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Supramolecular catalysis by recognition-encoded oligomers: discovery of a synthetic imine polymerase
Chemical Science ( IF 7.6 ) Pub Date : 2020-07-06 , DOI: 10.1039/d0sc02234a Luca Gabrielli 1, 1, 2, 3, 4 , Christopher A. Hunter 1, 2, 3, 4
Chemical Science ( IF 7.6 ) Pub Date : 2020-07-06 , DOI: 10.1039/d0sc02234a Luca Gabrielli 1, 1, 2, 3, 4 , Christopher A. Hunter 1, 2, 3, 4
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All key chemical transformations in biology are catalysed by linear oligomers. Catalytic properties could be programmed into synthetic oligomers in the same way as they are programmed into proteins, and an example of the discovery of emergent catalytic properties in a synthetic oligomer is reported. Dynamic combinatorial chemistry experiments designed to study the templating of a recognition-encoded oligomer by the complementary sequence have uncovered an unexpected imine polymerase activity. Libraries of equilibrating imines were formed by coupling diamine linkers with monomer building blocks composed of dialdehydes functionalised with either a trifluoromethyl phenol (D) or phosphine oxide (A) H-bond recognition unit. However, addition of the AAA trimer to a mixture of the phenol dialdehyde and the diamine linker did not template the formation of the DDD oligo-imine. Instead, AAA was found to be a catalyst, leading to rapid formation of long oligomers of D. AAA catalysed a number of different imine formation reactions, but a complementary phenol recognition group on the aldehyde reaction partner is an essential requirement. Competitive inhibition by an unreactive phenol confirmed the role of H-bonding in substrate recognition. AAA accelerates the rate of imine formation in toluene by a factor of 20. The kinetic parameters for this enzyme-like catalysis are estimated as 1 × 10−3 s−1 for kcat and the dissociation constant for substrate binding is 300 μM. The corresponding DDD trimer was found to catalyse oligomerisation the phosphine oxide dialdehyde with the diamine linker, suggesting an important role for the backbone in catalysis. This unexpected imine polymerase activity in a duplex-forming synthetic oligomer suggests that there are many interesting processes to be discovered in the chemistry of synthetic recognition-encoded oligomers that will parallel those found in natural biopolymers.
中文翻译：
识别编码的低聚物的超分子催化：合成亚胺聚合酶的发现
生物学中所有关键的化学转化都由线性低聚物催化。可以将催化性能编程为合成低聚物的方式与将其编程为蛋白质的方式相同，并且报道了在合成低聚物中发现新兴催化性能的一个实例。设计用于研究通过互补序列对识别编码低聚物进行模板化的动态组合化学实验，发现了意想不到的亚胺聚合酶活性。平衡亚胺的库是通过将二胺连接基与单体结构单元偶联而形成的，该单体结构单元由用三氟甲基苯酚（D）或氧化膦（A）H键识别单元官能化的二醛组成。但是，添加了AAA将三聚体与苯酚二醛和二胺连接基的混合物混合，不能形成DDD寡亚胺的模板。相反，发现AAA是催化剂，导致D的长低聚物快速形成。AAA催化了许多不同的亚胺形成反应，但醛反应伙伴上的互补苯酚识别基团是必不可少的要求。非反应性苯酚的竞争性抑制作用证实了H键在底物识别中的作用。AAA通过的20这种情况的动力学参数的因数加速的甲苯亚胺形成的速率酶样催化被估计为1×10 -3小号-1为k cat，底物结合的解离常数为300μM。发现相应的DDD三聚体可催化氧化膦二醛与二胺连接基的低聚反应，表明主链在催化中的重要作用。在形成双链体的合成低聚物中这种意想不到的亚胺聚合酶活性表明，在合成识别编码低聚物的化学结构中发现了许多有趣的过程，这些过程将与天然生物聚合物中发现的过程相似。
更新日期：2020-07-22
中文翻译：
识别编码的低聚物的超分子催化：合成亚胺聚合酶的发现
生物学中所有关键的化学转化都由线性低聚物催化。可以将催化性能编程为合成低聚物的方式与将其编程为蛋白质的方式相同，并且报道了在合成低聚物中发现新兴催化性能的一个实例。设计用于研究通过互补序列对识别编码低聚物进行模板化的动态组合化学实验，发现了意想不到的亚胺聚合酶活性。平衡亚胺的库是通过将二胺连接基与单体结构单元偶联而形成的，该单体结构单元由用三氟甲基苯酚（D）或氧化膦（A）H键识别单元官能化的二醛组成。但是，添加了AAA将三聚体与苯酚二醛和二胺连接基的混合物混合，不能形成DDD寡亚胺的模板。相反，发现AAA是催化剂，导致D的长低聚物快速形成。AAA催化了许多不同的亚胺形成反应，但醛反应伙伴上的互补苯酚识别基团是必不可少的要求。非反应性苯酚的竞争性抑制作用证实了H键在底物识别中的作用。AAA通过的20这种情况的动力学参数的因数加速的甲苯亚胺形成的速率酶样催化被估计为1×10 -3小号-1为k cat，底物结合的解离常数为300μM。发现相应的DDD三聚体可催化氧化膦二醛与二胺连接基的低聚反应，表明主链在催化中的重要作用。在形成双链体的合成低聚物中这种意想不到的亚胺聚合酶活性表明，在合成识别编码低聚物的化学结构中发现了许多有趣的过程，这些过程将与天然生物聚合物中发现的过程相似。
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