3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmethene difluoroborate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmethene difluoroborate
• 英文别名: 3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrromethene difluoroborate；1,3,5,7-tetraphenyl-8-aza-dipyrrolylmethenmethenedifluoroborate；difluoroborate 3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmetene；4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a,8-triaza-s-indacene；[3,5-diphenyl-1H-pyrrol-2-yl-3,5-diphenyl-2-ylideneamine]BF2；1,3,5,7-tetraphenyl-8-aza-BODIPY；1,3,5,7-tetraphenyl-aza-BODIPY；Aza-BODIPY；2,2-difluoro-4,6,10,12-tetraphenyl-3,8-diaza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• 化学式: C₃₂H₂₂BF₂N₃
• 分子量: 497.355
• InChiKey: ZRHFBKZCOBJRTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.69
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmethene difluoroborate 在 水 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 0.5h， 生成 (3,5-diphenyl-1H-pyrrol-2-yl)(3,5-diphenylpyrrol-2-ylidene)amine
  参考文献：
  名称：

  Synthesis, properties and reactivity of BCl₂ aza-BODIPY complexes and salts of the aza-dipyrrinato scaffold

  摘要：

  将F-aza-BODIPYs转化为Cl-aza-BODIPYs可使硼处于易位状态，使用芳基格氏试剂进行取代，同时进行受控的脱硼去保护作用，从而得到母体azadipyrrin。

  DOI：

  10.1039/d0ob00272k
• 作为产物：
  描述：

  4-硝基-1,3-二苯基-1-丁酮 在 乙酸铵 、 三氟化硼乙醚 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 25.5h， 生成 3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmethene difluoroborate
  参考文献：
  名称：

  In Vitro Demonstration of the Heavy-Atom Effect for Photodynamic Therapy

  摘要：

  Photodynamic therapy (PDT) is an emerging treatment modality for a range of disease classes, both cancerous and noncancerous. This has brought about an active pursuit of new PDT agents that can be optimized for the unique set of photophysical characteristics that are required for a successful clinical agent. We now describe a totally new class of PDT agent, the BF2-chelated 3,5-diaryl-1H-pyrrol-2-yl-3,5-diarylpyrrol-2-yl-ideneamines (tetraarylazadipyrromethenes). Optimized synthetic procedures have been developed to facilitate the generation of an array of specifically substituted derivatives to demonstrate how control of key therapeutic parameters such as wavelength of maximum absorbance and singlet-oxygen generation can be achieved. Photosensitizer absorption maxima can be varied within the body's therapeutic window between 650 and 700 rim, with high extinction coefficients ranging from 75 000 to 85 000 M-1 cm(-1). Photosensitizer singlet-oxygen generation level was modulated by the exploitation of the heavy atom effect. An array of photosensitizers with and without bromine atom substituents gave rise to a series of compounds with varying singlet-oxygen generation profiles. X-ray structural evidence indicates that the substitution of the bromine atoms has not caused a planarity distortion of the photosensitizer. Comparative singlet-oxygen production levels of each photosensitizer versus two standards demonstrated a modulating effect on singlet-oxygen generation depending upon substituent patterns about the photosensitizer. Confocal laser scanning microscopy imaging of 18a in HeLa cervical carcinoma cells proved that the photosensitizer was exclusively localized to the cellular cytoplasm. In vitro light-induced toxicity assays in HeLa cervical carcinoma and MRC5-SV40 transformed fibroblast cancer cell lines confirmed that the heavy-atom effect is viable in a live cellular system and that it can be exploited to modulate assay efficacy. Direct comparison of the efficacy of the photosensitizers 18b and 19b, which only differ in molecular structure by the presence of two bromine atoms, illustrated an increase in efficacy of more than a 1000-fold in both cell lines. All photosensitizers have very low to nondeterminable dark toxicity in our assay system.

  DOI：

  10.1021/ja047649e

文献信息

• The effect of heavy atom to two photon absorption properties and intersystem crossing mechanism in aza-boron-dipyrromethene compounds
  作者：Ahmet Karatay、M. Ceren Miser、Xiaoneng Cui、Betül Küçüköz、Halil Yılmaz、Gökhan Sevinç、Elif Akhüseyin、Xueyan Wu、Mustafa Hayvali、H. Gul Yaglioglu、Jianzhang Zhao、Ayhan Elmali

  DOI：10.1016/j.dyepig.2015.07.002

  日期：2015.11

  probability of intersystem crossing increases. Z-scan experiments at 800 nm wavelengths revealed considerably large (610 GM) two photon absorption cross section value with respect to literature for compounds showing intersystem crossing mechanism. The efficient intersystem crossing and enhanced two-photon absorption properties make the investigated aza-boron-dipyrromethene compounds good candidates

  设计并合成了各种位置含溴原子的新型氮杂硼-二吡咯亚甲基化合物，以增强三重态态种群和两个光子吸收特性，可用于二光子光动力疗法，三重态-三重态an灭上转换。稳态荧光和超快泵浦探针光谱技术显示，只有2、6个位置的氮杂硼-二吡咯二烯核心对三重态人口有显着贡献。密度泛函理论计算表明，当将溴原子引入氮杂硼-双-吡咯二烯中心的2、6位时，单线态和三线态能级越近，因此系统间交叉的可能性就越大。在800 nm波长下的Z扫描实验表明，相对于文献中显示出系统间交叉机理的化合物而言，两个光子吸收截面值相当大（610 GM）。有效的系统间穿越和增强的双光子吸收特性使所研究的氮杂硼-二吡咯亚甲基化合物成为双光子光动力疗法应用的良好候选者。
• Deep-Red-Fluorescent Zinc Probe with a Membrane-Targeting Cholesterol Unit
  作者：Jin Ju Kim、Jayeon Hong、Seungyeon Yu、Youngmin You

  DOI：10.1021/acs.inorgchem.0c01376

  日期：2020.8.17

  Organelle-targeting fluorescence probes are valuable because they can provide spatiotemporal information about the trafficking of analytes of interest. The spatiotemporal resolution can be improved by using low-energy emission signals because they are barely contaminated by autofluorescence noises. In this study, we designed and synthesized a deep-red-fluorescent zinc probe (JJ) with a membrane-targeting cholesterol unit. This zinc probe consists of a boron-azadipyrromethene (aza-BODIPY) fluorophore and a zinc receptor that is tethered to a tri(ethylene glycol)–cholesterol chain. In aqueous solutions buffered to pH 7.4, JJ exhibits weak fluorescence with a peak wavelength of 663 nm upon excitation at 622 nm. The addition of ZnCl2 elicits an approximately 5-fold enhancement of the fluorescence emission with a fluorescence dynamic range of 141000. Our electrochemical and picosecond transient photoluminescence investigations indicate that the fluorescence turn-on response is due to the zinc-induced abrogation of the formation of a nonemissive intramolecularly charge-separated species, which occurs with a driving force of 0.98 eV. The fluorescence zinc response was found to be fully reversible and to be unaffected by pH changes or the presence of biological metal ions. These properties are due to tight zinc binding with a dissociation constant of 4 pM. JJ was found to be nontoxic to HeLa cells up to submicromolar concentrations, which enables cellular imaging. Colocalization experiments were performed with organelle-specific stains and revealed that JJ is rapidly internalized into intracellular organelles, including lysosomes and endoplasmic reticula. Unexpectedly, probe internalization was found to permeabilize the cell membrane, which facilitates the influx of exogens such as zinc ions. Such permeabilization does not arise for a control probe without the tri(ethylene glycol)–cholesterol chain (JJC). Our results show that the membrane-targeting cholesterol unit can disrupt membrane integrity.

  靶向细胞器的荧光探针具有重要价值，因为它们能够提供感兴趣分析物的运输时空信息。通过使用低能发射信号可以提高时空分辨率，因为它们几乎不受自体荧光噪声的污染。在本研究中，我们设计并合成了一种深红色荧光锌探针（JJ），该探针具有膜靶向胆固醇单元。这种锌探针由硼-氮杂二吡咯甲烯（aza-BODIPY）荧光团和一个通过三（乙二醇）胆固醇链连接的锌受体组成。在pH值为7.4的缓冲水溶液中，JJ在622 nm激发下表现出663 nm的弱荧光，峰值波长为663 nm。加入ZnCl2可激发约5倍的荧光发射增强，荧光动态范围为141000。我们的电化学和皮秒瞬态光致发光研究表明，荧光开启响应是由于锌诱导的非发射性分子内电荷分离物种形成的终止，该过程的驱动力为0.98 eV。研究发现，荧光锌响应是完全可逆的，不受pH变化或生物金属离子存在的影响。这些特性源于锌的紧密结合，其解离常数为4 pM。研究发现，JJ对HeLa细胞的毒性在亚微摩尔浓度以下，这使得能够进行细胞成像。通过与特定细胞器的染色进行共定位实验，发现JJ能够迅速内化到溶酶体和内质网等细胞内细胞器。出乎意料的是，探针内化会使细胞膜通透化，从而促进锌离子等外来物的流入。这种通透化不会出现在没有三（乙二醇）胆固醇链的控探针（JJC）中。我们的结果表明，膜靶向胆固醇单元可以破坏膜的完整性。
• Synthesis of Aza-BODIPY Boron Difluoride PDT Agents to Promote Apoptosis in HeLa Cells
  作者：Ronny Priefer、Justin R. Griffiths、Janelle N. Ludwig、Graham Skelhorne-Gross、Robert S. Greene

  DOI：10.2174/157017811796064377

  日期：2011.7.1

  BF2 Chelated azadipyrromethene dyes fluoresce in the near infrared and have potential applications in photodynamic therapy. When irradiated above 600nm these aza-BODIPY compounds react with triplet O2 in the body to form a reactive singlet oxygen species which leads to cell death. A small library has been synthesized of these potential PDT agents via a four step process, with varying substituents on the aromatic ring of the starting benzaldehyde and acetophenone. In vitro studies on HeLa cells have revealed an effective photosensitive compound with low dark cytotoxicity and promotion of apoptotic cell death when exposed to light.

  BF2螯合的氮杂二吡咯甲烯染料在近红外区域发出荧光，并在光动力疗法中具有潜在应用。当这些氮-BODIPY化合物在600nm以上波长照射下，能与体内的三重态氧反应生成活性单线态氧物种，导致细胞死亡。通过四步合成过程，以苯甲醛和苯乙酮起始环上有不同取代基的条件下，构建了一个小型库，这些潜在的光动力疗法试剂得以合成。在HeLa细胞的体外研究中，发现了一种有效的光敏化合物，其在暗态下具有较低的细胞毒性，并在光照下促进细胞凋亡。
• Copper(<scp>ii</scp>)-promoted oxidative C–H/C–H cross-coupling for rapid access to aza-BODIPY-indole derivatives with broad optical absorption
  作者：Ruyong Jiang、Xiuguang Yang、Di Wu

  DOI：10.1039/c7ob01344b

  日期：——

  The direct C–H activation of electron-deficient aza-BODIPYs has been effectively achieved via a concise and inexpensive Cu(II)-promoted oxidative C–H/C–H coupling approach. The resulting indole-aza-BODIPY 6b covers a broad spectrum of 429–900 nm with a FWHM of 294 nm in solution and covers a UV-vis-NIR region up to 1100 nm in film.

  缺电子的aza-BODIPYs的直接C–H活化已通过一种简洁且廉价的Cu（II）促进的氧化C–H / C–H偶联方法得以有效实现。所得的吲哚-氮杂-BODIPY 6b覆盖429-900 nm的宽光谱，溶液的FWHM为294 nm，并覆盖膜中高达1100 nm的UV-vis-NIR区域。
• Synthesis, Photophysical, Electrochemical, and Electrogenerated Chemiluminescence Studies. Multiple Sequential Electron Transfers in BODIPY Monomers, Dimers, Trimers, and Polymer
  作者：Alexander B. Nepomnyashchii、Martin Bröring、Johannes Ahrens、Allen J. Bard

  DOI：10.1021/ja2010219

  日期：2011.6.8

  addition of monomer units from monomer to polymer for C(8) dyes. The aza-BODIPY dye shows red-shifted absorbance and fluorescence compared with the C(8) analogue. Cyclic voltammetry shows one, two, and three one-electron waves on both reduction and oxidation for the monomer, dimer, and trimer, respectively, for the C(8) BODIPYs. The separation for the reduction peaks for the C(8) dimers is 0.12 V compared

  进行了 C(8) BODIPY 单体、二聚体和三聚体、C(8) 聚合物和 N(8) 氮杂-BODIPY 单体和二聚体的合成。使用了甲基和甲基 C(8) 取代的单体、二聚体和三聚体。二聚体、三聚体和聚合物通过使用 FeCl(3) 的氧化偶联通过 β-β (2/6) 位置化学形成。C(8) 染料从单体到聚合物添加单体单元后，观察到吸光度和荧光的红移。与 C(8) 类似物相比，aza-BODIPY 染料显示红移吸光度和荧光。对于 C(8) BODIPYs，循环伏安法分别显示了单体、二聚体和三聚体的还原和氧化的一个、两个和三个单电子波。C(8) 二聚体的还原峰分离为 0.12 V，而氧化为 0.22 V，而三聚体显示还原峰之间的间隔为 0.09 V，氧化峰的间隔为 0.13 V。与第二个峰相比，第二个峰和第三个峰之间的较大分离，氧化为 0.25 V，还原为 0.2 V，这与去除或添加第三个电子的能量更大是一致的。BODIPY