Abstract
The hexanucleoside pentaphosphate d(m5CpGpm5CpGpm5CpG) has been studied in solution by ultra-violet absorption, circular dichroism and 31P nuclear magnetic resonance under various experimental conditions. In 0.2 M NaClO4 at low temperature, an hexamer duplex is formed which has a B or B-like conformation. As the salt concentration is increased, a transition from a B-form to the Z-form occurs and is complete in 3 M NaClO4. In 3 M NaClO4, the behavior of the Z double helix is complex as a function of temperature. The variation of the circular dichroism at 295 nm is biphasic. A first transition occurs over a large range of temperature and corresponds to a conformational change due to a non-cooperative intramolecular process. Ultra-violet absorption and 31P nuclear magnetic resonance show that the new conformation arising from a distortion of the backbone is not similar to that observed in low salt conditions (B-form). At high hexanucleotide concentration, aggregates are formed. The second transition is cooperative and corresponds to the melting of a double stranded helix into single strands.
Full text
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Selected References
These references are in PubMed. This may not be the complete list of references from this article.
- Albergo D. D., Marky L. A., Breslauer K. J., Turner D. H. Thermodynamics of (dG--dC)3 double-helix formation in water and deuterium oxide. Biochemistry. 1981 Mar 17;20(6):1409–1413. doi: 10.1021/bi00509a001. [DOI] [PubMed] [Google Scholar]
- Arnott S., Chandrasekaran R., Birdsall D. L., Leslie A. G., Ratliff R. L. Left-handed DNA helices. Nature. 1980 Feb 21;283(5749):743–745. doi: 10.1038/283743a0. [DOI] [PubMed] [Google Scholar]
- Behe M., Felsenfeld G. Effects of methylation on a synthetic polynucleotide: the B--Z transition in poly(dG-m5dC).poly(dG-m5dC). Proc Natl Acad Sci U S A. 1981 Mar;78(3):1619–1623. doi: 10.1073/pnas.78.3.1619. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Behe M., Zimmerman S., Felsenfeld G. Changes in the helical repeat of poly(dG-m5dC) . poly(dG-m5dC) and poly(dG-dC) . poly(dG-dC) associated with the B-Z transition. Nature. 1981 Sep 17;293(5829):233–235. doi: 10.1038/293233a0. [DOI] [PubMed] [Google Scholar]
- Cheng D. M., Kan S. L., Miller P. S., Leutzinger E. E., Ts'o P. O. An effective method for the assignment of 31P-NMR resonance(s) of oligonucleotides. Biopolymers. 1982 Mar;21(3):697–701. doi: 10.1002/bip.360210315. [DOI] [PubMed] [Google Scholar]
- Drew H., Takano T., Tanaka S., Itakura K., Dickerson R. E. High-salt d(CpGpCpG), a left-handed Z' DNA double helix. Nature. 1980 Aug 7;286(5773):567–573. doi: 10.1038/286567a0. [DOI] [PubMed] [Google Scholar]
- Edelstein S. J., Schachman H. K. The simultaneous determination of partial specific volumes and molecular weights with microgram quantities. J Biol Chem. 1967 Jan 25;242(2):306–311. [PubMed] [Google Scholar]
- Eigen M., Pörschke D. Co-operative non-enzymic base recognition. I. Thermodynamics of the helix-coil transition of oligoriboadenylic acids at ACIDIC PH. J Mol Biol. 1970 Oct 14;53(1):123–141. doi: 10.1016/0022-2836(70)90049-5. [DOI] [PubMed] [Google Scholar]
- Fujii S., Wang A. H., van der Marel G., van Boom J. H., Rich A. Molecular structure of (m5 dC-dG)3: the role of the methyl group on 5-methyl cytosine in stabilizing Z-DNA. Nucleic Acids Res. 1982 Dec 11;10(23):7879–7892. doi: 10.1093/nar/10.23.7879. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Gorenstein D. G., Luxon B. A., Goldfield E. M., Lai K., Vegeais D. Phosphorus-31 nuclear magnetic resonance of double- and triple-helical nucleic acids. Phosphorus-31 chemical shifts as a probe of phosphorus-oxygen ester bond torsional angles. Biochemistry. 1982 Feb 2;21(3):580–589. doi: 10.1021/bi00532a026. [DOI] [PubMed] [Google Scholar]
- Gupta G., Bansal M., Sasisekharan V. Conformational flexibility of DNA: polymorphism and handedness. Proc Natl Acad Sci U S A. 1980 Nov;77(11):6486–6490. doi: 10.1073/pnas.77.11.6486. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Hartmann B., Pilet J., Ptak M., Ramstein J., Malfoy B., Leng M. The B reversible Z transition of poly(dI-br5dC).poly(dI-br5dC). A quantitative description of the Z form dynamic structure. Nucleic Acids Res. 1982 May 25;10(10):3261–3277. doi: 10.1093/nar/10.10.3261. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Hogan M. E., Jardetzky O. Internal motions in DNA. Proc Natl Acad Sci U S A. 1979 Dec;76(12):6341–6345. doi: 10.1073/pnas.76.12.6341. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Hogan M. E., Jardetzky O. Internal motions in deoxyribonucleic acid II. Biochemistry. 1980 Jul 22;19(15):3460–3468. doi: 10.1021/bi00556a009. [DOI] [PubMed] [Google Scholar]
- Lafer E. M., Möller A., Nordheim A., Stollar B. D., Rich A. Antibodies specific for left-handed Z-DNA. Proc Natl Acad Sci U S A. 1981 Jun;78(6):3546–3550. doi: 10.1073/pnas.78.6.3546. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Lemeunier F., Derbin C., Malfoy B., Leng M., Taillandier E. Identification of left-handed Z-DNA by indirect immunofluorescence in polytene chromosomes of Chironomus thummi thummi. Exp Cell Res. 1982 Oct;141(2):508–513. doi: 10.1016/0014-4827(82)90245-2. [DOI] [PubMed] [Google Scholar]
- Lipps H. J., Nordheim A., Lafer E. M., Ammermann D., Stollar B. D., Rich A. Antibodies against Z DNA react with the macronucleus but not the micronucleus of the hypotrichous ciliate stylonychia mytilus. Cell. 1983 Feb;32(2):435–441. doi: 10.1016/0092-8674(83)90463-4. [DOI] [PubMed] [Google Scholar]
- Malfoy B., Leng M. Antiserum to Z-DNA. FEBS Lett. 1981 Sep 14;132(1):45–48. doi: 10.1016/0014-5793(81)80424-3. [DOI] [PubMed] [Google Scholar]
- Nelson J. W., Martin F. H., Tinoco I., Jr DNA and RNA oligomer thermodynamics: the effect of mismatched bases on double-helix stability. Biopolymers. 1981 Dec;20(12):2509–2531. doi: 10.1002/bip.1981.360201204. [DOI] [PubMed] [Google Scholar]
- Nordheim A., Pardue M. L., Lafer E. M., Möller A., Stollar B. D., Rich A. Antibodies to left-handed Z-DNA bind to interband regions of Drosophila polytene chromosomes. Nature. 1981 Dec 3;294(5840):417–422. doi: 10.1038/294417a0. [DOI] [PubMed] [Google Scholar]
- Patel D. J., Kozlowski S. A., Nordheim A., Rich A. Right-handed and left-handed DNA: studies of B- and Z-DNA by using proton nuclear Overhauser effect and P NMR. Proc Natl Acad Sci U S A. 1982 Mar;79(5):1413–1417. doi: 10.1073/pnas.79.5.1413. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Patel D. J. Proton and phosphorus NMR studies of d-CpG(pCpG)n duplexes in solution. Helix-coil transition and complex formation with actinomycin-D. Biopolymers. 1976 Mar;15(3):533–558. doi: 10.1002/bip.1976.360150310. [DOI] [PubMed] [Google Scholar]
- Pilet J., Leng M. Comparison of poly(dG-dC).poly(dG-dC) conformations in oriented films and in solution. Proc Natl Acad Sci U S A. 1982 Jan;79(1):26–30. doi: 10.1073/pnas.79.1.26. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Pohl F. M., Jovin T. M. Salt-induced co-operative conformational change of a synthetic DNA: equilibrium and kinetic studies with poly (dG-dC). J Mol Biol. 1972 Jun 28;67(3):375–396. doi: 10.1016/0022-2836(72)90457-3. [DOI] [PubMed] [Google Scholar]
- Pohl F. M. Thermodynamics of the helix-coil transition of (dG-dC) oligomers. Eur J Biochem. 1974 Mar 1;42(2):495–504. doi: 10.1111/j.1432-1033.1974.tb03364.x. [DOI] [PubMed] [Google Scholar]
- Quadrifoglio F., Manzini G., Vasser M., Dinkelspiel K., Crea R. Conformational stability of alternating d (CG) oligomers in high salt solution. Nucleic Acids Res. 1981 May 11;9(9):2195–2206. doi: 10.1093/nar/9.9.2195. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Ramaswamy N., Bansal M., Gupta G., Sasisekharan V. Left-handed helices for DNA: studies on poly[d(I-C)]. Proc Natl Acad Sci U S A. 1982 Oct;79(20):6109–6113. doi: 10.1073/pnas.79.20.6109. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Ramstein J., Leng M. Salt-dependent dynamic structure of poly(dG-dC) x poly(dG-dC). Nature. 1980 Nov 27;288(5789):413–414. doi: 10.1038/288413a0. [DOI] [PubMed] [Google Scholar]
- Thamann T. J., Lord R. C., Wang A. H., Rich A. The high salt form of poly(dG-dC).poly(dG-dC) is left-handed Z-DNA: Raman spectra of crystals and solutions. Nucleic Acids Res. 1981 Oct 24;9(20):5443–5457. doi: 10.1093/nar/9.20.5443. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Thuong N. T., Chassignol M., Lancelot G., Mayer R., Hartmann B., Leng M., Hélène C. Synthesis and structural studies of a self-complementary decadeoxynucleotide d(AATTGCAATT). I.-Synthesis and chemical characterization of the decanucleotide. Biochimie. 1981 Oct;63(10):775–784. doi: 10.1016/s0300-9084(81)80037-5. [DOI] [PubMed] [Google Scholar]
- Wang A. H., Quigley G. J., Kolpak F. J., Crawford J. L., van Boom J. H., van der Marel G., Rich A. Molecular structure of a left-handed double helical DNA fragment at atomic resolution. Nature. 1979 Dec 13;282(5740):680–686. doi: 10.1038/282680a0. [DOI] [PubMed] [Google Scholar]
- Wang A. J., Quigley G. J., Kolpak F. J., van der Marel G., van Boom J. H., Rich A. Left-handed double helical DNA: variations in the backbone conformation. Science. 1981 Jan 9;211(4478):171–176. doi: 10.1126/science.7444458. [DOI] [PubMed] [Google Scholar]