Despite a significant surge in the number of investigations into chirality at the nanoscale, especially thiolated chiral molecules capping gold clusters, only limited knowledge is currently available to elaborate the alloying effect on chiroptical behavior of bimetallic nanoparticles (NPs). Also, few successful cases as to the efforts toward the development of chirality-dependent applications on the optically active nanomaterial have been made. Herein, as a positive test case for chiral alloy nanoparticle synthesis, the stable and large chiroptical ultrafine Au-Ag alloy NPs were prepared by reduction of different molar fractions of HAuCl and AgNO with NaBH in the presence of d/l-penicillamine (d/l-Pen). Compared with those of monometallic Au and Ag counterparts with comparable size, the Au-Ag alloy NPs (Ag mole fraction, 70%) obviously displayed the largest optical activities with the maximum g-factors of ∼1.6 × 10. Impressively, the Pen-mediated synthesis of chiral Au-Ag alloy NPs possesses a colorimetric self-recognition function and can be used as an incisive circular dichroism (CD) probe toward d- and l-Pen enantiomers. The plasmonic CD signal amplification (ΔI) shows good linearity with the amount of Pen over the range of 5.0-80.0 μM with a detection limit (3σ) of 1.7 μM for l-Pen and 1.5 μM for d-Pen, respectively. In addition, the sensing system exhibits good selectivity toward d- and l-Pen in the presence of other enantiomers; therefore, it is highly expected that the approach described here would open new opportunities for design of more novel enantioselective analyses of important species related to biological processes.
Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of brightly emissive CuNCs, attributed to the conformation of racemic Pen being unfavorable for the electrostatic interaction, and thus suppressing the formation of cluster aggregates. In addition, the clusters display potential toward cytoplasmic staining and labelling due to the high photoluminescence (PL) quantum yields (QYs) and remarkable cellular uptake, in spite that no chirality-dependent effects in autophagy and subcellular localization are observed in the application of chiral cluster enantiomer-based cell imaging.
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