Self‐assembled peptide diphenylalanine (NH2‐Phe‐Phe‐COOH, FF) is one of the most important emergent functional materials, demonstrating wide range of fascinating physical and chemical properties including biocompatibility, chemical variability, exceptional rigidity, outstanding piezoelectric, pyroelectric and ferroelectric responses. Up to now, the phase transitions in FF nanotubes were investigated by scanning and transmission electron microscopy, atomic force microscopy, differential scanning calorimetry, thermogravimetry and mass spectroscopy. The Raman spectroscopy was implemented at room temperature only, and the microscopic details of these transitions remained unknown. In this work, the structural transformations in FF nanotubes at elevated temperatures (up to tubes destruction at 160 °C) were studied by Raman spectroscopy. Two structural transformations were observed in this region: hexagonal to orthorhombic transition at about 100 °C and the cyclization of FF molecules at about 150 °C. For the first time, these transformations were considered in the context of reconstruction of the water subsystem in the nanotubes, thus demonstrating the strong relation between the peptide tube and the state of the water inside. Using an effective frequency of nanotubes' lattice vibrations, we found that many effects observed earlier by other methods are induced by the variation of the water subsystem. The analysis of certain lines in the middle part of the Raman spectrum allowed us to describe the microscopic details of FF molecule cyclization. These results improve the understanding of the role of water in the origin of outstanding properties of FF nanotubes and thus promote developing new functional devices on their basis. Copyright © 2017 John Wiley & Sons, Ltd.
Various structural features, such as proton disorder or noncovalent interactions, determine the existence of switchable nonlinear optical properties under varying external conditions. Thus, for the single crystal of diiodobutenyl‐bis‐thioquinolinium triiodide with the bridge hydrogen atom, previously characterized under ambient conditions by C2/c symmetry, we have measured Raman spectra in the temperature range from 298 K down to 113 K. Variations in low‐wavenumber region of Raman spectra at temperatures below 153 K have been attributed to the change of the bridge hydrogen atom position in the [NHN]+ fragment, thus lowering the crystal symmetry from C2/c to Cc. Quantum chemical calculations in the solid state for noncentrosymmetric Cc structure predict high hyperpolarizability and second‐order electric susceptibilities, comparable to those of modern nonlinear optical materials. This indicates the emergence of nonlinear optical properties in the low‐temperature phase of the studied crystal. Copyright © 2017 John Wiley & Sons, Ltd.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.