C–H Stretch for Probing Kinetics of Self-Assembly into Macromolecular Chiral Structures at Interfaces by Chiral Sum Frequency Generation Spectroscopy

2013-03-26T00:00:00Z (GMT) by Zhuguang Wang Li Fu Elsa C. Y. Yan
Self-assembly of molecules into chiral macromolecular and supramolecular structures at interfaces is important in various fields, such as biomedicine, polymer sciences, material sciences, and supramolecular chemistry. However, probing the kinetics at interfaces remains challenging because it requires a real-time method that has selectivity to both interface and chirality. Here, we introduce an <i>in situ</i> approach of using the C–H stretch as a vibrational probe detected by chiral sum frequency generation spectroscopy (cSFG). We showed that the C–H stretch cSFG signals of an amphiphilic peptide (LK<sub>7</sub>β) can reveal the kinetics of its self-assembly into chiral β-sheet structures at the air–water interface. The cSFG experiments in conjunction with measurements of surface pressure allow us to propose a mechanism of the self-assembly process, which involves an immediate adsorption of disordered structures followed by a lag phase before the self-assembly into chiral antiparallel β-sheet structures. Our method of using the C–H stretch signals implies a general application of cSFG to study the self-assembly of bioactive, simple organic, and polymeric molecules into chiral macromolecular and supramolecular structures at interfaces, which will be useful in tackling problems, such as protein aggregation, rational design of functional materials, and fabrication of molecular devices.