Wang Chen, Shi Yi, Dan Yuan-Yuan, Nie Xing-Guo, Li Jian, Xia Xing-Hua
State Key Laboratory of Analytical Chemistry for Life Science and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
Key Laboratory of Biomedical Functional Materials, School of Science, China Pharmaceutical University, Nanjing, 211198, P. R. China.
Chemistry. 2017 May 17;23(28):6717-6723. doi: 10.1002/chem.201605380. Epub 2017 Mar 29.
Enzyme mimics have been widely used as alternatives to natural enzymes. However, the catalytic performances of enzyme mimics are often decreased due to different spatial structures or absence of functional groups compared to natural enzymes. Here, we report a highly efficient enzyme-like catalytic performance of gold nanoparticles (AuNPs) by visible-light stimulation. The enzyme-like reaction is evaluated by the catalytic reaction of AuNPs oxidizing a typical chromogenic substrate 3,3',5,5'-tetramethylbenzydine (TMB) with hydrogen peroxide as an oxidant. From investigations of the wavelength-dependent reaction rate, radical capture, hole-donor addition, and dark-field scattering spectroscopy experiments, it is revealed that the strong plasmonic absorption of AuNPs facilitates generation of hot electrons, which are transfered from AuNPs to the adsorbed reactant molecule, greatly promoting the catalytic performance of the enzyme-like catalytic reaction. The present work provides a simple method for improving the performance of enzyme mimics, which is expected to find further application in the field of plasmon-enhanced biocatalysis and biosensors.
酶模拟物已被广泛用作天然酶的替代品。然而,与天然酶相比,由于空间结构不同或缺乏官能团,酶模拟物的催化性能常常会降低。在此,我们报道了通过可见光刺激实现金纳米颗粒(AuNPs)具有高效的类酶催化性能。通过AuNPs以过氧化氢作为氧化剂氧化典型的显色底物3,3',5,5'-四甲基联苯胺(TMB)的催化反应来评估类酶反应。通过对波长依赖性反应速率、自由基捕获、空穴供体添加和暗场散射光谱实验的研究,发现AuNPs强烈的等离子体吸收促进了热电子的产生,这些热电子从AuNPs转移到吸附的反应物分子上,极大地促进了类酶催化反应的催化性能。目前的工作提供了一种提高酶模拟物性能的简单方法,有望在等离子体增强生物催化和生物传感器领域找到进一步的应用。