Sulfonatoacetaldehyde

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: Sulfonatoacetaldehyde
• 英文别名: 2-oxoethanesulfonate
• 化学式: C2H3O4S-
• 分子量: 123.11
• InChiKey: JTJIXCMSHWPJJE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.4
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  82.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  coenzyme A 、 NADP⁺ 、 Sulfonatoacetaldehyde 生成 氢(+1)阳离子 、 NADPH(4-) 、 sulfoacetyl-CoA(5-)
  参考文献：
  名称：

  Sulfoacetate Is Degraded via a Novel Pathway Involving Sulfoacetyl-CoA and Sulfoacetaldehyde in Cupriavidus necator H16

  摘要：

  Bacterial degradation of sulfoacetate, a widespread natural product, proceeds via sulfoacetaldehyde and requires a considerable initial energy input. Whereas the fate of sulfoacetaldehyde in Cupriavidus necator (Ralstonia eutropha) H16 is known, the pathway from sulfoacetate to sulfoacetaldehyde is not. The genome sequence of the organism enabled us to hypothesize that the inducible pathway, which initiates sau (sulfoacetate utilization), involved a four-gene cluster (sauRSTU; H16_A2746 to H16_A2749). The sauR gene, divergently orientated to the other three genes, probably encodes the transcriptional regulator of the presumed sauSTU operon, which is subject to inducible transcription. SauU was tentatively identified as a transporter of the major facilitator superfamily, and SauT was deduced to be a sulfoacetate-CoA ligase. SauT was a labile protein, but it could be separated and shown to generate AMP and an unknown, labile CoA-derivative from sulfoacetate, CoA, and ATP. This unknown compound, analyzed by MALDI-TOF-MS, had a relative molecular mass of 889.7, which identified it as protonated sulfoacetyl-CoA (calculated 889.6). SauS was deduced to be sulfoacetaldehyde dehydrogenase (acylating). The enzyme was purified 175-fold to homogeneity and characterized. Peptide mass fingerprinting confirmed the sauS locus w(H16_A2747). SauS converted sulfoacetyl-CoA and NADPH to sulfoacetaldehyde, CoA, and NADP(+), thus confirming the hypothesis.

  DOI：

  10.1074/jbc.m110.127043
• 作为产物：
  描述：

  2-氧代-戊二酸离子(2-) 、 牛磺酸 生成 2-氨基戊二酸酯 、 Sulfonatoacetaldehyde
  参考文献：
  名称：

  Dissimilation of the C2 sulfonates

  摘要：

  Organosulfonates are widespread in the environment, both as natural products and as xenobiotics; and they generally share the property of chemical stability. A wide range of phenomena has evolved in microorganisms able to utilize the sulfur or the carbon moiety of these compounds; and recent work has centered on bacteria. This Mini-Review centers on bacterial catabolism of the carbon moiety in the C-2-sulfonates and the fate of the sulfonate group. Five of the six compounds examined are subject to catabolism, but information on the molecular nature of transport and regulation is based solely on sequencing data. Two mechanisms of desulfonation have been established. First, there is the specific monooxygenation of ethanesulfonate or ethane-1,2-disulfonate. Second, the oxidative, reductive and fermentative modes of catabolism tend to yield the intermediate sulfoacetaldehyde, which is now known to be desulfonated to acetyl phosphate by a thiamin-diphosphate-dependent acetyltransferase. This enzyme is widespread and at least three subgroups can be recognized, some of them in genomic sequencing projects. These data emphasize the importance of acetyl phosphate in bacterial metabolism. A third mechanism of desulfonation is suggested: the hydrolysis of sulfoacetate.

  DOI：

  10.1007/s00203-002-0497-0

文献信息

• Genetic analysis of a<i>Rhodobacter capsulatus</i>gene region involved in utilization of taurine as a sulfur source
  作者：Bernd Masepohl、Frank Führer、Werner Klipp

  DOI：10.1111/j.1574-6968.2001.tb10932.x

  日期：2001.11

  Rhodobacter capsulatus was shown to grow efficiently with taurine as sole source of sulfur. We identified a gene region exhibiting similarity to the Escherichia coli tauABC genes coding for a taurine-specific ABC transporter. The R. capsulatus tauABC genes were flanked by two putative operons (orf459-484-590 and cysE-srpI-nifS2) both reading in opposite direction relative to tauABC. Orf459 shows strong similarity to taurine:pyruvate aminotransferase (Tpa) from Bilophila wadsworthia catalyzing the initial transamination during anaerobic taurine degradation, and Orf590 exhibits clear similarity to sulfoacetaldehyde sulfo-lyase from Desulfonispora thiosulfatigenes probably catalyzing the step following the taurine:pyruvate aminotransferase (Tpa) reaction, whereas nifS2 might code for a putative cysteine desulfurase. Expression of R. capsulatus tauABC and nifS2 was inhibited by sulfate, suggesting that tauABC and nifS2 might belong to the same regulon. In contrast, transcription of orf459 was not inhibited by sulfate but was induced by taurine. A tauAB deletion mutant showed significantly reduced growth compared to the wild-type with taurine as sole sulfur source in the presence of serine as a nitrogen source, whereas normal growth was observed in the presence of taurine and ammonium. Deletion of orf459-484-590 completely abolished growth with taurine/serine. Single mutations in any of the three genes resulted in the same phenotype, indicating that all three genes of this putative operon are essential for taurine sulfur utilization in the presence of serine. A model for anaerobic taurine sulfur assimilation in R. capsulatus is discussed.

  研究表明，荚膜罗氏菌在以牛磺酸为唯一硫源的情况下能够高效生长。我们发现了一个与大肠杆菌 tauABC 基因相似的基因区域，该基因编码牛磺酸特异性 ABC 转运体。R. capsulatus 的 tauABC 基因两侧有两个假定操作子（orf459-484-590 和 cysE-srpI-nifS2），这两个操作子的阅读方向与 tauABC 相反。Orf459 与来自 Bilophila wadsworthia 的牛磺酸：丙酮酸氨基转移酶（Tpa）非常相似，后者在厌氧牛磺酸降解过程中催化最初的转氨作用：丙酮酸氨基转移酶（Tpa）反应后的步骤，而 nifS2 可能编码一种假定的半胱氨酸脱硫酶。R. capsulatus tauABC 和 nifS2 的表达受到硫酸盐的抑制，这表明 tauABC 和 nifS2 可能属于同一个调节子。相反，orf459 的转录不受硫酸盐的抑制，但会被牛磺酸诱导。与野生型相比，tauAB缺失突变体在有丝氨酸作为氮源的情况下，以牛磺酸作为唯一的硫源，生长明显降低，而在有牛磺酸和铵的情况下，生长正常。orf459-484-590基因的缺失完全抑制了牛磺酸/丝氨酸的生长。这三个基因中任何一个基因的单突变都会导致相同的表型，这表明该假定操作子的所有三个基因对于在丝氨酸存在下的牛磺酸硫利用都是必不可少的。本文讨论了噬菌体厌氧牛磺酸硫同化的模型。
• Identification of the Gene Encoding Sulfopyruvate Decarboxylase, an Enzyme Involved in Biosynthesis of Coenzyme M
  作者：Marion Graupner、Huimin Xu、Robert H. White

  DOI：10.1128/jb.182.17.4862-4867.2000

  日期：2000.9

  of sulfopyruvic acid to sulfoacetaldehyde. This transformation is the fourth step in the biosynthesis of coenzyme M, a crucial cofactor in methanogenesis and aliphatic alkene metabolism. The M. jannaschii sulfopyruvate decarboxylase was found to be inactivated by oxygen and reactivated by reduction with dithionite. The two subunits, designated ComD and ComE, comprise the first enzyme for the biosynthesis

  詹氏甲烷球菌的染色体中两个相邻基因的产物类似于磷酸丙酮丙酮酸脱羧酶的氨基和羧基一半，后者是催化链霉菌中磷霉素生物合成第二步的酶。这两个詹氏甲烷球菌基因在大肠杆菌中重组表达，并测试了它们的基因产物催化一系列α-酮酸脱羧的能力。这两个亚基都需要形成一个α（6）beta（6）十二聚体，该十二聚体特别催化磺基丙酮酸脱羧为磺基乙醛。该转化是辅酶M生物合成的第四步，辅酶M是甲烷生成和脂肪族烯烃代谢中的关键辅助因子。M. 发现詹纳西氏硫丙酮酸脱羧酶被氧气灭活，并被连二亚硫酸盐还原而重新活化。命名为ComD和ComE的两个亚基构成了用于生物合成辅酶M的第一个酶。
• Sulphoacetaldehyde acetyltransferase yields acetyl phosphate: purification from Alcaligenes defragrans and gene clusters in taurine degradation
  作者：Jürgen RUFF、Karin DENGER、Alasdair M. COOK

  DOI：10.1042/bj20021455

  日期：2003.1.15

  The facultatively anaerobic bacterium Alcaligenes defragrans NKNTAU was found to oxidize taurine (2-aminoethanesulphonate) with nitrate as the terminal electron acceptor. Taurine was transaminated to 2-sulphoacetaldehyde. This was not converted into sulphite and acetate by a ‘sulphoacetaldehyde sulpho-lyase’ (EC 4.4.1.12), but into sulphite and acetyl phosphate, which was identified by three methods. The enzyme, which required the addition of phosphate, thiamin diphosphate and Mg2+ ions for activity, was renamed sulphoacetaldehyde acetyltransferase (Xsc; EC 2.3.1.-). Inducible Xsc was expressed at high levels, and a three-step 11-fold purification yielded an essentially homogeneous soluble protein, which was a homotetramer in its native form; the molecular mass of the subunit was found to be between about 63kDa (SDS/PAGE) and 65.3kDa (matrix-assisted laser-desorption ionization—time-of-flight MS). The N-terminal and two internal amino acid sequences were determined, and PCR primers were generated. The xsc gene was amplified and sequenced; the derived molecular mass of the processed protein was 65.0kDa. The downstream gene presumably encoded the inducible phosphate acetyltransferase (Pta) found in crude extracts. The desulphonative enzymes ('EC 4.4.1.12') from Achromobacter xylosoxidans NCIMB 10751 and Desulfonispora thiosulfatigenes GKNTAU were shown to be Xscs. We detected at least three subclasses of xsc in Proteobacteria and in Gram-positive bacteria, and they comprised a distinct group within the acetohydroxyacid synthase supergene family. Genome sequencing data revealed xsc genes in Burkholderia fungorum (80% sequence identity) and Sinorhizobium meliloti (61%) with closely linked pta genes. Different patterns of regulation for the transport and dissimilation of taurine were hypothesized for S. meliloti and B. fungorum.

  研究发现，兼性厌氧细菌 Alcaligenes defragrans NKNTAU 能以硝酸盐为终端电子受体氧化牛磺酸（2-氨基乙磺酸盐）。牛磺酸被转氨为 2-磺基乙醛。亚硫酸和乙酸并不是通过 "亚硫酰乙醛磺化裂解酶"（EC 4.4.1.12）转化为亚硫酸盐和乙酰磷酸的，而是通过三种方法确定的。这种酶的活性需要加入磷酸盐、二磷酸硫胺素和 Mg2+ 离子，因此被重新命名为硫代乙醛乙酰转移酶（Xsc；EC 2.3.1.-）。诱导型 Xsc 可高水平表达，经三步 11 倍纯化后可得到基本均一的可溶性蛋白质，其原生形式为同源四聚体；发现亚基的分子质量介于约 63kDa （SDS/PAGE）和 65.3kDa （基质辅助激光解吸电离飞行时间质谱）之间。确定了 N 端和两个内部氨基酸序列，并生成了 PCR 引物。对 xsc 基因进行了扩增和测序；得到的加工蛋白的分子质量为 65.0kDa。下游基因可能编码粗提取物中的诱导型磷酸乙酰转移酶（Pta）。Achromobacter xylosoxidans NCIMB 10751 和 Desulfonispora thiosulfatigenes GKNTAU 的脱硫酶（"EC 4.4.1.12"）被证明是 Xscs。我们在变形菌和革兰氏阳性菌中发现了至少三种亚类的 xsc，它们在乙酰羟基酸合成酶超级基因家族中组成了一个独特的群体。基因组测序数据显示，伯克霍尔德菌（Burkholderia fungorum）（80%的序列相同）和瓜萎镰刀菌（Sinorhizobium meliloti）（61%）中的 xsc 基因与 pta 基因密切相关。据此推测，S. meliloti 和 B. fungorum 的牛磺酸转运和异化作用具有不同的调节模式。
• Purification and Some Properties of Taurine Dehydrogenase from a Bacterium
  作者：Hiroyuki KONDO、Keiichi KAGOTANI、Mikiko OSHIMA、Makoto ISHIMOTO

  DOI：10.1093/oxfordjournals.jbchem.a130200

  日期：1973.6

  Taurine dehydrogenase was solubilized and purified 13-fold from a taurine-decomposing bacterium by ammonium sulfate precipitation and Sepharose 4B gel filtration. The partially purified enzyme did not catalyze the oxidation of taurine by oxygen directly, but did do so in the presence of phenazine methosulfate. The optimal pH was 8.4. Fifty percent of the enzyme activity was lost on incubation at 40°C for 20 min. The Km values of the enzyme for taurine and phenazine methosulfate were determined to be 2×10−2M and 5.6×10−5M, respectively. Taurine was the only substrate oxidized among a variety of amines. Nicotinamide nucleotides and flavin nucleotides did not serve as electron acceptors. The enzyme reaction was inhibited by isonicotinic acid 2-isopropylhydrazide, phenelzine, and p-chloromercuribenzoate. The reaction product was identified by paper chromatography and electrophoresis as sulfoacetaldehyde, and ammonia formation and oxygen consumption occurred stoichiometrically.

  通过硫酸铵沉淀和 Sepharose 4B 凝胶过滤，从牛磺酸分解细菌中溶解并纯化了 13 倍的牛磺酸脱氢酶。部分纯化的酶不能直接催化氧对牛磺酸的氧化，但在酚嗪甲硫酸盐存在的情况下可以做到这一点。最佳 pH 值为 8.4。在 40°C 的温度下培养 20 分钟后，酶的活性降低了 50%。经测定，该酶对牛磺酸和酚嗪甲磺酸盐的 Km 值分别为 2×10-2M 和 5.6×10-5M。牛磺酸是多种胺类中唯一被氧化的底物。烟酰胺核苷酸和黄素核苷酸不作为电子受体。2-isopropylhydrazide 异烟酸、苯乙肼和对氯脲苯甲酸酯对酶反应有抑制作用。经纸层析和电泳鉴定，反应产物为磺基乙醛，氨的形成和氧的消耗呈等比例关系。
• Isethionate formation from taurine in Chromohalobacter salexigens: purification of sulfoacetaldehyde reductase
  作者：Zdeněk Krejčík、Klaus Hollemeyer、Theo H. M. Smits、Alasdair M. Cook

  DOI：10.1099/mic.0.036699-0

  日期：2010.5.1

  Bacterial generation of isethionate (2-hydroxyethanesulfonate) from taurine (2-aminoethanesulfonate) by anaerobic gut bacteria was established in 1980. That phenomenon in pure culture was recognized as a pathway of assimilation of taurine-nitrogen. Based on the latter work, we predicted from genome-sequence data that the marine gammaproteobacterium Chromohalobacter salexigens DSM 3043 would exhibit this trait. Quantitative conversion of taurine to isethionate, identified by mass spectrometry, was confirmed, and the taurine-nitrogen was recovered as cell material. An eight-gene cluster was predicted to encode the inducible vectorial, scalar and regulatory enzymes involved, some of which were known from other taurine pathways. The genes (Csal_0153–Csal_0156) encoding a putative ATP-binding-cassette (ABC) transporter for taurine (TauAB₁B₂C) were shown to be inducibly transcribed by reverse transcription (RT-) PCR. An inducible taurine : 2-oxoglutarate aminotransferase [EC 2.6.1.55] was found (Csal_0158); the reaction yielded glutamate and sulfoacetaldehyde. The sulfoacetaldehyde was reduced to isethionate by NADPH-dependent sulfoacetaldehyde reductase (IsfD), a member of the short-chain alcohol dehydrogenase superfamily. The 27 kDa protein (SDS-PAGE) was identified by peptide-mass fingerprinting as the gene product of Csal_0161. The putative exporter of isethionate (IsfE) is encoded by Csal_0160; isfE was inducibly transcribed (RT-PCR). The presumed transcriptional regulator, TauR (Csal_0157), may autoregulate its own expression, typical of GntR-type regulators. Similar gene clusters were found in several marine and terrestrial gammaproteobacteria, which, in the gut canal, could be the source of not only mammalian, but also arachnid and cephalopod isethionate.

  1980年，通过厌氧肠道细菌从牛磺酸（2-氨基乙磺酸）生成异丝氨酸（2-羟基乙磺酸）的现象在纯培养中被确认为牛磺酸氮同化的途径。基于这项工作，我们从基因组序列数据中预测，海洋伽马变形菌Chromohalobacter salexigens DSM 3043将表现出这种特性。通过质谱法确认了牛磺酸向异丝氨酸的定量转化，并将牛磺酸氮作为细胞物质回收。预测有一个由八个基因组成的簇编码诱导的矢量、标量和调节酶，其中一些酶从其他牛磺酸途径已知。通过反转录（RT-PCR）显示编码牛磺酸（TauAB1B2C）的一个假定的ATP结合盒（ABC）转运体的基因（Csal_0153-Csal_0156）被诱导转录。发现了一个诱导的牛磺酸：2-酮戊二酸氨基转移酶[EC 2.6.1.55]（Csal_0158）；该反应产生谷氨酸和磺乙醛。磺乙醛通过NADPH依赖的磺乙醛还原酶（IsfD）还原为异丝氨酸，该酶是短链醇脱氢酶超家族的成员。通过肽质量指纹鉴定，27 kDa蛋白质（SDS-PAGE）被识别为Csal_0161的基因产物。异丝氨酸的假定转运蛋白（IsfE）由Csal_0160编码；isfE被诱导转录（RT-PCR）。假定的转录调节因子TauR（Csal_0157）可能会自调节其自身表达，这是GntR类型调节因子的典型特征。在几种海洋和陆地伽马变形菌中发现了类似的基因簇，在肠道中可能是哺乳动物、蜘蛛和头足类异丝氨酸的来源。