L-fuculose 1-phosphate(2-)

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: L-fuculose 1-phosphate(2-)
• 英文别名: [(3R,4R,5S)-3,4,5-trihydroxy-2-oxohexyl] phosphate
• 化学式: C6H11O8P-2
• 分子量: 242.12
• InChiKey: KNYGWWDTPGSEPD-LFRDXLMFSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -3.5
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  150
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  L-fuculose 1-phosphate(2-) 生成 (S)-乳醛 、 1,3-dihydroxyacetone phosphate
  参考文献：
  名称：

  l-岩藻糖-1-磷酸醛缩酶突变体的结构概述了催化过程中的运动。

  摘要：

  具有和不具有磷酸二羟基丙酮酯（DHAP）的连接类似物和许多活性中心突变体的1-岩藻糖-1-磷酸醛缩酶（FucA）的晶体结构已经建立了催化机理的模型。现在，通过对锌配位球和磷酸盐位点进一步突变的结构分析，证实了该模型。此外，这些突变体还揭示了催化作用的新方面：位于锌配位域外部的Tyr113'（来自相邻的亚基）的羟基将DHAP导向锌离子的生产性结合模式。Glu73在预期用于DHAP氧原子的两个配体位置之间接触锌，因此避免了四面体配位的羟基离子对这些位置的阻塞；FucA多肽没有假定其最低能量状态，而是在能量增加的两个状态之间振荡，这是由处于最低能量状态的突变体证明的。来回运动涉及一个可移动的环，该环将磷酸酯位点与亚基间的运动连接，从而与溶剂的布朗运动连接。磷酸根基团在给定距离上与锌离子牢固结合，从而防止形成过紧密的DHAP：锌络合物。该观察结果解释了我们未能找到接受DHAP的无磷酸盐替代物的突变

  DOI：

  10.1006/jmbi.2000.4153
• 作为产物：
  描述：

  adenosine 5'-triphosphate 、 L-墨角藻糖 生成 adenosine 5'-diphosphate 、 氢(+1)阳离子 、 L-fuculose 1-phosphate(2-)
  参考文献：
  名称：

  L-鼠李糖激酶的底物光谱与衍生自两个三元复杂结构的模型有关。

  摘要：

  来自大肠杆菌的酶L-鼠李糖激酶参与L-鼠李糖（一种常见的天然脱氧己糖）的降解途径。三元复合物及其底物ADP和L-鼠李糖的酶结构已在1.55A分辨率下测定，并精炼到0.179 / 0.209的R（结晶）/ R（游离）值。将结果与包含L-果糖而不是L-鼠李糖的相应复合物的较低分辨率结构进行了比较。鉴于两个确定的糖位置和构象，已将许多稀有糖建模到L-鼠李糖激酶的活性中心中，并将模型结构与已知的酶促磷酸化率进行了比较。稀有糖对于生物活性化合物的合成具有越来越高的兴趣。

  DOI：

  10.1016/j.febslet.2007.05.075

文献信息

• Metabolism of <scp>d</scp> -Arabinose: Origin of a <scp>d</scp> -Ribulokinase Activity in <i>Escherichia coli</i>
  作者：Donald J. LeBlanc、Robert P. Mortlock

  DOI：10.1128/jb.106.1.82-89.1971

  日期：1971.4

  The kinase responsible for the phosphorylation of d -ribulose was purified 45.5-fold from a strain of Escherichia coli K-12 capable of growth on d -arabinose with no separation of d -ribulo- or l -fuculokinase activities. Throughout the purification, the ratios of activities remained essentially constant. A nonadditive effect of combining both substrates in an assay mixture; identical K _m values for adenosine triphosphate with either l -fuculose or d -ribulose as substrate; and, the irreversible loss of activity on both substrates, after removal of magnesium ions from the enzyme preparation, suggest that the dual activity is due to the same enzyme. A fourfold greater affinity of the enzyme for l -fuculose than for d -ribulose, as well as a higher relative activity on l -fuculose, suggest that the natural substrate for this enzyme is l -fuculose. The product of the purified enzyme, with d -ribulose as substrate, was prepared. The ratio of total phosphorous to ribulose phosphate was 1.01:1, indicating that the product was ribulose monophosphate. The behavior of the kinase product in the cysteine-carbazole and orcinol reactions, as well as the results of periodate oxidation assays, provided evidence that it was not d -ribulose-5-phosphate. Reaction of this compound with a cell-free extract of E. coli possessing l -fuculose-l-phosphate aldolase activity resulted in the production of dihydroxyacetone phosphate and glycolaldehyde. The kinase product failed to reduce 2,3,5-triphenyltetrazolium and possessed a half-life of approximately 1.5 min in the presence of 1 n HCl at 100 C. These properties suggested that the phosphate group was attached to carbon atom 1 of d -ribulose.

  从能够在d-阿拉伯糖上生长的大肠杆菌K-12菌株中，分离了负责磷酸化d-核糖醇的激酶，其纯化程度为45.5倍。在纯化过程中，活性比例基本保持不变。在测定混合底物时，两种底物的Km值相同，且去除酶制剂中镁离子后，两种底物的活性都不可逆地丧失，表明双重活性是由同一酶引起的。酶对l-岩藻糖的亲和力比对d-核糖醇高4倍，并且在l-岩藻糖上的相对活性更高，这表明该酶的天然底物是l-岩藻糖。用d-核糖醇作为底物制备了纯化酶的产物，总磷与核糖醇磷酸的比值为1.01：1，表明产物是核糖醇一磷酸盐。该酶的产物在半胱氨酸-咔唑和奥卡酚反应中的行为，以及过碘酸盐氧化测定的结果，证明它不是d-核糖醇-5-磷酸盐。将该化合物与具有l-岩藻糖-l-磷酸醛缩酶活性的大肠杆菌无细胞提取物反应，产生二羟基丙酮磷酸盐和甘醛。该酶的产物无法还原2,3,5-三苯基四唑，并在1 N HCl存在下的半衰期约为1.5分钟。这些性质表明磷酸基附着在d-核糖醇的碳原子1上。
• Metabolism of <scp>d</scp> -Arabinose: a New Pathway in <i>Escherichia coli</i>
  作者：Donald J. LeBlanc、Robert P. Mortlock

  DOI：10.1128/jb.106.1.90-96.1971

  日期：1971.4

  Several growth characteristics of Escherichia coli K-12 suggest that growth on l -fucose results in the synthesis of all the enzymes necessary for growth on d -arabinose. Conversely, when a mutant of E. coli is grown on d -arabinose, all of the enzymes necessary for immediate growth on l -fucose are present. Three enzymes of the l -fucose pathway in E. coli , l -fucose isomerase, l -fuculokinase, and l -fuculose-l-phospháte aldolase possess activity on d -arabinose, d -ribulose, and d -ribulose-l-phosphate, respectively. The products of the aldolase, with d -ribulose-l-phosphate as substrate, are dihydroxyacetone phosphate and glycolaldehyde. l -Fucose, but not d -arabinose, is capable of inducing these activities in wild-type E. coli . In mutants capable of utilizing d -arabinose as sole source of carbon and energy, these activities are induced in the presence of d -arabinose and in the presence of l -fucose. Mutants unable to utilize l -fucose, selected from strains capable of growth on d -arabinose, are found to have lost the ability to grow on d -arabinose. Enzymatic analysis of cell-free extracts, prepared from cultures of these mutants, reveals that a deficiency in any of the l -fucose pathway enzymes results in the loss of ability to utilize d -arabinose. Thus, the pathway of d -arabinose catabolism in E. coli K-12 is believed to be: d -arabinose ⇌ d -ribulose → d -ribulose-l-phosphate ⇌ dihydroxyacetone phosphate plus glycolaldehyde. Evidence is presented which suggests that the glycolaldehyde is further oxidized to glycolate.

  大肠杆菌K-12的几个生长特征表明，在L-岩藻糖上生长会导致合成生长所需的D-阿拉伯糖酶。相反，当大肠杆菌的突变体在D-阿拉伯糖上生长时，即可立即合成生长所需的L-岩藻糖酶。大肠杆菌中L-岩藻糖途径的三种酶，即L-岩藻糖异构酶、L-岩藻糖激酶和L-岩藻糖醛酸酯酶，分别对D-阿拉伯糖、D-核糖醇和D-核糖醇-1-磷酸具有活性。以D-核糖醛酸为底物的醛酸酯的产物是二羟基乙酮磷酸和甘醛。L-岩藻糖而不是D-阿拉伯糖能够在野生型大肠杆菌中诱导这些活性。在能够利用D-阿拉伯糖作为碳和能源的突变体中，在D-阿拉伯糖和L-岩藻糖存在的情况下，这些活性被诱导。从能够在D-阿拉伯糖上生长的菌株中选择无法利用L-岩藻糖的突变体，发现它们已经失去了在D-阿拉伯糖上生长的能力。从这些突变体培养物中制备的细胞游离提取物的酶分析表明，任何L-岩藻糖途径酶的缺乏都会导致无法利用D-阿拉伯糖。因此，D-阿拉伯糖在大肠杆菌K-12中的分解途径被认为是：D-阿拉伯糖 ⇌ D-核糖醛糖 → D-核糖醛糖-1-磷酸 ⇌ 二羟基乙酮磷酸和甘醛。提供了证据表明，甘醛进一步被氧化为甘酸。
• Catalytic Mechanism of the Metal-dependent Fuculose Aldolase fromEscherichia colias Derived from the Structure
  作者：Matthias K. Dreyer、Georg E. Schulz

  DOI：10.1006/jmbi.1996.0332

  日期：1996.6

  ion of this metal-dependent class II aldolase with its hydroxyl and keto oxygen atoms, shifting Glu73 away from the zinc coordination sphere to a non-polar environment. At this position Glu73 accepts a proton in the initial reaction step, producing the enediolate which is then stabilized by the zinc ion. The other substrate moiety L-lactaldehyde was modeled, because no binding structure is yet available

  分别在有和没有抑制剂的情况下，分别测定了分辨率为2.4和2.7埃（1埃= 0.1 nm）的L-岩藻糖-1-磷酸醛缩酶的立方晶体结构。该抑制剂模拟底物部分磷酸二羟基丙酮的烯醇盐过渡态。结构表明，磷酸二羟基丙酮将这种金属依赖性II类醛缩酶的锌离子与其羟基和酮氧原子连接起来，从而将Glu73从锌配位球转移到非极性环境中。在初始反应步骤中，Glu73在此位置接受质子，生成烯二醇盐，然后通过锌离子将其稳定化。对其他底物部分L-丙醛进行了建模，因为尚无可用的结合结构。
• Heath E.C.; Ghalambor M.A., J Biol Chem, 1962, 0021-9258, 2423-6
  作者：Heath E.C.、Ghalambor M.A.

  DOI：——

  日期：——
• Catalytic Action of Fuculose 1-Phosphate Aldolase (Class II) As Derived from Structure-Directed Mutagenesis^,
  作者：Andreas C. Joerger、Claudius Gosse、Wolf-Dieter Fessner、Georg E. Schulz

  DOI：10.1021/bi9927686

  日期：2000.5.1

  Previous analyses established the structures of unligated L-fuculose 1-phosphate aldolase and of the enzyme ligated with an inhibitor mimicking the substrate dihydroxyacetone phosphate. These data allowed us to suggest a catalytic mechanism. On the basis of this proposal, numerous mutations were now introduced at the active center and tested with respect to their catalytic rates and their product distributions. For several mutants, the structures were determined. The results demonstrate the catalytic importance of some particular residues in defined conformations and in the mobile C-terminal chain end. Moreover, they led to a modification of the proposed mechanism. The effect of some mutations on enantioselectivity and on the ratio of diastereomer formation indicates clearly the binding site of the aldehyde moiety in relation to the other substrate dihydroxyacetone phosphate.