Kowalska Natalia, Bandalewicz Filip, Kowalski Jakub, Gómez-Graña Sergio, Bagiński Maciej, Pastoriza-Santos Isabel, Grzelczak Marek, Matraszek Joanna, Pérez-Juste Jorge, Lewandowski Wiktor
Laboratory of Organic Nanomaterials and Biomolecules, Faculty of Chemistry University of Warsaw, Pasteura 1 Street, 02-093 Warsaw, Poland.
Departamento de Química Física, CINBIO, Universidade de Vigo, Campus Universitario As Lagoas, Marcosende, 36310 Vigo, Spain.
ACS Appl Mater Interfaces. 2022 Oct 28;14(44):50013-23. doi: 10.1021/acsami.2c11925.
The development of plasmonic nanomaterials with chiral geometry has drawn extensive attention owing to their practical implications in chiral catalysis, chiral metamaterials, or enantioselective biosensing and medicine. However, due to the lack of effective synthesis methods of hydrophobic nanoparticles (NPs) showing intrinsic, plasmonic chirality, their applications are currently limited to aqueous systems. In this work, we resolve the problem of achieving hydrophobic Au NPs with intrinsic chirality by efficient phase transfer of water-soluble NPs using low molecular weight, liquid crystal-like ligands. We confirmed that, after the phase transfer, Au NPs preserve strong, far-field circular dichroism (CD) signals, attesting their chiral geometry. The universality of the method is exemplified by using different types of NPs and ligands. We further highlight the potential of the proposed approach to realize chiral plasmonic, inorganic/organic nanocomposites with block copolymers, liquid crystals, and compounds forming physical gels. All soft matter composites sustain plasmonic CD signals with electron microscopies confirming well-dispersed nanoinclusions. The developed methodology allows us to expand the portfolio of plasmonic NPs with intrinsic structural chirality, thereby broadening the scope of their applications toward soft-matter based systems.
具有手性几何结构的等离激元纳米材料因其在手性催化、手性超材料或对映选择性生物传感与医学等方面的实际应用而备受广泛关注。然而,由于缺乏能够展现固有等离激元手性的疏水性纳米颗粒(NPs)的有效合成方法,其应用目前仅限于水性体系。在这项工作中,我们通过使用低分子量、液晶状配体对水溶性 NPs 进行高效相转移,解决了制备具有固有手性的疏水性金 NPs 的问题。我们证实,相转移后,金 NPs 保留了强烈的远场圆二色性(CD)信号,证明了它们的手性几何结构。通过使用不同类型的 NPs 和配体,例证了该方法的通用性。我们进一步强调了所提出方法在利用嵌段共聚物、液晶和形成物理凝胶的化合物实现手性等离激元无机/有机纳米复合材料方面的潜力。所有软物质复合材料都保持等离激元 CD 信号,电子显微镜证实纳米夹杂物分散良好。所开发的方法使我们能够扩展具有固有结构手性的等离激元 NPs 的种类,从而拓宽其在基于软物质的体系中的应用范围。