Chirality of Metal Nanoparticles in Chiral Mesoporous Silica

Chiroptical properties of pure inorganic material have been achieved by dispersing small amounts of achiral Ag nanoparticles into highly ordered chiral mesoporous silica. There are three types of chirality in chiral mesoporous silica: i) the helical hexagonal surface, ii) the helical pore orientation, and iii) the helical arrangement of aminopropyl groups on the surface of the mesopores, all of which impart plasmonic circular dichroism and have been investigated by introducing Ag nanoparticles into the as-made, calcined and extracted chiral mesoporous silica, respectively. The three types of optical response originate from asymmetric plasmon-plasmon interactions of achiral Ag nanoparticles in three types of chiral environments. Among the three sources of chirality, the helical pore orientation was considered to be predominantly responsible for the optical response owing to the high efficiency of nanoscale chirality. Interestingly, large Ag nanoparticles aggregation as a result of calcination still resulted in a strong optical activity, even the chiral mesostructure was destroyed completely. Rather than the pitch length, the length of helical channel was more effective for increasing the intensity of plasmonic circular dichroism due to longitudinal propagation of Ag nanoparticles along helical channel. Such novel chiral inorganic material will bring new opportunities in non-linear optics, biosensors and chiral recognition.