Ring-Opening Polymerization of Imidazole Epoxides for the Synthesis of Imidazole-Substituted Poly(ethylene oxides)

Ramirez, Sean M.; Layman, John M.; Bissel, Philippe; Long, Timothy Edward

doi:10.1021/ma901745d

Cited by 11 publications

(10 citation statements)

References 21 publications

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“…Significantly, a buffering region from pH 3 to 8 is observed and this buffering agrees well with other polymeric materials having an imidazole as the only pH-responsive moiety. 19, 29 Within the pH range of 3 to 8, the histamine units transition between a protonated hydrophilic state and a deprotonated hydrophobic state which is in agreement with the design of the triblock copolymer architecture of PHGE- b -PEO- b -PHGE and should result in pH-triggered self-assembly into gels or micelles.…”

Section: Resultssupporting

confidence: 74%

pH-triggered self-assembly of biocompatible histamine-functionalized triblock copolymers

et al. 2013

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Histamine functionalized poly(allyl glycidyl ether)-b-poly(ethylene glycol)-b-poly(allyl glycidyl ether) (PAGE-PEO-PAGE) triblock copolymers represent a new class of physically cross-linked, pH-responsive hydrogels with significant potential for biomedical applications. These telechelic triblock copolymers exhibited abrupt and reversible hydrogelation above pH 7.0 due to a hudrophilic/hydrophobic transition of the histamine units to form a network of hydrophobic domains bridged by a hydrophilic PEO matrix. These hydrophobic domains displayed improved ordering upon increasing pH and self-assembled into a body centered cubic lattice at pH 8.0, while at lower concentrations formed well-defined micelles. Significantly, all materials were found to be non-toxic when evaluated on three different cell lines and suggests a range of medical and biomedical applications.

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Section: Resultssupporting

confidence: 74%

pH-triggered self-assembly of biocompatible histamine-functionalized triblock copolymers

et al. 2013

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“…To obtain imidazole functional PEG, Long and co-workers used a trityl-protected imidazole epoxide monomer for the AROP. 305 After removal of the trityl groups, these polyethers possessed imidazole units as a biofunctionality, the key functionality of histidine distributed along the polyether backbone. Imidazole functional polymers are known for their ability for proton transfer, 306 catalytic activity, 307 and metal coordination.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

et al. 2015

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The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a "polyether universe" may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.

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“…For the direct incorporation of primary and secondary amines, the amine functionality has to be masked by a protecting group during the copolymerization. Several glycidyl amines with trityl, benzyl, allyl, and other protecting groups were developed that are stable under AROP conditions . These protective groups can liberate primary or secondary amino functionalities in a post‐polymerization cleavage step.…”

Section: Methodsmentioning

confidence: 99%

Aminal Protection of Epoxide Monomer Permits the Introduction of Multiple Secondary Amine Moieties at Poly(ethylene glycol)

Blankenburg

Frey

2019

Macromol. Rapid Commun.

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In contrast to acetal groups, aminal moieties are almost unknown in polymer chemistry. The aminal‐protected isopropyl‐hexahydro‐pyrimidine glycidyl amine (PyGA) for the anionic ring‐opening polymerization (AROP) is introduced. The monomer is prepared in a two‐step synthesis and can be polymerized in a well‐controlled manner under AROP conditions. Several poly(ethylene glycol) block and triblock copolymers are synthesized in a molecular weight range from 2 700 to 11 400 g mol−1 with up to 11 mol% PyGA. The molecular weight distributions are monomodal with low dispersity (Đ = Mw/Mn) below 1.2. After the polymerization, the acid‐labile hexahydro‐pyrimidine rings can be conveniently cleaved in acidic media, liberating two secondary amines per PyGA monomer unit. The released 1,3‐diamine functionalities can be addressed via post‐polymerization modification and show complexation of copper(II) ions in aqueous solution. The compounds are promising for water‐soluble catalyst systems, the removal of transition metals from water, and as a building block for complexing polyethers for biomedical application.

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Ring-Opening Polymerization of Imidazole Epoxides for the Synthesis of Imidazole-Substituted Poly(ethylene oxides)

Cited by 11 publications

References 21 publications

pH-triggered self-assembly of biocompatible histamine-functionalized triblock copolymers

pH-triggered self-assembly of biocompatible histamine-functionalized triblock copolymers

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Aminal Protection of Epoxide Monomer Permits the Introduction of Multiple Secondary Amine Moieties at Poly(ethylene glycol)

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