abstract
We have designed and synthesized a helical cysteamine-terminated oligourea foldamer composed of ten urea residues featuring side carboxyl and amine groups. The carboxyl group is located in proximity to the C-terminus of the oligourea and hence at the negative pole of the helix dipole. The amine group is located close to the N-terminus and hence at the positive pole of the helix dipole. Beyond the already remarkable dipole moment inherent in oligourea 2.5 helices, the incorporation of additional charges originating from the carboxylic and amine groups is supposed to impact the overall charge distribution along the molecule. These molecules were self-assembled into monolayers on a gold substrate, allowing us to investigate the influence of an electric field on these polar helices. By applying surface-enhanced infrared reflection-absorption spectroscopy, we proved that molecules within the monolayers tend to reorient themselves more vertically when a negative bias is applied to the surface. It was also found that surface-confined oligourea molecules affected by the external electric field tend to rearrange the electron density at urea groups, leading to the stabilization of the resonance structure with charge transfer character. The presence of the external electric field also affected the nanomechanical properties of the oligourea films, suggesting that molecules also tend to reorient in the ambient environment without an electrolyte solution. Under the same conditions, the helical oligourea displayed a robust piezoresponse, particularly noteworthy given the slender thickness of the monolayer, which measured approximately 1.2 nm. This observation demonstrates that thin molecular films composed of oligoureas may exhibit stimulus-responsive properties. This, in turn, may be used in nanotechnology systems as actuators or functional films, enabling precise control of their thickness in the range of even fractions of nanometers.
keywords
SELF-ASSEMBLED MONOLAYERS; CORROSION PROTECTION; GOLD; SPECTROSCOPY; FOLDAMERS; SURFACE; THIOL; CHARGE; PROBE
subject category
Science & Technology - Other Topics; Materials Science
authors
Grempka, A; Dziubak, D; Puszko, AK; Bachurska-Szpala, P; Ivanov, M; Vilarinho, PM; Pulka-Ziach, K; Sek, S
our authors
Maxim Ivanov
Researcher
Paula Maria Lousada Silveirinha Vilarinho
Vice Directoracknowledgements
The authors are grateful to the National Science Centre (Poland) for financial support within the project no. 2017/26/E/ST5/00559.