Well-Defined Biomimicking Brush-Polymer Self-Assemblies Revealing Cholesterol- and Phosphorylcholine-Enriched Surface

Abstract

We have newly synthesized a series of welldefined brush polyethers bearing cholesterol (Chol) and phosphorylcholine (PC) moieties in various compositions which can mimic cell membrane. They were thermally stable up to at least 230 °C and soluble in common solvents, showing good solution processability. Excitingly, they all favorably selfassembled, forming multibilayer structures with 2 1 chain conformation; in comparison, the brush polyether bearing only PC-bristles formed orthorhombically packed cylinder (OPC) structure with 12 5 helical chain conformation. Such multibilayer structure formations could be driven by a strong self-assembling ability of the Chol-bristle in extended conformation; the multibilayer structure formation was further promoted by the presence of PC-bristles. The OPC structure formation could be driven by a lateral packing ability of the brush polymer chain in the helical confirmation resulted from the minimization of repulsive interactions in the neighbored zwitterionic PC-bristles. Because of such the self-assembling natures, all brush polymers always revealed Chol-and PC-enriched surface. Overall, all brush polyethers of this study successfully mimicked cell membrane features (Chol-and PC-surface based on selfassembling). They are very suitable for uses in the fields required cell membrane surface characteristics.

Glycidyl Triazolyl Polymers: Poly(ethylene glycol) Derivatives Functionalized by Azide–Alkyne Cycloaddition Reaction

“…Ree and co‐workers reported the synthesis of the GTP‐based homopolymer and copolymer bearing cholesterol and phosphorylcholine moieties (Figure , Polymers 66 , 68 , and Copolymer 67 ) . These polymers were designed for mimicking the cell membrane.…”

“…The solvent selection is also important . From this point of view, the achievement of Ree and co‐workers, who succeeded in preparing cholesterol‐, phosphorylcholine‐, and saccharide‐functionalized GTPs, is an important milestone to pave the way for biomedical applications of GTP . (5) The development of a facile work‐up process for the removal of copper catalysts is considered to be critical.…”

Pneumolysin/Plasma Protein Adsorption, Bacterial Adherence, and Cell Adhesion Characteristics of a Cell-Membrane-Mimicking Polymer System

“…Recently, we reported the new synthesis of a cell-membrane-mimicking polymer system in which the cholesterol (Chol) moieties were incorporated via the chemical bond formation of the nonpolar body end rather than the polar hydroxyl end, whereas the phosphorylcholine (PC) moieties were also chemically incorporated by using the nonpolar tale end: poly­[oxy­(4-(13-cholenoatenonyl)-1,2,3-triazoyl-1-methyl)­ethylene- random -oxy­(4-(13-phosphorylcholinenonyl)-1,2,3-triazoyl-1-methyl)-ethylene] (PGA-Chol m PC n : m = 0–100 mol % Chol-containing bristle and n = 100–0 mol % PC-containing bristle) (Figure ). These polymers in various compositions of Chol and PC moieties were soluble in common solvents, showing good solution processability.…”

Copper‐Free Synthesis of Glycidyl Triazolyl Polymers

“…However, the study on GTP began to receive much attention in the last 5 years, because GTP is obtainable from readily accessible polyepichlorohydrin . In addition, the application of GTP has been explored in the fields of stimuli‐responsive, self‐healing materials, ion‐conductive materials, and biomedical materials . All of GTPs reported after 2007 were synthesized by Cu(I)‐catalyzed AAC .…”

“…All of GTPs reported after 2007 were synthesized by Cu(I)‐catalyzed AAC . The complete removal of the copper ion from the sample was sometimes a difficult task . This will be a serious problem for the biomedical application of GTPs.…”