Cationic amphiphilic alternating copolymers with tunable morphology

Zhang, Jingling; Yu, Xiaoxi; Zheng, Bingqian; Shen, Jiachun; Bhatia, Surita R.; Sampson, Nicole S.

doi:10.1039/d0py00782j

Cited by 6 publications

(7 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ruthenium-catalyzed AROMP of low-strain cyclic olefins and bicylo[4.2.0]octenes has been investigated extensively and has been championed for producing copolymers that can display a variety of functional groups, controlled backbone sequences, and tunable material properties such as hydrophilicity and glass transition temperatures. − ,− To prepare the [4.2.0] glycopolymers, 4,7-dihydro-1,3-dioxepin or cyclohexene (B monomer) was allowed to react with bicyclo[4.2.0]oct-6-ene-7-carboxamide bearing mannose or fucose (A monomer) in the presence of Grubbs’ third generation catalyst 4 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Evolution in free radical polymerization and atom transfer radical polymerization has resulted in biocompatible polymers with increased water solubility and low cytotoxicity. The utilization of polycondensation or ring-opening polymerization to synthesize polyesters has inspired the development of biocompatible materials for dental, orthopedic, drug delivery, and heart regeneration applications. − In our laboratory, we have applied alternating ring-opening metathesis polymerization (AROMP) methods to synthesize sequence-controlled polymers with tunable hydrophilicity, morphology, and degradability. − …”

mentioning

confidence: 99%

See 1 more Smart Citation

Glycopolymers Prepared by Alternating Ring-Opening Metathesis Polymerization Provide Access to Distinct, Multivalent Structures for the Probing of Biological Activity

Mendez,

Boadi,

Kennedy

et al. 2024

ACS Bio Med Chem Au

View full text Add to dashboard Cite

A myriad of biological processes are facilitated by ligand−receptor interactions. The low affinities of these interactions are typically enhanced by multivalent engagements to promote binding. However, each biological interaction requires a unique display and orientation of ligands. Therefore, the availability and diversity of synthetic multivalent probes are invaluable to the investigation of ligand− receptor binding interactions. Here, we report glycopolymers prepared from bicyclo[4.2.0]oct-6-ene-7-carboxamide and 4,7-dihydro-1,3-dioxepin or cyclohexene. These glycopolymers, synthesized by alternating ring-opening metathesis polymerization, display precise ligand spacing as well as the option of a hydrophobic or acetalfunctionalized polymer backbone. Small-angle X-ray scattering (SAXS) data analysis revealed that these [4.2.0] glycopolymers adopted distinct conformations in solution. In aqueous media, [4.2.0]-dioxepin glycopolymers formed swollen polymer chains with rod-like, flexible structures while [4.2.0]cyclohexene glycopolymers assumed compact, globular structures. To illustrate how these glycopolymers could aid in the exploration of ligand−receptor interactions, we incorporated the [4.2.0] glycopolymers into a biological assay to assess their potential as activators of acrosomal exocytosis (AE) in mouse sperm. The results of the biological assay confirmed that the differing structures of the [4.2.0] glycopolymers would evoke distinct biological responses; [4.2.0]-cyclohexene glycopolymers induced AE in mouse sperm while [4.2.0]-dioxepin glycopolymers did not. Herein, we provide two options for glycopolymers with low to moderate molecular weight dispersities and low cytotoxicity that can be implemented into biological assays based on the desired hydrophobicity, rigidity, and structural conformation of the polymer probe.

show abstract

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Glycopolymers Prepared by Alternating Ring-Opening Metathesis Polymerization Provide Access to Distinct, Multivalent Structures for the Probing of Biological Activity

Mendez,

Boadi,

Kennedy

et al. 2024

ACS Bio Med Chem Au

View full text Add to dashboard Cite

show abstract

“…Sequence specific copolymers, such as multiblocks and strictly alternating AB copolymers, are also believed to have a high potential in the field of MSR polymers 103 . The latter are more conveniently obtained through ring‐opening and step‐growth polymerizations 104–108 . However, Ameduri and co‐workers 109 optimized a RAFT protocol that affords an alternating copolymer of t ‐butyl‐2‐trifluoromethacrylate and VA in a one‐pot reaction, owing to the inability of MAF‐TBA radical to self‐propagate.…”

Section: Background: Matching Building Block Studs For Specific Compositions Architectures and Functionsmentioning

confidence: 99%

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

D’Acunzo

Masci

2021

Journal of Polymer Science

View full text Add to dashboard Cite

In this review article, we survey the 2016–June 2021 scientific literature on the synthesis of multi‐stimuli responsive (MSR) polymers, the main focus being on reversible deactivation radical polymerization techniques (RDRPs, also known as controlled radical polymerizations). In fact, along more than 40 years of extensive research, RDRPs have boosted the synthesis of stimuli‐responsive polymers. RDRPs are now robust, versatile, relatively user‐friendly and even interconvertible, thus allowing control over composition, sequence, and topology of polymers. Such control can afford materials with well‐defined responses to physical, chemical, and biological external stimuli. Furthermore, “click” reactions are used to combine macromolecular precursors or to introduce specific functional groups in the target structure. As a result, MSR polymers are obtained from diverse combinations of commercial or specially synthesized building blocks arranged at will into desired sequences and architectures. Thanks to this versatility, self‐assembling polymeric structures are designed either to respond to triggers and perform specific applicative tasks, or to investigate the influence of structural variables on the responsivity of polymers. The “green” trend emerging in the field of responsive polymers and RDRPs is also briefly discussed.

show abstract

“…Ion-exchange membranes are of interest for electrochemical energy conversion technologies including fuel cells, electrolyzers, batteries, and redox flow batteries . Anion-exchange membranes (AEMs) specifically have been targeted as a promising material for all of these devices because alkaline systems allow for more facile catalysis and utilization of nonplatinum group metal (PGM) catalysts. , Block copolymer-based AEMs are of further interest due to their ability to self-assemble into phase-separated morphologies, which can ultimately lead to improvements in ion conduction and transport of reactant and product species across the membrane. − While phase separation in neutral block copolymers is well understood, experimental and computational studies have shown charge effects in block polyelectrolytes significantly impact the Flory–Huggins parameter and phase diagram, − where factors including chain length, charge fraction, charge size, and the strength of Coulombic interactions all impact morphology. − …”

Section: Introductionmentioning

confidence: 99%

Designing Anion-Exchange Ionomers with Oriented Nanoscale Phase Separation at a Silver Interface

Buggy

Kuo

et al. 2021

J. Phys. Chem. C

View full text Add to dashboard Cite

Performance of polymer electrolyte-based energy systems is significantly impacted by transport within the electrode catalyst layer, where ionomer thin films coat catalyst particles. Proton exchange ionomer thin films have been thoroughly characterized, but few studies have critically examined anion-exchange ionomer (AEI) thin films. Further, none have reported nanoscale phase separation for hydrocarbon AEIs, which is critical to mitigate transport resistances. In this work, a set of hydrocarbon-based AEIs with nanoscale phase separation are developed from tunable block copolymer systems composed of polyisoprene (PIp) and polychloromethylstyrene (PCMS). The effect of the PIp/PCMS ratio, architecture, and thickness on the thin-film morphology of the neutral block copolymer precursors on silicon and silver substrates is investigated using grazing-incidence small-angle X-ray scattering (GISAXS) and atomic force microscopy (AFM). AEIs are prepared by quaternizing with trimethylamine or methylpiperidine and their cation-dependent morphology is characterized at 60 °C and 95% RH. A perpendicularly aligned morphology is observed on silver, while no phase separation is observed on silicon, indicating that silver–polymer interfacial interactions drive phase separation. After quaternization, dipole–dipole interactions induce some disorder, but nanoscale phase separation is still maintained. GISAXS patterns are modeled using a Unified Fit approach to understand water uptake and swelling, and recommendations for AEI design are presented.

show abstract

Cationic amphiphilic alternating copolymers with tunable morphology

Abstract: A series of ionic amphiphilic alternating copolymers were characterized via SAXS, TEM and DLS to help understand factors that could potentially affect self-assembly, including the degree of polymerization, the length...

Cited by 6 publications

References 46 publications

Glycopolymers Prepared by Alternating Ring-Opening Metathesis Polymerization Provide Access to Distinct, Multivalent Structures for the Probing of Biological Activity

Glycopolymers Prepared by Alternating Ring-Opening Metathesis Polymerization Provide Access to Distinct, Multivalent Structures for the Probing of Biological Activity

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

Designing Anion-Exchange Ionomers with Oriented Nanoscale Phase Separation at a Silver Interface

Contact Info

Product

Resources

About