DNA包裹的金球对手性底物的手性催化氧化的研究
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- 英文论文题名：Engineering Gold Nanoparticles with DNA Ligands for Selective Catalytic Oxidation of Chiral Substrates
- 论文作者：湛鹏飞 ; 王振刚 ; 李娜 ; 丁宝全
- 英文论文作者：Pengfei Zhan ; Zhen-gang Wang ; Na Li ; Baoquan Ding ; National Center for Nanoscience and Technology (NCNST)
- 年：2016
- 作者机构：国家纳米科学中心;
- 论文关键词：金球 ; DNA ; 环境响应性 ; 手性选择性催化
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十七分会：纳米催化
- 语种：中文
- 分类号：O643.36
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十七分会 ; 纳米催化
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：2
- 文件大小：247k
- 原文格式：D
- 会议级别：全国
摘要
酶的催化可以在温和的条件下实现很高的活性和选择性~1。这些有吸引力的特性一直是合成新的催化剂的标杆。相比于合成的催化剂~2,可以使用的酶的催化剂少之又少。混合催化的目的就是为了把具有催化性能的过渡态金属与具有手性结构的生物大分子如DNA和蛋白质结合起来,创造出新的催化剂。实验表明,与DNA分子作用后金纳米粒子仍具有催化活性,由于DNA构象的不同,DNA与金属纳米粒子互相作用后会产生不同的手性催化效果。基于以上的研究,我们提出了一种可行的手性对映催化的方法。我们选择葡萄糖的催化氧化作为研究的系统,用DNA包裹的金纳米颗粒去替代葡萄糖氧化酶,催化D型葡萄糖(D-glucose)和L型葡萄糖(L-glucose)。通过与金球间的非共价键的吸附,螺旋结构的DNA会与底物之间相互作用形成一个选择性的催化面。实际上,金颗粒与DNA会以Au-N的形式相互作用。由于DNA的序列依赖性,DNA的构象会随着环境的变化而变化,比如pH的变化或者互补链的加入,这也会导致手性催化选择性的消失或者翻转。手性催化的选择性也与金纳米颗粒的生长动力学有关。通过这个工作,一方面,我们旨在通过改变手性配体的构型实现对手底物的催化选择性的翻转;另一方面,我们能够对手性选择性催化的机理有更深层次的理解。
Noble metal nanoparticles are promising materials for heterogeneous enantioselective catalysis because of their high surface-to-volume ratios,large concentrations of highly undercoordinated surface sites,and quantum confinement effects.In this work,we report on the use of DNA as an environment-responsive chiral ligand to engineer the selective catalytic behaviors of glucose oxidase-mimicking gold nanoparticles(AuNPs),with glucose enantiomers as the substrates.DNA can be stimulated externally to switch between randomcoiled and multistranded structures(e.g.,duplex,i-motif,or G-quadruplex).Random-coiled DNA-capped nanoparticles preferentially catalyze oxidation of L-glucose,and structured DNA-capped nanoparticles show higher activity toward D-glucose.pH-induced selectivity diminishment of DNA-treated AuNPs is also found,further demonstrating the chiral selector effect of DNA ligands.In the end,the selective catalysis of AuNPs allows control of the size enlargement of nanoparticles through self-catalytic Au deposition,in ligand-and substrate chirality-dependent manners.It is found that the effect of substrate chirality on the self-growth rate can be reversed by the hybridization of the capping DNA.The structural and chemical features of DNA grooves in the multistranded structures render binding sites with higher affinity to D-glucose than L-glucose.The results suggest a simple strategy for engineering the responsive enantioselective catalysis of metallic nanoparticles and advance the understanding of chiral interactions between nucleic acids and saccharide.
Noble metal nanoparticles are promising materials for heterogeneous enantioselective catalysis because of their high surface-to-volume ratios,large concentrations of highly undercoordinated surface sites,and quantum confinement effects.In this work,we report on the use of DNA as an environment-responsive chiral ligand to engineer the selective catalytic behaviors of glucose oxidase-mimicking gold nanoparticles(AuNPs),with glucose enantiomers as the substrates.DNA can be stimulated externally to switch between randomcoiled and multistranded structures(e.g.,duplex,i-motif,or G-quadruplex).Random-coiled DNA-capped nanoparticles preferentially catalyze oxidation of L-glucose,and structured DNA-capped nanoparticles show higher activity toward D-glucose.pH-induced selectivity diminishment of DNA-treated AuNPs is also found,further demonstrating the chiral selector effect of DNA ligands.In the end,the selective catalysis of AuNPs allows control of the size enlargement of nanoparticles through self-catalytic Au deposition,in ligand-and substrate chirality-dependent manners.It is found that the effect of substrate chirality on the self-growth rate can be reversed by the hybridization of the capping DNA.The structural and chemical features of DNA grooves in the multistranded structures render binding sites with higher affinity to D-glucose than L-glucose.The results suggest a simple strategy for engineering the responsive enantioselective catalysis of metallic nanoparticles and advance the understanding of chiral interactions between nucleic acids and saccharide.
引文
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