Quadrupolar and polar anisotropy in end-grafted α-helical poly(γ-benzyl-L-glutamate) on solid substrates

Abstract

Using grazing incidence reflectance Fourier transform infrared spectroscopy (GIR-FTIR) and electro-optic (EO) measurements, we have determined the degree of quadrupolar and polar anisotropy in end-grafted α-helical poly(γ-benzyl-L-glutamate) (PBLG) chains. The results are compared to data obtained on spin-cast and on Langmuir–Blodgett–Kuhn (LBK) films. End-grafted films were prepared by a vapor-deposition-polymerization (VDP) scheme and have thicknesses of up to 70 nm. The quadrupolar order of VDP films, as estimated by the nematic order parameter S, is higher than in spin-cast and LBK films. This result indicates a preferentially perpendicular alignment of PBLG chains in VDP films. Furthermore, after the removal of the physisorbed chains from the grafted films by intensive washing with solvent, the quadrupolar order is lowered while the polar order increases significantly, suggesting that the physisorbed chains might form anti-parallel pairs with the surface-grafted chains.