Stealth nanorods <i>via</i> the aqueous living crystallisation-driven self-assembly of poly(2-oxazoline)s

Finnegan, John R.; Pilkington, Emily H.; Alt, Karen; Rahim, Md. Arifur; Kent, Stephen J.; Davis, Thomas P.; Kempe, Kristian

doi:10.1039/d1sc00938a

Cited by 38 publications

(69 citation statements)

References 65 publications

(36 reference statements)

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“…[32,34] The most essential finding of the theoretical modelling was that for the varying chemical makeup of the antifouling ligands there exists an optimal ligand length and packing density that provides the degree of hydration and molecular dynamics required to maximize both the enthalpic and entropic penalties for non-specific protein adsorption. [32] Relatively few experimental studies exist of POx behavior in nanomedicines such as liposomes [37] and other nanoparticles, [38,39] compared to the PEG literature. [18] Regarding biomedical applications, many studies have shown the potential of POx-based nanoparticles for biosensing, drug delivery in cancer therapy, and as nanoreactors and artificial organelles.…”

Section: Introductionmentioning

confidence: 99%

“…Relatively few experimental studies exist of POx behavior in nanomedicines such as liposomes [ 37 ] and other nanoparticles, [ 38,39 ] compared to the PEG literature. [ 18 ] Regarding biomedical applications, many studies have shown the potential of POx‐based nanoparticles for biosensing, drug delivery in cancer therapy, and as nanoreactors and artificial organelles.…”

Section: Introductionmentioning

confidence: 99%

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Block Length‐Dependent Protein Fouling on Poly(2‐oxazoline)‐Based Polymersomes: Influence on Macrophage Association and Circulation Behavior

Najer

Belessiotis‐Richards

Kim

et al. 2022

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Polymersomes are vesicular structures self‐assembled from amphiphilic block copolymers and are considered an alternative to liposomes for applications in drug delivery, immunotherapy, biosensing, and as nanoreactors and artificial organelles. However, the limited availability of systematic stability, protein fouling (protein corona formation), and blood circulation studies hampers their clinical translation. Poly(2‐oxazoline)s (POx) are valuable antifouling hydrophilic polymers that can replace the current gold‐standard, poly(ethylene glycol) (PEG), yet investigations of POx functionality on nanoparticles are relatively sparse. Herein, a systematic study is reported of the structural, dynamic and antifouling properties of polymersomes made of poly(2‐methyl‐2‐oxazoline)‐block‐poly(dimethylsiloxane)‐block‐poly(2‐methyl‐2‐oxazoline) (PMOXA‐b‐PDMS‐b‐PMOXA). The study relates in vitro antifouling performance of the polymersomes to atomistic molecular dynamics simulations of polymersome membrane hydration behavior. These observations support the experimentally demonstrated benefit of maximizing the length of PMOXA (degree of polymerization (DP) > 6) while keeping PDMS at a minimal length that still provides sufficient membrane stability (DP > 19). In vitro macrophage association and in vivo blood circulation evaluation of polymersomes in zebrafish embryos corroborate these findings. They further suggest that single copolymer presentation on polymersomes is outperformed by blends of varied copolymer lengths. This study helps to rationalize design rules for stable and low‐fouling polymersomes for future medical applications.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Block Length‐Dependent Protein Fouling on Poly(2‐oxazoline)‐Based Polymersomes: Influence on Macrophage Association and Circulation Behavior

Najer

Belessiotis‐Richards

Kim

et al. 2022

Small

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“…While several approaches provide access to fiber- or wormlike morphologies, control of the length of such structures still remains a challenge. , Certainly, a breakthrough in this regard was the development of the crystallization-driven self-assembly (CDSA). However, it remains the only viable method to gain real control of the fiber length, particularly in seldomly reported aqueous systems. − Strong directional supramolecular interactions such as π–π interactions or hydrogen bonds represent an interesting and more dynamic alternative to crystallization processes in order to guide the assembly of polymeric building blocks . However, a similar length control in such complex assemblies, as reported for CDSA, has yet to be realized.…”

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confidence: 99%

Kinetically Controlling the Length of Self-Assembled Polymer Nanofibers Formed by Intermolecular Hydrogen Bonds

et al. 2021

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Strong directional hydrogen bonds represent a suitable supramolecular force to drive the one-dimensional (1D) aqueous self-assembly of polymeric amphiphiles resulting in cylindrical polymer brushes. However, our understanding of the kinetics in these assembly processes is still limited. We here demonstrate that the obtained morphologies for our recently reported benzene tris-urea and tris-peptide conjugates are strongly pathway-dependent. A controlled transfer from solutions in organic solvents to aqueous environments enabled a rate-dependent formation of kinetically trapped but stable nanostructures ranging from small cylindrical or spherical objects (<50 nm) to remarkably large fibers (>2 μm). A detailed analysis of the underlying assembly mechanism revealed a cooperative nature despite the steric demands of the polymers. Nucleation is induced by hydrophobic interactions crossing a critical water content, followed by an elongation process due to the strong hydrogen bonds. These findings open an interesting new pathway to control the length of 1D polymer nanostructures.

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“…[199] As low disperse 1D and 2D nano-objects can be efficiently prepared from BCPs containing crystallizable blocks, the CDSA strategy has been widely applied in drug delivery. [169][170][171][172][173][174][175] For example, Manners et al prepared a triblock copolymer with a crystallizable core-forming block poly(fluorene trimethyl carbonate) (PFTMC), a hydrophobic amorphous central block poly(butyl methacrylate) (PBMA), and a hydrophilic corona-forming block PNIPAm. [169] The copolymer PFTMC-b-PBMA-b-PNIPAm can be assembled into nano-fibers via living CDSA and used to load the Nile Red.…”

Section: Applications In Biomedical Materialsmentioning

confidence: 99%

Self‐Assembly of Copolymers Containing Crystallizable Blocks: Strategies and Applications

Shi

Shen

et al. 2022

Macromol. Rapid Commun.

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The self‐assembly of copolymers containing crystallizable blocks in solution has received increasing attention in the past few years. Various strategies including crystallization‐driven self‐assembly (CDSA) and polymerization‐induced CDSA (PI‐CDSA) have been widely developed. Abundant self‐assembly morphologies are captured and advanced applications have been attempted. In this review, the synthetic strategies including the mechanisms and characteristics are highlighted and a survey on the advanced applications of crystalline nano‐assemblies is collected. This review is hoped to depict a comprehensive outline for self‐assembly of copolymers containing crystallizable blocks in recent years and to prompt the development of the self‐assembly technology in interdisciplinary fields.

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Stealth nanorods via the aqueous living crystallisation-driven self-assembly of poly(2-oxazoline)s

Abstract: The morphology of nanomaterials critically influences their biological interactions. However, there is currently a lack of robust methods for preparing non-spherical particles from biocompatible materials. Here, we combine ‘living’ crystallisation-driven...

Cited by 38 publications

References 65 publications

Block Length‐Dependent Protein Fouling on Poly(2‐oxazoline)‐Based Polymersomes: Influence on Macrophage Association and Circulation Behavior

Block Length‐Dependent Protein Fouling on Poly(2‐oxazoline)‐Based Polymersomes: Influence on Macrophage Association and Circulation Behavior

Kinetically Controlling the Length of Self-Assembled Polymer Nanofibers Formed by Intermolecular Hydrogen Bonds

Self‐Assembly of Copolymers Containing Crystallizable Blocks: Strategies and Applications

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