3,7-二氨基吩噻嗪-5-鎓氯化物 | 26754-93-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻嗪类
• 中文名称: 3,7-二氨基吩噻嗪-5-鎓氯化物
• 英文名称: thionin
• 英文别名: 3,7-diamino-phenothiazine-5-ium；3,7-diamino-5-phenothiazinium；3,7-diaminophenothiazin-5-ium；thionine cation；Lauth's violet；Thionine
• CAS: 26754-93-8
• 化学式: C₁₂H₁₀N₃S
• 分子量: 228.297
• InChiKey: CBBMGBGDIPJEMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  64.93
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3,7-二氨基吩噻嗪-5-鎓氯化物 在 盐酸 、 europium(III) chloride hexahydrate 、 硫酸 、 水 、 硒脲酸 、 sodium sulfate 作用下， 以 水 为溶剂， 生成 leucothionine
  参考文献：
  名称：

  III（III）催化亚硒酸在硫酸水溶液中还原硫氨酸染料的动力学机理

  摘要：

  通过分光光度法在硫酸水溶液中以恒定的离子强度3.0 mol dm -3和在不同温度下（283-313 K ）。相对于[Th]和[Eu III ]都具有一阶依赖性，而相对于[Se IV ]和[H +]小于统一。反应介质的离子强度和介电常数的变化不影响反应速率。提出了在不存在和存在（（III）催化剂的情况下还原亚硫氨酸的可能机理方案。推导了与反应机理相关的速率规律，并计算了反应常数。计算并讨论了未催化反应和催化反应的慢步速率常数的活化参数以及平衡常数的热力学量。

  DOI：

  10.1002/kin.21012
• 作为产物：
  描述：

  leucothionine 在 铁粉 作用下， 以 硫酸 为溶剂， 生成 3,7-二氨基吩噻嗪-5-鎓氯化物
  参考文献：
  名称：

  无色染料和Fe之间的反应的电化学研究III在基于染料的photogalvanic系统

  摘要：

  已经在催化再生机理方面研究了在Fe 3+存在下电化学还原硫氨酸和亚甲蓝的方法。由于白血球和Fe 3+之间的均相化学反应而产生的催化电流已用于估算速率常数。

  DOI：

  10.1039/ft9908600105

文献信息

• Survey of Redox-Active Moieties for Application in Multiplexed Electrochemical Biosensors
  作者：Di Kang、Francesco Ricci、Ryan J. White、Kevin W. Plaxco

  DOI：10.1021/acs.analchem.6b02376

  日期：2016.11.1

  Recent years have seen the development of a large number of electrochemical sandwich assays and reagentless biosensor architectures employing biomolecules modified via the attachment of a redox-active “reporter.” Here we survey a large set of potential redox reporters in order to determine which exhibits the best long-duration stability in thiol-on-gold monolayer-based sensors and to identify reporter “sets” signaling at distinct, nonoverlapping redox potentials in support of multiplexing and error correcting ratiometric or differential measurement approaches. Specifically, we have characterized the performance of more than a dozen potential reporters that are, first, redox active within the potential window over which thiol-on-gold monolayers are reasonably stable and, second, are available commercially in forms that are readily conjugated to biomolecules or can be converted into such forms in one or two simple synthetic steps. To test each of these reporters we conjugated it to one terminus of a single-stranded DNA “probe” that was attached by its other terminus via a six-carbon thiol to a gold electrode to form an “E-DNA” sensor responsive to its complementary DNA target. We then measured the signaling properties of each sensor as well as its stability against repeated voltammetric scans and against deployment in and reuse from blood serum. Doing so we find that the performance of methylene blue-based, thiol-on-gold sensors is unmatched; the near-quantitative stability of such sensors against repeated scanning in even very complex sample matrices is unparalleled. While more modest, the stability of sensors employing a handful of other reporters, including anthraquinone, Nile blue, and ferrrocene, is reasonable. Our work thus serves as both to highlight the exceptional properties of methylene blue as a redox reporter in such applications and as a cautionary tale–we wish to help other researchers avoid fruitless efforts to employ the many, seemingly promising and yet ultimately inadequate reporters we have investigated. Finally, we hope that our work also serves as an illustration of the pressing need for the further development of useful redox reporters.

  近年来，大量的电化学夹心分析法和无试剂生物传感器架构得到了发展，这些架构采用了通过附着氧化还原活性"报告基团"修饰的生物分子。本文综述了一系列潜在的氧化还原报告基团，旨在确定哪些报告基团在巯基-金单层传感器中具有最佳的长期稳定性，并识别在不同、非重叠氧化还原电位上发出信号的报告基团"组合"，以支持多重检测和校正比率或差分测量方法的错误。具体而言，我们对十几种潜在的报告基团进行了性能表征，这些报告基团首先在巯基-金单层的稳定电位窗口内具有氧化还原活性，其次以易于与生物分子偶联的形式商业化，或者可以通过一两个简单的合成步骤转化为这种形式。为了测试每个报告基团，我们将其与单链DNA"探针"的一端偶联，该探针的另一端通过六个碳的巯基连接到金电极上，形成了一个对互补DNA目标敏感的"E-DNA"传感器。然后，我们测量了每个传感器的信号特性以及其对抗重复循环伏安扫描和在血清中使用及重复使用的稳定性。通过这些测试，我们发现亚甲蓝基的巯基-金传感器性能无与伦比；即使在非常复杂的样品矩阵中，这种传感器对抗重复扫描的近似定量稳定性也是前所未有的。虽然较为有限，但使用少数其他报告基团（包括蒽醌、尼罗蓝和二茂铁）的传感器的稳定性是合理的。因此，我们的工作既突出了亚甲蓝在这些应用中作为氧化还原报告基团的卓越特性，也为其他研究人员提供了一个警示——我们希望帮助他们避免我们在调查看似有前景但最终不充分的报告基团时所经历的无用功。最后，我们希望我们的工作也展现了进一步开发有用的氧化还原报告基团的迫切需要。
• [EN] METHODS OF CHEMICAL SYNTHESIS OF DIAMINOPHENOTHIAZINIUM COMPOUNDS INCLUDING METHYLTHIONINIUM CHLORIDE (MTC)<br/>[FR] PROCÉDÉS DE SYNTHÈSE CHIMIQUE DE COMPOSÉS DE DIAMINOPHÉNOTHIAZINIUM RENFERMANT DU CHLORURE DE MÉTHYLTHIONINIUM (MTC)
  申请人：WISTA LAB LTD

  公开号：WO2015052496A1

  公开（公告）日：2015-04-16

  Methods of synthesizing and purifying certain 3,7-diamino-phenothiazin-5-ium compounds (referred to herein as "diaminophenothiazinium compounds") including Methythioninium Chloride (MTC) (also known as Methylene Blue) are provided.

  提供了合成和纯化特定的3,7-二氨基苯并噻嗪-5-ium化合物（以下简称为“二氨基苯并噻嗪化合物”）的方法，包括氯甲基噻嗪盐（MTC）（也称为亚甲蓝）。
• [EN] METHODS OF CHEMICAL SYNTHESIS OF DIAMINOPHENOTHIAZINIUM COMPOUNDS INVOLVING THE USE OF PERSULFATE OXIDANTS<br/>[FR] PROCÉDÉS DE SYNTHÈSE CHIMIQUE ET DE COMPOSÉS DE DIAMINOPHÉNOTHIAZINIUM IMPLIQUANT L'UTILISATION D'OXYDANTS DE PERSULFATE
  申请人：WISTA LAB LTD

  公开号：WO2010130977A1

  公开（公告）日：2010-11-18

  This invention pertains generally to the field of chemical synthesis and purification, and more specifically to methods of synthesizing and purifying certain 3,7-diamino- phenothiazin-5-ium compounds (referred to herein as "diaminophenothiazinium compounds") including Methylthioninium Chloride (MTC) (also known as Methylene Blue). In one embodiment, the method comprises the steps of, in order: a thiosulfonic acid formation (TSAF) as illustrated below, wherein the reaction is carried out in the presence of a thiosulfate and an oxidizing agent that is or comprises persulfate an oxidative coupling (OC); and a ring closure (RC). The resulting compounds and compositions comprising them (e.g., tablets, capsules) are useful in methods of medical treatment and diagnosis, etc., for example, tauopathies, or Alzheimer's disease (AD).

  这项发明通常涉及化学合成和纯化领域，更具体地涉及合成和纯化某些3,7-二氨基苯并噻嗪-5-ium化合物（以下简称为"二氨基苯并噻嗪化合物"），包括氯化甲硫蓝（MTC）（又称亚甲蓝）。在一种实施例中，该方法包括按顺序进行以下步骤：如下图所示的硫代磺酸形成（TSAF）步骤，其中在硫代硫酸盐和氧化剂的存在下进行反应，该氧化剂是或包含过硫酸盐；氧化偶联（OC）；和环闭合（RC）。所得的化合物和包含它们的组合物（例如，片剂、胶囊）在医疗治疗和诊断等方法中具有用途，例如对于tau病变或阿尔茨海默病（AD）。
• CuFe₂O₄@PDA magnetic nanomaterials with a core–shell structure: synthesis and catalytic application in the degradation of methylene blue in water
  作者：Su-dai Ma、Jie Feng、Wen-jie Qin、Yu-yun Ju、Xing-guo Chen

  DOI：10.1039/c5ra09114d

  日期：——

  A highly efficient CuFe₂O₄@PDA MNPs catalyst was synthesized through in situ self-polymerization and application in the degradation of methylene blue.

  通过原位自聚合合成了高效的CuFe₂O₄@PDA MNPs催化剂，并应用于亚甲基蓝的降解。
• Methods of chemical synthesis and purification of diaminophenothiazinium compounds including methylthioninium chloride (MTC)
  申请人：Wischik M. Claude

  公开号：US20060287523A1

  公开（公告）日：2006-12-21

  This invention pertains generally to the field of chemical synthesis and purification, and more specifically to methods of synthesizing and purifying certain 3,7-diaminophenothiazin-5-ium compounds (referred to herein as “diaminophenothiazinium compounds”) including Methythioninium Chloride (MTC) (also known as Methylene Blue). In one embodiment, the method comprises the steps of, in order: nitrosylation (NOS); nitrosyl reduction (NR); thiosulfonic acid formation (TSAF); oxidative coupling (OC); Cr(VI) reduction (CR); isolation and purification of zwitterionic intermediate (IAPOZI); ring closure (RC); chloride salt formation (CSF); one of: sulphide treatment (ST); dimethyldithiocarbamate treatment (DT); carbonate treatment (CT); ethylenediaminetetraacetic acid treatment (EDTAT); organic extraction (OE); and recrystallisation (RX). The present invention also pertains to the resulting (high purity) compounds, compositions comprising them (e.g., tablets, capsules), and their use in methods of inactivating pathogens, and methods of medical treatment and diagnosis, etc., for example, for tauopathies, Alzheimer's disease (AD), skin cancer, melanoma, viral diseases, bacterial diseases, or protozoal diseases.

  本发明通常涉及化学合成和纯化领域，更具体地涉及合成和纯化某些3,7-二氨基苯并噻嗪-5-ium化合物（以下简称“二氨基苯并噻嗪化合物”），包括甲基硫脲氯化物（MTC）（也称亚甲蓝）。在一种实施例中，该方法按顺序包括以下步骤：亚硝酰化（NOS）；亚硝基还原（NR）；硫代磺酸形成（TSAF）；氧化偶合（OC）；Cr（VI）还原（CR）；离子对中间体的分离和纯化（IAPOZI）；环闭合（RC）；氯化物盐形成（CSF）；其中之一：硫化物处理（ST）；二甲基二硫脲酸盐处理（DT）；碳酸盐处理（CT）；乙二胺四乙酸处理（EDTAT）；有机萃取（OE）；和重结晶（RX）。本发明还涉及所得到的（高纯度）化合物、包含它们的组合物（例如片剂、胶囊）以及它们在灭活病原体、医疗治疗和诊断等方法中的使用，例如用于tau病理、阿尔茨海默病（AD）、皮肤癌、黑色素瘤、病毒性疾病、细菌性疾病或原虫性疾病。