Hydrogen bonding dominated self-assembly mechanism of amphiphilic molecules in Chinese Baijiu

Molecular mechanisms underlying the aging of Chinese Baijiu remained elusive. This study proposed the self-assembly behavior of amphiphilic molecules dominated by hydrogen bonds in Chinese Baijiu for the first time. The self-assembly degree of amphiphilic clusters gradually intensifies with the prolonged storage time of Baijiu, comprehensively characterized at both micro and macro levels. The results indicated that the blue-shift of the Raman hydrogen bond vibrational peak (about 11 cm^-1 and 7 cm^-1, respectively), the increase in viscosity (5.71% and 2.22%, respectively), and the rise in dielectric constant (95.63% and 94.99%, respectively) during the 17-year cellaring process of Strong-flavor Baijiu and Jiang-flavor Baijiu were consistent with the evolutionary trends observed in molecular dynamics simulations. The essential driving factors of cluster structure alteration of amphiphilic aroma substances in Chinese Baijiu during cellaring were demonstrated from molecular level. This study provided a research approach to comprehending the aging mechanism of Chinese Baijiu from the micro level.