4-硝基苯基-β-D-呋喃半乳糖脂 | 100645-45-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-硝基苯基-β-D-呋喃半乳糖脂
• 英文名称: (4-nitro)phenyl β-D-galactofuranoside
• 英文别名: p-nitrophenyl β-D-galactofuranoside；4-nitrophenyl beta-D-galactofuranoside；(2S,3R,4R,5S)-2-[(1R)-1,2-dihydroxyethyl]-5-(4-nitrophenoxy)oxolane-3,4-diol
• CAS: 100645-45-2
• 化学式: C₁₂H₁₅NO₈
• 分子量: 301.253
• InChiKey: RMQNVZDXEMOJCW-PZWNZHSQSA-N

物化性质

• 熔点：
  150-153°C
• 沸点：
  621.9±55.0 °C(Predicted)
• 密度：
  1.622±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于DMSO（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  145
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-硝基苯基-β-D-呋喃半乳糖脂 在 盐酸 、 sodium periodate 、 钾硼氢 作用下， 生成 L-(+)-arabinose
  参考文献：
  名称：

  Synthesis of p-nitrophenyl β-d-galactofuranoside. A convenient substrate for β-galactofuranosidase

  摘要：

  DOI：

  10.1016/s0008-6215(00)90153-8
• 作为产物：
  描述：

  (R)-1-((2S,3S,4R,5S)-3,4-diacetoxy-5-(4-nitrophenoxy)tetrahydrofuran-2-yl)ethane-1,2-diyl diacetate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以0.24 g的产率得到4-硝基苯基-β-D-呋喃半乳糖脂
  参考文献：
  名称：

  Identification and Characterization of a Novel Galactofuranose-Specific β-D-Galactofuranosidase from Streptomyces Species

  摘要：

  β-D-半乳糖呋喃糖（Galf）是多糖和糖共轭物的一种成分，其转移酶已被充分分析。然而，目前尚未在任何生物体中发现β-D-半乳糖呋喃糖苷酶（Galf-ase）基因。为了寻找半乳呋喃糖苷酶基因，我们对土壤样本进行了筛选，发现了一株通过 16S 核糖体 RNA 基因分析确定为链霉菌的菌株，该菌株在培养上清液中对 4-硝基苯基 β-D-半乳呋喃糖苷（pNP-β-D-Galf）具有半乳呋喃糖苷酶活性。通过对这株名为 JHA19 的菌株进行基因组测序，我们发现了四个编码 Galf 酶的候选基因。通过在大肠杆菌中表达重组蛋白，我们发现四个候选基因中有三个不仅具有 Galf-酶的活性，而且还具有 α-L-阿拉伯呋喃糖苷酶（Araf-ase）的活性，而另一个则只具有 Galf-酶的活性。这种新型的 Galf 特异性水解酶由 ORF1110 编码，对底物 pNP-β-D-Galf 的最适 pH 值为 5.5，Km 为 4.4 mM。此外，这种酶还能从丝状真菌曲霉制备的半乳甘露聚糖中释放半乳糖残基，这表明天然多糖也可以是底物。通过对ORF1110半乳糖酶的氨基酸序列进行BLAST检索，我们发现原核生物和真核生物中都存在同源基因，这表明微生物中广泛存在半乳糖特异性半乳糖酶。

  DOI：

  10.1371/journal.pone.0137230

文献信息

• Enzymatic synthesis of oligo-d-galactofuranosides and l-arabinofuranosides: from molecular dynamics to immunological assays
  作者：Ilona Chlubnová、Dominik Filipp、Vojtech Spiwok、Hana Dvořáková、Richard Daniellou、Caroline Nugier-Chauvin、Blanka Králová、Vincent Ferrières

  DOI：10.1039/b926988f

  日期：——

  D-Galactofuranosyl-containing conjugates are ubiquitous in many pathogenic microorganisms, but completely absent from mammals. As they may constitute interesting pharmacophores, recent works have been dedicated to their preparation. Besides well-reported chemical procedures, enzymatic approaches are still limited, mainly due to the lack of the corresponding biocatalysts. Based on the similarity between chemical structures, the arabinofuranosyl hydrolase Araf51 from Clostridium thermocellum was expected to recognize both the L-Araf motif and its D-Galf analogue. Molecular dynamics and STD-NMR were firstly used to confirm this hypothesis and increase our knowledge of the active site. Interestingly, this arabinofuranosidase was not only able to hydrolyze galactosyl derivatives, but was also really efficient in catalyzing oligomerisations using p-nitrophenyl furanosides as donors. The structures of the products obtained were determined using mass spectrometry and NMR. Amongst them, all the possible regioisomers of di-arabino and -galactofuranosides were synthesized, and the ratio of each regioisomer was easily tuned with respect to the reaction time. Especially, the galactofuranobioside displaying the biologically relevant sequence β-D-Galf-(1,6)-β-D-Galf was enzymatically prepared for the first time. All fractions going from di- to penta-arabino- and galactofuranosides were tested for their ability in eliciting the production of TNF-α. Interesting immunological properties were observed with arabinofuranosides as short as three sugar residues.

  含 D-半乳糖呋喃糖基的共轭物在许多病原微生物中无处不在，但在哺乳动物中却完全不存在。由于 D-半乳糖呋喃糖基共轭物可能构成有趣的药食同源物，近期的研究工作致力于制备这种共轭物。除了报道较多的化学方法外，酶解方法仍然有限，主要原因是缺乏相应的生物催化剂。基于化学结构之间的相似性，来自热梭菌的阿拉伯呋喃糖基水解酶 Araf51 预计既能识别 L-Araf 基序，也能识别其 D-Galf 类似物。我们首先利用分子动力学和 STD-NMR 验证了这一假设，并增加了对活性位点的了解。有趣的是，这种阿拉伯呋喃糖苷酶不仅能够水解半乳糖基衍生物，而且在催化以对硝基苯基呋喃糖苷为供体的寡聚反应方面也非常有效。利用质谱和核磁共振测定了所获得产物的结构。在这些产物中，合成了所有可能的二阿拉伯呋喃半乳糖苷和半乳糖呋喃苷的区域异构体，而且每种区域异构体的比例都很容易根据反应时间进行调整。特别是首次用酶法制备了具有生物学相关序列的半乳糖呋喃生物苷β-D-Galf-(1,6)-β-D-Galf。测试了从二-阿拉伯呋喃半乳糖苷到五-阿拉伯呋喃半乳糖苷的所有馏分诱导 TNF-α 生成的能力。在短至三个糖残基的阿拉伯呋喃糖苷中观察到了有趣的免疫特性。
• Fungal α-arabinofuranosidases of glycosyl hydrolase families 51 and 54 show a dual arabinofuranosyl- and galactofuranosyl-hydrolyzing activity
  作者：Boris Tefsen、Ellen L. Lagendijk、Joohae Park、Michiel Akeroyd、Doreen Schachtschabel、Robert Winkler、Irma van Die、Arthur F.J. Ram

  DOI：10.1515/hsz-2012-0134

  日期：2012.8.1

  Aspergillus niger possesses a galactofuranosidase activity, however, the corresponding enzyme or gene encoding this enzyme has never been identified. As evidence is mounting that enzymes exist with affinity for both arabinofuranose and galactofuranose, we investigated the possibility that α-l-arabinofuranosidases, encoded by the abfA and abfB genes, are responsible for the galactofuranosidase activity of A. niger. Characterization of the recombinant AbfA and AbfB proteins revealed that both enzymes do not only hydrolyze p-nitrophenyl-α-l-arabinofuranoside (pNp-α-Araf) but are also capable of hydrolyzing p-nitrophenyl-β-d-galactofuranoside (pNp-β-Galf). Molecular modeling of the AbfB protein with pNp-β-Galf confirmed the possibility for AbfB to interact with this substrate, similarly as with pNp-α-Araf. We also show that galactomannan, a cell wall compound of A. niger, containing β-linked terminal and internal galactofuranosyl moieties, can be degraded by an enzyme activity that is present in the supernatant of inulin-grown A. niger. Interestingly, purified AbfA and AbfB did not show this hydrolyzing activity toward A. nigergalactomannan. In summary, our studies demonstrate that AbfA and AbfB, α-l-arabinofuranosidases from different families, both contain a galactofuranose (Galf)-hydrolyzing activity. In addition, our data support the presence of a Galf-hydrolase activity expressed by A. niger that is capable of degrading fungal galactomannan.

  摘要：黑曲霉具有一种半乳糖醛酸酶活性，然而，尚未鉴定出相应的酶或编码该酶的基因。随着越来越多的证据表明存在对阿拉伯糖醛和半乳糖醛具有亲和力的酶，我们调查了α-l-阿拉伯糖苷酶，由abfA和abfB基因编码，是否负责黑曲霉的半乳糖醛酶活性。对重组AbfA和AbfB蛋白的表征显示，这两种酶不仅水解p-硝基苯基-α-l-阿拉伯糖苷（pNp-α-Araf），还能水解p-硝基苯基-β-d-半乳糖苷（pNp-β-Galf）。用pNp-β-Galf对AbfB蛋白进行的分子建模证实了AbfB与该底物相互作用的可能性，类似于与pNp-α-Araf的相互作用。我们还展示，包含β-连接的末端和内部半乳糖基的黑曲霉细胞壁化合物——半乳糖甘露聚糖，可以被存在于菊糖培养的黑曲霉培养基上清液中的一种酶活性降解。有趣的是，纯化的AbfA和AbfB对黑曲霉半乳糖甘露聚糖没有显示出这种水解活性。总之，我们的研究表明，来自不同家族的α-l-阿拉伯糖苷酶AbfA和AbfB都含有半乳糖醛（Galf）水解活性。此外，我们的数据支持黑曲霉表达的一种能够降解真菌半乳糖甘露聚糖的Galf-水解酶活性的存在。
• Regioselective Galactofuranosylation for the Synthesis of Disaccharide Patterns Found in Pathogenic Microorganisms
  作者：Laurent Legentil、Yari Cabezas、Olivier Tasseau、Charles Tellier、Franck Daligault、Vincent Ferrières

  DOI：10.1021/acs.joc.7b00565

  日期：2017.7.21

  Koenigs–Knorr glycosylation of acceptors with more than one free hydroxyl group by 2,3,5,6-tetrabenzoyl galactofuranosyl bromide was performed using diphenylborinic acid 2-aminoethyl ester (DPBA) as inducer of regioselectivity. High regioselectivity for the glycosylation on the equatorial hydroxyl group of the acceptor was obtained thanks to the transient formation of a borinate adduct of the corresponding

  使用二苯基硼酸2-氨基乙基酯（DPBA）作为区域选择性的诱导剂，进行了2,3,5,6-四苯甲酰半乳糖呋喃糖基溴的带有多个游离羟基的受体的Koenigs-Knorr糖基化反应。由于相应的1，2-顺式二醇的硼酸酯加合物的瞬时形成，获得了在受体的赤道羟基上的糖基化的高区域选择性。然而，原酸酯副产物的形成妨碍了该方法的效率。有趣的是，受体的O -6或C -1上的吸电子基团使反应发生位移，有利于所需的含半呋喃呋喃糖基的二糖。对于p的呋喃糖基化获得了最佳产率-硝基苯基6- O-乙酰基甘露吡喃糖苷。在某些病原体的糖杯中发现的其他二糖的前体是根据相同的方法合成的，收率范围为45％至86％。这是合成生物学相关糖缀合物的良好选择。
• The versatile enzyme Araf51 allowed efficient synthesis of rare pathogen-related β-<scp>d</scp>-galactofuranosyl-pyranoside disaccharides
  作者：Ilona Chlubnová、Blanka Králová、Hana Dvořáková、Petr Hošek、Vojtěch Spiwok、Dominik Filipp、Caroline Nugier-Chauvin、Richard Daniellou、Vincent Ferrières

  DOI：10.1039/c3ob42519c

  日期：——

  The preparation of galactofuranosyl-containing disaccharidic parts of natural glycoconjugates was performed according to a chemo-enzymatic synthesis. Our goals were firstly to develop an alternative approach to standard chemical strategies by limiting the number of reaction and purification steps, and secondly to evaluate the scope of the Araf51 biocatalyst to transfer a galactofuranosyl moiety to a set of pyranosidic acceptors differing from each other by the series, the anomeric configuration as well as the conformation. The study of binding mode of the resulting disaccharides was also performed by molecular modeling and showed significant differences between (1→2)- and (1→6)-linked disaccharides.

  我们通过化学酶合成法制备了天然糖共轭物中含有半乳糖呋喃糖基的二糖部分。我们的目标首先是通过限制反应和纯化步骤的数量，开发一种替代标准化学策略的方法；其次是评估 Araf51 生物催化剂将半乳糖呋喃糖基分子转移到一组不同系列、异构体构型和构象的吡喃糖接受体上的能力。此外，还通过分子建模研究了所得二糖的结合模式，结果表明(1â2)-和(1â6)-连接二糖之间存在显著差异。
• Environmentally benign glycosylation of aryl pyranosides and aryl/alkyl furanosides demonstrating the versatility of thermostable CGTase from Thermoanaerobacterium sp.
  作者：Alizé Pennec、Laurent Legentil、Luis Herrera-Estrella、Vincent Ferrières、Anne-Laure Chauvin、Caroline Nugier-Chauvin

  DOI：10.1039/c4gc00631c

  日期：——

  The specificity of transglycosylation of Thermoanaerobacterium sp. CGTase against aryl furanosides is reported.

  报道了Thermoanaerobacterium sp. CGTase对芳基呋喃苷的转糖基特异性。