Poly(2-ethyl-2-oxazoline) bottlebrushes: How nanomaterial dimensions can influence biological interactions

Pizzi, David; Mahmoud, Ayaat M.; Klein, Tobias; Morrow, Joshua P.; Humphries, James; Houston, Zachary H.; Fletcher, Nicholas L.; Bell, Craig A.; Thurecht, Kristofer J.; Kempe, Kristian

doi:10.1016/j.eurpolymj.2021.110447

Cited by 20 publications

(33 citation statements)

References 50 publications

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“…Then, 50 μl of the erythrocyte stock was added to 950 μl of PBS containing different concentrations of polymer (10,25,50, and 100 and 1000 μg ml À1 ), PBS as a negative control and ACK lysing buffer (Gibco) as a positive control. Samples were incubated in a shaker incubator (Ratek, Orbital Mixer Incubator) at a mixing frequency of 450 rpm and a temperature of 37 C for 1 h. Intact erythrocytes were removed by centrifugation at 10000 rpm for 5 min.…”

Section: Erythrocyte Hemolysis Assaymentioning

confidence: 99%

“…24a,24b Recently, the impact of side-chain length of comb-shaped PEtOx on their biodistribution has been explored, with longer side chains (DP = 8) showing increased blood circulation times and lower liver uptake compared with shorter side chains (DP = 4). 25 Analogous studies focused on comb-shaped POz are rare, with the only example to date demonstrating a similar LCST tuneability to POx and the potential of these materials for biomedical applications. 26 Herein, the LCST behavior of PiPrOz is investigated in detail with a particular focus on the comparison of PiPrOzcontaining linear and comb-shaped copolymers (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Using 2‐isopropyl‐2‐oxazine to explore the effect of monomer distribution and polymer architecture on the thermoresponsive behavior of copolymers

Warne

Finnegan

Feeney

et al. 2021

Journal of Polymer Science

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Poly(cyclic imino ether)s (PCIE) have emerged as a highly promising class of polymer for use in biomedical applications with their value being derived from their excellent biocompatibility, diverse chemistry, and tunable hydrophilicity.Here, we investigate the properties of poly(2-isopropyl-2-oxazine) (PiPrOz), a relatively unexplored PCIE, determining it to have a cloud point temperature (T cp ) below physiological temperature, not to crystallize from bulk or in solution, and to be highly biocompatible. Furthermore, a series of copolymers con-

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Section: Erythrocyte Hemolysis Assaymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Using 2‐isopropyl‐2‐oxazine to explore the effect of monomer distribution and polymer architecture on the thermoresponsive behavior of copolymers

Warne

Finnegan

Feeney

et al. 2021

Journal of Polymer Science

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“…As in other areas of biomedical research, a recent push to move away from PEG to polymers with comparable biocompatibility can also be seen in the MPB field. 75,77,137,151 Avoiding risks to succumb the rising concerns of anti-PEG antibodies is warranted, as they do not only cause increased clearance rates and loss of efficacy, but can further lead to anaphylactic or hypersensitivity reactions. 157 A recent paper by Hucknall, Chilkoti and co-workers showed that the influence of the PEG length may need more attention and perhaps holds a solution to minimize anti-PEG antigenicity, while preserving favourable stealth properties.…”

Section: Compositionmentioning

confidence: 99%

Molecular polymer bottlebrushes in nanomedicine: therapeutic and diagnostic applications

Müllner

2022

Chem. Commun.

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“…In this study, the effect of side-chain dispersity of polymer brushes assembled on flat substrates is specifically investigated for the case of graft polymers constituted by poly(methacrylate)s (PMAs) presenting oligomeric side chains. Here, these are based on poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs), − which were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization of oligo(2-ethyl-2-oxazoline) methacrylates (OEOXMAs), previously obtained by cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EOX).…”

Section: Introductionmentioning

confidence: 99%

Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties: The Case of Oligoxazoline-Based Graft Polymers

et al. 2021

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Many synthetic polymers used to form polymerbrush films feature a main backbone with functional, oligomeric side chains. While the structure of such graft polymers mimics biomacromolecules to an extent, it lacks the monodispersity and structural purity present in nature. Here we demonstrate that sidechain heterogeneity within graft polymers significantly influences hydration and the occurrence of hydrophobic interactions in the subsequently formed brushes and consequently impacts fundamental interfacial properties. This is demonstrated for the case of poly(methacrylate)s (PMAs) presenting oligomeric side chains of different length (n) and dispersity. A precise tuning of brush structure was achieved by first synthesizing oligo(2-ethyl-2oxazoline) methacrylates (OEOXMAs) by cationic ring-opening polymerization (CROP), subsequently purifying them into discrete macromonomers with distinct values of n by column chromatography, and finally obtaining poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs) by reversible addition−fragmentation chain-transfer (RAFT) polymerization. Assembly of POEOXMA on Au surfaces yielded graft polymer brushes with different side-chain dispersities and lengths, whose properties were thoroughly investigated by a combination of variable angle spectroscopic ellipsometry (VASE), quartz crystal microbalance with dissipation (QCMD), and atomic force microscopy (AFM) methods. Side-chain dispersity, or dispersity within brushes, leads to assemblies that are more hydrated, less adhesive, and more lubricious and biopassive compared to analogous films obtained from graft polymers characterized by a homogeneous structure.

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Poly(2-ethyl-2-oxazoline) bottlebrushes: How nanomaterial dimensions can influence biological interactions

Cited by 20 publications

References 50 publications

Using 2‐isopropyl‐2‐oxazine to explore the effect of monomer distribution and polymer architecture on the thermoresponsive behavior of copolymers

Using 2‐isopropyl‐2‐oxazine to explore the effect of monomer distribution and polymer architecture on the thermoresponsive behavior of copolymers

Molecular polymer bottlebrushes in nanomedicine: therapeutic and diagnostic applications

Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties: The Case of Oligoxazoline-Based Graft Polymers

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