Ab initio SCF molecular orbital calculations have been performed to ascertain the conformational preferences of protonated, neutral, and deprotonated amidine [HC(=NH)NHz], using the 3-21G split valence basis set. The states of eight stable species, eight transition states, and four higher-order sadd
Studies on the conformation of protonated DNA
✍ Scribed by Ch. Zimmer; G. Luck; H. Venner; J. Frič
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1968
- Tongue
- English
- Weight
- 598 KB
- Volume
- 6
- Category
- Article
- ISSN
- 0006-3525
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✦ Synopsis
Synopsis
Experiments were made to demonstrate the predominant protonation effects and structural changes of the ordered double helical DNA structure and denatured state of DNA. Spectrophotometric titrations performed a t different wavelengths indicate that cytosine can be protonated in the DNA double helical molecule to a high extent without breakdown of the secondary structure. With DKA heat-denatured under severe conditions the protonation of cytosine can be measured a t 280, 295, and 300 mp: the apparent pK value obtained was -4.6.
The protonated double helical conformation of the IINA molecule differs from the unprotonated state, which follows from the decrease of the thermal stability and from r.hanges in the ORD curves. The ORD of a GC-rich DNA indicates 3 novel Cotton efYect with positive rotations a t -260 mp in 0.02144 KCl below pH 4.0 to pH 3.3. The occurrence of the new peak parallels the extent of protonated cytosine measured by the spectrophotometric titrations. It is concluded that the protonated cytosine in the double helical structure is responsible for the difference bet,ween the protonated DKA conformation and the native state a t neutral pH.
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