trans-Caffeate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: trans-Caffeate
• 英文别名: 4-[(E)-2-carboxyethenyl]-2-hydroxyphenolate
• 化学式: C9H7O4-
• 分子量: 179.15
• InChiKey: QAIPRVGONGVQAS-DUXPYHPUSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  80.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-Caffeate 、 hydrocaffeoyl-CoA 生成 (E)-caffeoyl-CoA 、 3-(3,4-Dihydroxyphenyl)propanoate
  参考文献：
  名称：

  Caffeate Respiration in the Acetogenic Bacterium Acetobacterium woodii: a Coenzyme A Loop Saves Energy for Caffeate Activation

  摘要：

  摘要 厌氧产酸菌 木醋杆菌 以钠离子为偶联离子，通过化学渗透机制将咖啡酸还原与分子氢产生的电子耦合到 ATP 的合成中。咖啡酸酯在还原之前被活化为咖啡酰辅酶 A（caffeyl-CoA），咖啡酸酯还原操作子编码一种依赖 ATP 的咖啡酰辅酶 A 合成酶，该酶被认为催化了最初的咖啡酸酯活化。该操作子还编码一种潜在的 CoA 转移酶，它是 carA 的产物，它被认为参与了随后的不依赖于 ATP 的咖啡酸激活。为了证明 carA 的功能，我们在 大肠杆菌 然后将其纯化。纯化的 CarA 以氢咖啡酰-CoA 为 CoA 供体，驱动咖啡酸生成咖啡酰-CoA。该反应对咖啡酸酯和氢咖啡酰-CoA 的依赖性遵循 Michaelis-Menten 动力学，表观上 K m 为 75 ½ 5 μM，氢咖啡酰-CoA 为 8 ½ 2 μM。酶的活性具有广泛的最适 pH 值和温度范围。除了能够利用咖啡酸之外，CarA 还能利用 p -香豆酸酯和阿魏酸酯，但不能使用肉桂酸酯、山奈酸酯或 p -羟基苯甲酸作为 CoA 受体。乙酰-CoA 和丁酰-CoA 都不能作为 CarA 的 CoA 供体。该酶采用乒乓机制进行 CoA 转移，是第一类新的 I 族 CoA 转移酶亚类成员，在一条多肽链上有两个催化结构域。显然，在咖啡酸盐呼吸的稳定状态下，CarA 催化了咖啡酸盐活化的节能 CoA 循环。

  DOI：

  10.1128/aem.03604-12
• 作为产物：
  描述：

  左旋多巴 生成 trans-Caffeate 、 铵
  参考文献：
  名称：

  Combinatorial biosynthesis of plant-specific coumarins in bacteria

  摘要：

  Coumarins are plant secondary metabolites that have demonstrated a variety of important therapeutic properties, such as antibacterial, anti-inflammatory, and anti-coagulant effects, as well as anti-cancer and anti-AIDS activities. However, knowledge regarding their biosynthesis is relatively limited even for the simplest coumarin molecule, which serves as the gateway molecule to many pharmaceutically important coumarin derivatives. Here we reported the design and validation of artificial pathways leading to the biosynthesis of plant-specific simple coumarins in bacteria. First, Escherichia coli strains were engineered to convert inexpensive phenylpropanoid acid precursors, 4-coumarate and ferulate to simple coumarins, umbelliferone (4.3 mg/L) and scopoletin (27.8 mg/L), respectively. Furthermore, we assembled the complete artificial pathways in E. coli and achieved de novo biosynthesis of umbelliferone and scopoletin without addition of precursors. This study lays the foundation for microbial production of more diverse coumarin compounds. (C) 2013 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.ymben.2013.04.004

文献信息

• Characterization of Two cDNA Clones Which EncodeO-Methyltransferases for the Methylation of both Flavonoid and Phenylpropanoid Compounds
  作者：Antonin Gauthier、Patrick J. Gulick、Ragai K. Ibrahim

  DOI：10.1006/abbi.1997.0554

  日期：1998.3

  Enzymatic O-methylation of phenylpropanoid and flavonoid compounds is believed to be catalyzed by distinct classes of O-methyltransferases [EC 2.1.1.6x]. The O-methylated derivatives of phenylpropanoids and flavonoids play an important role in lignification and as antimicrobial compounds, respectively. Two cDNA clones, OMT1 and OMT2, which differ in three amino acid residues were isolated and characterized

  苯丙烷和类黄酮化合物的酶促O-甲基化被认为是由不同种类的O-甲基转移酶催化的[EC 2.1.1.6x]。苯丙烷和类黄酮的O-甲基化衍生物分别在木质化和抗菌化合物中起重要作用。从半水生美洲杂草（Saxifragaceae）的半水淡水杂草中分离并鉴定了两个在三个氨基酸残基上不同的cDNA克隆OMT1和OMT2。这两个新的cDNA克隆编码的酶可催化类黄酮苷元木犀草素和槲皮素的3'-O-甲基化，尽管它们也分别催化苯丙酸类咖啡因和5-羟基阿魏酸的3 / 5-O-甲基化。两种重组蛋白均从大肠杆菌表达系统中部分纯化，并使用两种类黄酮和两种苯基丙烷为底物比较了它们的动力学参数。尽管两种基因产物甲基化咖啡酸和5-羟基阿魏酸的程度相似，但它们对类黄酮化合物的亲和力和三倍增长了四到六倍。OMT1的基因产物以比OMT2更高的速率接受黄酮类底物木犀草素和槲皮素进行甲基化，这是由其Vmax值和周转率增加了2到3倍表明
• Isolation and Characterization of a Chlorogenic Acid Esterase from Aspergillus niger
  作者：B. Schöbel、W. Pollmann

  DOI：10.1515/znc-1980-3-407

  日期：1980.4.1

  The isolation and characterization of a specific chlorogenic acid esterase is described. The enzyme activity is measured by determination of the hydrolysis product caffeic acid. The enzyme had been concentrated by means of ultrafiltration and column-chromatography. The pH- and temperature optimum were 6.5 and 45 °C respectively. Divalent cations were not required for the enzyme activity. As other esterases, this enzyme is inhibited by di-isopropyl-phosphorofluoridate. The K_m-value is 0.70 mᴍ chlorogenic acid, the molecular weight 240000. The described enzyme is specific for chlorogenic acid.

  On the other hand a typical unspecific esterase like the pig liver esterases does not split chloro­genic acid.

  The isoelectric focusing reveals several isoenzymes of chlorogenase within a pI-range of 4.0-4.5.

  摘要 本文描述了一种特定的绿原酸酯酶的分离和表征。酶活性是通过测定水解产物咖啡酸来确定的。该酶已通过超滤和柱层析浓缩。pH和温度最适值分别为6.5和45°C。二价阳离子对酶活性不是必需的。与其他酯酶一样，这种酶被二异丙基氟磷酸酯抑制。Km值为0.70 mᴍ绿原酸，分子量为240000。所述酶对绿原酸具有特异性。 另一方面，像猪肝酯酶这样的典型非特异性酯酶无法分解绿原酸。 等电聚焦揭示了在pI范围为4.0-4.5内的几种绿原酸酶同工酶。
• Influence of Side-Chain Substituents on the Position of Cleavage of the Benzene Ring by <i>Pseudomonas fluorescens</i>
  作者：M. M. Seidman、Anne Toms、J. M. Wood

  DOI：10.1128/jb.97.3.1192-1197.1969

  日期：1969.3

  with phenol, p-hydroxybenzoic acid, p-hydroxy-phenylacetic acid, or p-hydroxy-trans-cinnamic acid as sole carbon and energy source. Each compound was first hydroxylated, ortho to the hydroxyl group on the benzene ring, to give catechol, protocatechuic acid (3,4-dihydroxy-benzoic acid), homoprotocatechuic acid (3,4-dihydroxy-phenylacetic acid), and caffeic acid (3,4-dihydroxy-trans-cinnamic acid), respectively

  荧光假单胞菌在含有苯酚，对羟基苯甲酸，对羟基苯乙酸或对羟基反式肉桂酸作为唯一碳和能源的矿物盐培养基上生长。首先将每种化合物羟基化至苯环上的羟基邻位，得到邻苯二酚，原儿茶酸（3,4-二羟基苯甲酸），高原儿茶酸（3,4-二羟基苯乙酸）和咖啡酸（ 3,4-二羟基-反式肉桂酸）分别作为裂解苯核之前的最终芳香族产物。已显示原儿茶酸和咖啡酸通过3,4-加氧酶机制通过邻位裂解被裂解，得到β-取代的顺式，顺式-粘康酸作为初始脂族产物。然而，儿茶酚和高原儿茶酸分别被2,3-和4,5-加氧酶裂解。得到α-羟基-粘康半醛和α-羟基-γ-羧甲基粘康半醛作为初始脂族中间体。咖啡酸：3,4-加氧酶，一种新的加氧酶，每摩尔底物消耗1摩尔O（2），最佳pH值为7.0。萤光假单胞菌降低了对取代的邻苯二酚的抑制作用，其酶的裂解机理显然随着邻链取代基的肾上腺素（电子供体）效应的增加而从邻位转变为间位。
• Identification of Glucosyltransferase Genes Involved in Sinapate Metabolism and Lignin Synthesis in Arabidopsis
  作者：Eng-Kiat Lim、Yi Li、Adrian Parr、Ros Jackson、David A. Ashford、Dianna J. Bowles

  DOI：10.1074/jbc.m007263200

  日期：2001.2

  identified. Combining sequence information in the Arabidopsis genomic data base with biochemical data from screening the activity of recombinant proteins in vitro, we have now identified five gene sequences encoding enzymes that can glucosylate sinapic acid, sinapyl alcohol, and their related phenylpropanoids. The data provide a foundation for future understanding and manipulation of sinapate metabolism

  芥子酸是十字花科中的主要苯基丙烷，在两个不同的代谢途径中提供中间体，从而导致芥子酸酯和木质素合成。葡萄糖基转移酶在这些中间体的形成中起关键作用，通过产生高能化合物1-O-芥子酰葡萄糖导致芥子酸苹果酸酯和芥子碱胆碱，或通过产生芥子醇-4-O-葡糖苷，可能导致丁香基单元在木质素中发现。尽管已经认识了这些葡糖基转移酶的重要性超过20年，但尚未鉴定出它们的相应基因。将拟南芥基因组数据库中的序列信息与通过体外筛选重组蛋白活性而获得的生化数据相结合，我们现在已经确定了五个编码酶的基因序列，这些酶可以使芥子酸，芥子醇及其相关的苯基丙烷类糖基化。这些数据为将来了解和操纵拟南芥中的芥子酸酯代谢和木质素生物学奠定了基础。
• Contribution of CoA Ligases to Benzenoid Biosynthesis in Petunia Flowers
  作者：Antje Klempien、Yasuhisa Kaminaga、Anthony Qualley、Dinesh A. Nagegowda、Joshua R. Widhalm、Irina Orlova、Ajit Kumar Shasany、Goro Taguchi、Christine M. Kish、Bruce R. Cooper、John C. D’Auria、David Rhodes、Eran Pichersky、Natalia Dudareva

  DOI：10.1105/tpc.112.097519

  日期：2012.5

  Biosynthesis of benzoic acid from Phe requires shortening of the side chain by two carbons, which can occur via the β-oxidative or nonoxidative pathways. The first step in the β-oxidative pathway is cinnamoyl-CoA formation, likely catalyzed by a member of the 4-coumarate:CoA ligase (4CL) family that converts a range of trans-cinnamic acid derivatives into the corresponding CoA thioesters. Using a functional genomics approach, we identified two potential CoA-ligases from petunia (Petunia hybrida) petal-specific cDNA libraries. The cognate proteins share only 25% amino acid identity and are highly expressed in petunia corollas. Biochemical characterization of the recombinant proteins revealed that one of these proteins (Ph-4CL1) has broad substrate specificity and represents a bona fide 4CL, whereas the other is a cinnamate:CoA ligase (Ph-CNL). RNA interference suppression of Ph-4CL1 did not affect the petunia benzenoid scent profile, whereas downregulation of Ph-CNL resulted in a decrease in emission of benzylbenzoate, phenylethylbenzoate, and methylbenzoate. Green fluorescent protein localization studies revealed that the Ph-4CL1 protein is localized in the cytosol, whereas Ph-CNL is in peroxisomes. Our results indicate that subcellular compartmentalization of enzymes affects their involvement in the benzenoid network and provide evidence that cinnamoyl-CoA formation by Ph-CNL in the peroxisomes is the committed step in the β-oxidative pathway.

  苯丙氨酸生物合成过程中，苯甲酸侧链需要缩短两个碳原子，这可以通过β-氧化或非氧化途径实现。β-氧化途径的第一步是形成肉桂酰-CoA，这很可能是由4-香豆酸：CoA连接酶（4CL）家族中的一员催化完成的，该酶可将一系列反式肉桂酸衍生物转化为相应的硫代酯CoA。我们采用功能基因组学方法，从矮牵牛（Petunia hybrida）花瓣特异性cDNA文库中鉴定出两种潜在的CoA连接酶。同源蛋白的氨基酸相似度仅为25%，在矮牵牛花冠中高度表达。重组蛋白的生化特性表明，其中一种蛋白（Ph-4CL1）具有广泛的底物特异性，是真正的4CL，而另一种是肉桂酰：CoA连接酶（Ph-CNL）。RNA干扰抑制Ph-4CL1不会影响矮牵牛的苯类气味，而下调Ph-CNL会导致苄基苯甲酸酯、苯乙基苯甲酸酯和甲基苯甲酸酯的释放减少。绿色荧光蛋白定位研究表明，Ph-4CL1蛋白定位于细胞质中，而Ph-CNL定位于过氧化物酶体中。我们的结果表明，酶的亚细胞区室化会影响它们在苯类网络中的参与，并提供了证据表明，Ph-CNL在过氧化物酶体中