[4R,S-2H2]-NADH | 60764-22-9

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - （5'->5'）-二核苷酸
• 英文名称: [4R,S-2H2]-NADH
• 英文别名: [4-²H₂]NADH；[[(2R,3S,4R,5R)-5-(6-aminopurin-9-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [(2R,3S,4R,5R)-5-(3-carbamoyl-4,4-dideuteriopyridin-1-yl)-3,4-dihydroxyoxolan-2-yl]methyl hydrogen phosphate
• CAS: 60764-22-9
• 化学式: C₂₁H₂₉N₇O₁₄P₂
• 分子量: 667.431
• InChiKey: BOPGDPNILDQYTO-UFTUVJRPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -5.7
• 重原子数：
  44
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  318
• 氢给体数：
  8
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  [4R,S-2H2]-NADH 在 poly(aniline)-poly(vinyl sulfonate) modified electrode 作用下， 以 various solvent(s) 为溶剂， 生成 [4-2H]-NAD(1+)
  参考文献：
  名称：

  在聚（苯胺）改性电极上氧化 NADH 的动力学同位素效应的测量

  摘要：

  使用 [4,4-2H2]NADH 和 [4-1H, 4-2H]NADH 的动力学同位素测量已被用于研究 NADH 在聚（苯胺）-聚（乙烯基磺酸盐）修饰电极上电化学氧化的机制. 实验显示了 4.2 反应的主要动力学同位素效应。这与在均相溶液中双电子氧化剂氧化 NADH 的相应同位素效应的文献值一致。结果表明，H 从 NADH 转移到修饰电极发生在反应复合物中的限速步骤中。

  DOI：

  10.1021/ja028943e
• 作为产物：
  描述：

  β-烟酰胺腺嘌呤二核苷酸 在 氢气 、 重水 、 苯乙酮 、 alcohol dehydrogenase 作用下， 以 aq. buffer 为溶剂， 反应 152.0h， 生成 [4R,S-2H2]-NADH
  参考文献：
  名称：

  Synthesis of [4 S ‐ ² H]NADH, [4 R ‐ ² H]NADH, [4‐ ² H ₂ ]NADH and [4‐ ² H]NAD ⁺ cofactors through heterogeneous biocatalysis in heavy water

  摘要：

  该操作协议描述了一系列重氢化的烟酰胺辅酶的合成： [4S-2H]NADH、[4R-2H]NADH、[4-2H2]NADH和[4-2H]NAD+。应用最近开发的H2驱动异相生物催化剂，使辅酶能够以超过90%的高重氢掺入率合成，仅使用2H2O作为同位素来源。

  DOI：

  10.1002/jlcr.3899

文献信息

• Oxidation of NADH involving rate-limiting one-electron transfer
  作者：Brian W. Carlson、Larry L. Miller、P. Neta、Jan Grodkowski

  DOI：10.1021/ja00335a062

  日期：1984.11

  Cinetique et mecanisme de l'oxydation de NADH par l'ion ferroceniumyle et quelques derives substitues de cet ion dans le propanol-1 aqueux

  Cinetique et mecanisme de l'oxydation de NADH par l'ion ferroceniumyle et quelques 衍生替代物 de cet ion dans le propanol-1 a​​queux
• Chemical formation of 4-hydroxy-2,5-dimethyl-3[2H]-furanone from d-fructose 1,6-diphosphate
  作者：Tobias Hauck、Christian Landmann、Thomas Raab、Fredi Brühlmann、Wilfried Schwab

  DOI：10.1016/s0008-6215(02)00121-0

  日期：2002.7

  The selective chemical formation of 4-hydroxy-2,5-dimethyl-3[2H]-furanone (HDF) from D-fructose 1,6-diphosphate in the presence of reduced nicotinamide-adenine-dinucleotides (NAD(P)H) was investigated by means of HPLC-DAD and HPLC-UV-MS/MS. The temperature optimum for HDF formation was 30 degreesC, whereas the pH value (pH 3-10) and chemical nature of the buffer had no significant influence. A linear correlation of reaction time and D-fructose 1,6-diphosphate concentration with the obtained HDF yield was observed. Proteins appeared to have a stabilizing effect. The NAD(P)H were mandatory, even in the presence of protein, implying a non-enzymatic hydride-transfer to an unknown intermediate which finally leads to the selective formation of HDF. The hydride-transfer was confirmed by the application of selectively pro-4R or pro-4S deuterium labeled NADH resulting in each case in the formation of HDF exhibiting a deuterium labeling of approx 30% and employment of [4R,S-H-2(2)]-NADH led to a deuterium labeling of approx 66%. The incubation of [1-C-13]-D-fructose 1,6-diphosphate with [4R,S-H-2(2)]-NADH revealed that the hydride is transferred to C-5 or C-6 of the D-fructose 1,6-diphosphate skeleton. Thus, a chemical HDF formation from D-fructose 1,6-diphosphate under physiological reaction conditions was shown and for the first time to our knowledge a non-enzymatic hydride-transfer from NADH to a carbohydrate structure was demonstrated. (C) 2002 Elsevier Science Ltd. All rights reserved.
• α-Secondary Isotope Effects as Probes of “Tunneling-Ready” Configurations in Enzymatic H-Tunneling:  Insight from Environmentally Coupled Tunneling Models
  作者：Christopher R. Pudney、Sam Hay、Michael J. Sutcliffe、Nigel S. Scrutton

  DOI：10.1021/ja0614619

  日期：2006.11.1

  Using alpha-secondary kinetic isotope effects (2 degrees KIEs) in conjunction with primary (1) KIEs, we have investigated the mechanism of environmentally coupled hydrogen tunneling in the reductive half-reactions of two homologous flavoenzymes, morphinone reductase (MR) and pentaerythritol tetranitrate reductase (PETNR). We find exalted 2 KIEs (1.17-1.18) for both enzymes, consistent with hydrogen tunneling. These 2 KIEs, unlike 1 KIEs, are independent of promoting motions-a nonequilibrium pre-organization of cofactor and active site residues that is required to bring the reactants into a "tunneling-ready" configuration. That these 2 KIEs are identical suggests the geometries of the "tunneling-ready" configurations in both enzymes are indistinguishable, despite the fact that MR, but not PETNR, has a clearly temperature-dependent 1 degrees KIE. The work emphasizes the benefit of combining studies of 1 and 2 KIEs to report on pre-organization and local geometries within the context of contemporary environmentally coupled frameworks for H-tunneling.
• Measurement of the Kinetic Isotope Effect for the Oxidation of NADH at a Poly(aniline)-Modified Electrode
  作者：Philip N. Bartlett、Evelyne Simon

  DOI：10.1021/ja028943e

  日期：2003.4.1

  measurements using [4,4-2H2]NADH and [4-1H, 4-2H]NADH have been used to investigate the mechanism of the electrochemical oxidation of NADH at poly(aniline)-poly(vinyl sulfonate)-modified electrodes. The experiments show a primary kinetic isotope effect for the reaction of 4.2. This is consistent with literature values for the corresponding isotope effect for the oxidation of NADH by two-electron oxidants

  使用 [4,4-2H2]NADH 和 [4-1H, 4-2H]NADH 的动力学同位素测量已被用于研究 NADH 在聚（苯胺）-聚（乙烯基磺酸盐）修饰电极上电化学氧化的机制. 实验显示了 4.2 反应的主要动力学同位素效应。这与在均相溶液中双电子氧化剂氧化 NADH 的相应同位素效应的文献值一致。结果表明，H 从 NADH 转移到修饰电极发生在反应复合物中的限速步骤中。
• Synthesis of [4 <i>S</i> ‐ ² H]NADH, [4 <i>R</i> ‐ ² H]NADH, [4‐ ² H ₂ ]NADH and [4‐ ² H]NAD ⁺ cofactors through heterogeneous biocatalysis in heavy water
  作者：Jack S. Rowbotham、Adam P. Hardy、Holly A. Reeve、Kylie A. Vincent

  DOI：10.1002/jlcr.3899

  日期：2021.4

  This practitioner protocol describes the synthesis of a family of deuterated nicotinamide cofactors: [4S-2H]NADH, [4R-2H]NADH, [4-2H2]NADH and [4-2H]NAD+. The application of a recently developed H2-driven heterogeneous biocatalyst enables the cofactors to be prepared with high (>90%) 2H-incorporation with 2H2O as the only isotope source.

  该操作协议描述了一系列重氢化的烟酰胺辅酶的合成： [4S-2H]NADH、[4R-2H]NADH、[4-2H2]NADH和[4-2H]NAD+。应用最近开发的H2驱动异相生物催化剂，使辅酶能够以超过90%的高重氢掺入率合成，仅使用2H2O作为同位素来源。