3-[(2Z,3S,4S)-5-[(4-ethenyl-3-methyl-5-oxo-1,2-dihydropyrrol-2-yl)methyl]-2-[(5R)-2-[(3-ethyl-5-formyl-4-methyl-1H-pyrrol-2-yl)methyl]-5-methoxycarbonyl-3-methyl-4-oxo-1H-cyclopenta[b]pyrrol-6-ylidene]-4-methyl-3,4-dihydropyrrol-3-yl]propanoate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 3-[(2Z,3S,4S)-5-[(4-ethenyl-3-methyl-5-oxo-1,2-dihydropyrrol-2-yl)methyl]-2-[(5R)-2-[(3-ethyl-5-formyl-4-methyl-1H-pyrrol-2-yl)methyl]-5-methoxycarbonyl-3-methyl-4-oxo-1H-cyclopenta[b]pyrrol-6-ylidene]-4-methyl-3,4-dihydropyrrol-3-yl]propanoate
• 化学式: C35H39N4O7-
• 分子量: 627.7
• InChiKey: ULSSSZOYSMVFIJ-NPQUFKRBSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  46
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  174
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [2Fe-2S]²⁺ 、 3-[(2Z,3S,4S)-5-[(4-ethenyl-3-methyl-5-oxo-1,2-dihydropyrrol-2-yl)methyl]-2-[(5R)-2-[(3-ethyl-5-formyl-4-methyl-1H-pyrrol-2-yl)methyl]-5-methoxycarbonyl-3-methyl-4-oxo-1H-cyclopenta[b]pyrrol-6-ylidene]-4-methyl-3,4-dihydropyrrol-3-yl]propanoate 生成 氢(+1)阳离子 、 red chlorophyll catabolite 、 [2Fe-2S]¹⁺
  参考文献：
  名称：

  Chlorophyll Breakdown in Senescent Chloroplasts (Cleavage of Pheophorbide a in Two Enzymic Steps)

  摘要：

  研究了老化叶绿体中Pheophorbide（Pheide）a裂解为主要荧光叶绿素（Chl）降解产物（pFCCs）的过程。从老化油菜（Brassica napus）子叶中分离出的叶绿体制备物，在添加ferredoxin（Fd）的检测混合物中，表现出光依赖性的pFCC产生。在溶剂化的膜中，pFCC的产生取决于存在Fd还原系统。Pheide a的裂解需要两种蛋白质的作用，即Pheide a氧化酶和一个基质蛋白质。在缺乏基质蛋白质的情况下，Pheide a氧化酶将Pheide a转化为红色的Chl降解产物（RCC），这是Pheide a裂解的推定中间产物。将基质蛋白质（RCC还原酶）与化学合成的RCC一起孵育，结果产生了三种不同的FCC。其中两种降解产物分别与油菜或大麦（Hordeum vulgare）（pFCC-1）和甜椒（Capsicum annuum）（pFCC-2）中的pFCC完全相同。因此，Pheide a转化为pFCC的过程可以被证明是分为两个连续步骤进行的，而且两个反应都取决于还原的Fd作为电子来源。Fd在Chl降解中的功能得到了免疫印迹证实，因为这种蛋白质在老化的晚期仍然明显存在。

  DOI：

  10.1104/pp.115.2.669

文献信息

• CHLOROPHYLL DEGRADATION DURING SENESCENCE
  作者：S. Hörtensteiner

  DOI：10.1146/annurev.arplant.57.032905.105212

  日期：2006.6.1

  The catabolic pathway of chlorophyll (Chl) during senescence and fruit ripening leads to the accumulation of colorless breakdown products (NCCs). This review updates an earlier review on Chl breakdown published here in 1999 ( 69 ). It summarizes recent advances in the biochemical reactions of the pathway and describes the characterization of new NCCs and their formation inside the vacuole. Furthermore, I focus on the recent molecular identification of three chl catabolic enzymes, chlorophyllase, pheophorbide a oxygenase (PAO), and red Chl catabolite reductase (RCCR). The analysis of Chl catabolic mutants demonstrates the importance of Chl breakdown for plant development and survival. Mutants defective in PAO or RCCR develop a lesion mimic phenotype, due to the accumulation of breakdown intermediates. Thus, Chl breakdown is a prerequisite to detoxify the potentially phototoxic pigment within the vacuoles in order to permit the remobilization of nitrogen from Chl-binding proteins to proceed during senescence.

  叶绿素（Chl）在衰老和果实成熟期间的分解途径会导致无色分解产物（NCCs）的积累。本文综述了1999年在此处发表的叶绿素分解的早期综述的最新进展。它总结了途径中的生化反应的最新进展，并描述了新NCCs的特征以及它们在液泡内的形成。此外，我重点关注了三种叶绿素分解酶的最新分子鉴定，即叶绿素酶，苤叶酸a氧化酶（PAO）和红色叶绿素分解产物还原酶（RCCR）。叶绿素分解突变体的分析证明了叶绿素分解对植物发育和生存的重要性。缺陷PAO或RCCR的突变体会发展出病变模仿表型，因为分解中间体的积累。因此，叶绿素分解是在液泡内解毒潜在光毒性色素的先决条件，以允许在衰老期间从叶绿素结合蛋白中解除氮素。
• In Vivo Participation of Red Chlorophyll Catabolite Reductase in Chlorophyll Breakdown
  作者：Adriana Pružinská、Iwona Anders、Sylvain Aubry、Nicole Schenk、Esther Tapernoux-Lüthi、Thomas Müller、Bernhard Kräutler、Stefan Hörtensteiner

  DOI：10.1105/tpc.106.044404

  日期：2007.2.27

  reaction of chlorophyll breakdown, porphyrin ring opening of pheophorbide a to the primary fluorescent chlorophyll catabolite (pFCC), requires pheophorbide a oxygenase (PAO) and red chlorophyll catabolite reductase (RCCR), with red chlorophyll catabolite (RCC) as a presumably PAO-bound intermediate. In subsequent steps, pFCC is converted to different fluorescent chlorophyll catabolites (FCCs) and nonfluorescent

  叶绿素a的卟啉开环与初级荧光叶绿素分解代谢物（pFCC）的叶绿素分解的中心反应需要脱镁叶绿素加氧酶（PAO）和红色叶绿素分解代谢物还原酶（RCCR），其中红色叶绿素分解代谢物（RCC）可能是PAO结合中间体。在随后的步骤中，pFCC被转换为不同的荧光叶绿素分解代谢物（FCC）和非荧光叶绿素分解代谢物（NCC）。在这里，我们表明，RCCR缺陷拟南芥在衰老过程中会积聚RCC和三种RCC样色素，以及FCC和NCC。我们还显示，拟南芥RCCR的立体特异性由一个小的蛋白质结构域定义，并且可以通过单个Phe-Val交换逆转。利用此功能，我们证明了RCCR在体内参与叶绿素分解。在RCCR突变体与具有替代特异性的RCCRs互补后，叶绿素分解代谢产物的模式遵循互补RCCRs的特异性。在不同的RCCR缺陷品系中观察到的光依赖性叶细胞死亡与RCC的积累和单线态氧的释放严格相关，PAO诱导先于病灶形成。这些发现表
• Partial Purification and Characterization of Red Chlorophyll Catabolite Reductase, a Stroma Protein Involved in Chlorophyll Breakdown
  作者：S. Rodoni、F. Vicentini、M. Schellenberg、P. Matile、S. Hortensteiner

  DOI：10.1104/pp.115.2.677

  日期：1997.10.1

  Red chlorophyll (Chl) catabolite (RCC) reductase, which catalyzes the reaction of an intermediary Chl catabolite (RCC) in the two-step cleavage reaction of pheophorbide (Pheide) a into primary fluorescent catabolites (pFCCs) during Chl breakdown, was characterized and partially purified. RCC reductase activity was present at all stages of barley leaf development and even in roots. The highest specific activity was found in senescent leaves, which were used to purify RCC reductase 1000-fold. Among the remaining three proteins, RCC reductase activity was most likely associated with a 55-kD protein. RCC reductase exhibited saturation kinetics for RCC, with an apparent Michaelis constant of 0.6 mM. The reaction depended on reduced ferredoxin and was sensitive to oxygen. Assays of purified RCC reductase with chemically synthesized RCC as a substrate yielded three different FCCs, two of which could be identified as the stereoisomeric pFCCs from canola (Brassica napus) (pFCC-1) and sweet pepper (Capsicum annuum) (pFCC-2), respectively. In the coupled reaction with Pheide a oxidase and RCC reductase, either pFCC-1 or pFCC-2 was produced, depending on the plant species employed as a source of RCC reductase. Data from 18 species suggest that the stereospecific action of RCC reductase is uniform within a plant family.

  红色叶绿素（Chl）降解物（RCC）还原酶，在叶绿素分解过程中，催化中间产物Chl降解物（RCC）在苯丙卟啉（Pheide）a的两步裂解反应中，将其转化为主要的荧光降解物（pFCCs），并进行了表征和部分纯化。RCC还原酶活性在大麦叶片发育的所有阶段以及根部中均存在。最高的特异性活性在衰老的叶片中发现，用于将RCC还原酶纯化1000倍。在剩余的三种蛋白质中，RCC还原酶活性最可能与55kD蛋白质相关。RCC还原酶对RCC表现出饱和动力学，表观米氏常数为0.6mM。反应依赖于还原型叶绿素和对氧敏感。用化学合成的RCC作为底物进行纯化的RCC还原酶测定，产生了三种不同的FCC，其中两种可以分别鉴定为油菜（Brassica napus）和甜椒（Capsicum annuum）的立体异构体pFCC-1和pFCC-2。在Pheide a氧化酶和RCC还原酶的耦合反应中，根据作为RCC还原酶来源的植物物种的不同，产生pFCC-1或pFCC-2。来自18种物种的数据表明，RCC还原酶的立体特异性作用在植物家族内是一致的。

• Cytochrome P450 CYP89A9 Is Involved in the Formation of Major Chlorophyll Catabolites during Leaf Senescence in <i>Arabidopsis</i>    
  作者：Bastien Christ、Iris Süssenbacher、Simone Moser、Nicole Bichsel、Aurelie Egert、Thomas Müller、Bernhard Kräutler、Stefan Hörtensteiner

  DOI：10.1105/tpc.113.112151

  日期：2013.6.27

  Nonfluorescent chlorophyll catabolites (NCCs) were described as products of chlorophyll breakdown in Arabidopsis thaliana. NCCs are formyloxobilin-type catabolites derived from chlorophyll by oxygenolytic opening of the chlorin macrocycle. These linear tetrapyrroles are generated from their fluorescent chlorophyll catabolite (FCC) precursors by a nonenzymatic isomerization inside the vacuole of senescing

  非荧光叶绿素分解代谢物 (NCC) 被描述为拟南芥中叶绿素分解的产物。NCC 是通过二氢卟酚大环的氧化开放从叶绿素衍生的甲酰胆碱型分解代谢物。这些线性四吡咯是从它们的荧光叶绿素分解代谢物 (FCC) 前体通过衰老细胞液泡内的非酶异构化产生的。在这里，我们确定了一组不同的二氧胆碱型叶绿素分解代谢物 (DCC) 作为野生型拟南芥中的主要分解产物，占绿叶叶绿素的 90% 以上。确定了最丰富的非荧光 DCC (NDCC) At-NDCC-1 的分子构成。我们进一步确定细胞色素 P450 单加氧酶 CYP89A9 负责野生型拟南芥中 NDCC 的积累；CYP89A9 功能缺陷的 cyp89a9 突变体没有 NDCC，但按比例积累了更多的 NCC。CYP89A9 位于叶绿体之外，这意味着 FCCs 可能是其天然底物。使用重组 CYP89A9，我们确认了 FCC 特异性并表明荧光 DCC 是 CYP89A9
• Molecular cloning, functional expression and characterisation of RCC reductase involved in chlorophyll catabolism
  作者：Karin L. Wuthrich、Lucien Bovet、Peter E. Hunziker、Iain S. Donnison、Stefan Hortensteiner

  DOI：10.1046/j.1365-313x.2000.00667.x

  日期：2000.1

  SummaryRed chlorophyll catabolite (RCC) reductase (RCCR) and pheophorbide (Pheide) a oxygenase (PaO) catalyse the key reaction of chlorophyll catabolism, porphyrin macrocycle cleavage of Pheide a to a primary fluorescent catabolite (pFCC). RCCR was purified from barley and a partial gene sequence was cloned (pHvRCCR). The gene was expressed at all stages of leaf development and in roots. By comparison with different databases, genomic sequences and expressed sequence tags similar to RCCR were found in phylogenetically diverse species, and activity of RCCR was demonstrated in two of them, Arabidopsis thaliana and Marchantia polymorpha. The gene of A. thaliana (AtRCCR) was employed for molecular cloning, heterologous expression and the production of polyclonal antibodies. With recombinant RCCR, the major product of RCC reduction was pFCC‐1, but small quantities of its C1 epimer, pFCC‐2, also accumulated. The reaction required reduced ferredoxin and was sensitive to oxygen. AtRCCR encoded a 35 kDa protein which was used for chloroplast import experiments. Upon transport, it was processed to a mature form of 31 kDa. The significance of cloning of RCCR is discussed in respect to the evolution of chlorophyll catabolism and to the cloning of PaO.