Micelles were prepared in organic solvents by using three topological polymer amphiphiles: (i) cyclic poly(n-decyl glycidyl ether-block-2-(2-(2-methoxyethoxy)ethoxy)ethyl glycidyl ether) (c-PDGE-b-PTEGGE) and (ii) its linear analogue (l-PDGE-b-PTEGGE); (iii) linear poly(6-phosphorylcholinehexylthiopropyl glycidyl ether-block-n-dodecanoyl glycidyl ether) (l-PPCGE-b-PDDGE). For the individual micelle solutions, the size and distribution were determined by dynamic light scattering (DLS) and synchrotron X-ray scattering analyses. The synchrotron X-ray scattering analysis further found that c-PDGE-b-PTEGGE forms oblate ellipsoidal micelle in an ethanol/water mixture, l-PDGE-b-PTEGGE makes prolate ellipsoidal micelle in an ethanol/water mixture, and l-PPCGE-b-PDDGE forms cylindrical micelle in chloroform. This comparative study found that there are large differences in the size and distribution results extracted by DLS and X-ray scattering analyses. All possible factors to cause such large differences are discussed. Moreover, a better use of the DLS instrument with keeping its merits is proposed.

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.

Poly(oxy(11-(biotinyl)undecylthiomethyl)ethylene-co-oxy(11-phosphoryl-cholineundecylthiomethyl)ethylene)s (PECH-BTmPCn: m = 0-100 mol % biotin (BT)-containing bristle; n = 100-0 mol % phosphorylcholine (PC)-containing bristle) were newly synthesized. All polymers exhibited excellent solution processability. They favorably self-assembled horizontal multibilayer structures in thin films with BT- and PC-enriched surfaces, which were driven by the lateral ordering of the fully extended upright bristles and the partial interdigitation between the BT and PC end groups of the bristles. Both hydrophilicity and water sorption of the films increased with the PC content. The PECH-BT100 films revealed remarkably distinctive sensitivity, selectivity, and adsorption ability for avidin against other proteins. Such remarkable performance was further significantly enhanced on the PECH-BTmPCn films in which PC moieties were incorporated to the BT-rich surface; in particular, the PECH-BT75PC25 films demonstrated the highest performance. Overall, the self-assembly brush copolymers of this study are very suitable for use in the high performance detection, adsorption, and separation of proteins and receptors, including avidin, which can reveal high affinity and selectivity to BT moiety.

This study delivers the first report on a cell-membrane-mimicking polymer system, 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 ) films in various compositions in terms of physicochemical properties, protein adsorptions, bacterial adherences, and human cell adhesions. Higher Chol-containing PGA-Chol m PC n in a self-assembled multi-bilayer membrane structure is confirmed to show excellently high affinity to pneumolysin (a cytolysin) and its C-terminal fragment (domain 4) but substantially suppressed affinity to the N-terminal fragment (domains 1–3) and further to plasma proteins. Furthermore, the adherences of pathogenic bacteria are increased favorably; however, the adhesion and proliferation of a human HEp-2 cell line are hindered severely. In contrast, higher-PC-containing PGA-Chol m PC n membranes promote HEp-2 cell adhesion and proliferation but significantly suppress the adsorptions of pneumolysin and its fragments and plasma proteins as well as bacterial adherence. The results collectively confirm that PGA-Chol m PC n can yield a membrane platform enriched with hydrophobic Chol and hydrophilic and zwitterionic PC moieties in any desired compositions, providing highly selective and sensitive physicochemical characters and biocompatibilities which are demanded for applications in various fields including biomedicine, cosmetics, and environmentally friendly consumer products.