2,4-dinitrophenyl β-D-glucopyranosyl-(1-4)-β-D-glucopyranosyl-(1-3)-β-D-glucopyranoside | 212392-00-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4-dinitrophenyl β-D-glucopyranosyl-(1-4)-β-D-glucopyranosyl-(1-3)-β-D-glucopyranoside
• 英文别名: 2,4-dinitrophenyl 3-O-β-cellobiosyl-β-D-glucopyranoside；Glc4βGlcβ3GlcβDNP；(2S,3R,4S,5S,6R)-2-[(2R,3S,4R,5R,6S)-6-[(2S,3R,4S,5R,6R)-2-(2,4-dinitrophenoxy)-3,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
• CAS: 212392-00-2
• 化学式: C₂₄H₃₄N₂O₂₀
• 分子量: 670.535
• InChiKey: HUCPYPLOLCVYBI-DLLNSMGHSA-N

物化性质

• 沸点：
  1031.8±65.0 °C(Predicted)
• 密度：
  1.82±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -4.3
• 重原子数：
  46
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  349
• 氢给体数：
  10
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  2,4-dinitrophenyl β-D-glucopyranosyl-(1-4)-β-D-glucopyranosyl-(1-3)-β-D-glucopyranoside 在 sodium azide 、 Bacillus licheniformis 1,3-1,4-β-glucanase mutant E134D 、 calcium chloride 作用下， 以 aq. phosphate buffer 为溶剂， 生成
  参考文献：
  名称：

  在保留的糖苷酶中，由催化亲核试剂通过Glu取代Asp的过渡水解酶转变为糖合酶突变体。

  摘要：

  已经开发了来自16个以上糖苷酶家族的糖苷合酶，用于有效合成寡糖和糖缀合物。使用衍生自地衣芽孢杆菌β-1,3-1,4-葡聚糖酶的糖合酶可以定量获得具有确定序列的β-1,3-1,4-葡聚糖寡糖和多糖。对该酶的亲核亲和力饱和文库的筛选产生了出乎意料的E134D突变体，该突变体具有较高的糖合酶效率（比迄今为止最好的糖合酶E134S高25％的kcat），但还保留了一些水解酶活性（相对于野生型酶为2％） ）。在这里，我们报告了该突变体与E134S和野生型酶相比的生化和结构分析。E134D显示了一般碱催化糖合酶活性的pH曲线，分配给Glu138的动力学pKa（在kcat / KM上）为5.8，而相同的残基以相同的pKa值作为水解酶活性中的一般酸。wt酶中Glu138的pKa为7.0，由于催化亲核试剂Glu134的存在而使plu的共轭碱基不稳定，因此pKa值很高。因此，相对于野生型酶，Glu138的pKa在突变体中下降了1

  DOI：

  10.1016/j.carres.2014.02.003
• 作为产物：
  描述：

  2,4-dinitrophenyl (2,3,4,6-tetra-O-acetyl-β-D-glucoyranosyl)-(1-4)-(2,3,6-tri-O-acetyl-β-D-glucopyranosyl)-(1-3)-2,4,6-tri-O-acetyl-β-D-glucopyranoside 在 甲醇 、 sodium methylate 作用下， 生成 2,4-dinitrophenyl β-D-glucopyranosyl-(1-4)-β-D-glucopyranosyl-(1-3)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of aryl 3-O-β-cellobiosyl-β-d-glucopyranosides for reactivity studies of 1,3-1,4-β-glucanases

  摘要：

  A series of substituted aryl beta-glycosides derived from 3-O-beta-cellobiosyl-D-glucopyranose with different phenol-leaving group abilities as measured by the pK(a) of the free phenol group upon enzymatic hydrolysis has been synthesised. Aryl beta-glycosides with a pK(a) of the free phenol leaving group > 5 were prepared by phase-transfer glycosidation of the per-O-acetylated alpha-glycosyl bromide with the corresponding phenol, whereas the 2,4-dinitrophenyl beta-glycoside was obtained by condensation of 1-fluoro-2,4-dinitrobenzene with the partially acetylated trisaccharide followed by acid de-O-acetylation. The aryl beta-glycosides have been used for reactivity studies of the wild-type Bacillus licheniformis 1,3-1,4-beta-D-glucan 4-glucanohydrolase. The Hammett plot log k(cat) versus pK(a) is biphasic with an upward curvature at low pK(a) values suggesting a change in transition-state structure depending on the aglycon. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00175-x

文献信息

• Synthesis of aryl 3-O-β-cellobiosyl-β-d-glucopyranosides for reactivity studies of 1,3-1,4-β-glucanases
  作者：Antoni Planas、Mireia Abel、Óscar Millet、Josep Palasi、Cristina Pallarés、Josep-Lluı́s Viladot

  DOI：10.1016/s0008-6215(98)00175-x

  日期：1998.8

  A series of substituted aryl beta-glycosides derived from 3-O-beta-cellobiosyl-D-glucopyranose with different phenol-leaving group abilities as measured by the pK(a) of the free phenol group upon enzymatic hydrolysis has been synthesised. Aryl beta-glycosides with a pK(a) of the free phenol leaving group > 5 were prepared by phase-transfer glycosidation of the per-O-acetylated alpha-glycosyl bromide with the corresponding phenol, whereas the 2,4-dinitrophenyl beta-glycoside was obtained by condensation of 1-fluoro-2,4-dinitrobenzene with the partially acetylated trisaccharide followed by acid de-O-acetylation. The aryl beta-glycosides have been used for reactivity studies of the wild-type Bacillus licheniformis 1,3-1,4-beta-D-glucan 4-glucanohydrolase. The Hammett plot log k(cat) versus pK(a) is biphasic with an upward curvature at low pK(a) values suggesting a change in transition-state structure depending on the aglycon. (C) 1998 Elsevier Science Ltd. All rights reserved.
• A transitional hydrolase to glycosynthase mutant by Glu to Asp substitution at the catalytic nucleophile in a retaining glycosidase
  作者：Hugo Aragunde、Estela Castilla、Xevi Biarnés、Magda Faijes、Antoni Planas

  DOI：10.1016/j.carres.2014.02.003

  日期：2014.5

  unexpected E134D mutant which has high glycosynthase efficiency (25% higher kcat than the best glycosynthase to date, E134S) but also retains some hydrolase activity (2% relative to the wild-type enzyme). Here, we report the biochemical and structural analyses of this mutant compared to E134S and wild-type enzymes. E134D shows a pH profile of general base catalysis for the glycosynthase activity, with

  已经开发了来自16个以上糖苷酶家族的糖苷合酶，用于有效合成寡糖和糖缀合物。使用衍生自地衣芽孢杆菌β-1,3-1,4-葡聚糖酶的糖合酶可以定量获得具有确定序列的β-1,3-1,4-葡聚糖寡糖和多糖。对该酶的亲核亲和力饱和文库的筛选产生了出乎意料的E134D突变体，该突变体具有较高的糖合酶效率（比迄今为止最好的糖合酶E134S高25％的kcat），但还保留了一些水解酶活性（相对于野生型酶为2％） ）。在这里，我们报告了该突变体与E134S和野生型酶相比的生化和结构分析。E134D显示了一般碱催化糖合酶活性的pH曲线，分配给Glu138的动力学pKa（在kcat / KM上）为5.8，而相同的残基以相同的pKa值作为水解酶活性中的一般酸。wt酶中Glu138的pKa为7.0，由于催化亲核试剂Glu134的存在而使plu的共轭碱基不稳定，因此pKa值很高。因此，相对于野生型酶，Glu138的pKa在突变体中下降了1