6-phytyltoluquinol | 75513-85-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 6-phytyltoluquinol
• 英文别名: 2-Methyl-6-phytylquinol；2-methyl-6-[(E,7R,11R)-3,7,11,15-tetramethylhexadec-2-enyl]benzene-1,4-diol
• CAS: 75513-85-8
• 化学式: C₂₇H₄₆O₂
• 分子量: 402.661
• InChiKey: GTWCNYRFOZKWTL-UOFXASEASA-N

物化性质

• 沸点：
  521.5±45.0 °C(Predicted)
• 密度：
  0.942±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  29
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-phytyltoluquinol 在 tocopherol cyclase from spheroplasts of Anabaena variabilis 作用下， 以 丙酮 为溶剂， 生成 (+)-δ-生育酚
  参考文献：
  名称：

  The substrate specificity of tocopherol cyclase

  摘要：

  The substrate specificity of the enzyme tocopherol cyclase from the blue-green algae Anabaena variabilis (Cyanobacteria) was investigated with 11 substrate analogues revealing the significance of three major recognition sites: (i) the OH group at C(1) of the hydroquinone, (ii) the (E) configuration of the double bond, and (iii) the length of the lipophilic side chain. Experiments with two affinity matrices suggest that substrates approach the enzyme's active site with the hydrophobic tail. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0968-0896(96)00125-3
• 作为产物：
  描述：

  2-methyl-6-phythyl-1,4-benzoquinone 在 甲醇 、 sodium tetrahydroborate 作用下， 反应 0.03h， 生成 6-phytyltoluquinol
  参考文献：
  名称：

  2-Methyl-6-phytylquinol and 2,3-dimethyl-5-phytylquinol as precursors of tocopherol synthesis in spinach chloroplasts

  摘要：

  The incorporation of [Me(methyl)-14C] from SAM(S-adenosylmethionine)-[Me-14C] into precursors indicates the following sequence of tocopherol synthesis in spinach: 2-methyl-6-phytylquinol (6-phytyltoluquinol) (1a) .fwdarw. 2,3-dimethyl-5-phytylquinol (phytylplastoquinol) (2a) .fwdarw. .gamma.-tocopherol (5a) .fwdarw. .alpha.-tocopherol (6). 1a is particularly preferred to 2-methyl-5-phytylquinol (1b) and 2-methyl-3-phytylquinol (1c). 1a only forms 2a. 2a is converted to 6 via 5a and, to a lesser extent, 2,5-dimethyl-6-phylquinol (2b) to 6 via .beta.-tocopherol (5b). Trimethylphytylquinol (3) is not an intermediate in the formation of 6. All reactions are independent of light.

  DOI：

  10.1016/s0031-9422(00)81963-9

文献信息

• Nucleic acid sequences to proteins involved in tocopherol synthesis
  申请人：——

  公开号：US20030170833A1

  公开（公告）日：2003-09-11

  Nucleic acid sequences and methods are provided for producing plants and seeds having altered tocopherol content and compositions. The methods find particular use in increasing the tocopherol levels in plants, and in providing desirable tocopherol compositions in a host plant cell.

  提供核酸序列和方法，用于生产具有改变生育酚含量和组成的植物和种子。该方法特别适用于增加植物中的生育酚水平，并在宿主植物细胞中提供理想的生育酚组成。
• Nucleic acid sequences to proteins involved in isoprenoid synthesis
  申请人：Calgene LLC

  公开号：US06541259B1

  公开（公告）日：2003-04-01

  Nucleic acid sequences and methods are provided for producing plants and seeds having altered tocopherol content and compositions. The methods find particular use in increasing the tocopherol levels in plants, and in providing desirable tocopherol compositions in a host plant cell.

  提供了核酸序列和方法，用于生产具有改变生育酚含量和组成的植物和种子。该方法特别适用于增加植物中的生育酚水平，并在宿主植物细胞中提供理想的生育酚组成。
• NUCLEIC ACID SEQUENCES TO PROTEINS INVOLVED IN TOCOPHEROL SYNTHESIS
  申请人：Subramaniam Sai S.

  公开号：US20100216204A1

  公开（公告）日：2010-08-26

  Nucleic acid sequences and methods are provided for producing plants and seeds having altered tocopherol content and compositions. The methods find particular use in increasing the tocopherol levels in plants, and in providing desirable tocopherol compositions in a host plant cell.

  提供了核酸序列和方法，用于产生具有改变的生育酚含量和组成的植物和种子。该方法特别适用于增加植物中的生育酚水平，并在宿主植物细胞中提供理想的生育酚组成。
• Characterization of Tocopherol Cyclases from Higher Plants and Cyanobacteria. Evolutionary Implications for Tocopherol Synthesis and Function
  作者：Scott E. Sattler、Edgar B. Cahoon、Sean J. Coughlan、Dean DellaPenna

  DOI：10.1104/pp.103.024257

  日期：2003.8.1

  Tocopherols are lipophilic antioxidants synthesized exclusively by photosynthetic organisms and collectively constitute vitamin E, an essential nutrient for both humans and animals. Tocopherol cyclase (TC) catalyzes the conversion of various phytyl quinol pathway intermediates to their corresponding tocopherols through the formation of the chromanol ring. Herein, the molecular and biochemical characterization of TCs from Arabidopsis (VTE1 [VITAMIN E 1]), Zea mays (SXD1 [Sucrose Export Deficient 1]) and Synechocystis sp. PCC6803 (slr1737) are described. Mutations in the VTE1, SXD1, or slr1737 genes resulted in both tocopherol deficiency and the accumulation of 2,3-dimethyl-6-phytyl-1,4-benzoquinone (DMPBQ), a TC substrate. Recombinant SXD1 and VTE1 proteins are able to convert DMPBQ to γ-tocopherol in vitro. In addition, expression of maize SXD1 in a Synechocystis sp. PCC6803 slr1737 knockout mutant restored tocopherol synthesis, indicating that TC activity is evolutionarily conserved between plants and cyanobacteria. Sequence analysis identified a highly conserved 30-amino acid C-terminal domain in plant TCs that is absent from cyanobacterial orthologs. vte1-2 causes a truncation within this C-terminal domain, and the resulting mutant phenotype suggests that this domain is necessary for TC activity in plants. The defective export of Suc in sxd1 suggests that in addition to presumed antioxidant activities, tocopherols or tocopherol breakdown products also function as signal transduction molecules, or, alternatively, the DMPBQ that accumulates in sxd1 disrupts signaling required for efficient Suc export in maize.

  生物合成的脂溶性抗氧化剂生育酚仅由光合生物合成，共同构成维生素E，是人类和动物的必需营养素。生育酚环化酶（TC）通过形成色酚环催化各种植物醌途径中间体的转化为相应的生育酚。本文描述了来自拟南芥（VTE1 [维生素E 1]）、玉米（SXD1 [蔗糖导出缺陷1]）和Synechocystis sp. PCC6803（slr1737）的TC的分子和生化特性。VTE1、SXD1或slr1737基因的突变导致生育酚缺乏和2,3-二甲基-6-植酰基-1,4-苯醌（DMPBQ）的积累，这是TC底物。重组的SXD1和VTE1蛋白能够在体外将DMPBQ转化为γ-生育酚。此外，将玉米SXD1在Synechocystis sp. PCC6803 slr1737敲除突变体中表达可恢复生育酚合成，表明植物和蓝细菌之间的TC活性在进化上是保守的。序列分析确定了植物TC中高度保守的30个氨基酸C端结构域，而蓝细菌同源物中则不存在。vte1-2导致该C端结构域的截短，导致的突变表型表明该结构域对于植物中的TC活性是必需的。sxd1中的蔗糖缺陷表明，除了预期的抗氧化活性外，生育酚或生育酚降解产物还起到信号转导分子的作用，或者是sxd1中积累的DMPBQ干扰了玉米高效蔗糖导出所需的信号传递。

• Vitamin E biosynthesis: functional characterization of the monocot homogentisate geranylgeranyl transferase
  作者：Wenyu Yang、Rebecca E. Cahoon、Sarah C. Hunter、Chunyu Zhang、Jixiang Han、Trissa Borgschulte、Edgar B. Cahoon

  DOI：10.1111/j.1365-313x.2010.04417.x

  日期：2011.1

  The biosynthesis of the tocotrienol and tocopherol forms of vitamin E is initiated by prenylation of homogentisate. Geranylgeranyl diphosphate (GGDP) is the prenyl donor for tocotrienol synthesis, whereas phytyl diphosphate (PDP) is the prenyl donor for tocopherol synthesis. We have previously shown that tocotrienol synthesis is initiated in monocot seeds by homogentisate geranylgeranyl transferase (HGGT). This enzyme is related to homogentisate phytyltransferase (HPT), which catalyzes the prenylation step in tocopherol synthesis. Here we show that monocot HGGT is localized in the plastid and expressed primarily in seed endosperm. Despite the close structural relationship of monocot HGGT and HPT, these enzymes were found to have distinct substrate specificities. Barley (Hordeum vulgare cv. Morex) HGGT expressed in insect cells was six times more active with GGDP than with PDP, whereas the Arabidopsis HPT was nine times more active with PDP than with GGDP. However, only small differences were detected in the apparent K_m values of barley HGGT for GGDP and PDP. Consistent with its in vitro substrate properties, barley HGGT generated a mixture of tocotrienols and tocopherols when expressed in the vitamin E‐null vte2‐1 mutant lacking a functional HPT. Relative levels of tocotrienols and tocopherols produced in vte2‐1 differed between organs and growth stages, reflective of the composition of plastidic pools of GGDP and PDP. In addition, HGGT was able to functionally substitute for HPT to rescue vte2‐1‐associated phenotypes, including reduced seed viability and increased fatty acid oxidation of seed lipids. Overall, we show that monocot HGGT is biochemically distinct from HPT, but can replace HPT in important vitamin E‐related physiological processes.

  摘要维生素 E 的生育三烯酚和生育酚形式的生物合成是通过同戊烯二酸的前炔化作用开始的。香叶基二磷酸甘油酯（GGDP）是生育三烯酚合成的前酰供体，而生育酚合成的前酰供体是植烯醇二磷酸酯（PDP）。我们之前已经证明，在单子叶植物种子中，生育三烯酚的合成是由同源戊二酸龙葵酰转移酶（HGGT）启动的。这种酶与催化生育酚合成中的前酰化步骤的同源戊二酸植物酰基转移酶（HPT）有关。在这里，我们发现单子叶植物的 HGGT 定位于质体，主要在种子胚乳中表达。尽管单子叶植物 HGGT 和 HPT 的结构关系密切，但我们发现这些酶具有不同的底物特异性。在昆虫细胞中表达的大麦（Hordeum vulgare cv. Morex）HGGT 对 GGDP 的活性是对 PDP 的活性的六倍，而拟南芥 HPT 对 PDP 的活性是对 GGDP 的活性的九倍。然而，大麦 HGGT 对 GGDP 和 PDP 的表观 Km 值仅有微小差异。与其体外底物特性相一致的是，大麦 HGGT 在缺乏功能性 HPT 的维生素 E 缺失 vte2-1 突变体中表达时，会产生生育三烯酚和生育酚的混合物。在不同器官和生长阶段，vte2-1 产生的生育三烯酚和生育酚的相对水平不同，这反映了质体 GGDP 和 PDP 池的组成。此外，HGGT 能够在功能上替代 HPT 来挽救 vte2-1 相关的表型，包括种子活力降低和种子脂质的脂肪酸氧化增加。总之，我们的研究表明，单子叶植物 HGGT 在生物化学上不同于 HPT，但在重要的维生素 E 相关生理过程中可以替代 HPT。