6-tuliposide A | 19870-31-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 糖脂
• 英文名称: 6-tuliposide A
• 英文别名: [(2R,3S,4S,5R)-3,4,5,6-tetrahydroxyoxan-2-yl]methyl 4-hydroxy-2-methylidenebutanoate
• CAS: 19870-31-6；24951-69-7；25375-21-7
• 化学式: C₁₁H₁₈O₈
• 分子量: 278.259
• InChiKey: NABVFHUVYXEKSQ-OGADHKOYSA-N

物化性质

• 沸点：
  546.7±50.0 °C(Predicted)
• 密度：
  1.504±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  137
• 氢给体数：
  5
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  6-tuliposide A 在 Tulipa gesneriana tuliposide-converting enzyme 作用下， 以 水 为溶剂， 反应 0.17h， 生成 2-甲烯基丁内酯
  参考文献：
  名称：

  Purification and Characterization of a Tuliposide-Converting Enzyme from Bulbs ofTulipa gesneriana

  摘要：

  一种催化6-郁金香苷转化为郁金香醇的酶从郁金香（Tulipa gesneriana）的鳞茎中被纯化和表征。该酶似乎是一个二聚体，每个亚单位的相对分子质量（Mr）为34,900；它在中性pH和适中的温度下具有最强的活性和稳定性。该酶优先作用于6-郁金香苷等葡萄糖酯，对对硝基苯乙酸酯的作用则较弱。

  DOI：

  10.1271/bbb.90226

文献信息

• Precursor of α-Methylene-γ-butyrolactone Involved in the Insecticidal Activity of Thunberg Spiraea,<i>Spiraea thunbergii</i>
  作者：Chul-Sa KIM、Probal Kanti DATTA、Tetsuro HARA、Eiji ITOH、Michio HORIIKE

  DOI：10.1271/bbb.63.152

  日期：1999.1

  6-Tuliposide A 6-O-(4-hydroxy-α-methylenebutyryl)-D-glucopyranose} was isolated from thunberg spiraea (Spiraea thunbergii) leaves. Acid-hydrolysis of this compound generated tulipalin A (α-methylene-γ-butyrolactone). This compound is thus considered as a precursor of insecticidal tulipalin A.

  6-郁金香苷A 6-O-(4-羟基-α-亚甲基丁酸酯)-D-葡萄糖} 是从唐棕榈（Spiraea thunbergii）叶中分离出来的。该化合物的酸水解产生了郁金香醛A（α-亚甲基-γ-丁内酯）。因此，该化合物被视为杀虫剂郁金香醛A的前体。
• A Novel Lactone-Forming Carboxylesterase: Molecular Identification of a Tuliposide A-Converting Enzyme in Tulip  
  作者：Taiji Nomura、Shinjiro Ogita、Yasuo Kato

  DOI：10.1104/pp.112.195388

  日期：2012.6.1

  Tuliposides, the glucose esters of 4-hydroxy-2-methylenebutanoate and 3,4-dihydroxy-2-methylenebutanoate, are major secondary metabolites in tulip (Tulipa gesneriana). Their lactonized aglycons, tulipalins, function as defensive chemicals due to their biological activities. We recently found that tuliposide-converting enzyme (TCE) purified from tulip bulbs catalyzed the conversion of tuliposides to tulipalins, but the possibility of the presence of several TCE isozymes was raised: TCE in tissues other than bulbs is different from bulb TCE. Here, to prove this hypothesis, TCE was purified from petals, which have the second highest TCE activity after bulbs. The purified enzyme, like the bulb enzyme, preferentially accepted tuliposides as substrates, with 6-tuliposide A the best substrate, which allowed naming the enzyme tuliposide A-converting enzyme (TCEA), but specific activity and molecular mass differed between the petal and bulb enzymes. After peptide sequencing, a novel cDNA (TgTCEA) encoding petal TCEA was isolated, and the functional characterization of the recombinant enzyme verified that TgTCEA catalyzes the conversion of 6-tuliposide A to tulipalin A. TgTCEA was transcribed in all tulip tissues but not in bulbs, indicating the presence of a bulb-specific TgTCEA, as suggested by the distinct enzymatic characters between the petal and bulb enzymes. Plastidial localization of TgTCEA enzyme was revealed, which allowed proposing a cytological mechanism of TgTCE-mediated tulipalin formation in the tulip defensive strategy. Site-directed mutagenesis of TgTCEA suggested that the oxyanion hole and catalytic triad characteristic of typical carboxylesterases are essential for the catalytic process of TgTCEA enzyme. To our knowledge, TgTCEA is the first identified member of the lactone-forming carboxylesterases, specifically catalyzing intramolecular transesterification.

  郁金香（Tulipa gesneriana）中的主要次生代谢产物是4-羟基-2-亚甲基丁酸酯和3,4-二羟基-2-亚甲基丁酸酯的葡萄糖酯，称为郁金香苷。它们的内酯化裸核，郁金香素，由于其生物活性而起防御作用。我们最近发现，从郁金香鳞茎中纯化的郁金香苷转化酶（TCE）催化郁金香苷转化为郁金香素，但提出了存在多种TCE同工酶的可能性：除鳞茎以外的组织中的TCE与鳞茎TCE不同。为了证明这一假设，我们从花瓣中纯化了TCE，花瓣在鳞茎之后具有第二高的TCE活性。纯化的酶与鳞茎酶一样，优先接受郁金香苷作为底物，其中6-郁金香苷A是最好的底物，这使得该酶被命名为郁金香苷A转化酶（TCEA），但特异活性和分子量在花瓣和鳞茎酶之间有所不同。在肽测序后，我们分离了编码花瓣TCEA的新型cDNA（TgTCEA），并对重组酶的功能进行了表征，验证了TgTCEA催化6-郁金香苷A转化为郁金香素A。TgTCEA在所有郁金香组织中转录，但不在鳞茎中，表明存在鳞茎特异性的TgTCEA，这由花瓣和鳞茎酶之间的不同酶特性所提示。TgTCEA酶的质体定位揭示了TgTCE介导的郁金香素形成的细胞学机制。TgTCEA的位点定向突变表明，典型羧酸酯酶的氧离子孔和催化三元组对TgTCEA酶的催化过程是必不可少的。据我们所知，TgTCEA是首个已鉴定的内酯形成羧酸酯酶成员，特异地催化分子内酯交换反应。

• Purification and Characterization of a Tuliposide-Converting Enzyme from Bulbs of<i>Tulipa gesneriana</i>
  作者：Yasuo KATO、Kazuaki SHOJI、Makoto UBUKATA、Kengo SHIGETOMI、Yukio SATO、Noriyuki NAKAJIMA、Shinjiro OGITA

  DOI：10.1271/bbb.90226

  日期：2009.8.23

  An enzyme that catalyzes the stoichiometric conversion of 6-tuliposide into tulipalin was purified and characterized from bulbs of Tulipa gesneriana. The enzyme appeared to be a dimer, the relative molecular mass (Mr) of each subunit being 34,900; it had maximum activity and stability at neutral pH and moderate temperature. The enzyme preferentially acted on such glucose esters as 6-tuliposides, and to a lesser extent on p-nitrophenylacetate.

  一种催化6-郁金香苷转化为郁金香醇的酶从郁金香（Tulipa gesneriana）的鳞茎中被纯化和表征。该酶似乎是一个二聚体，每个亚单位的相对分子质量（Mr）为34,900；它在中性pH和适中的温度下具有最强的活性和稳定性。该酶优先作用于6-郁金香苷等葡萄糖酯，对对硝基苯乙酸酯的作用则较弱。