sodium α,β-methyleneadenosine 5'-diphosphate

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷酸
• 英文名称: sodium α,β-methyleneadenosine 5'-diphosphate
• 英文别名: Ampcp；sodium;[[(2R,3S,4R,5R)-5-(6-aminopurin-9-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]methyl-hydroxyphosphinate
• 化学式: C₁₁H₁₅N₅O₉P₂*H*Na
• 分子量: 447.213
• InChiKey: RFGZKSPLJPHQMI-YCSZXMBFSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -5.26
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  226
• 氢给体数：
  5
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  硫酸氧钒水合物 、 sodium α,β-methyleneadenosine 5'-diphosphate 在 水 作用下， 以 水 为溶剂， 生成
  参考文献：
  名称：

  Molecular geometry of vanadyl-adenine nucleotide complexes determined by EPR, ENDOR, and molecular modeling

  摘要：

  The interactions of the vanadyl ion (VO2+) with the adenine nucleotides AMP, ADP, and ATP and the alpha,beta-methylene analogue of ADP (AMP-CP) have been investigated by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy. By spectrometric titration of VO2+ in solutions of different VO2+:nucleotide molar ratios near neutral pH, it was shown on the basis of the peak-to-peak amplitude of the -3/2 perpendicular EPR absorption feature that the stoichiometry of metal:ligand binding for ADP, AMP-CP, and ATP was 1:2. No evidence for the binding of AMP was observed. The proton ENDOR features of the -CH2- group of the terminal methylene-substituted pyrophosphate group in the VO(AMP-CP)2 complex in 50:50 aqueous-methanol yielded electron-proton distances of 4.2 and 4.9 angstrom. This observation, together with the detection of P-31 superhyperfine coupling in EPR and ENDOR spectra, established that chelation of VO2+ occurs via the phosphate groups. Analysis of proton ENDOR features of VO(ADP)2 and VO(AMP-CP)2 complexes indicated the presence of only axially coordinated solvent in the inner coordination sphere with no equatorially bound solvent. Except for the absence of the -CH2- resonance features, the proton ENDOR spectrum of VO(ADP)2 was identical with that of VO(AMP-CP)2, including resonance features assigned to the nucleoside moiety, corresponding to electron-proton separations of 5.3 and 6.0 angstrom, respectively. The metal-proton resonances of the nucleoside moiety and of the two methylene protons of AMP-CP required that the two AMP-CP or ADP molecules bind to the vanadyl ion in a 2-fold symmetric manner in equatorial positions through the alpha and beta-phosphate oxygens. Only with the ENDOR determined metal-proton distances of 5.3 and 6.0 angstrom assigned to H(8) of the guanine base and to H(5') of the ribose moiety, respectively, was a stereochemically acceptable conformation obtained by computer based torsion angle search calculations. The results of these calculations showed that (1) the orientation of the base with respect to the glycosidic C(1')-N(9) bond was anti, (2) the conformation about the C(4')-C(5') bond was gauche gauche, and (3) the conformation about the C(5')-O(5') bond was trans. In VO(ATP)2, proton ENDOR features characteristic of only axially bound water were observed, suggesting that the VO2+ was chelated via the terminal beta and gamma-phosphate groups. The EPR and ENDOR results indicate that with all three nucleotides only [VO(nucleotide)2eq(solvent)ax] species were formed.

  DOI：

  10.1021/ja00041a046

文献信息

• Molecular geometry of vanadyl-adenine nucleotide complexes determined by EPR, ENDOR, and molecular modeling
  作者：Devkumar Mustafi、Joshua Telser、Marvin W. Makinen

  DOI：10.1021/ja00041a046

  日期：1992.7

  The interactions of the vanadyl ion (VO2+) with the adenine nucleotides AMP, ADP, and ATP and the alpha,beta-methylene analogue of ADP (AMP-CP) have been investigated by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy. By spectrometric titration of VO2+ in solutions of different VO2+:nucleotide molar ratios near neutral pH, it was shown on the basis of the peak-to-peak amplitude of the -3/2 perpendicular EPR absorption feature that the stoichiometry of metal:ligand binding for ADP, AMP-CP, and ATP was 1:2. No evidence for the binding of AMP was observed. The proton ENDOR features of the -CH2- group of the terminal methylene-substituted pyrophosphate group in the VO(AMP-CP)2 complex in 50:50 aqueous-methanol yielded electron-proton distances of 4.2 and 4.9 angstrom. This observation, together with the detection of P-31 superhyperfine coupling in EPR and ENDOR spectra, established that chelation of VO2+ occurs via the phosphate groups. Analysis of proton ENDOR features of VO(ADP)2 and VO(AMP-CP)2 complexes indicated the presence of only axially coordinated solvent in the inner coordination sphere with no equatorially bound solvent. Except for the absence of the -CH2- resonance features, the proton ENDOR spectrum of VO(ADP)2 was identical with that of VO(AMP-CP)2, including resonance features assigned to the nucleoside moiety, corresponding to electron-proton separations of 5.3 and 6.0 angstrom, respectively. The metal-proton resonances of the nucleoside moiety and of the two methylene protons of AMP-CP required that the two AMP-CP or ADP molecules bind to the vanadyl ion in a 2-fold symmetric manner in equatorial positions through the alpha and beta-phosphate oxygens. Only with the ENDOR determined metal-proton distances of 5.3 and 6.0 angstrom assigned to H(8) of the guanine base and to H(5') of the ribose moiety, respectively, was a stereochemically acceptable conformation obtained by computer based torsion angle search calculations. The results of these calculations showed that (1) the orientation of the base with respect to the glycosidic C(1')-N(9) bond was anti, (2) the conformation about the C(4')-C(5') bond was gauche gauche, and (3) the conformation about the C(5')-O(5') bond was trans. In VO(ATP)2, proton ENDOR features characteristic of only axially bound water were observed, suggesting that the VO2+ was chelated via the terminal beta and gamma-phosphate groups. The EPR and ENDOR results indicate that with all three nucleotides only [VO(nucleotide)2eq(solvent)ax] species were formed.