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

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.     

Surface modification of polystyrene by photoinitiated introduction of cyano groups

The surface of polystyrene was modified by the introduction of CN groups. This was achieved by irradiating the polymer with UV light (254 nm) in the presence of gaseous cyanogen bromide (BrCN). X-ray photoelectron spectroscopy (XPS) and FTIR analysis showed that after irradiation both Br and CN groups were covalently bound to the polymer surface. Quantitative XPS analysis revealed that upon prolonged irradiation every second monomer unit at the surface was modified with a CN group. It was demonstrated that photochemical techniques can be employed to attach specific functional groups onto polymer surfaces.