Dehydromethionin

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Dehydromethionin
• 英文别名: 2-Imino-4-methylsulfanylbutanoic acid
• 化学式: C₅H₉NO₂S
• mdl: MFCD19229505
• 分子量: 147.198
• InChiKey: WEFMCFQVJIUASW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  86.4
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Dehydromethionin 在 水 作用下， 生成 4-甲硫基-2-氧代-丁酸
  参考文献：
  名称：

  离子液体作为酶促合成的性能添加剂

  摘要：

  电化学合成将氧化还原酶催化的反应与电化学反应物的供应结合起来。使用离子液体作为性能添加剂可有助于克服这些合成方法的现有局限性。在这里，我们报告了三种典型的电酶合成过程中不同水溶性离子液体对电导率，生物催化剂活性，稳定性或底物溶解度等关键参数的影响。在这些研究中，确定了有前途的离子液体，并已用作制备规模的三种电解体系的批量电解的添加剂。可以将NADPH的电化学再生的时空产率提高三倍。对于氨基酸氧化酶催化的蛋氨酸消旋体的拆分，以及二茂铁介导的酶结合辅因子FAD的电化学再生，可实现时空产率提高50％，催化剂利用率（TTN）提高140％。此外，对于氯过氧化物酶催化的（R）-苯基甲基亚砜通过电化学生成所需的共底物H 2 O 2，根据所使用的离子液体的不同，时空产率和催化剂利用率可提高至4.2倍。

  DOI：

  10.1002/chem.200901046
• 作为产物：
  描述：

  D-蛋氨酸 在 pseudomonas aeruginosa D-arginine dehydrogenase 、 5-甲基吩嗪硫酸甲酯 作用下， 以 水 为溶剂， 生成 Dehydromethionin
  参考文献：
  名称：

  Importance of glutamate 87 and the substrate α-amine for the reaction catalyzed by d-arginine dehydrogenase

  摘要：

  Pseudomonas aeruginosa D-arginine dehydrogenaie (PaDADH) catalyzes the oxidation of b-arginine to iminoarginine, which is non-enzymatically hydrolyzed to 2-ketoarginine and ammonia. Here, sitedirected mutagenesis and pH effects were used to investigate binding and catalysis of zwitterionic and cationic substrates for the enzyme. An unprotonated group with apparent pK(a) value >= 7.9 is required for binding D-arginine or D-lysine, but not D-methionine or D-leucine. This group is E87, as suggested by its replacement with leucine. An unprotonated group with pK(a) of 9.5, which persists in the H48F and E87L variants, is required for amine oxidation with all substrates. Since Y53 and Y249 were previously ruled out, the pK(a) is assigned to the substrate alpha-NH3+ group, which previous QM/MM and K-d pH-profile demonstrated to be protonated for preferred binding to the enzyme. Lack of pH effects on the Dk(red) with D-leucine established 9.5 as the intrinsic pK(a), and D-leucine as a non-sticky substrate. D-Arginine, D-lysine and D-methionine and their corresponding iminoproducts were significantly stickier than D-leucine, as indicated by apparent pK(a) values <9.5 in both k(cat)/K-m and k(cat). Restricted proton movements in catalysis were established from hollowed k(cat) pH profiles in wild-type PaDADH with D-lysine and in the H48F and E87L enzymes with D-arginine. (C) 2015 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.abb.2015.01.017

文献信息

• Metal Modulation: An Effortless Tactic for Refining Photoredox Catalysis in Living Cells
  作者：Le Yu、Kyung-Woo Lee、Yu-Qiang Zhao、Yunjie Xu、Ying Zhou、Mingle Li、Jong Seung Kim

  DOI：10.1021/acs.inorgchem.3c03284

  日期：2023.11.13

  quest for novel photoredox catalysts (PCs) suitable for living systems, or the enhancement of catalytic efficacy in existing biocompatible PC systems, persists as a formidable challenge. Within this context, we introduce a readily applicable metal modulation strategy that significantly augments photoredox catalysis within living cells, exemplified by a set of metalloporphyrin complexes termed M-TCPPs

  光氧化还原催化化学的显着影响引发了一股创新浪潮，为催化抗肿瘤治疗领域的新型生物技术打开了大门。然而，寻找适合生命系统的新型光氧化还原催化剂（PC），或提高现有生物相容性 PC 系统的催化效率，仍然是一项艰巨的挑战。在此背景下，我们引入了一种易于应用的金属调节策略，可显着增强活细胞内的光氧化还原催化作用，例如一组称为 M-TCPP（M = Zn、Mn、Ni、Co、Cu）的金属卟啉复合物。在这些配合物中，Zn-TCPP 作为一种特殊的催化剂而出现，在烟酰胺腺嘌呤二核苷酸 (NADH)、烟酰胺腺嘌呤二核苷酸磷酸 (NADPH) 和特定氨基酸的氧化中表现出显着的光催化活性。值得注意的是，综合研究表明，Zn-TCPP 卓越的催化能力主要来自于为 PC 建立了有效的氧化循环，这与之前报道的参与还原循环的 PC 不同。此外，理论计算表明，Zn-TCPP 中系间交叉率的放大和几何结构的改变有助于提高其光催化性能。体外研究表明，Zn-TCPP
• Importance of glutamate 87 and the substrate α-amine for the reaction catalyzed by d-arginine dehydrogenase
  作者：Jacob Ball、Quan V.V. Bui、Swathi Gannavaram、Giovanni Gadda

  DOI：10.1016/j.abb.2015.01.017

  日期：2015.2

  Pseudomonas aeruginosa D-arginine dehydrogenaie (PaDADH) catalyzes the oxidation of b-arginine to iminoarginine, which is non-enzymatically hydrolyzed to 2-ketoarginine and ammonia. Here, sitedirected mutagenesis and pH effects were used to investigate binding and catalysis of zwitterionic and cationic substrates for the enzyme. An unprotonated group with apparent pK(a) value >= 7.9 is required for binding D-arginine or D-lysine, but not D-methionine or D-leucine. This group is E87, as suggested by its replacement with leucine. An unprotonated group with pK(a) of 9.5, which persists in the H48F and E87L variants, is required for amine oxidation with all substrates. Since Y53 and Y249 were previously ruled out, the pK(a) is assigned to the substrate alpha-NH3+ group, which previous QM/MM and K-d pH-profile demonstrated to be protonated for preferred binding to the enzyme. Lack of pH effects on the Dk(red) with D-leucine established 9.5 as the intrinsic pK(a), and D-leucine as a non-sticky substrate. D-Arginine, D-lysine and D-methionine and their corresponding iminoproducts were significantly stickier than D-leucine, as indicated by apparent pK(a) values <9.5 in both k(cat)/K-m and k(cat). Restricted proton movements in catalysis were established from hollowed k(cat) pH profiles in wild-type PaDADH with D-lysine and in the H48F and E87L enzymes with D-arginine. (C) 2015 Elsevier Inc. All rights reserved.
• Ionic Liquids as Performance Additives for Electroenzymatic Syntheses
  作者：Christina Kohlmann、Lasse Greiner、Walter Leitner、Christian Wandrey、Stephan Lütz

  DOI：10.1002/chem.200901046

  日期：2009.11.2

  Electroenzymatic syntheses combine oxidoreductase‐catalysed reactions with electrochemical reactant supply. The use of ionic liquids as performance additives can contribute to overcoming existing limitations of these syntheses. Here, we report on the influence of different water‐miscible ionic liquids on critical parameters such as conductivity, biocatalyst activity and stability or substrate solubility

  电化学合成将氧化还原酶催化的反应与电化学反应物的供应结合起来。使用离子液体作为性能添加剂可有助于克服这些合成方法的现有局限性。在这里，我们报告了三种典型的电酶合成过程中不同水溶性离子液体对电导率，生物催化剂活性，稳定性或底物溶解度等关键参数的影响。在这些研究中，确定了有前途的离子液体，并已用作制备规模的三种电解体系的批量电解的添加剂。可以将NADPH的电化学再生的时空产率提高三倍。对于氨基酸氧化酶催化的蛋氨酸消旋体的拆分，以及二茂铁介导的酶结合辅因子FAD的电化学再生，可实现时空产率提高50％，催化剂利用率（TTN）提高140％。此外，对于氯过氧化物酶催化的（R）-苯基甲基亚砜通过电化学生成所需的共底物H 2 O 2，根据所使用的离子液体的不同，时空产率和催化剂利用率可提高至4.2倍。