𝔖 Bobbio Scriptorium
✦   LIBER   ✦

On the application of polyelectrolyte “limiting laws” to the helix-coil transition of DNA. I. Excess univalent cations

✍ Scribed by Gerald S. Manning

Publisher
Wiley (John Wiley & Sons)
Year
1972
Tongue
English
Weight
758 KB
Volume
11
Category
Article
ISSN
0006-3525

No coin nor oath required. For personal study only.

✦ Synopsis

A general theory of polyelectrolyte solutions is here used to calculate the differences in Gibbs free energy, enthalpy, and entropy between the coil and helix forms of DNA a t any temperature and salt concentration. The salt has univalent cations and is assumed present in excess over the base concentration. The results are restricted to sufficiently dilute solutions. It is shown that the salt concentration effect is entirely entropic in origin. When applied to the melting temperature, the calculations yield a relation between the enthalpy difference at the melting temperature and the slope of the plot of melting temperature vs. the logarithm of the salt concentration. In accord with observation, both the Gibbs free energy difference at any fixed temperature and the melting temperature are predicted to be linear functions of the log of the salt concentration.

Data on various colligative and trailsport properties of both helix and coil forms are reviewed in the text and in Appendix B, and good agreement is found with theory for both forms. No attempt is made to explain why the theory is quantitative for these properties but not for heat measurements.

Finally, in Appendix A, an approximate calculation is made of the free energy coutributions due to ionic effects not associated with the salt concentration.

However, the theory is not in quantitative agreement with enthalpy data.

📜 SIMILAR VOLUMES

On the Application of Polyelectrolyte “L
On the Application of Polyelectrolyte “Limiting Laws” to the Helix-Coil Transition of DNA. II. The Effect of Mg++ Counterions
✍ Gerald S. Manning 📂 Article 📅 1972 🏛 Wiley (John Wiley & Sons) 🌐 English ⚖ 294 KB 👁 2 views

The techniques of the previous article are here applied to the case for which the solution contains, in addition to excess uni-univalent salt, one equivalent of divalent counterions per mole nucleotide. In agreement with the melting temperature measurements of Dove and Davidson for Mg++, it is predi

On the application of polyelectrolyte li
On the application of polyelectrolyte limiting laws to the helix–coil transition of DNA. V. Ionic effects on renaturation kinetics
✍ Gerald S. Manning 📂 Article 📅 1976 🏛 Wiley (John Wiley & Sons) 🌐 English ⚖ 682 KB

New Brunswick, New Jersey 08903 ## Synopsis The bimolecular rate constant k z for the association of complementary polynucleotide strands has been observed to increase strongly with increasing ionic strength-in fact, proportional to its third or fourth power. This effect is here interpreted quant

On the application of polyelectrolyte li
On the application of polyelectrolyte limiting laws to the helix–coil transition of DNA. III. Dependence of helix stability on excess univalent salt and on polynucleotide phosphate concentration for variable equivalent ratios of divalent metal ion to phosphate
✍ Nancy De Marky; Gerald S. Manning 📂 Article 📅 1975 🏛 Wiley (John Wiley & Sons) 🌐 English ⚖ 819 KB

## Abstract Using the free energy difference between double‐helix and random‐coil forms of DNA as a measure of the stability of the double helix, we calculate the dependence of the stability on excess univalent cation concentration and on polynucleotide phosphate concentration, both as functions of

The application of polyelectrolyte limit
The application of polyelectrolyte limiting laws to the helix–coil transition of DNA. VI. The numerical value of the axial phosphate spacing for the coil form
✍ Gerald S. Manning 📂 Article 📅 1976 🏛 Wiley (John Wiley & Sons) 🌐 English ⚖ 391 KB 👁 2 views

## Abstract It is concluded on the basis of comparison of polyelectrolyte theory with published data that the mean phosphate spacing __b__ along the contour axis of an unfolded polynucleotide single strand is in the range 3–4 Å (polyelectrolyte parameter ξ ≈ 2), regardless of temperature, base comp

Application of modified ising model to t
Application of modified ising model to the helix-coil transition of DNA molecules
✍ M. Leung; F. C. Choo; B. Y. Tong 📂 Article 📅 1977 🏛 Wiley (John Wiley & Sons) 🌐 English ⚖ 561 KB

## Abstract Equilibrium properties of heterogeneous DNA near the melting temperature __T__~__m__~ are investigated using the grand partition function. The present approach gives exact and analytical solutions. The algebraic expressions enhance a more thorough understanding of the correlation among

A semiempirical extension of polyelectro
A semiempirical extension of polyelectrolyte theory to the treatment of oligoelectrolytes: Application to oligonucleotide helix-coil transitions
✍ M. Thomas Record; Timothy M. Lohman 📂 Article 📅 1978 🏛 Wiley (John Wiley & Sons) 🌐 English ⚖ 415 KB 👁 2 views

The interaction of counterions with a suitably long, charged oligomer appears susceptible to treatment in the context of polyelectrolyte theory by the introduction of an end-effect parameter that reflects the reduced association of counterions with the terminal regions of the oligo-ion. Use of a phy