Detection of hydrogen-deuterium exchange in purines by laser-Raman spectroscopy. Adenosine 5'-monophosphate and polyriboadenylic acid

Livramento, J.; Thomas, George J.

doi:10.1021/ja00827a054

Cited by 30 publications

(11 citation statements)

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“…As in the case of adenine derivatives, the concentrations of 8-CH and 8-CD forms of the purine ring in an isotopic mixture are best measured by the intensities of the corresponding Raman lines near 1480 and 1460 cm"1, respectively (Livramento & Thomas, 1974; Thomas & Livramento, 1975). Kinetics of Exchange in S'-rGMP and cGMP.…”

Section: Resultsmentioning

confidence: 99%

Raman spectral studies of nucleic acids. 18. Kinetics of hydrogen-deuterium exchange in guanosine 5'-monophosphate and guanosine 3':5'-monophosphate determined by laser-Raman spectroscopy

Mj¹,

Gj²

1979

Biochemistry

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Pseudo-first-order rate constants governing the deuterium exchange of 8-CH groups in guanosine 5'-monophosphate (5'-rGMP) and guanosine 3':5'-monophosphate (cGMP) were determined as a function of temperature in the range 30-80 degrees C by means of laser-Raman spectroscopy. For each guanine nucleotide the logarithm of the rate constant exhibits a strictly linear dependence on reciprocal temperature: i.e., k psi = Ae-Ea/RT with A = 8.84 X 10(14) h-1 and Ea = 24.6 kcal/mol for 5'-rGMP and A = 3.33 X 10(13) h-1 and Ea = 22.2 kcal/mol for cGMP. Exchange of the 8-CH groups in guanine nucleotides is generally 2-3 times more rapid than in adenine nucleotides [cf. g. j. thomas, Jr., & J. Livramento (1975) Biochemistry 14, 5210-5218]. As in the case of adenine nucleotides, cyclic and 5' nucleotides of guanine exchange at markedly different rates at lower temperatures, with exchange in the cyclic nucleotide being the more facile. Each of the guanine nucleotides was prepared in four different isotopic modifications for Raman spectral analysis. The Raman frequency shifts resulting from the various isotopic substitutions have been tabulated, and assignments have been given for most of the observed vibrational frequencies.

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Section: Resultsmentioning

confidence: 99%

Raman spectral studies of nucleic acids. 18. Kinetics of hydrogen-deuterium exchange in guanosine 5'-monophosphate and guanosine 3':5'-monophosphate determined by laser-Raman spectroscopy

Mj¹,

Gj²

1979

Biochemistry

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“…For this purpose, advantage has been taken of the slow exchange of the C-8 hydrogen atoms of purine nucleotides (277)(278)(279)(280)(281)(282)(283). This hydrogen may be exchanged fo r solvent tritium.…”

Section: Recognition As Studied By Mutationally Altered Trnasmentioning

confidence: 99%

Aminoacyl-tRNA Synthetases: General Features and Recognition of Transfer RNAs

Schimmel¹,

Söll²

1979

Annu. Rev. Biochem.

620

271

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“…In k' =In A ' -E : / R T (1) where k' is the exchange-rate constant, A' is the temperature-independent frequency factor and E: is the Arrhenius activation energy for isotope i. The superscript i(=H or D) refers to the isotope of hydrogen being replaced at 8-C.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of hydrogen‐deuterium exchange and kinetic isotope effects in inosine‐5′‐ monophosphate and inosine‐3′5′‐ monophosphate determined by laser Raman spectroscopy

Ferreira

Thomas

1981

J Raman Spectroscopy

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The rates (kH) of deuterium exchange of 8-CH groups, as well as the rates (kD) of protium exchange of 8-CD groups in 5'-IMP and cIMP, were measured by laser Raman spectrophotometry over the temperature range 30-80'C. The k H , or 'forward' rates, were determined from exchange in D,O solutions, while the kD, or 'reverse' rates, were determined from exchange in H 2 0 solutions of the nucleotides. The hypoxanthine nucleotides were found to exchange with rates intermediate between those of corresponding adenine and guanine nucleotides, reported previously. The values obtained for the rate constants as a function of temperature (k = A exp (-E./RT)) yield the following Arrhenius activation energies and frequency factors. For 5'-IMP: E: = 25.5f0.6 kcal mol-l, AH = 2.61 x 10'5h-1; E y = 24.9f0.6 kcal mol-', AD = 4.32 x 1014h-'. For cIMP: E: = 22.2f0.6 kcal mol-', AH = 2.52 x 10"h-l; E: = 21.4f0.6 kcal mol-', AU = 3.93 x 10"h-l. The lower activation energy for cIMP accounts for its more rapid exchange vis-a-vis 5'-IMP, confirming the trend observed also for adenine and guanine nucleotides. Moreover, as in the cases of adenine and guanine isomers, the differential exchange between cyclic and 5'-nucleotides of hypoxanthine is large at lower temperatures and small at higher temperatures. These results confirm that exchange at 8-C is influenced by the ribosyl phosphate group. The present data also provide evidence of small kinetic isotope effects in the 8-C exchange reactions. For 5'-IMP, k H / k D z 2 . 5 , and for cIMP, k"/k"=: 1.7. The isotope effects of 5'-IMP and cIMP are close to the values observed for guanine nucleotides. Finally, Raman vibrational spectra of four isotopic modifications of the hypoxanthine nucleotides are compared to provide specific assignments of the Raman bands to vibrations of the purine skeleton and its exocyclic substituents. ~~ EXPERIMENTALSodium salts of 5'-IMP and cIMP were obtained from Sigma Chemical. DzO, DC1 solution and NaOD solution were obtained from Aldrich Chemical. Nucleotide solutions were prepared at 0.1 M in H 2 0 (pH 7.6) or D 2 0 (pD 8.0). p H and pD (=pH+0.4) were measured on a Beckman Expandomatic SS-2 meter with Fisher micro-

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Detection of hydrogen-deuterium exchange in purines by laser-Raman spectroscopy. Adenosine 5'-monophosphate and polyriboadenylic acid

Abstract: since generated considerable attention. In D20 solu-

Cited by 30 publications

References 0 publications

Raman spectral studies of nucleic acids. 18. Kinetics of hydrogen-deuterium exchange in guanosine 5'-monophosphate and guanosine 3':5'-monophosphate determined by laser-Raman spectroscopy

Raman spectral studies of nucleic acids. 18. Kinetics of hydrogen-deuterium exchange in guanosine 5'-monophosphate and guanosine 3':5'-monophosphate determined by laser-Raman spectroscopy

Aminoacyl-tRNA Synthetases: General Features and Recognition of Transfer RNAs

Kinetics of hydrogen‐deuterium exchange and kinetic isotope effects in inosine‐5′‐ monophosphate and inosine‐3′5′‐ monophosphate determined by laser Raman spectroscopy

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