화학공학소재연구정보센터
Macromolecules, Vol.36, No.15, 5863-5872, 2003
Effect of intrachain mismatch on loop-to-coil transition of an associating chain
The conformation of a telechelic chain, such as ssDNA with complementary bases at both ends, fluctuates from loop (closed) to coil (open) state. The transition between open and closed states can be successfully described by the two-state model. However, the mismatch between one end with complementary bases in the central region along the chain complicates the transition. We investigate the kinetics of conformational fluctuations for an associating polymer of chain length N with an attractive site at both ends (a and) and another attractive site in the midpoint (gamma) by Monte Carlo simulations. The binding energy of alpha with beta and gamma is -is an element of(1) and -is an element of(2), respectively. The probability of the coil state, which varies with temperature and corresponds to the melting curve in experiments, is obtained. A three-state model including open (o), closed (c), and mismatch (m) states is proposed and agrees quite well with the simulation results. It is interesting that direct transition between mismatch and closed states is observed significantly at low enough temperature. The rate constants k(ij) from i to j state are determined as well. k(o),(m), k(o),(c), and k(m),(c) are found to be independent of temperature but proportional to N-2. On the contrary, k(m),(n), k(o),(c), and k(o),(c), are independent of chain length but proportional to e(-is an element of2/kBT) and e(-is an element of1/kBT), respectively. Nevertheless, the transition from closed to mismatch states k(c),(m), follows N-2 e(-(is an element of1-is an element of2)kBT). For a long enough chain with is an element of(1) > is an element of(2), the two-state model is adequate since the mismatch state becomes insignificant.