Loop to linear: exploring the impact of corona topology on the properties of self-assembled polymer nanoparticles DOI
Haoxiang Zeng,

Markus Müllner

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(16), P. 1648 - 1659

Published: Jan. 1, 2024

Cyclic block copolymers with photo-cleavable linkers were prepared, allowing looped-to-linear corona transformations via UV-induced post-assembly modification, and showcasing their versatility as topology-tuned drug delivery systems.

Language: Английский

Supramolecular Polymer Bottlebrushes: In Situ Assessment of Noncovalent Assemblies in Human Serum by Analytical Ultracentrifugation DOI Creative Commons
Ilya Anufriev, Tobias Klein, Stephanie Hoeppener

et al.

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Abstract For nanomedical targeting and drug delivery purposes, the noncovalent assembly of polymer building blocks into defined nanostructures is an intense area research. One key assets desirable to know for potential nanocarrier stability under conditions close those in application scenarios. Here, a series based on poly(ethylene glycol) (PEG), which comprise functional end group facilitating self‐assembly supramolecular bottlebrushes (SPBs), hydrodynamically studied. The blocks, consequently assemblies, are labeled with cyanine5 (Cy5) dye enabling selective tracing materials human serum (HS) analytical ultracentrifugation (AUC) experiments. Our experiments reveal long‐term assemblies over one month storage HS at body temperature. At same time, interaction some Cy5 moieties transport protein albumin (HSA) evidenced.

Language: Английский

Citations

0

Molecular Structure of Foldable Bottlebrush Polymers in Melts DOI Creative Commons
Li‐Heng Cai

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

A bottlebrush polymer consists of a long linear backbone densely grafted with many relatively short side chains. widely accepted view is that strong steric repulsion among the highly overlapped chains prestrains backbone, resulting in low extensibility. However, we recently discovered melt polymers incompatible and collapses to reduce interfacial free energy, regardless Despite this discovery, molecular structure these so-called "foldable" their assemblies remains poorly understood. Here, present deterministic relationships architecture, mesoscopic conformation, macroscopic properties foldable polymers. combination scaling theory experiments reveals as chain grafting density decreases, diameter increases, whereas end-to-end distance decreases. These behaviors contradict existing understanding polymers, which assumes are compatible. Since store lengths can be released upon large deformations, they offer way decouple intrinsic stiffness-extensibility trade-off single-network elastomers. findings provide foundational insights into using building blocks for designing soft (bio)materials.

Language: Английский

Citations

0

Design and synthesis of amphiphilic statistical copolymers forming unimeric micelles with thermoresponsive behaviour in the physiological range DOI Creative Commons

Florian Tondock,

David G. Nash,

Cathleen Hudziak

et al.

Polymer Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A crucial aspect of drug development is designing carriers that efficiently solubilise therapeutic agents while ensuring stability, minimising cytotoxicity, and enabling targeted delivery.

Language: Английский

Citations

0

Polypept(o)ide‐Based Core–Shell Bottlebrush Polymers: A Versatile Platform for Drug Encapsulation DOI Creative Commons

Bonan Zhao,

Jinjia Wei, Rüdiger Berger

et al.

Macromolecular Bioscience, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Abstract Cylindrical bottlebrush polymers (CBPs) enable the precise adjustment of nanoparticle properties such as size, shape, and functionality exclusively by polymer synthesis. In addition, block copolymer side chains direct access to core–shell structure. this study, synthesis polypept(o)ides‐based CBPs is presented through a “grafting‐from” strategy. While, poly‐lysine (pLys) serves backbone, poly(γ‐benzyl‐ l ‐glutamic acid)‐block‐polysarcosine (pGlu(OBn)‐ b ‐pSar) copolymers form chains. This approach enables nanoparticles, referred brushes (CSBs), with hydrodynamic radius ( R h ) from 17 70 nm, molecular weights (1320–4000 kg mol −1 dispersity indices ≈1.3 determined size‐exclusion chromatography. Dasatinib chosen drug molecule model explore potential synthetical CSBs platform for encapsulation π – ‐interactions. An overall loading efficiency 10% achieved, which also displayed sustained release within 72 h, cellular uptake into human glioblastoma (U‐87 MG) cells, drug‐related therapeutic efficacy. While can be further optimized covalent attachment, these results establish strong foundation use in nanomedicine.

Language: Английский

Citations

0

Ammonium-Containing Methacrylic Polymer Brushes with Adjustable Hydrophilicity: Synthesis and Properties in Aqueous Solutions DOI Open Access
Д. М. Каморин, А. С. Симагин, О. А. Казанцев

et al.

Polymers, Journal Year: 2025, Volume and Issue: 17(9), P. 1200 - 1200

Published: April 27, 2025

Reversible addition–fragmentation chain-transfer (RAFT) polymerization was used to synthesize novel thermoresponsive cationic molecular brushes with high yields—namely of copolymers methoxyoligo(ethylene glycol) methacrylate, alkoxyoligo(ethylene and N-methacryloylaminopropyl-N,N-dimethyl-N-propylammonium bromide. Controlled yielded polymers a weight dispersity ≤1.3 conversions exceeding 80%. The influence the brushes’ composition on their solubility in water organic solvents, interfacial tension at water–oil interface, aggregation behavior aqueous solutions investigated. For first time, we report design combining an antibacterial potential tunable hydrophilic–hydrophobic properties, enabling highly precise control over LCST (17–68 °C) through tuning. solubilization capacity hydrophobic compounds brush micelles increased comonomer content. These exhibited activity, significantly reducing tension, critical micelle concentrations (CMCs) 3–10 mg/L. It shown that amphiphilic properties can be easily tuned desired direction by varying content units. obtained data indicate as micellar nanocarriers for controlled drug delivery.

Language: Английский

Citations

0

Amphiphilic Heterografted Molecular Bottlebrushes with Tertiary Amine‐Containing Side Chains as Efficient and Robust pH‐Responsive Emulsifiers DOI Creative Commons

Michael T. Kelly,

Zhan Chen, Thomas P. Russell

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 13, 2023

By combining the unique characteristics of molecular bottlebrushes (MBBs) and properties stimuli-responsive polymers, we show that MBBs with randomly grafted poly(n-butyl acrylate) pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient robust emulsifiers. Water-in-toluene emulsions were formed at pH 4.0 disrupted by increasing to 10.0. The emulsion generation disruption was reversible over ten cycles investigated, remained intact. exceptional stability stemmed from high interfacial binding energy MBBs, imparted their large size Janus architecture interface, as evidenced jamming wrinkling assemblies upon reducing area. At 10.0, PDEAEMA became water-insoluble, desorbed causing de-emulsification. Consequently, have shown judicious design can generate particle emulsifiers size, while responsiveness enables more potential applications.

Language: Английский

Citations

10

Monomer Emulsified Aqueous Ring-Opening Metathesis Polymerization (ME-ROMP) for the Synthesis of Water-Soluble Molecular Bottlebrushes with a Precise Structure DOI
Wangmeng Hou,

Yingqing Zhou,

Xiuzhe Yin

et al.

Macromolecules, Journal Year: 2023, Volume and Issue: 56(19), P. 7889 - 7897

Published: Aug. 21, 2023

Water-soluble molecular bottlebrushes (MBBs) with various functions and tunable morphologies have found promising application prospects in the biorelevant field. However, facile synthesis of water-soluble MBBs well-defined architectures is challenging by different chemistry. Herein, we explore versatility monomer emulsified aqueous ring-opening metathesis polymerization (ME-ROMP) for via a grafting-through strategy. The ME-ROMP was carried out injecting tiny amount Grubbs' third-generation catalyst (G3) solution CH2Cl2 into norbornene macromonomers (NB MMs) without deoxygenation, forming NB MMs-stabilized CH2Cl2/H2O emulsions. In this ME-ROMP, moieties G3 are concentrated droplets so that decomposition could be significantly suppressed steric hindrance MMs reduced, leading to an accelerated polymerization. results demonstrate living ultrafast rates near quantitative initiation conversion, producing diverse compositions contour lengths.

Language: Английский

Citations

9

Zwitterionic Amino Acid Polymer-Grafted Core-Crosslinked Particle toward Tumor Delivery DOI
Shota Fujii, Kazuo Sakurai

Biomacromolecules, Journal Year: 2022, Volume and Issue: 23(9), P. 3968 - 3977

Published: Aug. 26, 2022

Zwitterionic amino acid polymers (ZAPs) exhibit biocompatibility and recognition capability for transporters (AATs) overexpressed on cancer cells. They are potential cancer-targeting ligands in nanoparticle-based nanomedicines utilized chemotherapy. Here, a poly(glutamine methacrylate) (pGlnMA)-grafted core-crosslinked particle (pGlnMA-CCP) is prepared through the formation of nanoemulsions stabilized using amphiphilic block copolymers comprising pGlnMA as hydrophilic block. The chain conformation grafted polymer structure pGlnMA-CCP precisely elucidated by dynamic light scattering, X-ray transmission electron microscopy. demonstrates active cellular uptake deep penetration behaviors cells spheroids, respectively, via an AAT-mediated mechanism. vivo pharmacokinetics practically comparable to those CCP covered with poly(polyethylene glycol (pPEGMA), which inhibits protein adsorption prolongs blood retention, implying that biocompatible properties similar pPEGMA. Furthermore, accumulates tissues at higher level than pPEGMA systems. results demonstrate targetability, tumor permeability, efficient accumulation, can be obtained grafting onto nanoparticles, suggesting high ligand nanomedicines.

Language: Английский

Citations

13

Bottlebrush Polyethylene Glycol Nanocarriers Translocate across Human Airway Epithelium via Molecular Architecture-Enhanced Endocytosis DOI Creative Commons

Zhi-Jian He,

Baiqiang Huang, Li‐Heng Cai

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(27), P. 17586 - 17599

Published: June 27, 2024

Pulmonary drug delivery is critical for the treatment of respiratory diseases. However, human airway surface presents multiple barriers to efficient delivery. Here, we report a bottlebrush poly(ethylene glycol) (PEG-BB) nanocarrier that can translocate across all within surface. Guided by molecular theory, design PEG-BB molecule consisting linear backbone densely grafted many (∼1000) low weight (∼1000 g/mol) polyethylene glycol (PEG) chains; this results in highly anisotropic, wormlike featuring contour length ∼250 nm, cross-section ∼20 and hydrodynamic diameter ∼40 nm. Using classic air-liquid-interface culture system recapitulate essential biological features surface, show rapidly penetrates through endogenous mucus periciliary brush layer (mesh size 20-40 nm) be internalized cells whole epithelium. By quantifying cellular uptake polymeric carriers various architectures manipulating cell proliferation endocytosis pathways, translocation epithelium driven architecture-enhanced endocytosis. Our demonstrate large, PEG polymers, if properly designed, used as carrier pulmonary mucosal

Language: Английский

Citations

2

Ultrastable and Redispersible Zwitterionic Bottlebrush Micelles for Drug Delivery DOI
Jeonghun Lee, Yao Tang, Karla E. Cureño Hernandez

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 6, 2024

Bottlebrush copolymers are increasingly used for drug delivery and biological imaging applications in part due to the enhanced thermodynamic stability of their self-assemblies. Herein, we discuss effect hydrophilic block chemistry on bottlebrush micelles. Amphiphilic bottlebrushes with zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) nonionic polyethylene glycol (PEG) blocks were synthesized by "grafting from" polymerization self-assembled into well-defined spherical Colloidal against disassembly challenged under high concentrations NaCl, MgSO

Language: Английский

Citations

2