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Hydrophobic Porphyrin Assemblies with Oxygen-Transporting Capability

具有输氧能力的疏水性卟啉组装体

基本信息

批准号：
13031072
负责人：
NISHIDE Hiroyuki
金额：
$ 24.32万
依托单位：
Waseda University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

Hemoglobin is a protein containing iron porphyrin as an oxygen-binding site and uptakes and carries molecular oxygen from air selectively. Designing assemblies focused on hydrophobicity of the precisely synthesized porphyrin enables to realize novel oxygen-carrying materials which work under conditions that different from that of hemoglobin.The hydrophobic iron porphyrin was hybridized with the xylanase which Nakamura have previously reported its stability against temperature. The red-colored aqueous solution of porphyrin-xylanase hybrid displayed a reversible oxygen-binding to the iron porphyrin even at high temperature at ca. 90℃. The catalytic activity as the xylanase was not interfered because the coordination site is different from that of the catalytic activity. This simple strategy using hydrophobic interactions will be applicable to the other host-guest combinations, which could afford a totally new class of artificial hemoprotein architectures.Meso-tetra(2-pyridyl) porphyrin f … More orms a duplex with tetrahydroxylcalix[4]arene via triplicate or quadruple hydrogen bonds, to provide a capping structure on the porphyrin plane, which was accompanied by the spontaneous equilibrium shift of the atropisomers. This was the first example of a hydrogen-bonded porphyrin-calix[4]arene duplex.Polymeric cobalt tetraphenylporphyrin thin membrane was obtained with nanometer thickness (80nm from SEM). The homogeneous red membrane reversibly binds and releases molecular oxygen at room temperature under high pressure. Oxygen permeability coefficient was large and steeply increased with decrease in oxygen upstream pressure. Oxygen permselectivity at 1cmHg difference between upstream and downstream was over 150. This indicates that the fixed cobalt porphyrin in the solid membrane facilitated oxygen transport in the membrane. Compressed air was applied to the upstream in the same condition to give the oxygen concentration above 900% at downstream. This indicates weak oxygen-binding affinity is preferable for the efficient oxygen facilitated transport. Less

血红蛋白是一种含有铁卟啉作为氧结合部位的蛋白质，它选择性地从空气中摄取和携带分子氧。针对精确合成的卟啉的疏水性设计的组装使得能够在与血红蛋白不同的条件下工作的新型载氧材料成为可能。疏水性的铁卟啉与木聚糖酶杂交，Nakamura先前报道了其对温度的稳定性。在90℃左右的高温下，卟啉-木聚糖酶杂化的红色水溶液仍与铁卟啉发生可逆氧结合。由于木聚糖酶的配位位置不同于木聚糖酶的催化活性，因此不影响木聚糖酶的催化活性。这种利用疏水相互作用的简单策略将适用于其他主客体组合，这可能提供一类全新的人工血蛋白结构。Meso-四(2-吡啶基)卟啉f…更多的是通过三重或四重氢键与四羟基杯[4]芳烃形成双链体，在卟啉平面上提供一个封顶结构，并伴随着阿托品的自发平衡位移。这是第一个氢键化的卟啉-杯[4]芳烃双链的例子，得到了纳米厚度(扫描电子显微镜下观察到80 nm)的四苯基卟啉钴聚合物薄膜。均一红膜在常温高压下可逆地结合和释放分子氧。氧气渗透系数较大，且随着氧气上游压力的降低而急剧增加。氧渗透选择性在上下游相差1 cmHg时超过150。这表明固体膜中固定的钴卟啉促进了氧在膜中的转运。在相同条件下，向上游加压空气，使下游氧气浓度达到900%以上。这表明弱的氧结合亲和力更有利于高效的氧促进运输。较少