrations of benzimidazole raised the Tg, and the resulting conductivity thus depended on a balance between the charge carrier density and the mobility. Conductivities close to 80 μS/cm were reached at 160 C by these materials under completely anhydrous conditions. (Less)

Cationic polymerization of allyl glycidyl ether in solvents of different basicity

The boron trifluoride tetrahydrofuranate-catalyzed cationic polymerization of allyl glycidyl ether in carbon tetrachloride proceeds via an oxirane cycle to form initially cyclic products and, at later stages, high-molecular-mass products. In the case of 1,2-dimethoxyethane, the polymerization of allyl glycidyl ether occurs via insertion of the monomer into a dissociated bond of a Lewis acid-dimethoxyethane complex and yields a linear polymer with end methoxy groups.

Poly(allyl glycidyl ether)‐block‐poly(ethylene oxide): A novel promising polymeric intermediate for the preparation of micellar drug delivery systems

AbstractNovel diblock copolymers designed for the preparation of micellar drug delivery systems, consisting of hydrophobic poly(allyl glycidyl ether) (PAGE) and hydrophilic poly(ethylene oxide) (PEO), were prepared, and their self‐assembly into micellar structures was studied. Copolymers differing in the length of the polymer blocks were purified and characterized. These amphiphilic copolymers with narrow molecular weight distributions were prepared through the anionic polymerization of allyl glycidyl ether with PEO monomethyl ether sodium salt as the macroinitiator. The PAGE–PEO copolymer readily formed small micelles with narrow size distributions via simple dissolution in water. The addition of pendant double bonds to the hydrophobic part of the chain was intended for further covalent modifications. Catalytic hydrogenation, the radical crosslinking of the micelle core, and the addition of thiol to double bonds of the copolymer were examples of such modifications that were proved to proceed with a quantitative yield for this copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 201–211, 2005

Synthesis and photopolymerization of 1‐propenyl glycidyl ether

AbstractThe ambifunctional monomer, 1‐propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium‐catalyzed isomerization reaction in high yield. 1‐Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using 1H‐ and, 13C‐NMR spectroscopies and employing well‐characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF3OEt2 followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether‐bearing pendant 1‐propenyl ether groups was subjected to a diaryliodonium salt‐photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc.