Acyl guanidine functional poly(2‐oxazoline)s as reactive intermediates and stimuli‐responsive materials

Guyse, Joachim F. R. Van; Xu, Xiaowen; Hoogenboom, Richard

doi:10.1002/pola.29542

Cited by 17 publications

(14 citation statements)

References 63 publications

(103 reference statements)

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“…The off-target molecular weight can be attributed to the fact that the M n was calculated relative to PEtOx standards. A small high molecular weight shoulder is observed which results from unavoidable chain transfer reactions and subsequent chain coupling often observed in PAOx synthesis [ 52 , 53 , 54 ]. The 1 H NMR spectrum shows all the characteristic peaks for both EtOx and C 3 MestOx repeat units, confirming the theoretical monomer ratio.…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Hybrid Thermo-Responsive Hydrogels Based on Poly(2-oxazoline) and Gelatin Derivatives

Podevyn

Vlierberghe

Dubruel

et al. 2022

Gels

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The combination of natural and synthetic polymers to form hybrid hydrogels offers the potential of fabricating new materials that possess a combination of properties resulting from both types of polymer classes. Within this work, two alkene-functionalized poly(2-alkyl/aryl–2-oxazoline) (PAOx) copolymers and one gelatin derivative, thiolated gelatin (gel-SH), are synthesized as precursors for hybrid hydrogels through a photo-induced radical thiol-ene crosslinking process. In-situ photo-rheology revealed an increased mechanical stability for hydrogels that possess an excess amount of PAOx precursor. A final qualitative investigation of the thermo-responsive properties of a P(EtOx270–norbornenOx30):gel-SH (2:1) hydrogel film revealed a cloud point temperature (Tcp) in the same range as the Tcp of the P(EtOx270–norbornenOx30) polymer precursor, which is around 30 °C. This promising result demonstrates that thermo-responsive hybrid poly(2-oxazoline)-gelatin hydrogels could be prepared with predictable Tcps and that further investigation into this appealing feature might be of interest. Ultimately, this work shows a proof-of-concept of using PAOx as potential hybrid hydrogel precursor in combination with cell-interactive gelatin derivatives to potentially improve the mechanical stability of the final scaffolds and introduce additional features such as thermo-responsiveness for the purpose of drug delivery.

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Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Hybrid Thermo-Responsive Hydrogels Based on Poly(2-oxazoline) and Gelatin Derivatives

Podevyn

Vlierberghe

Dubruel

et al. 2022

Gels

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“…In order to obtain adamantane functional PAOx, a copolymerization of 2-ethyl-2-oxazoline (EtOx) with 2-methoxycarbonylpropyl-2-oxazoline (C3MestOx) with a feed ratio of 9:1 was performed, where the EtOx provided overall water solubility while the C3MestOx enabled straightforward modification with a wide variety of primary amines [ 59 , 62 , 63 ]. The statistical copolymerization was initiated with MeOTs under microwave irradiation and was terminated with piperidine.…”

Section: Resultsmentioning

confidence: 99%

Adamantane Functionalized Poly(2-oxazoline)s with Broadly Tunable LCST-Behavior by Molecular Recognition

2021

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Smart or adaptive materials often utilize stimuli-responsive polymers, which undergo a phase transition in response to a given stimulus. So far, various stimuli have been used to enable the modulation of drug release profiles, cell-interactive behavior, and optical and mechanical properties. In this respect, molecular recognition is a powerful tool to fine-tune the stimuli-responsive behavior due to its high specificity. Within this contribution, a poly(2-oxazoline) copolymer bearing adamantane side chains was synthesized via triazabicyclodecene-catalyzed amidation of the ester side chains of a poly(2-ethyl-2-oxazoline-stat-2-methoxycarbonylpropyl-2-oxazoline) statistical copolymer. Subsequent complexation of the pendant adamantane groups with sub-stoichiometric amounts (0–1 equivalents) of hydroxypropyl β-cyclodextrin or β-cyclodextrin enabled accurate tuning of its lower critical solution temperature (LCST) over an exceptionally wide temperature range, spanning from 30 °C to 56 °C. Furthermore, the sharp thermal transitions display minimal hysteresis, suggesting a reversible phase transition of the complexed polymer chains (i.e., the β-cyclodextrin host collapses together with the polymers) and a minimal influence by the temperature on the supramolecular association. Analysis of the association constant of the polymer with hydroxypropyl β-cyclodextrin via 1H NMR spectroscopy suggests that the selection of the macrocyclic host and rational polymer design can have a profound influence on the observed thermal transitions.

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“…Considering the negatively charged bovine serum albumin (BSA) in neutral pH, [37] the negative zeta potentials of PN/BSA complexes suggest the possible neutral (or slightly positive) charge of PNs, especially for Ph‐CG. It is reported that the acylation on guanidine results in a sharp p K a decrease from 12–13 to ≈8 [38] . The p K a values of CG derivatives were measured as ≈6.1 using the pH titration method (Figure S2); [26, 39] therefore, Ph‐CG exists as neutral in the physiological environment.…”

Section: Figurementioning

confidence: 98%

Carbamoylated Guanidine‐Containing Polymers for Non‐Covalent Functional Protein Delivery in Serum‐Containing Media

2022

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Despite the high potential of controlling cellular processes and treating various diseases by intracellularly delivered proteins, current delivery systems exhibit poor efficiency due to poor serum stability, cellular entry, and cytosolic availability of proteins. Here, we report a novel functional group, phenyl carbamoylated guanidine (Ph‐CG), that greatly enhances the delivery efficiency to various types of cells. Owing to the substantially lowered pKa, the hydrophobic Ph‐CG offers optimized inter‐macromolecular interactions via enhanced hydrogen‐bonding and hydrophobic interactions. The coplanarity of Ph‐CG also leads to the better intracellular entry of protein complexes. Intracellularly delivered apoptosis‐inducing enzymes and antibodies significantly induce cell viability inhibitions in a serum‐containing medium. The newly developed Ph‐CG can be introduced to various existing carriers, leading to the realization of future therapeutic protein delivery.

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Acyl guanidine functional poly(2‐oxazoline)s as reactive intermediates and stimuli‐responsive materials

Cited by 17 publications

References 63 publications

Design and Synthesis of Hybrid Thermo-Responsive Hydrogels Based on Poly(2-oxazoline) and Gelatin Derivatives

Design and Synthesis of Hybrid Thermo-Responsive Hydrogels Based on Poly(2-oxazoline) and Gelatin Derivatives

Adamantane Functionalized Poly(2-oxazoline)s with Broadly Tunable LCST-Behavior by Molecular Recognition

Carbamoylated Guanidine‐Containing Polymers for Non‐Covalent Functional Protein Delivery in Serum‐Containing Media

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