tolonium | 56109-24-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻嗪类
• 英文名称: tolonium
• 英文别名: (7-amino-8-methyl-phenothiazin-3-ylidene)-dimethyl-ammonium；2-methyl-3-dimethylamino-7-aminophenothiazin-5-ium；Toluidine Blue cation；toluidine blue O；Toluidine Blue；3-amino-7-dimethylamino-2-methyl-phenothiazinylium
• CAS: 56109-24-1
• 化学式: C₁₅H₁₆N₃S
• 分子量: 270.378
• InChiKey: RQNADZJRELIICT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  19.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  42.15
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  tolonium 在 盐酸 、 铜 、 苯肼 作用下， 以 乙醇 、 水 为溶剂， 生成 toluidine white
  参考文献：
  名称：

  Cu(II) catalyzed reaction between phenyl hydrazine and toluidine blue?dual role of acid

  摘要：

  The detailed kinetics of Cu(II) catalyzed reduction of toluidine blue (TB+) by phenyl hydrazine (Pz) in aqueous solution is studied. Toluidine white (TBH) and the diazonium ions are the main products of the reaction. The diazonium ion further decomposes to phenol (PhOH) and nitrogen. At low concentrations of acid, H+ ion autocatalyzes the uncatalyzed reaction and hampers the Cu(II) catalyzed reaction. At high concentrations, H+ hinders both the uncatalyzed and Cu(II) catalyzed reactions. Cu(II) catalyzed had stoichiometry similar to the uncatalyzed reaction, Pz + 2 TB+ + H2O = PhOH + 2 TBH + 2 H+ + N-2, Cu(II) catalyzed reaction occurs possibly through ternary complex formation between the unprotonated toluidine blue and phenyl hydrazine and catalyst. The rate coefficient for the Cu(II) catalyzed reaction is 2.1 X 10(4) M-2 s(-1). A detailed 13-step mechanistic scheme for the Cu(il) catalyzed reaction is proposed, which is supported by simulations, (C) 1999 John Wiley & Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1999)31:4<271::aid-kin4>3.0.co;2-v
• 作为产物：
  描述：

  在 Escherichia coli ribonucleotide reductase active-R₂ form 作用下， 以 phosphate buffer 为溶剂， 生成 tolonium
  参考文献：
  名称：

  Mechanistic Implications of a Linear Free-Energy Correlation of Rate Constants for the Reduction of Active- and Met-R2 Forms of E. coli Ribonucleotide Reductase with Eight Organic Radicals

  摘要：

  Cross-reaction rate constants k(12) (22 degrees C) at pH 7.0 have been determined for the reduction of Fe-2(III) and tyrosyl-radical-containing active-R2 from E. coli ribonucleotide reductase with eight organic radicals (OR), e.g., MV.+ from methyl viologen. The more reactive OR's were generated in situ using pulse radiolysis (PR) techniques, and other OR's were generated by prior reduction of the parent with dithionite, followed by stopped-flow (SF) studies. In both procedures it was necessary to include consideration of doubly-reduced parent forms. Values of k(12) are in the range 10(9) to 10(4) M-1 s(-1) and reduction potentials E-1(o) for the OR vary from -0.446 to +0.194 V. Samples of E. coli active-R2 also have an Fe-2(III) met-R2 component (with no Tyr(.)), which in the present work was close to 40%. From separate experiments met-R2 gave similar kit rate constants ton average 66% bigger) to those for active-R2, suggesting that reduction of the Fe-2(III) center is the common rate-limiting seep. A single Marcus free-energy plot of log k(12) - 0.5 log f vs -E-1(o)/0.059 describes all the data, and the slope of 0.54 is in satisfactory agreement with the theoretical value of 0.50. It is concluded that the rate-limiting step involves electron transfer. In addition, the intercept at -E-1(o)/0.059 = 0 is 5.94, where values of the reduction potential and self-exchange rate constant for met-R2 contribute to this value. To maintain electroneutrality at the similar to 10 Angstrom buried active site H+ uptake is also required. For both e(-) and H+ transfer the conserved pathway Trp-48, Asp-237, His-118 to Fe-A is a possible candidate requiring further examination.

  DOI：

  10.1021/ja993412k

文献信息

• Fatty Acid Conjugates of Toluidine Blue O as Amphiphilic Photosensitizers: Synthesis, Solubility, Photophysics and Photochemical Properties ^†
  作者：José Robinson‐Duggon、Nancy Pizarro、Germán Gunther、Daniel Zúñiga‐Núñez、Ana María Edwards、Alexander Greer、Denis Fuentealba

  DOI：10.1111/php.13304

  日期：2021.1

  Toluidine blue O (TBO) is a water‐soluble photosensitizer that has been used in photodynamic antimicrobial and anticancer treatments, but suffers from limited solubility in hydrophobic media. In an effort to incrementally increase TBO’s hydrophobicity, we describe the synthesis of hexanoic (TBOC6) and myristic (TBOC14) fatty acid derivatives of TBO formed in low to moderate percent yields by condensation

  甲苯胺蓝 O (TBO) 是一种水溶性光敏剂，已用于光动力抗菌和抗癌治疗，但在疏水介质中的溶解度有限。为了逐步增加 TBO 的疏水性，我们描述了通过与游离胺位点缩合形成的 TBO 的己酸 (TBOC6) 和肉豆蔻 (TBOC14) 脂肪酸衍生物的合成，产率从低到中等。共价连接 6 和 14 个碳链不仅会改变 TBO 的溶解度，还会改变其光物理和光化学性质。TBOC6 和 TBOC14 衍生物更易溶于有机溶剂，并在其吸收和发射带中显示出低色移。TBOC6 和 TBOC14 在磷酸盐缓冲液中的溶解度都很低，但出乎意料的是后者略高。TBOC6 和 TBOC14 在乙腈中的三线态激发态寿命和单线态氧量子产率均降低，这归因于这些共轭物的聚集增​​强，尤其是在高浓度下，由于疏水性“尾部”。而在稀释的缓冲水溶液中，间接测量显示与 TBO 相比，TBOC14 的单线态氧生成效率相似。这项工作证明了脂肪酸 TBO
• Binding of toluidine blue-myristic acid derivative to cucurbit[7]uril and human serum albumin: computational and biophysical insights towards a biosupramolecular assembly
  作者：Felipe Andrade-Villalobos、Daniel Zúñiga-Núñez、Denis Fuentealba、Angelica Fierro

  DOI：10.1039/d1cp04307b

  日期：——

  Simulated supramolecular and biomolecular interactions provide insights on ternary photosensitizer-cucurbit[n]uril–protein complex formation.

  模拟超分子和生物分子相互作用有助于了解三元光敏剂-葫芦[n]葫芦-蛋白质复合物形成的机制。
• Reduction of Toluidine Blue by Sulfur(IV) in Acetate Buffer Medium: Kinetics and Mechanism
  作者：Pratik K. Sen、Rabindra N. Bera、Biswajit Pal

  DOI：10.14233/ajchem.2015.18285

  日期：——

  The reduction of toluidine blue (TB+) by sulfite [S(IV)] was studied spectrophtometrically in acetic acid-sodium acetate buffer medium in the temperature range 293-308 K. The reaction showed first order dependence on toluidine blue. The reaction was found to be first order in S(IV) at lower substrate concentration ([S(IV)] £ 0.07 mol dm-3) but the reaction became second order in S(IV) at high substrate concentration ([S(IV)] > 0.07 mol dm-3). H+ ions were found to inhibit the reaction in the pH range 4.0-5.4. The rate decreased with increase in the ionic strength of the medium, but remained unchanged with decreasing dielectric constant of the medium. The oxidation reaction possibly involved a one-electron transfer step via a free radical mechanism. An overall enthalpy and entropy of activation were computed. A plausible mechanism and rate law corroborating the experimental results have been put forward.

  在温度范围为 293-308 K 的醋酸-醋酸钠缓冲介质中，用分光光度法研究了亚硫酸盐[S(IV)]还原甲苯胺蓝（TB+）的情况。在底物浓度较低时（[S(IV)] £ 0.07 mol dm-3），反应在 S(IV)中呈一阶，但在底物浓度较高时（[S(IV)] > 0.07 mol dm-3），反应在 S(IV)中呈二阶。在 pH 值为 4.0-5.4 的范围内，H+ 离子对反应有抑制作用。速率随介质离子强度的增加而降低，但随介质介电常数的降低而保持不变。氧化反应可能涉及通过自由基机制进行的单电子转移步骤。计算了总的活化焓和活化熵。提出了与实验结果相吻合的合理机制和速率定律。
• Thiol-reacting toluidine blue derivatives: Synthesis, photophysical properties and covalent conjugation with human serum albumin
  作者：Nory Mariño-Ocampo、Juan S. Reyes、Germán Günther、Belinda Heyne、Denis Fuentealba

  DOI：10.1016/j.dyepig.2022.110225

  日期：2022.5

  characterized toluidine blue (TBO) derivates directed towards forming a covalent conjugation with human serum albumin (HSA) as a delivery vehicle under physiologically relevant conditions. We described herein the synthesis of 3-(2-pyridyldithio)propionate (PDP) and 6-maleimidocaproate (EMC) derivatives of TBO (TBOPDP and TBOEMC, respectively), their photophysical/photochemical properties and reactivity towards

  改进的光敏剂的开发用于光动力疗法（PDT）仍然是当前的研究需要。从这个意义上说，第三代光敏剂采用不同的递送载体来提高肿瘤细胞对健康组织的选择性。考虑到这一目的，我们合成并表征了甲苯胺蓝 (TBO) 衍生物，这些衍生物旨在与人血清白蛋白 (HSA) 在生理相关条件下作为递送载体形成共价结合。我们在本文中描述了 TBO 的 3-(2-吡啶基二硫代)丙酸酯 (PDP) 和 6-马来酰亚胺己酸酯 (EMC) 衍生物（分别为 TBOPDP 和 TBOEMC）的合成、它们的光物理/光化学性质和对 HSA 的反应性。与 TBO 相比，在它们的吸收和发射带、更高的光稳定性和增加的单线态氧生成中观察到了低色移。而且，这些衍生物通过二硫化物交换或硫代-迈克尔加成在半胱氨酸 34 残基处与 HSA 反应。通过 MALDI-TOF 分析 HSA-TBOPDP 和 HSA-TBOEMC 缀合物质谱、吸收/荧光发射光
• INHIBITORS OF PROTEIN AGGREGATION
  申请人：Wischik Claude Michel

  公开号：US20090209526A1

  公开（公告）日：2009-08-20

  The invention relates generally to the use of diaminophenothiazine compounds to inhibit or reverse the aggregation of synuclein, and for their use in the manufacture of medicaments for this purpose (e.g. for the treatment of Parkinson's Disease). Also provided are related methods of detecting or labelling of aggregated synuclein.

  本发明通常涉及使用二氨基苯并噻嗪化合物来抑制或逆转突触核蛋白聚集，并将其用于制造用于此目的的药物（例如用于治疗帕金森病）。还提供了相关的检测或标记聚集的突触核蛋白的方法。