Highly protein-resistant, self-assembled monolayers (SAMs) of dendritic polyglycerols (PGs) on gold can easily be obtained by simple chemical modification of these readily available polymers with a surface-active disulfide linker group. Several disulfide-functionalized PGs were synthesized by N,N'-dicyclohexylcarbodiimide-mediated ester coupling of thioctic acid. Monolayers of the disulfide-functionalized PG derivatives spontaneously form on a semitransparent gold surface and effectively prevent the adsorption of proteins, as demonstrated by surface plasmon resonance (SPR) kinetic measurements. A structure-activity relationship relating the polymer architecture to its ability to effectuate protein resistance has been derived from results of different surface characterization techniques (SPR, attenuated total reflectance infrared (ATR-IR), and contact-angle measurements). Dendritic PGs combine the characteristic structural features of several highly protein-resistant surfaces: a highly flexible aliphatic polyether, hydrophilic surface groups, and a highly branched architecture. PG monolayers are as protein resistant as poly(ethylene glycol) (PEG) SAMs and are significantly better than dextran-coated surfaces, which are currently used as the background for SPR spectroscopy. Due to the higher thermal and oxidative stability of the bulk PG as compared to the PEG and the easy accessibility of these materials, dendritic polyglycerols are novel and promising candidates as surface coatings for biomedical applications.
We describe the synthesis and the swelling behavior of a weak polyacid brush attached to a solid surface. Monolayers of poly methacrylic acid are generated by using self-assembled monolayers of an azo initiator and radical chain polymerization of methacrylic acid monomer at the surface of a planar substrate in situ. The thickness of the resulting surface-attached polyelectrolyte brush can be adjusted between 5 and 400 nm in the dry, collapsed state. The swelling behavior in water as a function of pH and salt concentration is investigated by multiple-angle null-ellipsometry. At high salt concentrations the brush thickness decreases due to electrostatic screening. At low concentration, however, an increase of thickness with ion concentration is found.
Disguise tactics: Peptide–polymer hybrid nanotubes are constructed in which self‐assembled cyclic peptides govern the structure, and a synthetic polymer coating determines the surface chemistry. Formation of the latter is initiated in situ from preorganized peptide building blocks. The picture shows an AFM image of nanotubes on a silicon wafer.
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