UpG | 3474-04-2

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - （3'->5'）-二核苷酸和类似物
• 英文名称: UpG
• 英文别名: Uridylyl-(3'-5')-guanosine；[(2R,3S,4R,5R)-5-(2-amino-6-oxo-1H-purin-9-yl)-3,4-dihydroxyoxolan-2-yl]methyl [(2R,3S,4R,5R)-5-(2,4-dioxopyrimidin-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate
• CAS: 3474-04-2
• 化学式: C₁₉H₂₄N₇O₁₃P
• 分子量: 589.412
• InChiKey: BJDSHVBWORJTID-VMIOUTBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -5.4
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  290
• 氢给体数：
  8
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  UpG 在 Crotalus adamanteus snake venom phosphodiesterase I 、 三羟甲基氨基甲烷盐酸盐 、 sodium chloride 、 magnesium chloride 作用下， 反应 0.08h， 生成 尿嘧啶核苷
  参考文献：
  名称：

  对RNA酶A具有显着抗性的RNA修饰。

  摘要：

  3'-脱氧-3'-C-亚甲基膦酸酯修饰的二核糖核苷酸对脾脏磷酸二酯酶具有很高的抗性，而蛇毒磷酸二酯酶则完全不对其进行切割。最引人注目的发现是，尽管附近的2-羟基亲核试剂和5'-氧阴离子离去基团都完整无缺，但3'-亚甲基膦酸RNA修饰对RNase A的作用也具有高度抗性。

  DOI：

  10.1039/c3cc44621b
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 bismuth Hydroxide 、 水 作用下， 生成 UpG
  参考文献：
  名称：

  Dimroth; Witzel, Justus Liebigs Annalen der Chemie, 1959, vol. 620, p. 109,110,116,118

  摘要：

  DOI：

文献信息

• Guanidine-Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases
  作者：Claudia Savelli、Riccardo Salvio

  DOI：10.1002/chem.201406526

  日期：2015.4.7

  Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety

  通过原子转移自由基聚合（ATRP）制备了接枝到二氧化硅纳米颗粒表面的聚合物刷，并研究了其作为磷酸二酯裂解的催化剂。二氧化硅纳米颗粒的表面用ATRP引发剂官能化。表面引发的ATRP反应以不同的比例被苯基胍部分官能化的甲基丙烯酸酯部分和惰性的亲水性甲基丙烯酸酯物质提供了杂化的纳米颗粒，并通过电位滴定，热重分析和SEM对其进行了表征。在RNA模型化合物2-羟丙基对位酯的酯交换反应中测试了杂化纳米颗粒的活性-硝基苯基磷酸酯（HPNP）和二核糖核苷单磷酸酯。较高的催化效率和显着的有效摩尔浓度，从而克服了先前在可比系统中观察到的有效摩尔浓度，表明在胍/胍单元中存在有效的协同作用，并且在纳米结构中存在高度的预组织。所研究的系统还对二核糖核苷序列CpA表现出显着和前所未有的选择性。提出的结果为制备超分子催化剂的新颖而直接的策略开辟了道路。
• Phosphine-Free Stille-Migita Chemistry for the Mild and Orthogonal Modification of DNA and RNA
  作者：André Krause、Alexander Hertl、Fabian Muttach、Andres Jäschke

  DOI：10.1002/chem.201404843

  日期：2014.12.8

  An optimized catalyst system of [Pd2(dba)3] and AsPh3 efficiently catalyzes the Stille reaction between a diverse set of functionalized stannanes and halogenated mono‐, di‐ and oligonucleotides. The methodology allows for the facile conjugation of short and long nucleic acid molecules with moieties that are not compatible with conventional chemical or enzymatic synthesis, among them acid‐, base‐, or

  优化的[Pd 2（dba）3 ]和AsPh 3催化剂体系可有效催化各种功能化的锡烷与卤化的单，二和寡核苷酸之间的Stille反应。该方法允许将短和长核酸分子与不兼容常规化学或酶促合成的部分轻松偶联，其中酸，碱或氟化物不敏感的保护基，发荧光和难于合成的具有挑战性的部分接近定量的收益率。值得注意的是，甚至叠氮化物也可以直接引入寡核苷酸和（脱氧）核苷三磷酸中，从而直接进入“可点击的”核酸。
• Catalysis of Diribonucleoside Monophosphate Cleavage by Water Soluble Copper(II) Complexes of Calix[4]arene Based Nitrogen Ligands
  作者：Roberta Cacciapaglia、Alessandro Casnati、Luigi Mandolini、David N. Reinhoudt、Riccardo Salvio、Andrea Sartori、Rocco Ungaro

  DOI：10.1021/ja0632106

  日期：2006.9.1

  Calix[4]arenes functionalized at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with [12]ane-N-3 ligating units were synthesized, and their bi-and trimetallic zinc(II) and copper( II) complexes were investigated as catalysts in the cleavage of phosphodiesters as RNA models. The results of comparative kinetic studies using monometallic controls indicate that the subunits of all of the zinc(II) complexes and of the 1,3-distal bimetallic copper(II) complex 7-Cu-2 act as essentially independent monometallic catalysts. The lack of cooperation between metal ions in the above complexes is in marked contrast with the behavior of the 1,2-vicinal bimetallic copper(II) complex 6-Cu-2, which exhibits high catalytic efficiency and high levels of cooperation between metal ions in the cleavage of HPNP and of diribonucleoside monophosphates NpN'. A third ligated metal ion at the upper rim does not enhance the catalytic efficiency, which excludes the simultaneous cooperation in the catalysis of the three metal ions in 8-Cu-3. Rate accelerations relative to the background brought about by 6-Cu-2 and 8-Cu-3 (1.0 mM catalyst, water solution, pH 7.0, 50 degrees C) are on the order of 10(4)-fold, largely independent of the nucleobase structure, with the exception of the cleavage of diribonucleoside monophosphates in which the nucleobase N is uracil, namely UpU and UpG, for which rate enhancements rise to 10(5)-fold. The rationale for the observed selectivity is discussed in terms of deprotonation of the uracil moiety under the reaction conditions and complexation of the resulting anion with one of the copper(II) centers.
• The p<i>K</i>_a of the Internucleotidic 2‘-Hydroxyl Group in Diribonucleoside (3‘→5‘) Monophosphates
  作者：S. Acharya、A. Földesi、J. Chattopadhyaya

  DOI：10.1021/jo026545o

  日期：2003.3.1

  Ionization of the internucleotidic 2'-hydroxyl group in RNA facilitates transesterification reactions in Group I and II introns (splicing), hammerhead and hairpin ribozymes, self-cleavage in lariat-RNA, and leadzymes and tRNA processing by RNase P RNA, as well as in some RNA cleavage reactions promoted by ribonucleases. Earlier, the pK(a) of 2'-OH in mono- and diribonucleoside (3'-->5') monophosphates had been measured under various nonuniform conditions, which make their comparison difficult. This work overcomes this limitation by measuring the pK(a) values for internucleotidic 2'-OH of eight different diribonucleoside (3'-5') monophosphates under a set of uniform noninvasive conditions by H-1 NMR. Thus the pK(a) is 12.31 (+/-0.02) for ApG and 12.41 (+/-0.04) for ApA, 12.73 (+/-0.04) for GpG and 12.71 (+/-0.08) for GpA, 12.77 (+/-0.03) for CpG and 12.88 (+/-0.02) for CpA, and 12.76 (+/-0.03) for UpG and 12.70 (+/-0.03) for UpA. By comparing the pK(a)s of the respective 2'-OH of monomeric nucleoside 3'-ethyl phosphates with that of internucleotidic 2'-OH in corresponding diribonucleoside (3'-5') monophosphates, it has been confirmed that the aglycons have no significant effect on the pKa values of their 2'-OH under our measurement condition, except for the internucleotidic 2'-OH of 9-adeninyl nucleotide at the 5'-end (ApA and ApG), which is more acidic by 0.3-0.4 pK(a) units.