Effects of one dimentional confined cylindrical nanogeometries on structure and dynamics of polypeptides

Synthetic polypeptides are kind of polymers which have a significant role due to their close relation to proteins so as their ability to assemble hierarchically stable ordered conformations. Even though there are many applications of nano-sized polypeptides, there are few reports [1-4] which indicate diameter size dependence on their structural and dynamic behaviors. Since macromolecules in nanoporous alumina (AAO) might have different segmental dynamics compared to bulk, in this thesis, the structural properties and the segmental dynamics of poly (Z-L-lysine) (PZLL), poly-L-alanine (PAla) and poly-glycine (PGly) confined in self-ordered AAO containing aligned and straight cylindrical nanopores as a function of pore size were investigated. This research study was carried out by using Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), Solid-State NMR (13C CPMAS NMR), Wide-Angle X-Ray Scattering (WAXS) and Dielectric Spectroscopy (DS). The structural characterization of the nanoconfined PZLL and the nanoconfined PAla revealed the nanorods mostly consist of alpha-helix structure (PZLL) and the nanorods consist of both alpha-helix and beta-sheet structures (PAla) independent of pore diameter. Bulk PZLL exhibits a glass transition temperature (Tg) at about 301 K, while PZLL nanorods showed slightly lower Tg at around 294 K. The dynamic investigation by DS also revealed a small decrease (~4 K) in Tg between bulk and nanoconfined PZLL samples. Subsequently, DS have been employed to study the effect of confinement on the local and global polypeptide dynamics. DS is a very sensitive probe of the local and global (alpha-helical) secondary structure relaxation through the large dipole. The results revealed that the local segmental dynamics, associated with broken hydrogen bonds, speed-up on confinement. The results of this study is of paramount importance, since the understanding the self-assembly, thermodynamics and dynamics of soft materials under confinement will allow for their rational design as functional devices with tunable mechanical strength, processability, electronic and optical properties.