Maniappan Sonia, Dutta Camelia, Cheran Arunima, Solís Diego M, Kumar Jatish
Department of Chemistry Indian Institute of Science Education and Research (IISER) Tirupati Tirupati 517507 India
Departamento de Tecnología de los Computadores y de las Comunicaciones, University of Extremadura 10003 Cáceres Spain.
Chem Sci. 2024 Apr 16;15(19):7121-7129. doi: 10.1039/d4sc00477a. eCollection 2024 May 15.
The formation of chiral nanosystems and their subsequent enantioselective interaction with chiral amino acids are vital steps in many biological processes. Due to their potential to mimic biological systems, the synthesis of chiral nanomaterials has garnered significant attention over the years. Despite the emergence of diverse nanomaterials showcasing strong chiral responses, the in-depth understanding of the mechanism of plasmonic chirality in copper nanoparticles and their subsequent application in various fields are least explored. Herein, we demonstrate a facile approach for the synthesis of chiral copper nanoparticles using cysteine as a chiral precursor and capping ligand. Ligand-mediated chiral induction, established through experimental findings and a theoretical model, is ascribed as the major contributor to the origin of plasmonic chirality. The enantioselective recognition of chiral copper nanoparticles towards histidine, an amino acid with vast biological functions, was meticulously investigated by leveraging the strong copper-histidine binding ability. Ligand-induced dissolution, a unique phenomenon in nanoparticle reactions, was identified as the underlying mechanism for the nanoparticle-to-complex conversion. Understanding the mechanism of chiral induction in copper nanoparticles coupled with their enantioselective recognition of biomolecules not only holds promise in biomedical research but also sheds light on their potential as catalysts for asymmetric synthesis.
手性纳米系统的形成及其随后与手性氨基酸的对映选择性相互作用是许多生物过程中的关键步骤。由于它们具有模拟生物系统的潜力，多年来手性纳米材料的合成受到了广泛关注。尽管出现了各种展示出强烈手性响应的纳米材料，但对铜纳米颗粒中表面等离子体激元手性机制的深入理解及其在各个领域的后续应用却鲜有探索。在此，我们展示了一种简便的方法，使用半胱氨酸作为手性前体和封端配体来合成手性铜纳米颗粒。通过实验结果和理论模型确定的配体介导的手性诱导被认为是表面等离子体激元手性起源的主要因素。利用铜与组氨酸的强结合能力，对手性铜纳米颗粒对具有广泛生物学功能的氨基酸组氨酸的对映选择性识别进行了细致研究。配体诱导溶解是纳米颗粒反应中的一种独特现象，被确定为纳米颗粒向配合物转化的潜在机制。了解铜纳米颗粒中的手性诱导机制及其对生物分子的对映选择性识别不仅在生物医学研究中具有前景，也为它们作为不对称合成催化剂的潜力提供了启示。
