p-nitrophenyl O-β-D-galactopyranosyl-(1->4)-β-D-xylopyranoside | 144683-70-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-nitrophenyl O-β-D-galactopyranosyl-(1->4)-β-D-xylopyranoside
• 英文别名: 4-nitrophenyl β-D-galactopyranosyl-(1->4)-β-D-xylopyranoside；4-nitrophenyl β-D-galactopyranosyl-(1→4)-β-D-xylopyranoside；Gal(b1-4)Xyl(b)-O-Ph(4-NO2)；(2S,3R,4S,5R,6R)-2-[(3R,4R,5R,6S)-4,5-dihydroxy-6-(4-nitrophenoxy)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
• CAS: 144683-70-5
• 化学式: C₁₇H₂₃NO₁₂
• 分子量: 433.369
• InChiKey: OLWXILKRYIFKNV-FQXYRLNWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  204
• 氢给体数：
  6
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  p-nitrophenyl O-β-D-galactopyranosyl-(1->4)-β-D-xylopyranoside 在 β-D-galactosidase (EC 3.2.1.23; E. coli) 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 p-nitrophenyl O-β-D-galactopyranosyl-(1->3)-O-(6-O-acetyl-β-D-galactopyranosyl)-(1->4)-β-D-xylopyranoside
  参考文献：
  名称：

  利用β-d-化学合成Gal（β1-3）Gal（β1-4）Xyl（β）-1-Ser和Gal（β1-3）Gal（β1-4）Xyl（β）-MU半乳糖苷酶

  摘要：

  通过三糖对硝基苯基（PNP）糖苷合成蛋白质，该蛋白构成糖胺聚糖和蛋白聚糖中蛋白质之间的连接区域的标题三糖-丝氨酸缀合物1，该三糖对硝基苯基（PNP）糖苷是用β-d-半乳糖苷酶逐步酶促糖基化为Xyl-PNP制备的。在第二个糖基转移步骤中，对二糖中间体Gal-Xyl-PNP的部分保护提供了在3'-位的选择性半乳糖基化。过乙酰化后，PNP基团的裂解，与丝氨酸的化学偶联和最终的脱保护得到1。荧光标记的三糖，Gal（β1-3）Gal（β1-4）Xyl（β）-MU（MU：4-methylumbelliferyl）（2）也以类似的方式合成。

  DOI：

  10.1016/s0040-4039(96)01462-1
• 作为产物：
  描述：

  1-bromo-2,3,4,6-tetra-O-acetyl-D-galactopyranose 在 phosphate buffer 、 β-galactosidase from E. coli 、 sodium methylate 、 silver fluoride 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 24.0h， 生成 p-nitrophenyl O-β-D-galactopyranosyl-(1->4)-β-D-xylopyranoside
  参考文献：
  名称：

  Chemoenzymatic Synthesis of a Trisaccharide–Serine Conjugate, Gal(β1-3)Gal(β1-4)Xyl(β1-O)–L-Ser, Use of Galactosyl Fluoride as a Donor for Transglycosylation

  摘要：

  三糖-丝氨酸偶联物[Gal(β1-3)Gal(β1-4)Xyl(β)-Ser]，构成蛋白聚糖中糖胺聚糖与蛋白质之间的连接区域，是通过使用β-D-半乳糖苷酶作为关键反应的酶促转糖苷作用合成的。与传统的对硝基苯(PNP)半乳糖苷作为供体相比，使用半乳糖氟化物作为供体显著提高了转糖苷作用的产量。在酶促合成了Gal(β1-3)Gal(β1-4)Xyl(β)-PNP后，完全乙酰化的三糖的PNP基团的裂解，与丝氨酸的化学偶联，以及最终的去保护作用，得到了Gal(β1-3)Gal(β1-4)Xyl(β)-Ser。

  DOI：

  10.1246/bcsj.74.1123

文献信息

• Glycosynthase with Broad Substrate Specificity - an Efficient Biocatalyst for the Construction of Oligosaccharide Library
  作者：Jinhua Wei、Xun Lv、Yang Lü、Gangzhu Yang、Lifeng Fu、Liu Yang、Jianjun Wang、Jianhui Gao、Shuihong Cheng、Qian Duan、Cheng Jin、Xuebing Li

  DOI：10.1002/ejoc.201201507

  日期：2013.4

  A versatile glycosynthase (TnG-E338A) with strikingly broad substrate scope has been developed from Thermus nonproteolyticus β-glycosidase (TnG) by using site-directed mutagenesis. The practical utility of this biocatalyst has been demonstrated by the facile generation of a small library containing various oligosaccharides and a steroidal glycoside (total 25 compounds) in up to 100 % isolated yield

  通过使用定点诱变从非蛋白水解栖热菌 β-糖苷酶 (TnG) 中开发出一种多功能糖合酶 (TnG-E338A)，其底物范围非常广泛。这种生物催化剂的实际效用已通过以高达 100% 的分离产率轻松生成包含各种寡糖和甾体糖苷（总共 25 种化合物）的小型文库得到证明。此外，该酶在一锅平行反应中很容易合成了一系列八种低聚糖，这突出了其在碳水化合物库的组合构建中的潜力，这将有助于糖组学和糖治疗研究。值得注意的是，该酶提供了一种可以将糖合酶技术扩展到组合化学的方法。
• Synthesis and evaluation of xylopyranoside derivatives as “decoy acceptors” of human β-1,4-galactosyltransferase 7
  作者：Juan Francisco García-García、Guillermo Corrales、Josefina Casas、Alfonso Fernández-Mayoralas、Eduardo García-Junceda

  DOI：10.1039/c0mb00206b

  日期：——

  Proteoglycans (PGs), including heparan sulfate forms, are important regulators of tumor progression. In the PGs biosynthetic process, the core protein is synthesized on a ribosomal template and the sugar chains are assembled post-translationally, one sugar at a time, starting with the linkage of xylose to a serine residue of the core protein and followed by galactosidation of the xylosylprotein. Hydrophobic xylopyranosides have been previously shown to prime heparan sulfate synthesis, a property that was required to cause growth inhibition of tumor cells. To know if the antiproliferative activity of synthetic xylopyranosides is related to their ability to act as “decoy acceptors” of xylosylprotein 4-β-galactosyltransferase, we have heterologously expressed the catalytic domain of the human β-1,4-GalT 7 and studied the ability of a variety of synthetic xylopyranoside derivatives to act as substrates or inhibitors of the recombinant enzyme.

  包括硫酸乙酰肝素在内的蛋白聚糖（PGs）是肿瘤进展的重要调控因子。在PGs的生物合成过程中，核心蛋白在核糖体模板上合成，糖链则是翻译后逐个糖基化组装而成，起始于木糖与核心蛋白丝氨酸残基的连接，随后是木糖蛋白的半乳糖基化。此前研究表明，疏水的木糖吡喃糖苷能启动硫酸乙酰肝素的合成，这一特性对于诱导肿瘤细胞生长抑制是必需的。为了了解合成木糖吡喃糖苷的抗增殖活性是否与其作为木糖蛋白4-β-半乳糖基转移酶的“诱饵受体”的能力有关，我们异源表达了人β-1,4-半乳糖基转移酶7的催化结构域，并研究了多种合成木糖吡喃糖苷衍生物作为重组酶底物或抑制剂的能力。
• Acceptor-dependent regioselectivity of glycosynthase reactions by Streptomyces E383A β-glucosidase
  作者：Magda Faijes、Marc Saura-Valls、Xavi Pérez、Marta Conti、Antoni Planas

  DOI：10.1016/j.carres.2006.04.049

  日期：2006.9

  The normucleophilic mutant E383A beta-glucosidase from Streptomyces sp. has proven to be an efficient glycosynthase enzyme, catalyzing the condensation of alpha-glucosyl and alpha-galactosyl fluoride donors to a variety of acceptors. The enzyme has maximal activity at 45 degrees C, and a pH-dependence reflecting general base catalysis with an apparent kinetic pK(a) of 7.2. The regioselectivity of the new glycosidic linkage depends unexpectedly on the acceptor substrate. With aryl monosaccharide acceptors, beta-(1 -> 3) disaccharides are obtained in good to excellent yields, thus expanding the synthetic products available with current exo-glycosynthases. With xylopyranosyl acceptor, regioselectivity is poorer and results in the formation of a mixture of beta-(1 -> 3) and beta-(1 -> 4) linkages. In contrast, disaccharide acceptors produce exclusively beta-(1 -> 4) linkages. Therefore, the presence of a glycosyl unit in subsite +II redirects regioselectivity from beta-(1 -> 3) to beta-(1 -> 4). To improve operational performance, the E383A mutant was immobilized on a Ni(2+)-chelating Sepharose resin. Immobilization did not increase stability to pH and organic solvents, but the operational stability and storage stability were clearly enhanced for recycling and scaling-up. (c) 2006 Elsevier Ltd. All rights reserved.
• Nitropyridyl glycosides: new glycosyl donors for enzymatic transglycosylation
  作者：Takashi Yasukochi、Chikako Inaba、Koichi Fukase、Shoichi Kusumoto

  DOI：10.1016/s0040-4039(99)01279-4

  日期：1999.9

  New glycosyl donors, 3-nitro-2-pyridyl and 5-nitro-2-pyridyl glycosides, proved to be effective for transglycosylation reaction catalyzed by glycosidases, such as beta-galactosidase, B-glucosidase, and N-acetyl-beta-hexosaminidase. The high solubility in water and the high reactivity of the nitropyridyl glycosides enabled the reactions under high concentrations of the donors and consequently rapid glycosyl transfer to glycosyl accepters. The yields of the transglycosylated products with the nitropyridyl glycosides were much higher than those with conventional p-nitrophenyl glycosides. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Enzymic .beta.-Galactosidation of Modified Monosaccharides: Study of the Enzyme Selectivity for the Acceptor and Its Application to the Synthesis of Disaccharides
  作者：Rosa Lopez、Alfonso Fernandez-Mayoralas

  DOI：10.1021/jo00083a013

  日期：1994.2

  The selectivity of the E. coli beta-galactosidase-catalyzed glycosylation of monosaccharides differently substituted at the anomeric position has been studied. Substituents bearing a phenyl ring increase the enzyme-acceptor binding; however, partial enzyme inhibition occurs. The regioselectivity of the glycosylation was dependent on small variations in the monosaccharide accceptor, such as the atom linked to the anomeric carbon and the number of methylenes between this atom and aromatic ring. A schematic model is proposed that accounts for the results. The information from this study allows the direct synthesis of disaccharides, with high regioselectivity and yields ranging from 30 to 40%.