Proton Magnetic Resonance Studies of 2′-Deoxythymidine, its 3′- and 5′-Monophosphates and 2′-Deoxythymidylyl-(3′, 5′)-2′ -deoxythymidine in Aqueous Solution

1974 ◽  
Vol 52 (19) ◽  
pp. 3353-3366 ◽  
Author(s):  
Donald J. Wood ◽  
Frank E. Hruska ◽  
Kelvin K. Ogilvie

Proton magnetic resonance studies of 2′-deoxythymidine, its 3′ and 5′-monophosphates and the dideoxynucleoside monophosphate, 2′-deoxythymidylyl-(3′,5′)-2′-deoxythymidine are described. Assignment of the spectral bands are carried out and the derived chemical shift and coupling constant data are discussed in terms of the conformational properties of these molecules. The main conclusion reached is that 3′- and 5′-phosphorylation as well as incorporation into the dinucleoside monophosphate at either the 3′- or 5′-terminus has only slight effects on the conformation of thymidine under the experimental conditions employed.

1975 ◽  
Vol 53 (18) ◽  
pp. 2781-2790 ◽  
Author(s):  
Donald J. Wood ◽  
Kelvin K. Ogilvie ◽  
Frank E. Hruska

Proton magnetic resonance studies of 2′-deoxythymidine, its 3′-and 5′-monophosphate, its 3′,5′-diphosphate, and the dimer molecules d(TpT) and d(TpTp) in aqueous solution are de scribed. Spectral analysis yields 1H–1H and 1H–31P coupling constants and 1H chemical shifts which can be discussed in terms of the conformational properties of the nucleoside fragments. An important observation is the apparent phosphate–phosphate interaction in a 3′,5′-diphosphate fragment which stabilizes the gauche-gauche conformation about the C4′—C5′ bond.


1978 ◽  
Vol 56 (4) ◽  
pp. 522-529 ◽  
Author(s):  
James Peeling ◽  
Frank E. Hruska ◽  
Peter C. Loewen

This 1Hmr study initiates our examination of the conformations of dinucleoside monophosphates possessing ribo 2′- or 3′-nucleotidyl units linked to 5′-nucleotidyl units possessing the 2′-deoxyribo sugar. The syntheses of uridylyl-3′,5′-2′-deoxythymidine (3′,5′-UpdT) and its 2′,5′-isomer, 2′,5′-UpdT, were carried out with standard techniques. The 1Hmr data were obtained at frequencies up to 270 MHz and used to derive the dominant conformation of the dimers in aqueous solution. Comparison with data for the component mononucleotides reveals that dimerization does not lead to drastic changes in the molecular conformation. Literature data for dimers possessing only the ribo sugar (3′,5′-UpU) and the 2′-deoxyribo sugar (3′,5′-d(TpT)) are also presented. The results indicate that, at least for our dipyrimidine dimers, the molecular conformation of a particular fragment is not critically dependent on the nature (ribo or 2′-deoxyribo) of the other nucleotide unit.


1984 ◽  
Vol 62 (1) ◽  
pp. 56-63 ◽  
Author(s):  
O. Desrosiers ◽  
T. Van Dinter ◽  
J. K. Saunders

The 13C chemical shift, T1 and 2H T1 data for 2-butoxyethanol (BE) in D2O as a function of concentration are presented. The nmr parameters are consistent with thermodynamic data for the same system in that it appears that 2-butoxyethanol in water undergoes a pseudo phase transition at about 1.2 M. The chemical shift for each carbon is different in the microphase relative to either aqueous solution or pure BE. The shift differences are due to a combination of factors, conformer population changes, changes in the polarity of the oxygen, and a solvent effect on chemical shift. The more organic the medium, the higher the population of trans relative to gauche conformers. The motion of BE is more restricted in the microphase than in either dilute aqueous solution or in the pure liquid. The number of adsorbed D2O molecules per molecule of BE is less in the microphase than in aqueous solution.


1978 ◽  
Vol 56 (17) ◽  
pp. 2243-2248 ◽  
Author(s):  
Donald W. Hughes ◽  
Russell A. Bell ◽  
Thomas E. England ◽  
Thomas Neilson

Proton magnetic resonance bas been used to investigate the double stranded RNA helix GAGC:GCUC, whose sequence corresponds to the duplex neck region of several tRNAs, a possible aminoacyl-tRNA synthetase recognition site. The nonexchangeable base and ribose anomeric resonances of the separate tetranucleotides were characterized by linear and predominantly upfield chemical shift changes as the temperature was decreased from 65 to 15 °C. When these strands were mixed nonlinear, sigmoidal shift changes consistent with base pairing were observed. The melting temperature of the duplex was determined to be 42 ± 1 °C which was in excellent agreement with the value obtained from optical methods. This is the first 1Hmr study of a non-self-complementary duplex prepared from synthetic tetraribonucleotides.


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