5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(n-hexyloxy)calix[4]arene, 1,3-alternate | 212071-52-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(n-hexyloxy)calix[4]arene, 1,3-alternate
• 英文别名: tetra(5-hexenyloxy)-p-tert-butylcalix[4]arene；tetrakis(O-n-hexyloxy)calix[4]arene；HBCalix；5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahexoxycalix[4]arene；5,11,17,23-Tetratert-butyl-25,26,27,28-tetrahexoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene；5,11,17,23-tetratert-butyl-25,26,27,28-tetrahexoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene
• CAS: 212071-52-8；816437-58-8；1123626-00-5
• 化学式: C₆₈H₁₀₄O₄
• 分子量: 985.571
• InChiKey: NAFREVJQRFWJLZ-UHFFFAOYSA-N

物化性质

• 熔点：
  232 °C
• 沸点：
  909.2±65.0 °C(Predicted)
• 密度：
  0.961±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  23.6
• 重原子数：
  72
• 可旋转键数：
  28
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(n-hexyloxy)calix[4]arene, 1,3-alternate 在 sodium nitrate 、 三氟乙酸 作用下， 反应 16.0h， 以52%的产率得到5,11,17,23-tetranitro-25,26,27,28-tetra(hexyloxy)calix[4]arene
  参考文献：
  名称：

  Preparation and physicochemical characterization of a novel paclitaxel-loaded amphiphilic aminocalixarene nanoparticle platform for anticancer chemotherapy

  摘要：

  本文描述了利用一种新型两性载体四己氧基四对氨基卡立[4]芳烃(A4C6)开发和优化纳米颗粒递送平台，用于抗癌药物紫杉醇的传递。

  通过乳液蒸发法成功制备了纳米颗粒，其中有机相含有紫杉醇：A4C6（摩尔比1:10），通过探头超声将其分散到含有0.5% w/v聚乙烯醇稳定剂的水相中，pH值为4。

  载药纳米颗粒的平均尺寸为78.7 ± 20.7 nm，表面电位为38.3 ± 7.67 mV，紫杉醇负载和包封效率分别为69.1 ± 5.3 µg药物/mg载体和50.4 ± 3.2%。透射电子显微镜照片显示离散的颗粒，没有凝聚的迹象。体外溶解实验显示，加入4%牛血清白蛋白的磷酸盐缓冲液中，分别在5、72和120小时释放的封装紫杉醇负荷量为32.7 ± 3.9%、82.6 ± 5.3%和91.0 ± 6.0%。

  这是首次报道使用氨基取代的两性卡立芳烃封装抗癌药物。所制备的纳米颗粒明显小于Abraxane纳米颗粒，但具有可比较的药物载荷，有潜力实现紫杉醇对肿瘤组织的靶向传递。

  DOI：

  10.1111/j.2042-7158.2012.01518.x
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 、 6-溴-1-己烯 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 反应 72.0h， 以32%的产率得到5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(n-hexyloxy)calix[4]arene, 1,3-alternate
  参考文献：
  名称：

  制备热敏性杯[4]芳烃并入P（NIPAM-co-HBCalix）水凝胶作为镍（II）离子可重复使用的吸附剂

  摘要：

  甲杯共轭热响应含有15％四（5-己烯氧基）水凝胶-对-叔丁基杯[4]芳烃（HBCalix），P（NIPAM-共-HBCalix），被用来从除去镍（II）离子水。研究了制备的P（NIPAM- co- HBCalix）水凝胶的热敏性能和Ni 2+吸附能力。单体HBCalix的引入通过己烯氧基与金属离子之间的螯合大大增强了Ni 2+在水凝胶上的吸附。当HBCalix单元捕获Ni 2+并形成HBCalix / Ni 2+主体-客体络合物时，由于带电的HBCali / Ni之间的排斥，水凝胶的较低临界溶液温度转变为较高温度。2+组和水凝胶内的渗透压。通过改变接触时间，抗衡离子和Ni 2+的初始浓度进行吸附研究。吸附性能的评估表明，水凝胶与Langmuir等温线模型表现出更好的相关性。只需改变环境温度即可重复使用P（NIPAM- co- HBCalix），而吸附能力几乎没有损失。这种离子识别水凝胶有望成为一种新型的吸附和分离Ni

  DOI：

  10.1002/pola.26625

文献信息

• Sensing and Fixation of NO₂/N₂O₄ by Calix[4]Arenes
  作者：Grigory V. Zyryanov、Yanlong Kang、Dmitry M. Rudkevich

  DOI：10.1021/ja029166l

  日期：2003.3.1

  NO(+) is found encapsulated within the calixarene cavity, and stable charge-transfer complexes result with K(ass) > 10(6) M(-1) (CDCl(3)). The NO(+) encapsulation was also demonstrated in titration experiments with calixarenes 1, 2, and 5 and commercially available NO(+)SbF(6)(-) salt in chloroform. The complexation process is reversible, and the complexes dissociate upon addition of water and alcohol

  提出了一种对 NO(2)/N(2)O(4) 进行视觉检测和化学利用的方法，该方法采用简单的杯 [4] 芳烃。四-O-烷基化杯[4]芳烃 1 和 2，具有锥形或 1,3-交替构象，暴露于 NO(2)/N(2)O(4)，无论是在氯仿溶液中还是在氯仿溶液中固态，产生深颜色的杯芳烃-亚硝基鎓 (NO(+)) 络合物。在路易斯酸的存在下，如 SnCl(4)，稳定的杯芳烃-NO(+) 配合物 7 和 8 以定量产率分离出来，并通过紫外-可见光、FTIR、高分辨率 (1) H NMR 光谱表征和元素分析。NO(+) 被发现封装在杯芳烃腔内，稳定的电荷转移复合物导致 K(ass) > 10(6) M(-1) (CDCl(3))。NO(+) 包封也在杯芳烃 1、2、和 5 和市售的 NO(+)SbF(6)(-) 盐在氯仿中。络合过程是可逆的，加入水和醇后，络合物解离，回收母体杯芳烃。展示了功能化杯[4] 芳烃与硅胶的连接，这提供了一种固体材料
• A procedure for filling calixarene nanotubes
  作者：Valentina Sgarlata、Voltaire G. Organo、Dmitry M. Rudkevich

  DOI：10.1039/b509299j

  日期：——

  Alkyl nitrites readily transfer nitrosonium into calixarene-based synthetic nanotubes thus offering a mild, effective and precise method to fill them.

  亚硝酸烷基酯很容易将硝氮转移到基于杯芳烃的合成纳米管中，因此提供了一种温和，有效和精确的填充方法。
• Supramolecular Materials: Molecular Packing of Tetranitrotetrapropoxycalix[4]arene in Highly Stable Films with Second-Order Nonlinear Optical Properties
  作者：Paul J. A. Kenis、Oscar F. J. Noordman、Holger Schönherr、Esther G. Kerver、Bianca H. M. Snellink-Ruël、Gerrit J. van Hummel、Sybolt Harkema、Cornelis P. J. M. van der Vorst、Jeff Hare、Stephen J. Picken、Johan F. J. Engbersen、Niek F. van Hulst、G. Julius Vancso、David N. Reinhoudt

  DOI：10.1002/(sici)1521-3765(19980710)4:7<1225::aid-chem1225>3.0.co;2-6

  日期：1998.7.10

  Highly stable films of tetranitrotetrapropoxycalix[4]arene (9) with second-order nonlinear optical (NLO) properties and a noncentrosymmetric structure were obtained by a novel crystallization process at 130-140 degrees C in a de electric field. The packing of 9 in these films was elucidated by a combination of X-ray diffraction, angle-dependent second-harmonic generation, and scanning force microscopy (SFM). The experimental results agree well with solid-state molecular dynamics calculations for these films. No crystalline phase was observed for nitrocalix[4]arene derivatives with longer or branched alkyl chains; this explains the limited NLO stability of films of these calixarenes. Scanning force microscopy on the aligned films of 9 showed two distinct surface lattice structures: a rectangular lattice (a = 9.3, b = 11.7 Angstrom) and a pseudohexagonal lattice (d approximate to 11.4 Angstrom). The combination of these data with the interlayer distance of 8.9 Angstrom (X-ray diffraction) allowed the packing of molecules of 9 in these structures to be fully elucidated at the molecular level.
• Toward Synthetic Tubes for NO₂/N₂O₄:  Design, Synthesis, and Host−Guest Chemistry
  作者：Grigory V. Zyryanov、Dmitry M. Rudkevich

  DOI：10.1021/ja0392869

  日期：2004.4.1

  Design of molecular nanotubes is proposed for entrapment and conversion of NO2/N2O4 gases. Synthesis of 1,3-alternate bis-calix[4]arene tube 3 of 5 x 11 Angstrom internal dimensions is presented, and its reversible reactions with NO2/N2O4 in solution are studied. Exposure of 3 to NO2/N2O4 in chlorinated solvents results in the rapid encapsulation of nitrosonium (NO+) cations within its interior. Mono- and dinitrosonium complexes 4 and 5, respectively, were isolated and characterized by UV-vis, FTIR, and H-1 NMR spectroscopies, and also molecular modeling. The NO+ entrapment process is reversible, and addition of water quickly recovered starting tube 3. Encapsulated within the tube NO+ species act as nitrosating agents for secondary amides. These findings open wider perspectives toward NO2/NOx storing and converting materials and also offer a promise for further development of supramolecular chemistry of synthetic nanotubes.
• Preparation and physicochemical characterization of a novel paclitaxel-loaded amphiphilic aminocalixarene nanoparticle platform for anticancer chemotherapy
  作者：Clare Weeden、Karel J Hartlieb、Lee Yong Lim

  DOI：10.1111/j.2042-7158.2012.01518.x

  日期：2012.9.4

  This paper describes the development and optimization of a nanoparticle delivery platform for the anticancer agent, paclitaxel, using a novel amphiphilic carrier, tetrahexyloxy-tetra-p-aminocalix[4]arene (A4C6).

  Nanoparticles were successfully prepared at pH 4 by an emulsion evaporation method whereby an organic phase containing paclitaxel : A4C6 (molar ratio 1 : 10) was dispersed by probe sonication into an aqueous phase containing 0.5% w/v polyvinyl alcohol as stabilizer.

  The drug-loaded nanoparticles had a mean size of 78.7 ± 20.7 nm, surface potential of 38.3 ± 7.67 mV, and paclitaxel loading and encapsulation efficiencies of 69.1 ± 5.3 µg drug/mg carrier and 50.4 ± 3.2%, respectively. Transmission electron micrographs showed discrete particles with no evidence of agglomeration. In-vitro dissolution into phosphate buffered saline supplemented with 4% bovine serum albumin showed 32.7 ± 3.9%, 82.6 ± 5.3% and 91.0 ± 6.0% of the encapsulated paclitaxel load was released at 5, 72 and 120 h, respectively.

  This is the first report on the use of amino-substituted amphiphilic calixarenes for the encapsulation of anticancer agents. The nanoparticles produced were significantly smaller than, but had comparable drug loads to the Abraxane nanoparticles, and have the potential to achieve targeted delivery of paclitaxel to tumour tissues.

  本文描述了利用一种新型两性载体四己氧基四对氨基卡立[4]芳烃(A4C6)开发和优化纳米颗粒递送平台，用于抗癌药物紫杉醇的传递。

  通过乳液蒸发法成功制备了纳米颗粒，其中有机相含有紫杉醇：A4C6（摩尔比1:10），通过探头超声将其分散到含有0.5% w/v聚乙烯醇稳定剂的水相中，pH值为4。

  载药纳米颗粒的平均尺寸为78.7 ± 20.7 nm，表面电位为38.3 ± 7.67 mV，紫杉醇负载和包封效率分别为69.1 ± 5.3 µg药物/mg载体和50.4 ± 3.2%。透射电子显微镜照片显示离散的颗粒，没有凝聚的迹象。体外溶解实验显示，加入4%牛血清白蛋白的磷酸盐缓冲液中，分别在5、72和120小时释放的封装紫杉醇负荷量为32.7 ± 3.9%、82.6 ± 5.3%和91.0 ± 6.0%。

  这是首次报道使用氨基取代的两性卡立芳烃封装抗癌药物。所制备的纳米颗粒明显小于Abraxane纳米颗粒，但具有可比较的药物载荷，有潜力实现紫杉醇对肿瘤组织的靶向传递。