Diphenylalanine (FF) peptide nanotubes (PNTs) present a unique class of selfassembled functional biomaterials owing to a wide range of useful properties including nanostructural variability, mechanical rigidity, and chemical stability. In addition, a strong piezoelectric activity has been recently observed paving the way to their use as nanoscale sensors and actuators. In this work, we fabricated both horizontal and vertical FF PNTs and examined their optical second harmonic generation and local piezoresponse as a function of temperature. The measurements show gradual decrease of polarization with increasing temperature accompanied by irreversible phase transition into another crystalline phase at about 140-150 ºC. The results are corroborated by the molecular dynamic simulations predicting order-disorder phase transition into centrosymmetric (possibly, orthorhombic) phase with antiparallel polarization orientation in neighboring FF rings. Partial piezoresponse hysteresis indicates incomplete polarization switching due to high coercive field in FF PNTs.
A near-surface structural phase transition on a SrTiO3 single crystal, occurring at T(*) about 45 K above the bulk cubic-to-tetragonal transition, is observed by means of optical second harmonic generation. The temperature dependence of the second harmonic field in the vicinity of T(*) is described with a phenomenological Landau-type model.
Self-assembled peptide nanotubes are unique nanoscale objects that have great potential for a multitude of applications, including biosensors, nanotemplates, tissue engineering, biosurfactants, etc. The discovery of strong piezoactivity and polar properties in aromatic dipeptides [A. Kholkin, N. Amdursky, I. Bdikin, E. Gazit, and G. Rosenman, ACS Nano 4, 610 (2010)] opened up a new perspective for their use as biocompatible nanoactuators, nanomotors, and molecular machines. Another, as yet unexplored functional property is the ability to switch polarization and create artificial polarization patterns useful in various electronic and optical applications. In this work, we demonstrate that diphenylalanine peptide nanotubes are indeed electrically switchable if annealed at a temperature of about 150 °C. The new orthorhombic antipolar structure that appears after annealing allows for the existence of a radial polarization component, which is directly probed by piezoresponse force microscopy (PFM) measurements. Observation of the relatively stable polarization patterns and hysteresis loops via PFM testifies to the local reorientation of molecular dipoles in the radial direction. The experimental results are complemented with rigorous molecular calculations and create a solid background of electric-field induced deformation of aromatic rings and corresponding polarization switching in this emergent material.
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