(E,E′)-4,4′-bis[p-methoxystyryl]-2,2′-bipyridine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (E,E′)-4,4′-bis[p-methoxystyryl]-2,2′-bipyridine
• 英文别名: (E,E')-4,4'-bis[p-methoxystyryl]-2,2'-bipyridine；4,4'-bis((E)-4-methoxystyryl)-2,2'-bipyridine；4-[(E)-2-(4-methoxyphenyl)ethenyl]-2-[4-[(E)-2-(4-methoxyphenyl)ethenyl]pyridin-2-yl]pyridine
• 化学式: C₂₈H₂₄N₂O₂
• 分子量: 420.511
• InChiKey: QLYURKQGQHATLH-GGWOSOGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E,E′)-4,4′-bis[p-methoxystyryl]-2,2′-bipyridine 、 锇二(2,2'-联吡啶)氯化物 以 乙二醇 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  带有不同取代的 4,4'-二（苯乙烯基）-2,2'-联吡啶配体的钌和锇光敏剂的物理、光谱和生物学特性

  摘要：

  利用先前对二苯乙烯基配位 Ru( II) 的鉴定) 聚吡啶配合物作为一种有前途的光动力疗法光敏剂，通过修饰配体或改变金属配位合成了八种新配合物。我们在这项工作中报告了这些修饰对合成复合物的物理、光谱和生物学特性的影响。二苯乙烯基配体的细微结构修饰仅对相应配合物的可见光吸收和单线态氧量子产率产生中等影响。然而，这些修饰对复合物的亲脂性、细胞摄取和光毒性具有显着影响。尽管复合物的亲脂性对其细胞摄取有某种预期的影响，但最后一个参数不能与其光毒性直接相关，揭示了其他潜在现象。

  DOI：

  10.1039/d1dt02083h
• 作为产物：
  描述：

  4,4'-二甲基-2,2'-联吡啶 、 4-甲氧基苯甲醛 在 potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 (E,E′)-4,4′-bis[p-methoxystyryl]-2,2′-bipyridine
  参考文献：
  名称：

  Ru（II）聚吡啶复合物在大型多细胞肿瘤球体和荷瘤小鼠缺氧中心的1和2光子光疗效果。

  摘要：

  在过去的几十年中，光动力疗法（PDT）是一种批准的医学技术，在治疗某些类型的癌症方面受到越来越多的关注。尽管最近有改进，但是由于光敏剂（PS）穿透3D细胞结构的能力低以及肿瘤中心存在的低氧浓度，大肿瘤的治疗仍然是临床上的主要挑战。为了模拟临床肿瘤中发现的疾病，这项工作中使用了直径为800μm的超大型3D多细胞肿瘤球体（MCTS），以测试一系列新型Ru II多吡啶复合物为单光子和双光子PS。发现这些金属络合物完全穿透3D细胞结构并在光照射下在低氧中心产生单线态氧。尽管没有观察到暗毒性，但这项研究的先导化合物在临床相关的单光子（595 nm）或双光子（800 nm）激发下显示出令人印象深刻的光毒性，并完全消除了MCTS的低氧中心。重要的是，这种功效还在携带腺癌人类肺泡基底上皮肿瘤的小鼠身上得到了证实。

  DOI：

  10.1002/chem.202003486

文献信息

• Rationally designed ruthenium complexes for 1- and 2-photon photodynamic therapy
  作者：Johannes Karges、Shi Kuang、Federica Maschietto、Olivier Blacque、Ilaria Ciofini、Hui Chao、Gilles Gasser

  DOI：10.1038/s41467-020-16993-0

  日期：——

  The use of photodynamic therapy (PDT) against cancer has received increasing attention over recent years. However, the application of the currently approved photosensitizers (PSs) is limited by their poor aqueous solubility, aggregation, photobleaching and slow clearance from the body. To overcome these limitations, there is a need for the development of new classes of PSs with ruthenium(II) polypyridine

  近年来，针对癌症的光动力疗法（PDT）的使用受到越来越多的关注。但是，目前批准的光敏剂（PSs）的应用受到水溶性差，聚集，光致漂白和从体内清除缓慢的限制。为了克服这些局限性，需要开发新型的带有钌（II）聚吡啶配合物的新型聚苯乙烯。然而，这些化合物通常在生物光谱窗口中缺乏明显的吸收，从而限制了它们在治疗深部或大肿瘤中的应用。为克服此缺点，在计算机上设计了具有（E，E的钌（II）聚吡啶络合物'）-4,4'-双苯乙烯基-2,2'-联吡啶配体显示出令人印象深刻的1和2光子吸收率，其幅度比迄今为止公布的值高。尽管这些化合物在黑暗中无毒，但它们在各种2D单层细胞，3D多细胞肿瘤球体中具有光毒性，并在临床相关的1-Photon和2-Photon激发下能够根除小鼠模型内的多抗性肿瘤。
• [EN] METAL COMPLEXES BEARING BISSTYRYL-BIPYRIDINE LIGAND AND THEIR USE AS PHOTOSENSITIZER AGENT IN ONE AND TWO-PHOTON PHOTODYNAMIC THERAPY<br/>[FR] COMPLEXES MÉTALLIQUES PORTANT UN LIGAND BISSTYRYL-BIPYRIDINE ET LEUR UTILISATION EN TANT QU'AGENT PHOTOSENSIBILISANT DANS UNE THÉRAPIE PHOTODYNAMIQUE À UN ET DEUX PHOTONS
  申请人：PARIS SCIENCES LETTRES QUARTIER LATIN

  公开号：WO2021089644A1

  公开（公告）日：2021-05-14

  The present invention relates to metal complexes bearing at least one (E-E')-4,4'- bisstyryl-2,2'-bipyridine ligand (LIG1) of the following formula (I): or a pharmaceutically acceptable salt and/or solvate thereof. The present invention also relates to pharmaceutical compositions comprising these complexes and at least one pharmaceutically acceptable excipient. The present invention also relates to the use of compounds of formula (I) or pharmaceutical compositions comprising thereof as drug and as photosensitizer agent in photodynamic therapy. The present invention also relates to methods of preparation of said complexes.

  本发明涉及具有至少一个(E-E')-4,4'-双亚基苯基-2,2'-联吡啶配体（LIG1）的金属配合物的以下结构式（I）：或其药学上可接受的盐和/或溶剂。本发明还涉及包括这些配合物和至少一种药学上可接受的赋形剂的制药组合物。本发明还涉及将结构式（I）的化合物或包含其的制药组合物用作药物和光动力疗法中的光敏剂的用途。本发明还涉及所述配合物的制备方法。
• High Molar Extinction Coefficient Heteroleptic Ruthenium Complexes for Thin Film Dye-Sensitized Solar Cells
  作者：Daibin Kuang、Seigo Ito、Bernard Wenger、Cedric Klein、Jacques-E Moser、Robin Humphry-Baker、Shaik M. Zakeeruddin、Michael Grätzel

  DOI：10.1021/ja058540p

  日期：2006.3.1

  Two novel heteroleptic sensitizers, Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-hexyloxystyryl)-2,2-bipyridine)(NCS)(2) and Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-methoxystyryl)-2,2'bipyricline) (NCS)(2), coded as K-19 and K-73, respectively, have been synthesized and characterized by 1 H NMR, FTIR, UV-vis absorption, and emission spectroscopy and excited-state lifetime and spectroelectrochemical measurements. The introduction of the alkoxystyryl group extends the conjugation of the bipyridine donor ligand increasing markedly their molar extinction coefficient and solar light harvesting capacity. The dynamics of photoinduced charge separation following electronic excitation of the K-19 dye was scrutinized by time-resolved laser spectroscopy. The electron transfer from K-19 to the conduction band of TiO2 is completed within 20 fs while charge recombination has a half-life time of 800 mu s. The high extinction coefficients of these sensitizers enable realization of a new generation of a thin film dye sensitized solar cell (DSC) yielding high conversion efficiency at full sunlight even with viscous electrolytes based on ionic liquids or nonvolatile solvents. An unprecedented yield of over 9% was obtained under standard reporting conditions (simulated global air mass 1.5 sunlight at 1000 W/m(2) intensity) when the K-73 sensitizer was combined with a nonvolatile "robust" electrolyte. The K-19 dye gave a conversion yield of 7.1% when used in conjunction with the binary ionic liquid electrolyte. These devices exhibit excellent stability under light soaking at 60 degrees C. The effect of the mesoscopic TiO2 film thickness on photovoltaic performance has been analyzed by electrochemical impedance spectroscopy (EIS).
• Synthesis, Characterisation and Biological Evaluation of π-Extended Fe(II) Bipyridine Complexes as Potential Photosensitizers for Photodynamic Therapy
  作者：Johannes Karges、Gilles Gasser

  DOI：10.1016/j.ica.2019.119196

  日期：2020.1

  Photodynamic therapy (PDT) has received increasing attention over the recent years to treat a variety of cancers. The use of metal complexes as PDT agents is currently a highly investigated alternative due to the attractive chemical and photophysical properties of these compounds. However, most of the metal complexes studied so far are based on rare metals, limiting their use since these metals are neither cheap nor abundant. It would be therefore of high interest to develop compounds based on a cheap, abundant metal. Having this in mind, we designed Fe(II) polypyridine complexes with an absorption in the biological spectral window (600-900 nm) through extension of the pi-system. Importantly, the complexes were found to be stable in human plasma and upon light irradiation. A cytotoxic effect in the micromolar range in the dark and a slight effect upon exposure to irradiation at 480 and 540 nm in cancerous human cervical carcinoma (HeLa) cells was observed.
• Physical, spectroscopic, and biological properties of ruthenium and osmium photosensitizers bearing diversely substituted 4,4′-di(styryl)-2,2′-bipyridine ligands
  作者：Robin Vinck、Johannes Karges、Mickaël Tharaud、Kevin Cariou、Gilles Gasser

  DOI：10.1039/d1dt02083h

  日期：——

  Capitalising on the previous identification of a distyryl coordinated Ru(II) polypyridine complex as a promising photosensitizer for photodynamic therapy, eight new complexes were synthesized by modifications of the ligands or by changing the metal coordinated. We report in this work the effects of these modifications on the physical, spectroscopic, and biological properties of the synthesized complexes

  利用先前对二苯乙烯基配位 Ru( II) 的鉴定) 聚吡啶配合物作为一种有前途的光动力疗法光敏剂，通过修饰配体或改变金属配位合成了八种新配合物。我们在这项工作中报告了这些修饰对合成复合物的物理、光谱和生物学特性的影响。二苯乙烯基配体的细微结构修饰仅对相应配合物的可见光吸收和单线态氧量子产率产生中等影响。然而，这些修饰对复合物的亲脂性、细胞摄取和光毒性具有显着影响。尽管复合物的亲脂性对其细胞摄取有某种预期的影响，但最后一个参数不能与其光毒性直接相关，揭示了其他潜在现象。