N¹,N³,N⁵-tris(1-hydroxy-3,6,9,12-tetraoxatetracosan-24-yl)benzene-1,3,5-tricarboxamide | 1424097-86-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N¹,N³,N⁵-tris(1-hydroxy-3,6,9,12-tetraoxatetracosan-24-yl)benzene-1,3,5-tricarboxamide
• 英文别名: 1-N,3-N,5-N-tris[12-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]dodecyl]benzene-1,3,5-tricarboxamide
• CAS: 1424097-86-8
• 化学式: C₆₉H₁₂₉N₃O₁₈
• 分子量: 1288.79
• InChiKey: ASEAMMXZAITJNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  90
• 可旋转键数：
  75
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  259
• 氢给体数：
  6
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  N¹,N³,N⁵-tris(1-hydroxy-3,6,9,12-tetraoxatetracosan-24-yl)benzene-1,3,5-tricarboxamide 、 [(2R,3R,4S,5S,6S)-3,4,5-三苯甲酰氧基-6-(2,2,2-三氯亚氨代乙酰)氧基-四氢吡喃-2-基]甲基苯甲酸酯 在 三氟甲磺酸三甲基硅酯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.58h， 生成
  参考文献：
  名称：

  Elucidating the Ordering in Self-Assembled Glycocalyx Mimicking Supramolecular Copolymers in Water

  摘要：

  Polysaccharides present in the glycocalyx and extracellular matrix are highly important for a multitude of functions. Oligo- and polysaccharides-based biomaterials are being developed to mimic the glycocalyx, but the spatial functionalization of these polysaccharides represents a major challenge. In this paper, a series of benzene-1,3,5-tricarboxamide (BTA) based supramolecular monomers is designed and synthesized with mono- (BTA-beta-D-glucose; BTA-Glc and BTA-alpha-D-mannose; BTA-Man) or disaccharides (BTA-beta-D-cellobiose; BTA-Cel) at their periphery or a monosaccharide (BTA-OEG(4)-alpha-D-mannose; BTA-OEG,-Man) at the end of a tetraethylene glycol linker. These glycosylated BTAs have been used to generate supramolecular assemblies and it is shown that the nature of the carbohydrate appendage is crucial for the supramolecular (co)polymerization behavior. BTA-Glc and BTA-Man are shown to assemble into micrometers long 1D (bundled) fibers with opposite helicities, whereas BTA-Cel and BTA-OEG,-Man formed small spherical micelles. The latter two monomers are used in a copolymerization approach with BTA-Glc, BTA-Man, or ethylene glycol BTA (BTA-OEG(4)) to give 1D fibers with BTA-Cel or BTA-OEG(4)-Man incorporated. Consequently, the carbohydrate appendage influences both the assembly behavior and the internal order. Using this approach it is possible to create ID-fibers with adjustable saccharide densities exhibiting tailored dynamic exchange profiles. Furthermore, hydrogels with tunable mechanical properties can be achieved, opening up possibilities for the development of multicomponent functional biomaterials.

  DOI：

  10.1021/jacs.9b06607
• 作为产物：
  描述：

  tris(1-phenyl-2,5,8,11,14-pentaoxahexacosan-26-yl) benzene-1,3,5-tricarboxylate 在 palladium on activated charcoal 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 以26%的产率得到N¹,N³,N⁵-tris(1-hydroxy-3,6,9,12-tetraoxatetracosan-24-yl)benzene-1,3,5-tricarboxamide
  参考文献：
  名称：

  H-键对超分子聚合物在水中生长过程中顺序放大的影响

  摘要：

  虽然关于蛋白质中氢键和疏水性作用的大量知识导致了合理设计和功能性肽结构的产生，但这些力对水中纯合成超分子结构的作用已证明难以确定。专注于基于 1,3,5-苯三甲酰胺 (BTA) 的超分子聚合物，我们设计了一种分子建模策略来剖析自组装（静电、疏水等）对两种有序 BTA 生长的能量贡献堆栈和随机 BTA 聚合。利用这组模拟，我们揭示了聚合物生长的合作机制，其中必须在聚集体中达到临界尺寸，然后才能出现和放大实验观察到的纤维中的顺序。此外，我们发现仅基于静电相互作用，有序纤维的形成优于无序聚集体。对模拟数据的详细分析表明，氢键是这种稳定能量的主要来源。与新合成的 1,3,5-苯三羧酸酯 (BTE) 衍生物进行实验和计算比较，该衍生物缺乏形成 H 键网络的能力，表明这种 BTE 变体也能够形成纤维，尽管持续长度减少。这项工作为氢键的关键一维驱动力提供了明确的证据，该驱动力增强了单体堆积的持久性，并放大了水中生长的超分子聚合物的有序水平。

  DOI：

  10.1021/jacs.6b07530

文献信息

• Supramolecular polymerization in water harnessing both hydrophobic effects and hydrogen bond formation
  作者：Christianus M. A. Leenders、Lorenzo Albertazzi、Tristan Mes、Marcel M. E. Koenigs、Anja R. A. Palmans、E. W. Meijer

  DOI：10.1039/c3cc38949a

  日期：——

  The formation of supramolecular polymers in water through rational design of a benzene-1,3,5-tricarboxamide (BTA) motif is presented. Intermolecular hydrogen bonding and hydrophobic effects cooperate in the self-assembly into long fibrillar aggregates. Minimal changes in molecular structure significantly affect the internal packing of the aggregates.

  通过合理设计苯-1,3,5-三甲酰胺（BTA）基元，在水相中形成了超分子聚合物。分子间氢键和疏水效应协同作用，实现了向长纤维状聚集物的自组装。分子结构的微小变化对聚集物的内部堆积产生了显著影响。
• Elucidating the Ordering in Self-Assembled Glycocalyx Mimicking Supramolecular Copolymers in Water
  作者：Simone I. S. Hendrikse、Lu Su、Tim P. Hogervorst、René P. M. Lafleur、Xianwen Lou、Gijsbert A. van der Marel、Jeroen D. C. Codee、E. W. Meijer

  DOI：10.1021/jacs.9b06607

  日期：2019.9.4

  Polysaccharides present in the glycocalyx and extracellular matrix are highly important for a multitude of functions. Oligo- and polysaccharides-based biomaterials are being developed to mimic the glycocalyx, but the spatial functionalization of these polysaccharides represents a major challenge. In this paper, a series of benzene-1,3,5-tricarboxamide (BTA) based supramolecular monomers is designed and synthesized with mono- (BTA-beta-D-glucose; BTA-Glc and BTA-alpha-D-mannose; BTA-Man) or disaccharides (BTA-beta-D-cellobiose; BTA-Cel) at their periphery or a monosaccharide (BTA-OEG(4)-alpha-D-mannose; BTA-OEG,-Man) at the end of a tetraethylene glycol linker. These glycosylated BTAs have been used to generate supramolecular assemblies and it is shown that the nature of the carbohydrate appendage is crucial for the supramolecular (co)polymerization behavior. BTA-Glc and BTA-Man are shown to assemble into micrometers long 1D (bundled) fibers with opposite helicities, whereas BTA-Cel and BTA-OEG,-Man formed small spherical micelles. The latter two monomers are used in a copolymerization approach with BTA-Glc, BTA-Man, or ethylene glycol BTA (BTA-OEG(4)) to give 1D fibers with BTA-Cel or BTA-OEG(4)-Man incorporated. Consequently, the carbohydrate appendage influences both the assembly behavior and the internal order. Using this approach it is possible to create ID-fibers with adjustable saccharide densities exhibiting tailored dynamic exchange profiles. Furthermore, hydrogels with tunable mechanical properties can be achieved, opening up possibilities for the development of multicomponent functional biomaterials.
• Effect of H-Bonding on Order Amplification in the Growth of a Supramolecular Polymer in Water
  作者：Matteo Garzoni、Matthew B. Baker、Christianus M. A. Leenders、Ilja K. Voets、Lorenzo Albertazzi、Anja R. A. Palmans、E. W. Meijer、Giovanni M. Pavan

  DOI：10.1021/jacs.6b07530

  日期：2016.10.26

  peptidic structures, the roles of these forces on purely synthetic supramolecular architectures in water have proven difficult to ascertain. Focusing on a 1,3,5-benzenetricarboxamide (BTA)-based supramolecular polymer, we have designed a molecular modeling strategy to dissect the energetic contributions involved in the self-assembly (electrostatic, hydrophobic, etc.) upon growth of both ordered BTA

  虽然关于蛋白质中氢键和疏水性作用的大量知识导致了合理设计和功能性肽结构的产生，但这些力对水中纯合成超分子结构的作用已证明难以确定。专注于基于 1,3,5-苯三甲酰胺 (BTA) 的超分子聚合物，我们设计了一种分子建模策略来剖析自组装（静电、疏水等）对两种有序 BTA 生长的能量贡献堆栈和随机 BTA 聚合。利用这组模拟，我们揭示了聚合物生长的合作机制，其中必须在聚集体中达到临界尺寸，然后才能出现和放大实验观察到的纤维中的顺序。此外，我们发现仅基于静电相互作用，有序纤维的形成优于无序聚集体。对模拟数据的详细分析表明，氢键是这种稳定能量的主要来源。与新合成的 1,3,5-苯三羧酸酯 (BTE) 衍生物进行实验和计算比较，该衍生物缺乏形成 H 键网络的能力，表明这种 BTE 变体也能够形成纤维，尽管持续长度减少。这项工作为氢键的关键一维驱动力提供了明确的证据，该驱动力增强了单体堆积的持久性，并放大了水中生长的超分子聚合物的有序水平。