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10 The Statistical Basis of Bioenergetics
Fig. 10.4 Average helical fraction. The ‘independent’ folding model (slowly dropping line)
compared to the fully ‘cooperative’ folding model (quickly dropping line). Here, we took N = 20
helical-turn segments (72 residues), a melting temperature of 318 K, i.e. body temperature plus
8 ◦ C, and the ratio of the heat released per turn per k B T m to be 27.5
x = exp
−
H − T TS
k B T
= exp
−
Q
k B T m
T − T m
T
(10.180)
where Q is the (positive) energy released on forming the hydrogen bonds in one
helical segment.
Typical values are T m ∼ 318 K (8 ◦ C above normal body temperature) and Q ≈
0.754 eV per helical segment as a full turn (that is 0.20936 eV for each hydrogen
bond times 3.6 residues per turn).
We should expect little or no temperature dependence of S, as it depends
only on a count of the reduction in disorder as a helical segment is produced. For
high temperatures, f H approaches a small number, and for low temperatures, f H
approaches one.
The two cases, ‘independent’ and ‘cooperative’ helix formation, are shown in
Fig. 10.4, plotting the average helical fraction defined by f H /N as a function of
temperature. The cooperative case shows a strong sigmoid shape characteristic of
a sharp transition from all helical to all open as the temperature increases. This
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