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Question #44960

Difficulty: 8/10 | 🟢 Free

The Question

Consider the rare keto-enol tautomerization of the purine base Guanine (\ceG⇌G∗\ce{G \rightleftharpoons G^*}) within a deoxyribonucleotide residue in a DNA strand at 298 K298\text{ K} and physiological pH. Evaluate the following statements regarding its stereoelectronic properties and structural geometry:

I. In the enol tautomer (\ceG∗\ce{G^*}), the N1 atom transitions from a hydrogen bond donor to a hydrogen bond acceptor due to proton migration to the C6 oxygen. II. \ceG∗\ce{G^*} forms a stable mispair with Thymine (\ceT\ce{T}) because the altered hydrogen-bonding profile perfectly complements the N3-H donor and C4=O acceptor of Thymine. III. The tautomeric shift alters the dipole moment and effective pairing distance, inducing a conformational shift of the β\beta-N-glycosidic linkage towards the \textit{syn} geometry to alleviate steric hindrance with the sugar-phosphate backbone. IV. The standard Gibbs free energy change (ΔG∘\Delta G^\circ) for the \ceG⇌G∗\ce{G \rightleftharpoons G^*} transition is highly negative, which drives the spontaneous formation of Z-DNA.

Which of the given statements are correct?

Options

  • A.

    I, II, and III

  • B.

    I and II only

  • C.

    II, III, and IV

  • D.

    I, III, and IV

Check Your Answer

Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Mechanism_Trap

Don't get tricked by the process! Learn the mechanical traps used in competitive exam questions.

Concepts Behind This Question

Glycosidic Linkage Geometry|Nucleoside vs Nucleotide|Nitrogenous Base Keto-Enol Tautomerism

Why This Question Is Tricky

Common Mistakes

Students typically memorize that purines in B-DNA are strictly in the anti conformation and that tautomerization merely causes a base-pair substitution (wobble pairing) without affecting the backbone geometry.

The 'Hidden Variable' being tested is the stereochemical consequence of the tautomeric shift: the migration of the proton alters the dipole moment and the spatial requirements of the base pair.

This forces a rotation around the β\beta-N-glycosidic bond (towards the syn conformation) to relieve steric strain with the sugar-phosphate backbone while maintaining the necessary hydrogen-bonding distance for the \ceG∗\ce{G^*}-T mispair.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterBiomolecules - Class 12
ConceptGlycosidic Linkage Geometry
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree