9,9-bis(6'-bromohexyl)-2,7-diethynylfluorene | 909723-79-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9,9-bis(6'-bromohexyl)-2,7-diethynylfluorene
• 英文别名: 2,7-diethynyl-9,9-bis(6-bromohexyl)fluorene；2,7-diethynyl-9,9-di(6-bromohexyl)fluorene；9,9-Bis(6-bromohexyl)-2,7-diethynylfluorene；9,9-bis(6-bromohexyl)-2,7-diethynylfluorene
• CAS: 909723-79-1
• 化学式: C₂₉H₃₂Br₂
• 分子量: 540.381
• InChiKey: AKMHPCPNEOJVFP-UHFFFAOYSA-N

物化性质

• 熔点：
  54 °C(Solv: methanol (67-56-1); dichloromethane (75-09-2))
• 沸点：
  607.1±45.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  31
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  9,9-bis(6'-bromohexyl)-2,7-diethynylfluorene 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以21 mg的产率得到5-amino-1-(β-D-ribofuranosyl)imidazole-4-[N-(4-aminobutyl)]carboxamide 5'-monophosphate
  参考文献：
  名称：

  AICAR 5'-单磷酸酯 (ZMP) 及其 4-N-烷基衍生物的简便固相合成

  摘要：

  我们在此报告了一种简便的固相合成 5-amino-1-β-D-ribofuranosylimidazole-4-carboxamide-5'-monophosphate (ZMP)，一种嘌呤核苷酸的生物合成前体，以及它的一小部分4-N-烷基衍生物。5-amino-1-β-D-ribofuranosylimidazole-4-carboxamide (AICAR) 非常困难、直接的化学磷酸化通过在 N-1-的 5'-位安装一个合适的、完全保护的磷酸基团来规避(2,4-二硝基苯基)-肌苷，在嘌呤降解之前通过 2',3'-位连接到固体支持物，导致 5-氨基-咪唑-4-甲酰胺部分。还报道了形成 ZMP 咪唑的合理反应机制。

  DOI：

  10.1002/ejoc.200901271
• 作为产物：
  描述：

  1,6-二溴己烷 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四丁基溴化铵 、 potassium carbonate 、 二异丙胺 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 9,9-bis(6'-bromohexyl)-2,7-diethynylfluorene
  参考文献：
  名称：

  A pH-Responsive Drug Delivery System Based on Conjugated Polymer for Effective Synergistic Chemo-/Photodynamic Therapy

  摘要：

  刺激响应药物释放和光动力疗法（PDT）在抗肿瘤治疗中的巨大潜力引起了广泛关注。本研究构建了基于水溶性共轭聚合物的 pH 响应给药系统（PFE-DOX-1 和 PFE-DOX-2），其中抗癌药物多柔比星（Doxorubicin，DOX）通过耐酸亚胺键和酰基腙键共价连接到共轭聚合物的侧链上，实现了高效的化疗/光动力疗法协同作用。同时，由于 PFE 共轭骨架和 DOX 之间的能量/电子转移（ET），聚（芴-乙炔）（PFE）的强烈荧光被有效淬灭。在酸性肿瘤细胞内微环境中，酰腙连接的裂解实现了 PFE-DOX-2 有效的 pH 值响应药物释放。此外，药物释放过程可通过共轭聚合物的荧光恢复进行监测。此外，在酸性环境中释放药物后，共轭聚合物在光照射下可产生活性氧（ROS），从而防止对正常组织可能产生的光毒性。报告指出，PFE-DOX-2 具有显著的抗肿瘤细胞性能，这归功于其高效的细胞吸收和强大的化疗/PDT 协同疗效。因此，本报告通过构建一种刺激响应型多功能给药系统，为体内抗癌治疗提供了一种前景广阔的策略。

  DOI：

  10.3390/molecules28010399

文献信息

• Polyfluorenes bearing N1-Alkylcytosine, Alkylphosphoryl, and Alkylammonium side chains: Synthesis, chemical properties, and sensing ability for metal ions
  作者：Isao Yamaguchi、Ryoga Ooe、Aohan Wang

  DOI：10.1016/j.reactfunctpolym.2021.104900

  日期：2021.6

  sensing behavior of the polymers for metal ions was investigated by UV–vis, photoluminescence (PL), and PL lifetime measurements. Polymer PL decreased with the addition of metal ions, such as Cu+, Cu2+, Pd2+, Ag+, and Pt2+, while it remained virtually unchanged with the addition of Na+ and Fe3+. The decrease in PL intensity upon the addition of metal ions is most likely caused by polymer aggregation

  聚（9,9-双（6- Ñ 1 -cytosinehexyl）芴-2,7-二基ALT -9,9-双（6'- diethoxyphosphorylhexyl）芴-2,7-二基）（聚合物-1），并聚（9,9-双（6- ñ 1 -cytosinehexyl）芴-2,7-二基ALT -9,9--b，是（6- ñ，ñ，ñ -trimethylammoniumhexyl）芴-2,7-二基通过Pd-络合物催化的缩合反应合成了）（聚合物-2）。在中号ñ和中号w ^通过GPC测定聚合物的百分数。通过紫外可见光，光致发光（PL）和PL寿命测量研究了聚合物对金属离子的传感行为。聚合物PL随添加金属离子（例如Cu +，Cu 2 +，Pd 2 +，Ag +和Pt 2+）而降低，而在添加Na +和Fe 3+时几乎保持不变。添加金属离子后PL强度的降低很可能是由于胞嘧啶基团与金属络合导致聚合物聚集而引起的。聚合物的循环伏安法分析显示了它们的电化学活性。
• Conjugated ethynylene-fluorenepolymers with electro-donating TTF as pendant groups: Synthesis, electrochemical and spectroscopic properties
  作者：Xuechao Zhang、Chengyun Wang、Guoqiao Lai、Lei Zhang、Yongjia Shen

  DOI：10.1039/b9nj00520j

  日期：——

  A series of conjugated ethynylene-fluorene polymers with electro-donating TTF as pendant groups (P2–P4) were synthesized by using Sonogashira coupling reaction, and two functionalization methods, i.e. prepolymerization and postpolymerization, were developed. The composition and purity of the corresponding products were analyzed by 1H NMR. The results proved the functionalization of P2 (pre) and P2 (post) were 40% and 100%, respectively. The results also indicated that the postpolymerization method would be a better approach to prepare TTF-pendant conjugated ethynylene-fluorene polymers. The postpolymerization methodology could be extended to synthesize other conjugated fluorene-based polymers bearing TTF units (P3 and P4). The polymers mentioned above exhibited good solubility in normal organic solvents and higher conductivity (neutral conductivity ∼2–4 × 10−6 S cm−1; doped conductivity ∼1–3 × 10−3 S cm−1). Moreover, the fluorescence intensity of P2 (post) could be modulated by the oxidation of TTF units, which makes it an attractive candidate for the fluorescence switch.

  通过Sonogashira偶联反应，合成了一系列带有电给体TTF作为侧基（P2-P4）的共轭乙烯基芴聚合物，并开发了两种官能化方法，即预聚和后聚。通过1H NMR分析了相应产品的组成和纯度。结果表明，P2（预）和P2（后）的官能化率分别为40%和100%。结果还表明，后聚合法是制备TTF侧基共轭乙烯基芴聚合物的更好方法。后聚合法可以扩展到合成其他带有TTF单元的共轭芴基聚合物（P3和P4）。上述聚合物在普通有机溶剂中具有良好的溶解性，并且具有较高的电导率（中性电导率约为2-4×10-6 S cm-1；掺杂电导率约为1-3×10-3 S cm-1）。此外，P2（后）的荧光强度可以通过TTF单元的氧化来调节，这使其成为荧光开关的有吸引力的候选材料。
• Fluorescent Dynamic Covalent Polymers for DNA Complexation and Templated Assembly
  作者：Clément Kotras、Maxime Leclercq、Maxime Roger、Camille Bouillon、Antonio Recupido、Aurélien Lebrun、Yannick Bessin、Philippe Gerbier、Sébastien Richeter、Sébastien Ulrich、Sébastien Clément、Mathieu Surin

  DOI：10.3390/molecules27196648

  日期：——

  π-conjugated fluorescent moieties based on thiophene-ethynyl-fluorene cores. Two types of fluorescent building blocks bearing neutral or cationic side groups on the fluorene moiety are considered in order to assess the role of the number of cationic units on complexation with DNA. The (chir)optical properties of the building blocks, the DCPs, and their complexes with several types of DNA are explored

  动态共价聚合物 (DCP) 为生物分子的靶向、传感和传递提供了作为特别感兴趣的适应性材料的机会。在这种观点中，将阳离子单元和荧光单元沿 DCP 链组合对于实现用于识别和递送核酸的光学探针具有吸引力。在这里，我们报告了基于噻吩-乙炔基-芴核的基于酰基腙的 DCP 的设计，该 DCP 结合了阳离子精氨酸单元和 π 共轭荧光部分。考虑了两种在芴部分上带有中性或阳离子侧基的荧光结构单元，以评估阳离子单元的数量对与 DNA 络合的作用。探索了构建块、DCP 及其与多种类型 DNA 的复合物的（手性）光学特性，提供有关超分子复合物形成及其在水溶液中稳定性的详细信息。展示了以 DNA 为模板的 DCP 形成，为基于核酸结构的荧光 DCP 组装提供了新的视角。
• High-Efficiency Polymer Solar Cells via the Incorporation of an Amino-Functionalized Conjugated Metallopolymer as a Cathode Interlayer
  作者：Shengjian Liu、Kai Zhang、Junming Lu、Jie Zhang、Hin-Lap Yip、Fei Huang、Yong Cao

  DOI：10.1021/ja408363c

  日期：2013.10.16

  An amino-functionalized conjugated metallopolymer PFEN-Hg was developed as a cathode interlayer for inverted polymer solar cells. The resulting devices exhibited significantly improved performance with power conversion efficiencies exceeding 9%. Moreover, good device performance was achievable with the PFEN-Hg over a wider range of film thickness, likely due to the Hg-Hg interactions and improved pi-pi stacking.
• Water-Soluble Conjugated Polymers for Amplification of One- and Two-photon Properties of Photosensitizers
  作者：Fang He、Xinsheng Ren、Xiaoqin Shen、Qing-Hua Xu

  DOI：10.1021/ma2008805

  日期：2011.7.12

  Two new water-soluble polyfluorene-based conjugated polymers have been designed and synthesized to act as two-photon light harvesting complexes to amplify the two-photon property of photosensitizers and organic dyes through fluorescence resonance energy transfer (FRET). The two-photon absorption cross sections of the conjugated polymers at 800 nm have been significantly improved by inserting ethynylene and vinylene groups as the bridges, which extend the conjugation length and electron delocalization. By using these conjugated polymers as two-photon light harvesting complexes, the two-photon excitation emission of the photosensitizer, Rose Bengal, was found to be significantly enhanced (by up to 85 fold) through FRET. These studies are expected to provide insight on designing systems with further improved performance for potential applications in two-photon photodynamic therapy, sensing, and imaging.