4-coumaric acid methyl thio ester

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 4-coumaric acid methyl thio ester
• 英文别名: thiomethyl p-coumaric acid；S-methyl (E)-3-(4-hydroxyphenyl)prop-2-enethioate
• 化学式: C₁₀H₁₀O₂S
• 分子量: 194.254
• InChiKey: RFQMBUPXJLCAIT-QPJJXVBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  四乙基醋酸铵 、 4-coumaric acid methyl thio ester 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  溶剂和 H/D 同位素对异共轭氢键合苯酚-羧酸阴离子中质子转移途径的影响，通过紫外-可见光和核磁共振联合光谱观察

  摘要：

  已通过低温紫外-可见光和 ( ) 组合研究了溶解在 CD2Cl2 和 CDF3/CDF2Cl 中的酚 (AH) 和羧酸/无机酸 (HX) 的杂共轭氢键阴离子 A…H…X(-) 1) H/(13)C 核磁共振光谱 (UVNMR)。该系统构成了蛋白质中氢键辅助因子的小分子模型，例如光活性黄色蛋白 (PYP)。因此，研究的酚类包括 PYP 辅因子 4-羟基肉桂酸甲基硫酯，以及模拟电子激发辅因子状态的酸性更强的 4-硝基苯酚和 2-氯-4-硝基苯酚。结果表明，A...H...X(-) 的酚残基的 (13)C 化学位移，参考 A...H...A(-) 的相应值，构成了极好的平均质子位置的探针。这些位移与氢键质子的位移相关，以及 H/D 同位素对 (13)C 化学位移的影响。UV-vis 和 NMR 数据的组合分析用于以定性方式阐明质子转移途径。酚部分的双吸收带表明所研究的最短 OHO 氢键的双井情况

  DOI：

  10.1021/ja400611x
• 作为产物：
  描述：

  p-coumaric acid anhydride 、 sodium thiomethoxide 以 N,N-二甲基甲酰胺 为溶剂， 以235 mg的产率得到4-coumaric acid methyl thio ester
  参考文献：
  名称：

  Photo-isomerization upshifts the pKa of the Photoactive Yellow Protein chromophore to contribute to photocycle propagation

  摘要：

  The influence of chromophore structure on the protonation constant of the Photoactive Yellow Protein chromophore is explored with isolated para-coumaric acid (pCA) and thiomethyl-para-coumaric acid model chromophores in solution. pH titration coupled with visible absorption spectra of the trans and photogenerated cis conformer of isolated pCA demonstrates that the isomerization of the chromophore increases the pK(a) of the phenolate group by 0.6 units (to 10.1 +/- 0.22). Formation of the pCA thioester reduces the pK(a) of the phenolic group by 0.3 units (from 9.5 +/- 0.15 to 9.2 +/- 0.16). Unfortunately, a macroscopic cis-TMpCA population was not achieved via photoexcitation. Both trends were explained with electronic structure calculations including a Natural Bond Orbital analysis that resolves that the pK(a) upshift for the cis configuration is attributed to increased Columbic repulsion between the coumaryl tail and the phenolate moieties. This structurally induced pK(a) upshift after isomerization is argued to aid in the protonation of the chromophore within the PYP protein environment and the subsequent propagation of the photocycle response and in vivo photo-activity. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jphotochem.2013.06.019

文献信息

• ENZYMES OF LUCIFERIN BIOSYNTHESIS AND USE THEREOF
  申请人：Light Bio, Inc

  公开号：EP3816282A1

  公开（公告）日：2021-05-05

  Present invention is aimed at identification of new fungal luciferin biosynthesis enzymes, nucleic acids able to encode these enzymes, and proteins able to catalyze certain stages of the fungal luciferin biosynthesis. The invention also provides for application of nucleic acids for producing said enzymes in a cell or organism. Methods for in vitro or in vivo preparation of chemical compounds identical to fungal luciferins and preluciferins are also provided. Vectors comprising nucleic acid described in the present invention are also provided. In addition, the present invention provides expression cassettes comprising the nucleic acid of the present invention and regulatory elements necessary for nucleic acid expression in a selected host cell. Besides, cells, stable cell lines, transgenic organisms (e.g. plants, animals, fungi, or microorganisms) including nucleic acids, vectors, or expression cassettes of the present invention are also provided. Present invention also provides combinations of nucleic acids to obtain autonomously luminous cells, cell lines, or transgenic organisms. In preferred embodiments, cells or transgenic organisms are capable to produce fungal luciferin from precursors. In some embodiments, cells or transgenic organisms are capable to produce fungal preluciferin from precursors. In some embodiments, cells or transgenic organisms are capable of bioluminescence in the presence of a fungal luciferin precursor. In some embodiments, cells or transgenic organisms are capable of autonomous bioluminescence. Combinations of proteins for producing luciferin or its precursors from more simple chemical compounds are also provided. A kit containing nucleic acids, vectors, or expression cassettes of the present invention for producing luminous cells, cell lines, or transgenic organisms is also provided.

  本发明旨在鉴定新的真菌荧光素生物合成酶、能够编码这些酶的核酸以及能够催化真菌荧光素生物合成某些阶段的蛋白质。本发明还提供了核酸在细胞或生物体内产生上述酶的应用。本发明还提供了体外或体内制备与真菌荧光素和预荧光素相同的化合物的方法。还提供了包含本发明所述核酸的载体。此外，本发明还提供了包含本发明核酸和在所选宿主细胞中表达核酸所需的调控元件的表达盒。此外，本发明还提供了包括本发明核酸、载体或表达盒的细胞、稳定细胞系、转基因生物（如植物、动物、真菌或微生物）。本发明还提供了核酸组合，以获得自主发光的细胞、细胞系或转基因生物。在优选的实施方案中，细胞或转基因生物能够从前体产生真菌荧光素。在某些实施方案中，细胞或转基因生物能够从前体产生真菌前荧光素。在某些实施方案中，细胞或转基因生物能够在真菌荧光素前体存在的情况下发出生物荧光。在某些实施方案中，细胞或转基因生物能够自主发出生物荧光。此外，还提供了从更简单的化合物中生产荧光素或其前体的蛋白质组合。还提供了含有本发明核酸、载体或表达盒的试剂盒，用于生产发光细胞、细胞系或转基因生物。
• Ultrafast Dynamics of Isolated Model Photoactive Yellow Protein Chromophores:  “Chemical Perturbation Theory” in the Laboratory
  作者：Mikas Vengris、Delmar S. Larsen、Michael A. van der Horst、Olaf F. A. Larsen、Klaas J. Hellingwerf、Rienk van Grondelle

  DOI：10.1021/jp045763d

  日期：2005.3.1

  Pump-probe and pump-dump probe experiments have been performed on several isolated model chromophores of the photoactive yellow protein (PYP). The observed transient absorption spectra are discussed in terms of the spectral signatures ascribed to solvation, excited-state twisting, and vibrational relaxation. It is observed that the protonation state has a profound effect on the excited-state lifetime of p-coumaric acid. Pigments with ester groups on the cournaryl tail end and charged phenolic moieties show dynamics that are significantly different from those of other pigments. Here, an unrelaxed ground-state intermediate could be observed in pump-probe signals. A similar intermediate could be identified in the sinapinic acid and in isomerization-locked chromophores by means of pump-dump probe spectroscopy; however, in these compounds it is less pronounced and could be due to ground-state solvation and/or vibrational relaxation. Because of strong protonation-state dependencies and the effect of electron donor groups, it is argued that charge redistribution upon excitation determines the twisting reaction pathway, possibly through interaction with the environment. It is suggested that the same pathway may be responsible for the initiation of the photocycle in native PYP.
• Solvent and H/D Isotope Effects on the Proton Transfer Pathways in Heteroconjugated Hydrogen-Bonded Phenol-Carboxylic Acid Anions Observed by Combined UV–vis and NMR Spectroscopy
  作者：Benjamin Koeppe、Jing Guo、Peter M. Tolstoy、Gleb S. Denisov、Hans-Heinrich Limbach

  DOI：10.1021/ja400611x

  日期：2013.5.22

  states. It is shown that the (13)C chemical shifts of the phenolic residues of A···H···X(-), referenced to the corresponding values of A···H···A(-), constitute excellent probes for the average proton positions. These shifts correlate with those of the H-bonded protons, as well as with the H/D isotope effects on the (13)C chemical shifts. A combined analysis of UV-vis and NMR data was employed to elucidate

  已通过低温紫外-可见光和 ( ) 组合研究了溶解在 CD2Cl2 和 CDF3/CDF2Cl 中的酚 (AH) 和羧酸/无机酸 (HX) 的杂共轭氢键阴离子 A…H…X(-) 1) H/(13)C 核磁共振光谱 (UVNMR)。该系统构成了蛋白质中氢键辅助因子的小分子模型，例如光活性黄色蛋白 (PYP)。因此，研究的酚类包括 PYP 辅因子 4-羟基肉桂酸甲基硫酯，以及模拟电子激发辅因子状态的酸性更强的 4-硝基苯酚和 2-氯-4-硝基苯酚。结果表明，A...H...X(-) 的酚残基的 (13)C 化学位移，参考 A...H...A(-) 的相应值，构成了极好的平均质子位置的探针。这些位移与氢键质子的位移相关，以及 H/D 同位素对 (13)C 化学位移的影响。UV-vis 和 NMR 数据的组合分析用于以定性方式阐明质子转移途径。酚部分的双吸收带表明所研究的最短 OHO 氢键的双井情况
• Photo-isomerization upshifts the pKa of the Photoactive Yellow Protein chromophore to contribute to photocycle propagation
  作者：Sadia Naseem、Adèle D. Laurent、Elizabeth C. Carroll、Mikas Vengris、Masato Kumauchi、Wouter D. Hoff、Anna I. Krylov、Delmar S. Larsen

  DOI：10.1016/j.jphotochem.2013.06.019

  日期：2013.10

  The influence of chromophore structure on the protonation constant of the Photoactive Yellow Protein chromophore is explored with isolated para-coumaric acid (pCA) and thiomethyl-para-coumaric acid model chromophores in solution. pH titration coupled with visible absorption spectra of the trans and photogenerated cis conformer of isolated pCA demonstrates that the isomerization of the chromophore increases the pK(a) of the phenolate group by 0.6 units (to 10.1 +/- 0.22). Formation of the pCA thioester reduces the pK(a) of the phenolic group by 0.3 units (from 9.5 +/- 0.15 to 9.2 +/- 0.16). Unfortunately, a macroscopic cis-TMpCA population was not achieved via photoexcitation. Both trends were explained with electronic structure calculations including a Natural Bond Orbital analysis that resolves that the pK(a) upshift for the cis configuration is attributed to increased Columbic repulsion between the coumaryl tail and the phenolate moieties. This structurally induced pK(a) upshift after isomerization is argued to aid in the protonation of the chromophore within the PYP protein environment and the subsequent propagation of the photocycle response and in vivo photo-activity. (C) 2013 Elsevier B.V. All rights reserved.