TY - JOUR ID - pittir17221 UR - http://d-scholarship-dev.library.pitt.edu/17221/ IS - 26 A1 - Lu, M A1 - Ahmed, Z A1 - Mikhonin, AV A1 - Asher, SA Y1 - 2007/07/05/ N2 - UV resonance Raman spectroscopy has been used to determine the conformational energy landscape of polyL-lysine (PLL) in the presence of NaClO4 as a function of temperature. At 1 °C, in the presence of 0.83 M NaClO4, PLL shows an ?86% ?-helix-like content, which contains ?-helix and ?-bulge/helix conformations. The high a-helix-like content of PLL occurs because of charge screening due to strong ion-pair formation between ClO4- and the lysine side chain -NH3+. As the temperature increases from 1 to 60 °C, the ?-helix and ?-bulge/helix conformations melt into extended conformations (PPII and 2.51-helix). We calculate the ? Ramachandran angle distribution of the PLL peptide bonds from the UV Raman spectra which allows us to calculate the PLL (un)folding energy landscapes along the ? reaction coordinate. We observe a basin in the ? angle conformational space associated with ?-helix and ?-bulge/helix conformations and another basin for the extended PPII and 2.5 1-helical conformations. © 2007 American Chemical Society. JF - Journal of Physical Chemistry B VL - 111 SN - 1520-6106 TI - UV resonance raman measurements of poly-L-lysine's conformational energy landscapes: Dependence on perchlorate concentration and temperature SP - 7675 AV - public EP - 7680 ER -