β-D-Gal-(1->3)-β-D-Glc-OC6H4NO2-p

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: β-D-Gal-(1->3)-β-D-Glc-OC6H4NO2-p
• 英文别名: 4-nitrophenyl β-D-galactopyranosyl-(1→3)-β-D-glucopyranoside；4-nitrophenyl β-D-galactopyranosyl-(1->3)-β-D-glucopyranoside；Gal(b1-3)Glc(b)-O-Ph(4-NO2)；(2S,3R,4S,5R,6R)-2-[(2R,3R,4S,5R,6S)-3,5-dihydroxy-2-(hydroxymethyl)-6-(4-nitrophenoxy)oxan-4-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
• 化学式: C₁₈H₂₅NO₁₃
• 分子量: 463.395
• InChiKey: LBTDRWMZFQVCAR-GSCNJGCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  224
• 氢给体数：
  7
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  cytidine-5'-monophospho-β-D-N-acetylneuraminic acid, disodium salt 、 β-D-Gal-(1->3)-β-D-Glc-OC6H4NO2-p 在 recombinant rat α-(2->3)-N-sialyltransferase 、 alkaline phosphatase 作用下， 以 various solvent(s) 为溶剂， 反应 1.5h， 生成 α-D-Neu5Ac-(2->3)-β-D-Gal-(1->3)-β-D-Glc-OC6H4NO2-p
  参考文献：
  名称：

  唾液酸N-乙酰基乳糖胺，唾液酸Lex和相关化合物的对硝基苯基寡糖系列的便利酶促合成。

  摘要：

  从β-D-Gal-（1→4）-β-D-GlcNAc-OC6H4NO2-p（1）通过环回芽孢杆菌的β-半乳糖苷酶的转糖基化反应制得，α-D-Neu5Ac-（2-- > 3）-beta-D-Gal-（1-> 4）-beta-D-GlcNAc-OC6H4NO2-p（9）和alpha-D-Neu5Ac-（2-> 6）-beta-D-Gal -（1-> 4）-beta-D-GlcNAc-OC6H4NO2-p（10）通过重组大鼠α-（2-> 3）-N-唾液酸转移酶和大鼠以等摩尔比的CMP-Neu5Ac有效合成分别为肝α-（2-> 6）-N-唾液酸转移酶。前一种酶还有效地将CMP-Neu5Ac的Neu5Ac残基转移到OH-3在β-D-Gal-（1-> 4）-β-D-Gal-OC6H4NO2-p的非还原末端的位置或β-D-Gal-（1→4）-β-D-Gal-（1→4）-β-D-GlcNAc-OC6H4NO

  DOI：

  10.1016/j.carres.2005.08.019
• 作为产物：
  描述：

  α-galactosyl fluoride 、 4-硝基苯-Β-D-吡喃葡萄糖苷 在 E383A mutant β-glycosidase 作用下， 以 phosphate buffer 为溶剂， 以77%的产率得到β-D-Gal-(1->3)-β-D-Glc-OC6H4NO2-p
  参考文献：
  名称：

  Acceptor-dependent regioselectivity of glycosynthase reactions by Streptomyces E383A β-glucosidase

  摘要：

  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.

  DOI：

  10.1016/j.carres.2006.04.049

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。
• Galactosyl Transfer onto<i>p</i>-Nitrophenyl<i>β</i>-<scp>d</scp>-Glucoside Using β-<scp>d</scp>-Galactosidase from<i>Bacillus civculans</i>
  作者：Takeomi Murata、Satoru Akimoto、Miki Horimoto、Taichi Usui

  DOI：10.1271/bbb.61.1118

  日期：1997.1

  β-d-Gal-(1→4)-β-d-Glc-OC6H4NO2-p and its isomers (β-d-Gal-(l→3)-β-d-GIc-OC6H4NO2-p and β-d-Gal-(1→6)-β-d-Glc-OC6H4NO2-p) were synthesized from lactose and β-d-Glc-OC6H4NO2-p, using transglycosylation by the β-d-galactosidase from Bacillus circulans. This reaction was efficient enough for us to do a one-pot preparation of galactosyl-glucoside from lactose. The order of the production of the transfer products was (1→4) ≫ (1→3) > (1→6) in the initial stage of the reaction, and the same relationship was observed for the hydrolytic rate toward the three galactosyl-glucosides. The production of (1→4)- and (1→3)-linkages greatly decreased during the subsequent reaction and much more of the (1→6)- than of the (1→4)- and (1→3)-transfer products was found in the later stage of the reaction.

  以乳糖和β-d-Glc-OC6H4NO2-p为原料，利用环状芽孢杆菌的β-d-半乳糖苷酶进行转糖基化，合成了β-d-Gal-(1→4)-β-d-Glc-OC6H4NO2-p及其异构体（β-d-Gal-(l→3)-β-d-GIc-OC6H4NO2-p和β-d-Gal-(1→6)-β-d-Glc-OC6H4NO2-p）、利用环状芽孢杆菌中的β-d-半乳糖苷酶进行转糖基化。这一反应的效率足以让我们从乳糖中一次性制备半乳糖苷-葡萄糖苷。在反应初始阶段，转移产物的生成顺序为（1→4）≫（1→3）＞（1→6），三种半乳糖苷的水解速率也有相同的关系。在随后的反应中，(1→4)-和(1→3)-连接的产生量大大减少，在反应的后期阶段，发现(1→6)-转移产物比(1→4)-和(1→3)-转移产物多得多。
• 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.
• Engineering of glucoside acceptors for the regioselective synthesis of β-(1→3)-disaccharides with glycosynthases
  作者：Zsuzanna Marton、Vinh Tran、Charles Tellier、Michel Dion、Jullien Drone、Claude Rabiller

  DOI：10.1016/j.carres.2008.07.018

  日期：2008.11

  Glycosynthase mutants obtained from Thermotoga maritima were able to catalyze the regioselective synthesis of aryl beta-D-Galp-(1 -> 3)-beta-D-Glcp and aryl beta-D-Glcp-(1 -> 3)-beta-D-Glcp in high yields (up to 90 %) using aryl beta-D-glucosides as acceptors. The need for an aglyconic aryl group was rationalized by molecular modeling calculations, which have emphasized a high stabilizing interaction of this group by stacking with W312 of the enzyme. Unfortunately, the deprotection of the aromatic group of the disaccharides was not possible without partial hydrolysis of the glycosidic bond. The replacement of aryl groups by benzyl ones could offer the opportunity to deprotect the anomeric position under very mild conditions. Assuming that benzyl acceptors could preserve the stabilizing stacking, benzyl beta-D-glucoside firstly assayed as acceptor resulted in both poor yields and poor regioselectivity. Thus, we decided to undertake molecular modeling calculations in order to design which suitable substituted benzyl acceptors could be used. This study resulted in the choice of 2-biphenylmethyl beta-D-glucopyranoside. This choice was validated experimentally, since the corresponding beta-(1 -> 3) disaccharide was obtained in good yields and with a high regioselectivity. At the same time, we have shown that phenyl 1-thio-beta-D-glucopyranoside was also an excellent substrate leading to similar results as those obtained with the O-phenyl analogue. The NBS deprotection of the S-phenyl group afforded the corresponding disaccharide quantitatively. (C) 2008 Elsevier Ltd. All rights reserved.
• Convenient enzymatic synthesis of a p-nitrophenyl oligosaccharide series of sialyl N-acetyllactosamine, sialyl Lex and relevant compounds
  作者：Xiaoxiong Zeng、Hirotaka Uzawa

  DOI：10.1016/j.carres.2005.08.019

  日期：2005.11

  From the beta-D-Gal-(1-->4)-beta-D-GlcNAc-OC6H4NO2-p (1) prepared by the transglycosylation of beta-galactosidase from Bacillus circulans, alpha-D-Neu5Ac-(2-->3)-beta-D-Gal-(1-->4)-beta-D-GlcNAc-OC6H4NO2-p (9) and alpha-D-Neu5Ac-(2-->6)-beta-D-Gal-(1-->4)-beta-D-GlcNAc-OC6H4NO2-p (10) were effectively synthesized with an equimolar ratio of CMP-Neu5Ac by recombinant rat alpha-(2-->3)-N-sialyltransferase

  从β-D-Gal-（1→4）-β-D-GlcNAc-OC6H4NO2-p（1）通过环回芽孢杆菌的β-半乳糖苷酶的转糖基化反应制得，α-D-Neu5Ac-（2-- > 3）-beta-D-Gal-（1-> 4）-beta-D-GlcNAc-OC6H4NO2-p（9）和alpha-D-Neu5Ac-（2-> 6）-beta-D-Gal -（1-> 4）-beta-D-GlcNAc-OC6H4NO2-p（10）通过重组大鼠α-（2-> 3）-N-唾液酸转移酶和大鼠以等摩尔比的CMP-Neu5Ac有效合成分别为肝α-（2-> 6）-N-唾液酸转移酶。前一种酶还有效地将CMP-Neu5Ac的Neu5Ac残基转移到OH-3在β-D-Gal-（1-> 4）-β-D-Gal-OC6H4NO2-p的非还原末端的位置或β-D-Gal-（1→4）-β-D-Gal-（1→4）-β-D-GlcNAc-OC6H4NO