BF2 chelate of [3-(4-methoxyphenyl)-5-phenyl-1H-pyrrol-2-yl][3-(4-methoxyphenyl)-5-phenylpyrrol-2-ylidene]amine

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: BF2 chelate of [3-(4-methoxyphenyl)-5-phenyl-1H-pyrrol-2-yl][3-(4-methoxyphenyl)-5-phenylpyrrol-2-ylidene]amine
• 英文别名: 3,5-diphenyl-1,7-bis(4-methoxyphenyl)-4,4-difluoro-3a-azonia-4a,8-diaza-4-bora(IV)-s-indacene；4,4-difluoro-1,7-bis(4-methoxyphenyl)-3,5-diphenyl-4-bora-3a,4a,8-triaza-s-indancene
• 化学式: C₃₄H₂₆BF₂N₃O₂
• 分子量: 557.407
• InChiKey: BGXJVQIABPOTLK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  42.0
• 可旋转键数：
  6.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  38.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  BF2 chelate of [3-(4-methoxyphenyl)-5-phenyl-1H-pyrrol-2-yl][3-(4-methoxyphenyl)-5-phenylpyrrol-2-ylidene]amine 在 N-溴代丁二酰亚胺(NBS) 、 三氯化硼 作用下， 以 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  不含硼的近红外IR氮杂-BODIPY-谷氨酰胺通过硼官能化结合

  摘要：

  通过在硼原子上进行取代，合成了三种无接头的氮杂-BODIPY-谷氨酰胺共轭物及其2,6-二溴衍生物。谷氨酰胺结合的方式决定了结合物的性质。

  DOI：

  10.1002/ejoc.201901772
• 作为产物：
  描述：

  [3-(4-methoxyphenyl)-5-phenyl-1H-pyrrol-2-yl][3-(4-methoxyphenyl)-5-phenylpyrrol-2-ylidene]amine 在 三氟化硼乙醚 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以53%的产率得到BF2 chelate of [3-(4-methoxyphenyl)-5-phenyl-1H-pyrrol-2-yl][3-(4-methoxyphenyl)-5-phenylpyrrol-2-ylidene]amine
  参考文献：
  名称：

  In vitro photodynamic treatment of cancer cells induced by aza-BODIPYs

  摘要：

  我们从商业产品出发，以相当高的产率合成了两种杂氮-BODIPY光敏剂（PSs，化合物 7 和 8），其结构的每个吡咯单元上都有一个碘原子，并对两种人类癌细胞系（HCT116 和 SKOV3）进行了体外测试，以评估它们的光动力功效。用不同浓度的 7 或 8 处理细胞培养物并培养所需时间后，用红光发光二极管（LED）装置照射细胞两小时；然后用 MTT 法测定细胞的死亡程度。除杀灭效果外，研究人员还对新型 PS 进行了研究，以确定与光动力功效有关的其他参数，如对光漂白的耐受性、单线态氧产生率、荧光量子产率、细胞吸收和在细胞内的定位，最后还对细胞凋亡进行了流式细胞分析。从整体结果来看，这些氮杂-BODIPYs 的 IC50 值低于微摩尔浓度，而且具有更多有趣的特征，因此可以被认为是很有前途的光敏剂。事实上，这些分子已被证明：(a) 对光漂白相当稳定；(b) 能产生良好的单线态氧；(c) 对细胞的穿透力强，在细胞液中分布广泛。此外，由于单线态氧的产生率很高，凋亡细胞达到了 30%，这使得我们可以假定体内光致脱色疗法的炎症效应很低；因此，这些氮杂-BODIPYs 在体内的应用可能是可行的。

  DOI：

  10.1039/d0pp00026d

文献信息

• Synthesis, optical properties and ultrafast dynamics of aza-boron-dipyrromethene compounds containing methoxy and hydroxy groups and two-photon absorption cross-section
  作者：Betül Küçüköz、Mustafa Hayvalı、Halil Yılmaz、Birhan Uğuz、Ulaş Kürüm、H. Gul Yaglioglu、Ayhan Elmali

  DOI：10.1016/j.jphotochem.2012.08.003

  日期：2012.11

  (aza-BODIPY) compounds containing methoxy and hydroxy groups were synthesized. The effects of substitution and intramolecular charge transfer on linear and nonlinear optical absorptions (especially two photon absorption) of these BODIPY derivatives were investigated. Drastic spectral changes of aza-BODIPY compounds containing hydroxy group were observed in linear absorption spectra depending on basicity of

  在这项工作中，合成了含有甲氧基和羟基的氮杂硼二吡咯亚甲基（aza-BODIPY）化合物。研究了取代和分子内电荷转移对这些BODIPY衍生物的线性和非线性光学吸收（尤其是两个光子吸收）的影响。根据溶液的碱性，在线性吸收光谱中观察到含羟基的氮杂-BODIPY化合物的剧烈光谱变化。这些化合物的酚盐形式的线性吸收光谱中的新谱带在THF溶液中出现在500 nm以下和700 nm以上。这些发现是由于酚盐形式的分子内电荷转移状态的发生。超快泵探针光谱实验表明，酚醛形式仅在600 nm附近显示漂白信号。另一方面，酚盐形式除了在600 nm附近的漂白信号外，还在500 nm及700 nm以上的区域显示快速增长的非线性吸收信号。分子内的电荷转移状态发生在700 nm以上，并且该状态的寿命以超快时间尺度为单位。由于荧光实验的激发是在600 nm处进行的，因此由于分子内电荷转移状态下的能量弛豫而没有荧光信号。含甲
• In Vitro Demonstration of the Heavy-Atom Effect for Photodynamic Therapy
  作者：Aoife Gorman、John Killoran、Caroline O'Shea、Tony Kenna、William M. Gallagher、Donal F. O'Shea

  DOI：10.1021/ja047649e

  日期：2004.9.1

  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.
• Synthesis and properties of hexaarylated AzaBODIPYs
  作者：Sunit Kumar、Tamanna K. Khan、Mangalampalli Ravikanth

  DOI：10.1016/j.tet.2015.07.074

  日期：2015.10

  Sterically crowded 1,2,3,5,6,7-hexaarylated azaBODIPYs were synthesized in 25-35% yields by coupling 1,3,5,7-tetraaryl azaBODIPYs with six different aryl boronic acids under Pd(0) coupling conditions. The moderate reaction yields were attributed to steric congestion caused by two additional aryl groups introduced at the tetraaryl azaBODIPY core. The compounds were characterized by HRMS, 1D and 2D NMR spectroscopic techniques. The H-1, F-19 and B-11 NMR studies of hexaarylated azaBODIPYs showed slight upfield shifts compared to tetraaryl azaBODIPY indicating the slight alteration of electronic properties of azaBODIPY core upon introduction of two additional aryl groups on tetrararyl azaBODIPY. The absorption and fluorescence bands of hexaarylated azaBODIPYs experienced 7-10 nm hypsochromic shifts compared to tetraaryl azaBODIPY. The hexaarylated azaBODIPYs are weakly fluorescent with significant reduction in quantum yields and singlet state lifetimes compared to tetraarylated azaBODIPY. (C) 2015 Elsevier Ltd. All rights reserved.
• Linker-Free Near-IR Aza-BODIPY-Glutamine Conjugates Through Boron Functionalization
  作者：Maodie Wang、Guanyu Zhang、Nichole E. M. Kaufman、Petia Bobadova-Parvanova、Frank R. Fronczek、Kevin M. Smith、M. Graça H. Vicente

  DOI：10.1002/ejoc.201901772

  日期：2020.2.28

  Three linker‐free aza‐BODIPY‐glutamine conjugates, and their 2,6‐dibromo derivatives, were synthesized via substitution on the boron atom. The mode of glutamine conjugation determines the conjugate's properties.

  通过在硼原子上进行取代，合成了三种无接头的氮杂-BODIPY-谷氨酰胺共轭物及其2,6-二溴衍生物。谷氨酰胺结合的方式决定了结合物的性质。
• In vitro photodynamic treatment of cancer cells induced by aza-BODIPYs
  作者：Miryam Chiara Malacarne、Stefano Banfi、Enrico Caruso

  DOI：10.1039/d0pp00026d

  日期：2020.6

  Two aza-BODIPY photosensitizes (PSs, compounds 7 and 8), featuring an iodine atom on each pyrrolic unit of their structure, were synthesized in fairly good yields starting from commercial products and tested in vitro on two human cancer cell lines (HCT116 and SKOV3) to assess their photodynamic efficacy. After treating the cell cultures with variable concentrations of 7 or 8 and incubating for the desired incubation time, the cells were irradiated for two hours with a red-light emitting diode (LED) device; afterwards the extent of cell death was determined by MTT assay. Besides the killing effect, the new PSs were also studied to determine further parameters related to photodynamic efficacy, such as the resistance towards photobleaching, the rate of singlet oxygen production, the fluorescence quantum yields, the cellular uptake and the localization inside the cells and, finally, flow cytometric analysis for apoptosis. Considering the results as a whole, these aza-BODIPYs can be considered to be promising photosensitizers because of their IC50 values being below micromolar concentrations and for more rather interesting features. Actually, these molecules have proved to be: (a) quite stable towards photobleaching; (b) good producers of singlet oxygen and (c) highly penetrating the cells with a wide distribution in the cytosol. Furthermore, in accordance with the good rate of singlet oxygen production, the apoptotic cells reach 30% and this allows us to assume a low inflammatory effect of the in vivo PDT treatment; thus a possible in vivo application of these aza-BODIPYs might be plausible.

  我们从商业产品出发，以相当高的产率合成了两种杂氮-BODIPY光敏剂（PSs，化合物 7 和 8），其结构的每个吡咯单元上都有一个碘原子，并对两种人类癌细胞系（HCT116 和 SKOV3）进行了体外测试，以评估它们的光动力功效。用不同浓度的 7 或 8 处理细胞培养物并培养所需时间后，用红光发光二极管（LED）装置照射细胞两小时；然后用 MTT 法测定细胞的死亡程度。除杀灭效果外，研究人员还对新型 PS 进行了研究，以确定与光动力功效有关的其他参数，如对光漂白的耐受性、单线态氧产生率、荧光量子产率、细胞吸收和在细胞内的定位，最后还对细胞凋亡进行了流式细胞分析。从整体结果来看，这些氮杂-BODIPYs 的 IC50 值低于微摩尔浓度，而且具有更多有趣的特征，因此可以被认为是很有前途的光敏剂。事实上，这些分子已被证明：(a) 对光漂白相当稳定；(b) 能产生良好的单线态氧；(c) 对细胞的穿透力强，在细胞液中分布广泛。此外，由于单线态氧的产生率很高，凋亡细胞达到了 30%，这使得我们可以假定体内光致脱色疗法的炎症效应很低；因此，这些氮杂-BODIPYs 在体内的应用可能是可行的。