| Insight into the CSA tensors of nucleobase carbons in RNA polynucleotides from solution measurements of residual CSA: towards new long-range orientational constraints. | |
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MedLine Citation:
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PMID: 16431143 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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Using residual chemical shift anisotropies (RCSAs) measured in a weakly aligned stem-loop RNA, we examined the carbon chemical shift anisotropy (CSA) tensors of nucleobase adenine C2, pyrimidine C5 and C6, and purine C8. The differences between the measured RCSAs and the values back-calculated using three nucleobase carbon CSA sets [D. Stueber, D.M. Grant, 13C and 15N chemical shift tensors in adenosine, guanosine dihydrate, 2'-deoxythymidine, and cytidine, J. Am. Chem. Soc. 124 (2002) 10539-10551; D. Sitkoff, D.A. Case, Theories of chemical shift anisotropies in proteins and nucleic acids, Prog. NMR Spectrosc. 32 (1998) 165-190; R. Fiala, J. Czernek, V. Sklenar, Transverse relaxation optimized triple-resonance NMR experiments for nucleic acids, J. Biomol. NMR 16 (2000) 291-302] reported previously for mononucleotides (1.4 Hz) is significantly smaller than the predicted RCSA range (-10-10 Hz) but remains larger than the RCSA measurement uncertainty (0.8 Hz). Fitting of the traceless principal CSA values to the measured RCSAs using a grid search procedure yields a cytosine C5 CSA magnitude (CSAa=(3/2.(delta11(2)+delta22(2)+delta33(2)))1/2=173+/-21 ppm), which is significantly higher than the reported mononucleotide values (131-138 ppm) and a guanine C8 CSAa (148+/-13 ppm) that is in very good agreement with the mononucleotide value reported by solid-state NMR [134 ppm, D. Stueber, D.M. Grant, 13C and (15)N chemical shift tensors in adenosine, guanosine dihydrate, 2'-deoxythymidine, and cytidine, J. Am. Chem. Soc. 124 (2002) 10539-10551]. Owing to a unique sensitivity to directions normal to the base plane, the RCSAs can be translated into useful long-range orientational constraints for RNA structure determination even after allowing for substantial uncertainty in the nucleobase carbon CSA tensors. |
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Authors:
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Alexandar L Hansen; Hashim M Al-Hashimi |
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Publication Detail:
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Type: Journal Article; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't Date: 2006-01-23 |
Journal Detail:
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Title: Journal of magnetic resonance (San Diego, Calif. : 1997) Volume: 179 ISSN: 1090-7807 ISO Abbreviation: J. Magn. Reson. Publication Date: 2006 Apr |
Date Detail:
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Created Date: 2006-04-03 Completed Date: 2006-06-08 Revised Date: 2007-11-14 |
Medline Journal Info:
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Nlm Unique ID: 9707935 Medline TA: J Magn Reson Country: United States |
Other Details:
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Languages: eng Pagination: 299-307 Citation Subset: IM |
Affiliation:
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Department of Chemistry and Biophysics Research Division, The University of Michigan, Ann Arbor, MI 48109, USA. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Adenine
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chemistry Anisotropy Carbon Isotopes Molecular Conformation Molecular Structure Nitrogen Isotopes Nuclear Magnetic Resonance, Biomolecular / methods* Polynucleotides / chemistry* Purines / chemistry Pyrimidines / chemistry RNA / chemistry* Solutions |
| Grant Support | |
ID/Acronym/Agency:
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R01 AI066975-01/AI/NIAID NIH HHS |
| Chemical | |
Reg. No./Substance:
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0/Carbon Isotopes; 0/Nitrogen Isotopes; 0/Polynucleotides; 0/Purines; 0/Pyrimidines; 0/Solutions; 120-73-0/purine; 289-95-2/pyrimidine; 63231-63-0/RNA; 73-24-5/Adenine |
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