人工模拟酶的制备、性质及分析应用研究

Artificial enzymes, an emerging branch of catalysts to imitate the essential and general principles of natural enzymes, overcome the shortages of natural enzymes due to their simple preparation, low cost, high stability and easy storage. Within the tremendous progress in the field of nano-research, nanomaterials-based artificial enzymes to mimic different kinds of enzymes have drawn widespread attentions. Based on the achievements in nanotechnology, a variety of enzyme-like nanomaterials can be synthesized controllably and modified by the chemical or biological approaches in order to obtain high performances, such as prominent catalytic efficiency, specificity, stability and biocompatibility. To develop the enzymatic reaction model for artificial enzymes needs the further understanding of the catalytic mechanism of nanomaterials-based enzyme mimetics. The aim is to exploit their potential and wide applications in chemical/biochemical analysis, biofuel cells, cells, tissue and in vivo analysis and provide more data for understanding life activities.

人工模拟酶作为一类新兴的催化剂，弥补了天然生物酶的诸多不足，并且制备简单，成本低廉，稳定性好，易于保存。随着纳米科技的蓬勃发展，纳米材料优异的类酶特性引起人们的普遍关注。本项目拟借助于纳米科技发展的新成果，发掘新型人工模拟酶，可控合成高催化性能、高稳定性的具有类酶性质的纳米材料，通过化学修饰和生物改造，优化其性能以达到高特异性和生物相容性。深层次理解纳米材料作为人工模拟酶的催化机制，建立人工模拟酶催化反应模型。另外，着重于化学/生物化学分析的研究热点，发挥类酶纳米材料独有的优势，实现其在化学/生物化学分析和生物燃料电池领域的广泛应用，进而开发其在细胞、组织乃至活体内的应用潜能，为进一步研究生命活动提供依据。

纳米酶的提出和发展极大地推动了人工模拟酶的进步，并已在生物分析等领域展现了重要的潜力。然而，以往发表的纳米酶研究报告在活性、特异性和催化机制等方面与天然酶仍有很大的差距。在本项目中，我们揭示了普鲁士蓝模拟天然过氧化物酶的催化机理，并创新设计制备基于单原子催化剂的模拟酶，很大的提高了催化活性，并且提出了单原子纳米酶的概念。针对纳米酶特异性差这一缺点，我们通过学习天然酶的活性中心配位结构，合成了MOF-818，模拟天然儿茶酚（多酚氧化酶）的结构，呈现出多酚氧化酶的性质，并且对儿茶酚的催化氧化有非常高的特异性。此外我们合成的多种纳米酶在过氧化氢的检测和葡萄糖传感方面均取得了明显提高。通过本项目的研究，对于设计高活性和特异性的纳米酶具有重要指导意义。