tris[8-carboxy-2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d′]bis-([1,3]dithiole)-4-yl]methyl radical | 774161-17-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: tris[8-carboxy-2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d′]bis-([1,3]dithiole)-4-yl]methyl radical
• 英文别名: tris(8-carboxy-2,2,6,6-tetra(trideuteromethyl)benzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl；tris(8-carboxyl-2,2,6,6-tetramethyl-(d12)-benzo-[1,2-d;4,5-dc]bis[1,3]dithiol-4-yl)methyl radical
• CAS: 774161-17-0
• 化学式: C₄₀H₃₉O₆S₁₂
• 分子量: 1036.25
• InChiKey: WIMHBUCPDZINLY-MCDHJEQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.9
• 重原子数：
  58
• 可旋转键数：
  5
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  416
• 氢给体数：
  3
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  tris[8-carboxy-2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d′]bis-([1,3]dithiole)-4-yl]methyl radical 在 氯化亚砜 、 三乙胺 作用下， 以 氯仿 为溶剂， 生成 tris[8-chloro-carbonyl-2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methyl radical
  参考文献：
  名称：

  Synthesis, Characterization, and Nanoencapsulation of Tetrathiatriarylmethyl and Tetrachlorotriarylmethyl (Trityl) Radical Derivatives—A Study To Advance Their Applicability as in Vivo EPR Oxygen Sensors

  摘要：

  Tissue oxygenation plays an important role in the pathophysiology of various diseases and is often a marker of prognosis and therapeutic response. EPR (ESR) is a suitable noninvasive oximetry technique. However, to reliably deploy soluble EPR probes as oxygen sensors in complex biological systems, there is still a need to investigate and improve their specificity, sensitivity, and stability. We reproducibly synthesized various derivatives of tetrathiatriarylmethyl and tetrachlorotriarylmethyl (trityl) radicals. Hydrophilic radicals were investigated in aqueous solution mimicking physiological conditions by, e.g., variation of viscosity and ionic strength. Their specificity was satisfactory, but the oxygen sensitivity was low. To enhance the capability of trityl radicals as oxygen sensors, encapsulation into oily core nanocapsules was performed. Thus, different lipophilic triesters were prepared and characterized in oily solution employing oils typically used in drug formulations, i.e., middle-chain triglycerides and isopropyl myristate. Our screening identified the deuterated ethyl ester of D-TAM (radical 13) to be suitable. It had an extremely narrow single EPR line under anoxic conditions and excellent oxygen sensitivity. After encapsulation, it retained its oxygen responsiveness and was protected against reduction by ascorbic acid. These biocompatible and highly sensitive nanosensors offer great potential for future EPR oximetry applications in preclinical research.

  DOI：

  10.1021/acs.joc.5b00918
• 作为产物：
  描述：

  tris[8-tert-butoxycarbonyl-2,2,6,6-(2H3-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methanol 在 三氟乙酸 作用下， 以100%的产率得到tris[8-carboxy-2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d′]bis-([1,3]dithiole)-4-yl]methyl radical
  参考文献：
  名称：

  芬兰三苯甲基氘代衍生物的合成、结构和 EPR 表征

  摘要：

  取代的三苯甲基自由基是重要的自旋探针，用于功能性电子顺磁共振波谱和成像，包括体内氧气和 pH 值绘图。在这里，我们报告了大规模合成氘代芬兰三苯甲基自由基的合成程序，该过程具有优异的 EPR 光谱特性和对溶液中氧浓度的更高灵敏度。此外，芬兰三苯甲基自由基被适合连接肽或其他合成前体的接头取代。已经评估了氘代取代对同源衍生物的 EPR 光谱的影响。这些化合物是 EPR 成像中靶向自旋探针的潜在候选者。

  DOI：

  10.1016/j.bmcl.2010.05.006

文献信息

• Large-scale synthesis of a monophosphonated tetrathiatriarylmethyl spin probe for concurrent <i>in vivo</i> measurement of <i>p</i>O₂, pH and inorganic phosphate by EPR
  作者：Teresa D. Gluth、Martin Poncelet、Stephen DeVience、Marieta Gencheva、Emily. H. Hoblitzell、Valery V. Khramtsov、Timothy D. Eubank、Benoit Driesschaert

  DOI：10.1039/d1ra04551b

  日期：——

  We report a new strategy for the synthesis of a mono-phosphonated triarylmethyl radical spin probe and a standalone application with a user-friendly interface for automatic spectrum fitting and extraction of pO₂, pH, and [P_i] values.

  我们报告了一种合成单膦基三芳基甲基自由基自旋探针的新策略，并提供了一个用户友好界面的独立应用程序，用于自动光谱拟合和提取pO2、pH和[P_i]值。
• Room-Temperature Electron Spin Relaxation of Triarylmethyl Radicals at the X- and Q-Bands
  作者：Andrey A. Kuzhelev、Dmitry V. Trukhin、Olesya A. Krumkacheva、Rodion K. Strizhakov、Olga Yu. Rogozhnikova、Tatiana I. Troitskaya、Matvey V. Fedin、Victor M. Tormyshev、Elena G. Bagryanskaya

  DOI：10.1021/acs.jpcb.5b03027

  日期：2015.10.29

  Triarylmethyl radicals (trityls, TAMs) represent a relatively new class of spin labels. The long relaxation of trityls at room temperature in liquid solutions makes them a promising alternative for traditional nitroxides. In this work we have synthesized a series of TAMs including perdeuterated Finland trityl (D-36 form), mono-, di-, and triester derivatives of Finland-D-36 trityl, the deuterated form of OX63, the dodeca-n-butyl homologue of Finland trityl, and triamide derivatives of Finland trityl with primary and secondary amines attached. We have studied room-temperature relaxation properties of these TAMs in liquids using pulsed electron paramagnetic resonance (EPR) at two microwave frequency bands. We have found the clear dependence of phase memory time (T-m similar to T-2) on the magnetic field: room-temperature T-m values are similar to 1.5-2.5 times smaller at the Q-band (34 GHz, 1.2 T) than at the X-band (9 GHz, 0.3 T). This trend is ascribed to the contribution from g-anisotropy that is negligible at lower magnetic fields but comes into play at the Q-band. In agreement with this, the difference between T-1 and T-m becomes more pronounced at the Q-band than at the X-band due to increased contributions from incomplete motional averaging of g-anisotropy. Linear dependence of (1/T-m - 1/T-1) on viscosity implies that g-anisotropy is modulated by rotational motion of the trityl radical. On the basis of the analysis of previous data and results of the present work, we conclude that, in the general situation where the spin label is at least partly mobile, the X-band is most suitable for application of trityls for room-temperature pulsed EPR distance measurements.
• Esterified Dendritic TAM Radicals with Very High Stability and Enhanced Oxygen Sensitivity
  作者：Yuguang Song、Yangping Liu、Craig Hemann、Frederick A. Villamena、Jay L. Zweier

  DOI：10.1021/jo301849k

  日期：2013.2.15

  In this work, we have developed a new class of dendritic TAM radicals (TG, TdG, and dTdG) through a convergent method based on the TAM core CT-03 or its deuterated analogue dCT-03 and trifurcated Newkome-type monomer. Among these radicals, dTdG exhibits the best EPR properties with sharpest EPR singlet and highest O-2 sensitivity due to deuteration of both the ester linker groups and the TAM core CT-03. Like the previous dendritic TAM radicals, these new compounds also show extremely high stability toward various reactive species owing to the dendritic encapsulation. The highly charged nature of these molecules resulting from nine carboxylate groups prevents concentration-dependent EPR line broadening at physiological pH. Furthermore, we demonstrate that these TAM radicals can be easily derivatized (e.g., PEGylation) at the nine carboxylate groups and the resulting PEGylated analogue dTdG PEG completely inhibits the albumin binding, thereby enhancing suitability for in vivo applications. These new dendritic TAM radicals show great potential for in vivo EPR oximetric applications and provide insights on approaches to develop improved and targeted EPR oximetric probes for biomedical applications.
• Synthesis, Characterization, and Nanoencapsulation of Tetrathiatriarylmethyl and Tetrachlorotriarylmethyl (Trityl) Radical Derivatives—A Study To Advance Their Applicability as in Vivo EPR Oxygen Sensors
  作者：Juliane Frank、Marwa Elewa、Mohamed M. Said、Hosam A. El Shihawy、Mohamed El-Sadek、Diana Müller、Annette Meister、Gerd Hause、Simon Drescher、Hendrik Metz、Peter Imming、Karsten Mäder

  DOI：10.1021/acs.joc.5b00918

  日期：2015.7.2

  Tissue oxygenation plays an important role in the pathophysiology of various diseases and is often a marker of prognosis and therapeutic response. EPR (ESR) is a suitable noninvasive oximetry technique. However, to reliably deploy soluble EPR probes as oxygen sensors in complex biological systems, there is still a need to investigate and improve their specificity, sensitivity, and stability. We reproducibly synthesized various derivatives of tetrathiatriarylmethyl and tetrachlorotriarylmethyl (trityl) radicals. Hydrophilic radicals were investigated in aqueous solution mimicking physiological conditions by, e.g., variation of viscosity and ionic strength. Their specificity was satisfactory, but the oxygen sensitivity was low. To enhance the capability of trityl radicals as oxygen sensors, encapsulation into oily core nanocapsules was performed. Thus, different lipophilic triesters were prepared and characterized in oily solution employing oils typically used in drug formulations, i.e., middle-chain triglycerides and isopropyl myristate. Our screening identified the deuterated ethyl ester of D-TAM (radical 13) to be suitable. It had an extremely narrow single EPR line under anoxic conditions and excellent oxygen sensitivity. After encapsulation, it retained its oxygen responsiveness and was protected against reduction by ascorbic acid. These biocompatible and highly sensitive nanosensors offer great potential for future EPR oximetry applications in preclinical research.
• Synthesis, structure, and EPR characterization of deuterated derivatives of Finland trityl radical
  作者：Ilirian Dhimitruka、Olga Grigorieva、Jay L. Zweier、Valery V. Khramtsov

  DOI：10.1016/j.bmcl.2010.05.006

  日期：2010.7

  Substituted trityl radicals are important spin probes for functional electron paramagnetic resonance spectroscopy and imaging including oxygen and pH mapping in vivo. Here we report the synthetic procedure for large scale synthesis of deuterated Finland trityl radical with superior EPR spectral properties and higher sensitivity towards oxygen concentrations in solution. Additionally Finland trityl radicals

  取代的三苯甲基自由基是重要的自旋探针，用于功能性电子顺磁共振波谱和成像，包括体内氧气和 pH 值绘图。在这里，我们报告了大规模合成氘代芬兰三苯甲基自由基的合成程序，该过程具有优异的 EPR 光谱特性和对溶液中氧浓度的更高灵敏度。此外，芬兰三苯甲基自由基被适合连接肽或其他合成前体的接头取代。已经评估了氘代取代对同源衍生物的 EPR 光谱的影响。这些化合物是 EPR 成像中靶向自旋探针的潜在候选者。