Departments of Chemistry, University of Illinois at Urbana Champaign, Urbana, Illinois 61801, United States.
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana Champaign, Urbana, Illinois 61801, United States.
J Am Chem Soc. 2022 Mar 16;144(10):4410-4421. doi: 10.1021/jacs.1c11333. Epub 2022 Mar 2.
It is desirable to rationally engineer plasmonic metal nanostructures with sets of structural parameters that lead to specific functions. However, it is still challenging to predict the nanostructured outcome of a synthesis reaction by design because not only the exact kinetic path for the structural evolution is very complicated but also the relationships among various functional and structural parameters are often tangled. It is necessary to deconvolute the structure-function relationships and understand the co-evolution of structural and functional parameters as the nanostructures grow. DNA is a programable biomolecular capping ligand that was shown to be capable of precisely controlling the evolution of metal nanostructures. In this study, we systematically analyzed the evolution of two structural parameters and several functional parameters in the growth of Au-Ag nanostructures controlled by two DNA sequences. We deconvoluted the contributions from the two structural parameters in affecting the plasmonic properties in different kinetic and geometric domains. We further designed new nanostructures by exchanging DNA sequences in the growth environment, which also changed their evolution pathways. The resulting structural and functional parameters could be predictively tuned by the timing of the exchange. This study demonstrates the powerful toolbox provided by programable biomolecules in producing novel nanostructures in a predictable manner. It also shows that by understanding the kinetic evolution of the structural parameters and their relationships with the function parameters, it is possible to design the precise combinations of structural and functional parameters in the nanostructured products.
理性设计具有特定功能的金属等离子体纳米结构需要一组结构参数。然而，通过设计来预测合成反应的纳米结构结果仍然具有挑战性，因为不仅结构演化的确切动力学路径非常复杂，而且各种功能和结构参数之间的关系通常也很复杂。有必要对结构-功能关系进行解卷积，并了解纳米结构生长过程中结构和功能参数的共同演化。DNA 是一种可编程的生物分子盖帽配体，已被证明能够精确控制金属纳米结构的演化。在这项研究中，我们系统地分析了由两个 DNA 序列控制的 Au-Ag 纳米结构生长过程中两个结构参数和几个功能参数的演化。我们解卷积了两个结构参数在不同动力学和几何区域对等离子体性质的影响。我们通过在生长环境中交换 DNA 序列进一步设计了新的纳米结构，这也改变了它们的演化途径。通过交换的时间，可以对结构和功能参数进行可预测的调整。这项研究展示了可编程生物分子在以可预测的方式产生新型纳米结构方面提供的强大工具包。它还表明，通过了解结构参数的动力学演化及其与功能参数的关系，可以设计出纳米结构产物中结构和功能参数的精确组合。
