Calorimetric unfolding of the bimolecular and i-motif complexes of the human telomere complementary strand, d(C3TA2)4

Mahima Kaushik, Nathan Suehl, Luis A Marky

Research output: Contribution to journalArticle

64 Citations (Scopus)

Abstract

A combination of spectroscopic and calorimetric techniques is used to determine the unfolding thermodynamics of the complexes formed by the complementary sequence of the human telomere, d(C3TA2)4, in the pH range of 4.2 to 6. Calorimetric melting curves show biphasic transitions; both transitions are shifted to higher temperatures as the pH is decreased, indicative of cytosine protonation, which favors the formation of C•C+ base pairs. Furthermore, the transition temperature, TM, of the lower transition depends on strand concentration, while the TM of the higher transition is independent of strand concentration, indicating the following sequential melting: bimolecular complex(s)→intramolecular complex→random coil. The thermodynamic profiles for the formation of each complex, bimolecular and i-motif reveals small favorable free energy terms resulting from favorable enthalpy-unfavorable entropy compensations, uptake of protons, marginal uptake of counterions (i-motif) and marginal release of water molecules (i-motif). Furthermore, an enthalpy of 3.2 kcal/mol (bimolecular complex) and 5.0 kcal/mol (i-motif) is estimated for a single C•C+/C•C+ base-pair stack.

Original languageEnglish (US)
Pages (from-to)154-164
Number of pages11
JournalBiophysical Chemistry
Volume126
Issue number1-3
DOIs
StatePublished - Mar 1 2007

Fingerprint

telomeres
Telomere
Thermodynamics
Base Pairing
strands
Freezing
Enthalpy
Melting
Transition Temperature
Protonation
Cytosine
Entropy
Free energy
Protons
enthalpy
melting
thermodynamics
Molecules
Temperature
Water

Keywords

  • DSC
  • Proton/counterion/water binding
  • Thermodynamics
  • i-Motif DNA

ASJC Scopus subject areas

  • Biophysics
  • Biochemistry
  • Organic Chemistry

Cite this

Calorimetric unfolding of the bimolecular and i-motif complexes of the human telomere complementary strand, d(C3TA2)4. / Kaushik, Mahima; Suehl, Nathan; Marky, Luis A.

In: Biophysical Chemistry, Vol. 126, No. 1-3, 01.03.2007, p. 154-164.

Research output: Contribution to journalArticle

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AB - A combination of spectroscopic and calorimetric techniques is used to determine the unfolding thermodynamics of the complexes formed by the complementary sequence of the human telomere, d(C3TA2)4, in the pH range of 4.2 to 6. Calorimetric melting curves show biphasic transitions; both transitions are shifted to higher temperatures as the pH is decreased, indicative of cytosine protonation, which favors the formation of C•C+ base pairs. Furthermore, the transition temperature, TM, of the lower transition depends on strand concentration, while the TM of the higher transition is independent of strand concentration, indicating the following sequential melting: bimolecular complex(s)→intramolecular complex→random coil. The thermodynamic profiles for the formation of each complex, bimolecular and i-motif reveals small favorable free energy terms resulting from favorable enthalpy-unfavorable entropy compensations, uptake of protons, marginal uptake of counterions (i-motif) and marginal release of water molecules (i-motif). Furthermore, an enthalpy of 3.2 kcal/mol (bimolecular complex) and 5.0 kcal/mol (i-motif) is estimated for a single C•C+/C•C+ base-pair stack.

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