Toward understanding the effect of substitutes and solvents on entropic and enthalpic elasticity of single dendronized copolymers

Using single molecule force spectroscopy (SMFS), we have investigated the single chain elasticity of a series of dendronized copolymers, whose original backbone is styryl dendron and maleic anhydride. The amilysis reaction of maleic anhydride introduces amide and carboxyl side groups. Hence, the copolymer bears three type side groups, Fréchet type dendrons, amides and carboxyls. The single chain elasticity of the polymers in tetrahydrofuran (THF) and chloroform (CHCl₃) has been obtained, respectively. There is no hysteresis between the stretching and relaxing force curves of individual polymer chain, indicating that the elongation is carried out at the equilibrium condition. The force curves can be fitted well by the modified freely jointed chain model, which suggests that the elongation of the polymer chain is controlled by the entropic elasticity in the low-force region but dominated by enthalpic elasticity in the high-force region. The polymer with first-generation dendrons shows different elasticities in the two solvents, which should result from the different hydrogen bonds of the dendronized copolymer in two solvents. When the dendron groups are changed to be second and third generations, the single chain elasticity of the polymers is the same in two solvents. Hence, the elasticity of the polymer chain can be different depending on the properties of side groups and solvents.