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• W2045366909 abstract "The helix−coil transition of poly[d(I-C)] and poly[d(A-T)] was studied as a function of hydrostatic pressure, temperature, and sodium ion concentration. These studies were undertaken in light of a recently published phase diagram for double stranded nucleic acids [Dubins et al. J. Am. Chem. Soc. 2001, 123, 9254−9259]. The sign and magnitude of the volume change for the heat-induced helix−coil transition, ΔVT, of poly[d(I-C)] and poly[d(A-T)] were dependent on the helix−coil transition temperature, TM, at atmospheric pressure. The sign of ΔVT changed from negative to positive as TM was increased by increasing the sodium ion concentration. For poly[d(I-C)], ΔVT = 0 cm3 mol-1, when the sodium ion concentration is such that the spectroscopically monitored TM = 55 °C at atmospheric pressure. For poly[d(A-T)], the value of ΔVT = 0 under conditions such that TM = 47 °C at atmospheric pressure. Negative values of ΔVT imply that the helical form is destabilized at high pressure. Under experimental conditions where the ΔVT for the transition is negative, the transition could be caused by increasing the pressure under isothermal conditions. At temperatures below TM measured at atmospheric pressure the midpoint of the pressure-induced helix−coil transition, PM, decreases with increasing temperature. The volume change of the pressure-induced transitions helix−coil transition, ΔVP, was calculated assuming a two-state model. The magnitude of ΔVP (per cooperative length) was much larger than the volume change (per base pair) measured for the heat-induced transition, ΔVT, calculated using the Clapeyron equation. The ratio of these two volume changes was used to calculate the cooperative length for the pressure-induced transition. This parameter depends strongly on temperature, becoming greater closer to TM measured at atmospheric pressure. At temperatures approaching TM the magnitude of the cooperative length of the pressure-induced transition is approximately twice that observed for the heat-induced transition (NT). On the basis of the temperature dependence of the ΔVT for the two polymers the coefficient of thermal expansion of the two polymers was found to be 0.17 and 0.16 cm3 K-1 mol-1 for poly[d(I-C)] and poly[d(A-T)], respectively." @default.
• W2045366909 created "2016-06-24" @default.
• W2045366909 creator A5041182519 @default.
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• W2045366909 date "2005-07-26" @default.
• W2045366909 modified "2023-10-16" @default.
• W2045366909 title "Comparison of the Heat- and Pressure-Induced Helix−Coil Transition of Two DNA Copolymers" @default.
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• W2045366909 doi "https://doi.org/10.1021/jp050899c" @default.
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