Department of Materials Science and Engineering, Seoul National University, Seoul, 08826, Republic of Korea.
Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk, 37673, Republic of Korea.
Nat Commun. 2022 Jul 2;13(1):3831. doi: 10.1038/s41467-022-31513-y.
Precise control of morphology and optical response of 3-dimensional chiral nanoparticles remain as a significant challenge. This work demonstrates chiral gold nanoparticle synthesis using single-stranded oligonucleotide as a chiral shape modifier. The homo-oligonucleotide composed of Adenine nucleobase specifically show a distinct chirality development with a dissymmetric factor up to g ~ 0.04 at visible wavelength, whereas other nucleobases show no development of chirality. The synthesized nanoparticle shows a counter-clockwise rotation of generated chiral arms with approximately 200 nm edge length. The molecular dynamics and density functional theory simulations reveal that Adenine shows the highest enantioselective interaction with Au(321) facet in terms of binding orientation and affinity. This is attributed to the formation of sequence-specific intra-strand hydrogen bonding between nucleobases. We also found that different sequence programming of Adenine-and Cytosine-based oligomers result in chiral gold nanoparticles' morphological and optical change. These results extend our understanding of the biomolecule-directed synthesis of chiral gold nanoparticles to sequence programmable deoxyribonucleic acid and provides a foundation for programmable synthesis of chiral gold nanoparticles.
精确控制三维手性纳米粒子的形态和光学响应仍然是一个重大挑战。本工作展示了使用单链寡核苷酸作为手性形状修饰剂合成手性金纳米粒子。由腺嘌呤碱基组成的同源寡核苷酸在可见光波长下表现出明显的手性发展，不对称因子高达 g~0.04，而其他碱基则没有手性发展。合成的纳米粒子显示出生成的手性臂的逆时针旋转，其边缘长度约为 200nm。分子动力学和密度泛函理论模拟表明，腺嘌呤在结合方向和亲和力方面表现出与 Au(321)面最高的对映选择性相互作用。这归因于碱基之间形成序列特异性的内链氢键。我们还发现，腺嘌呤和胞嘧啶基寡聚物的不同序列编程导致手性金纳米粒子的形态和光学变化。这些结果扩展了我们对手性金纳米粒子的生物分子导向合成的理解，使其扩展到可编程的脱氧核糖核酸，并为手性金纳米粒子的可编程合成提供了基础。
