Visualizing Chiral Interactions in Carbohydrates Adsorbed on Au(111) by High‐Resolution STM Imaging

authored by: Johannes Seibel, Giulio Fittolani, Hossein Mirhosseini, Xu Wu, Stephan Rauschenbach, Kelvin Anggara, Peter H. Seeberger, Martina Delbianco, Thomas D. Kühne, Uta Schlickum, Klaus Kern
Abstract: Carbohydrates are the most abundant organic material on Earth and the structural “material of choice” in many living systems. Nevertheless, design and engineering of synthetic carbohydrate materials presently lag behind that for protein and nucleic acids. Bottom-up engineering of carbohydrate materials demands an atomic-level understanding of their molecular structures and interactions in condensed phases. Here, high-resolution scanning tunneling microscopy (STM) is used to visualize at submolecular resolution the three-dimensional structure of cellulose oligomers assembled on Au(1111) and the interactions that drive their assembly. The STM imaging, supported by ab initio calculations, reveals the orientation of all glycosidic bonds and pyranose rings in the oligomers, as well as details of intermolecular interactions between the oligomers. By comparing the assembly of D- and L-oligomers, these interactions are shown to be enantioselective, capable of driving spontaneous enantioseparation of cellulose chains from its unnatural enantiomer and promoting the formation of engineered carbohydrate assemblies in the condensed phases.
Type: Article
Journal: Angewandte Chemie International Edition
Volume: 62
ISSN: 1521-3773
Publication date: 17.09.2023
Publication status: Published
Peer reviewed: Yes
ASJC Scopus subject areas: Chemistry(all), Catalysis
Electronic version(s): https://doi.org/10.1002/anie.202305733 (Access: Open)
http://dx.doi.org/10.1002/anie.202305733 (Access: Unknown)

BibTeX

@article{ae534372084a4437b734acce8bdb5562,
title = "Visualizing Chiral Interactions in Carbohydrates Adsorbed on Au(111) by High‐Resolution STM Imaging",
abstract = "Carbohydrates are the most abundant organic material on Earth and the structural “material of choice” in many living systems. Nevertheless, design and engineering of synthetic carbohydrate materials presently lag behind that for protein and nucleic acids. Bottom-up engineering of carbohydrate materials demands an atomic-level understanding of their molecular structures and interactions in condensed phases. Here, high-resolution scanning tunneling microscopy (STM) is used to visualize at submolecular resolution the three-dimensional structure of cellulose oligomers assembled on Au(1111) and the interactions that drive their assembly. The STM imaging, supported by ab initio calculations, reveals the orientation of all glycosidic bonds and pyranose rings in the oligomers, as well as details of intermolecular interactions between the oligomers. By comparing the assembly of D- and L-oligomers, these interactions are shown to be enantioselective, capable of driving spontaneous enantioseparation of cellulose chains from its unnatural enantiomer and promoting the formation of engineered carbohydrate assemblies in the condensed phases.",
keywords = "Carbohydrate Materials, Chirality, Electrospray Ionization, Scanning Probe Microscopy, Self-Assembly",
author = "Johannes Seibel and Giulio Fittolani and Hossein Mirhosseini and Xu Wu and Stephan Rauschenbach and Kelvin Anggara and Seeberger, {Peter H.} and Martina Delbianco and K{\"u}hne, {Thomas D.} and Uta Schlickum and Klaus Kern",
note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",
year = "2023",
month = sep,
day = "17",
doi = "10.1002/anie.202305733",
language = "English",
volume = "62",
journal = "Angewandte Chemie International Edition",
issn = "1521-3773",
publisher = "John Wiley and Sons Ltd",
number = "39",
}