“Clickable PEG” via anionic copolymerization of ethylene oxide and glycidyl propargyl ether

Herzberger, Jana; Leibig, Daniel; Langhanki, Jens; Moers, Christian; Opatz, Till

doi:10.1039/c7py00173h

Cited by 20 publications

(22 citation statements)

References 37 publications

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“…Thus, this was the synthesis route established to obtain copolymers with increasing percentage of GPE. The poorer results in the other cases can be explained by the low reactivity of the GPE compared to the reactivity of the other two monomers: r EO = 14.8 and r GPE = 0.076 for the copolymerization of EO and GPE, and r EO = 3.1 and r PO = 0.3 for the copolymerization reaction of EO and PO . The low reactivity of the GPE results in a limitation of the growth of the copolymer chain when it is added at the same time as the PO, which is in agreement with previous research …”

Section: Resultssupporting

confidence: 90%

Different drug incorporation routes in ethylene oxide based copolymers

Carrero

Borreguero

Rodrı́guez

et al. 2020

Polymer International

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Coumarin is successfully incorporated in poly(ethylene oxide)‐poly(propylene oxide) block copolymers functionalized with terminal alkynes, PEO‐b‐PPO‐b‐GPE, by click reactions at atmospheric pressure and in CO2 supercritical conditions (scCO2). The presence of glycidyl propargyl ether (GPE), an alkynyl‐terminated monomer, in the copolymer chain allows the covalent attachment of the coumarin by click chemistry, obtaining polymer–drug conjugates. First, the most suitable synthesis procedure for the above‐mentioned copolymers was established. Then, the click reactions were carried out confirming the coumarin attachment by Fourier transform IR and 1H NMR analyses, achieving good yields in both cases with a coumarin content of about 9.3 wt% and avoiding the use of toxic solvents in the case of scCO2. In addition, thanks to the amphiphilic character of the copolymer due to the presence of hydrophilic (PEO) and hydrophobic (PPO) segments, micelle formation is also possible and was confirmed by dynamic light scattering and high resolution SEM. Finally, coumarin incorporation was achieved by micelle formation using the direct dissolution method in order to compare the polymer–drug system properties. This second route allows a drug entrapment efficiency of 14 wt% to be reached. In both cases, the size of the polymeric micelles obtained is in a suitable range to enable permeability. However, an interesting point is the reduction in the size of the micelles with increase in the GPE percentage and with the covalent attachment of the coumarin to the copolymer, which is supposed to improve their permeability. © 2019 Society of Chemical Industry

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Section: Resultssupporting

confidence: 90%

Different drug incorporation routes in ethylene oxide based copolymers

Carrero

Borreguero

Rodrı́guez

et al. 2020

Polymer International

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“…Alternatively, post-polymerization modification offers an avenue to access multifunctional polymers while circumventing the incompatibility of desirable functional groups with polymerization conditions. , Many post-polymerization modification strategies are based on the increasing convergence of organic chemistry and polymer synthesis, spearheaded by the introduction of click chemistry by Sharpless and colleagues . For example, post-polymerization modification of many classes of polymers has been achieved through various chemical transformations, including azide–alkyne cycloaddition, , transesterification, thiol–ene addition, Diels–Alder reactions, Suzuki–Miyaura coupling, and sulfur fluoride exchange . For this strategy, the development of a suitable monomer that is compatible with a polymerization needs to be accompanied.…”

Section: Introductionmentioning

confidence: 99%

Anionic Polymerization of Azidoalkyl Glycidyl Ethers and Post-Polymerization Modification

et al. 2019

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Polyethers like poly(ethylene glycol) have been widely used for a variety of valuable applications, although their functionalization still poses challenges due to the absence of functional handles along the polymer backbone. Herein, a series of novel azide-functionalized glycidyl ether monomers are presented as a universal approach to synthesize functional polyethers by post-polymerization modification. Three azide-functionalized glycidyl ether monomers possessing different alkyl spacers (ethyl, butyl, and hexyl) were designed and synthesized by a simple two-step substitution reaction. Organic superbase-catalyzed anionic ring-opening polymerization can proceed under mild conditions compatible with an azide pendant group, affording wellcontrolled azide-functionalized polyethers with low dispersity (Đ < 1.2). The azide pendant groups on the resulting polymers were readily modified to a variety of functional groups via copper-catalyzed azide−alkyne cycloaddition reactions and Staudinger reduction. Furthermore, copolymerization of azidohexyl glycidyl ether with allyl glycidyl ether was demonstrated to provide an additional orthogonal functional handle. We anticipate that this work provides a new platform for the preparation of diverse functional polyethers.

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“…The hydrodynamic volume ( V h ) of the copolymers differs from that of the PEG standard with increasing content of the hydrophobic comonomer, which leads to a deviation from the targeted molecular weights. In all cases, monomodal molecular weight distributions were obtained with moderate dispersities ( Đ < 1.86), which are common for the MAROP of EO . Because of the lack of an integrable initiator (like in the AROP), no molecular weight can be determined via 1 H NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 98%

“…In the monomer-activated anionic ring-opening polymerization (MAROP), a weak nucleophile is applied in combination with an organo aluminum compound acting as a catalyst as well as an activator for the epoxide monomers . Functional groups like nitriles or propargyl groups were incorporated into PEG using MAROP. , …”

Section: Introductionmentioning

confidence: 99%

Ester Functional Epoxide Monomers for Random and Gradient Poly(ethylene glycol) Polyelectrolytes with Multiple Carboxylic Acid Moieties

et al. 2020

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The tailormade ester functional epoxides, methyl 4,5epoxypentenoate (MEP) and t butyl 4,5-epoxypentenoate ( t BEP), were synthesized in good overall yields (60−65%) in short reaction sequences. Both MEP and t BEP were investigated as comonomers in the statistical copolymerization with ethylene oxide (EO) via the monomer-activated anionic ring-opening polymerization (MAROP), using triisobutyl-aluminum as a catalyst. Homopolymers and a series of copolymers of EO with varied molar contents of MEP and t BEP (0.6−31.3 mol %) were prepared, possessing molecular weights up to 11,800 g mol −1 . Surprisingly, in situ 1 H NMR kinetics studies revealed an ideally random copolymer microstructure for EO/MEP copolymers (r EO = 0.99, r MEP = 1.0) via MAROP for the first time. t BEP was found to be a less reactive comonomer, yielding gradient polyether structures (r EO = 2.9, r t BEP = 0.35). After polymerization, the ester-protecting groups were fully cleaved under basic or acidic conditions, respectively, resulting in either random or gradient distribution of carboxyl moieties. MTT assays demonstrated good biocompatibility of the novel carboxylic acid functional poly(ethylene glycol) (PEG) copolymers. The thermal properties of the copolymers were investigated via differential scanning calorimetry, showing the highly flexible nature of the PEG-based polyelectrolytes after deprotection. The liberated carboxylic acid groups were addressed with Ca 2+ cations, resulting in cross-linked polymer networks.

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“Clickable PEG” via anionic copolymerization of ethylene oxide and glycidyl propargyl ether

Abstract: First one-step synthesis of poly(ethylene glycol) bearing multiple alkyne-groups along the polyether backbone and subsequent generation of PEG-glycopolymers by CuAAC.

Cited by 20 publications

References 37 publications

Different drug incorporation routes in ethylene oxide based copolymers

Different drug incorporation routes in ethylene oxide based copolymers

Anionic Polymerization of Azidoalkyl Glycidyl Ethers and Post-Polymerization Modification

Ester Functional Epoxide Monomers for Random and Gradient Poly(ethylene glycol) Polyelectrolytes with Multiple Carboxylic Acid Moieties

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