- Differential scanning calorimetric study of calf thymus DNA was carried out to measure midpoint of thermal denaturation (Tm). ΔHm (enthalpy change at Tm) and ΔCP (constant-pressure heat capacity change). It has been observed that ΔCP =O, Tm =75.50C and ΔHm=50.4
kcal/mole. The Gibbs free energy change at 370C is
(1) 25.5 kcal/mole (2) 2.6 kcal/mole
(3) 0.6 kcal/mole (4) 5.6 kcal/mole
Introduction
Differential scanning calorimetry (DSC) provides key thermodynamic parameters to characterize DNA thermal denaturation, including:
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Tm: Midpoint temperature of denaturation (°C or K)
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ΔHm: Enthalpy change at Tm (kcal/mole)
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ΔCp: Heat capacity change at constant pressure (kcal/mol·K)
Given these values, the Gibbs free energy change (ΔG) at any temperature T can be estimated using thermodynamic equations derived from the Gibbs-Helmholtz relation.
Given Data
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Tm = 75.5°C = 348.65 K
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ΔHm = 50.4 kcal/mole
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ΔCp = 0 (given)
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Temperature of interest: 37°C = 310 K
Thermodynamic Background
The Gibbs free energy change for DNA denaturation at temperature T (in Kelvin) can be approximated by:
ΔGD(T)=ΔHm(1−TTm)−ΔCp[(Tm−T)−TlnTmT]
Since ΔCp = 0, the equation simplifies to:
ΔGD(T)=ΔHm(1−TTm)
Calculation Steps
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Convert temperatures to Kelvin:
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Tm=75.5+273.15=348.65 K
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T=37+273.15=310.15 K
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Calculate the ratio TTm:
310.15348.65≈0.889
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Calculate 1−TTm:
1−0.889=0.111
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Calculate ΔG at 37°C:
ΔGD(310 K)=50.4 kcal/mol×0.111=5.6 kcal/mol
Interpretation
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A positive ΔG indicates that at 37°C, the DNA is predominantly in the double-stranded (folded) state, as denaturation is not spontaneous at this temperature.
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The calculated ΔG of approximately 5.6 kcal/mol aligns with typical DNA stability values near physiological temperature.
Summary Table of Options
Option ΔG (kcal/mole) Match with Calculation? (1) 25.5 No (2) 2.6 No (3) 0.6 No (4) 5.6 Yes
Conclusion
Using the given DSC parameters and the simplified Gibbs-Helmholtz equation (with ΔCp = 0), the Gibbs free energy change for calf thymus DNA denaturation at 37°C is approximately 5.6 kcal/mole.
Keywords
Gibbs free energy DNA, DNA thermal denaturation, differential scanning calorimetry, ΔHm, Tm, ΔCp, Gibbs-Helmholtz equation, calf thymus DNA stability, DNA melting temperature, DNA folding thermodynamics
Final answer:
(4) 5.6 kcal/mole -