Metal surfaces with intrinsic chirality play an irreplaceable role in many significant enantioselective chemical processes such as enantioselective catalysis, sensing, and separation. Nonetheless, current methods for the precise preparation of such chiral surfaces suffer with issues of unscalable production and low surface areas. Herein, we report the synthesis of chiral Au nanoparticles with precisely determined homochiral facets. Though a scalable wet chemical method, {125̅8}R and {85̅12}S high-Miller-index facets are obtained with the l- and d-chiral Au nanocrystals, respectively. The growth process of these homochiral facets is investigated, and a new nanocrystal growth pathway is revealed. More importantly, the remarkable enantioselective recognition properties of these homochiral surfaces are demonstrated and enable an efficient electrochemical method for chiral discrimination of l-/d-tryptophan. These results provide a foundation of fundamental studies of heterogeneous enantioselective processes and may pave way for the development of nanocatalysts for enantioselective chemistry.

Synthesis of Chiral Au Nanocrystals with Precise Homochiral Facets for Enantioselective Surface Chemistry.

Recently, advanced optical materials with circularly polarized phosphorescence (CPP) have attracted much attention. However, such materials are limited due to the difficulty of preparation and the scarcity of precursors. Herein, CPP materials are constructed for the first time using water‐soluble, pseudo‐chiral silver nanoclusters with atomic precision ((NH4)9 [Ag9 (mba)9], H2mba = 2‐mercaptobenzoic acid, abbreviated to Ag9‐NCs hereafter). Induced by the complexation of l‐ or d‐tartaric acid (TrA) through hydrogen bonding, Ag9‐NCs crystallize from aqueous solutions, during which the chirality of the hybrid is amplified and the phosphorescence of Ag9‐NCs is enhanced. It is speculated that the chiral transfer from TrA to Ag9‐NCs is the main source of the well‐defined circular dichroism signals with good repeatability. The Ag9‐NCs/TrA cocrystals exhibit good CPP performance with dissymmetric factors up to 1.05 × 10−2, which is the highest value for metal NCs‐based CPP materials. This work is expected to be an inspiration for preparing metal NCs‐based CPP materials by supramolecular strategy. The so‐obtained organic–inorganic CPP materials can find a variety of applications in optoelectronic devices.

Circularly Polarized Phosphorescence from Cocrystallization of Atomic Precise Silver Nanoclusters with Tartaric Acid

Chiral Au nanorods (c-Au NRs) with diverse architectures constitute an interesting nanospecies in the field of chiral nanophotonics. The numerous possible plasmonic behaviors of Au NRs can be coupled with chirality to initiate, tune, and amplify their chiroptical response. Interdisciplinary technologies have boosted the development of fabrication and applications of c-Au NRs. Herein, we have focused on the role of chirality in c-Au NRs which helps to manipulate the light-matter interaction in nontraditional ways. A broad overview on the chirality origin, chirality transfer, chiroptical activities, artificially synthetic methodologies, and circularly polarized applications of c-Au NRs will be summarized and discussed. A deeper understanding of light-matter interaction in c-Au NRs will help to manipulate the chirality at the nanoscale, reveal the natural evolution process taking place, and set up a series of circularly polarized applications.

Chiral Au Nanorods: Synthesis, Chirality Origin, and Applications.

Glucose monitoring is essential to evaluate the degree of glucose metabolism disorders. The enzymatic determination has been the most widely used method in glucose detection because of its high efficiency, accuracy, and sensitivity. Noble metal nanomaterials (NMs, i.e., Au, Ag, Pt, and Pd), inheriting their excellent electronic, optical, and enzyme-like properties, are classified as noble metal nanozymes (NMNZs). As the NMNZs are often involved in two series of reactions, the oxidation of glucose and the chromogenic reaction of peroxide, here the chemical mechanism by employing NMNZs with glucose oxidase (GOx) and peroxidase (POD) mimicking activities is briefly summarized first. Subsequently, the regulation strategies of the GOx-like, POD-like and tandem enzyme-like activities of NMNZs are presented in detail, including the materials, size, morphology, composition, and the reaction condition of the representative NMs. In addition, in order to further mimic the enantioselectivity of enzyme, the design of NMNZs with enantioselective recognition of d-glucose and l-glucose by using different chiral compounds (DNA, amino acids, and cyclodextrins) and molecular imprinting is further described in this review. Finally, the feasible solutions to the existing challenges and a vision for future development possibilities are discussed.

Detection of Glucose Based on Noble Metal Nanozymes: Mechanism, Activity Regulation, and Enantioselective Recognition.

Chirality in inorganic nanoparticles and nanostructures has gained increasing scientific interest, because of the possibility to tune their ability to interact differently with left- and right-handed circularly polarized light. In some cases, the optical activity is hypothesized to originate from a chiral morphology of the nanomaterial. However, quantifying the degree of chirality in objects with sizes of tens of nanometers is far from straightforward. Electron tomography offers the possibility to faithfully retrieve the three-dimensional morphology of nanomaterials, but only a qualitative interpretation of the morphology of chiral nanoparticles has been possible so far. We introduce herein a methodology that enables us to quantify the helicity of complex chiral nanomaterials, based on the geometrical properties of a helix. We demonstrate that an analysis at the single particle level can provide significant insights into the origin of chiroptical properties.

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Quantification of the Helical Morphology of Chiral Gold Nanorods

Chiral growth and chirality transfer associated with plasmonic nanostructures have rejuvenated the field of chirality. As the precise regioselective growth of inorganic crystals into chiral shapes at the nanoscale is extremely challenging, "bottom-up" synthesis of intrinsically chiral nanoparticles with structural stability is obviously attractive and important. With the thiolated bimolecular cosurfactants, we demonstrated a chemical strategy for the synthesis of intrinsically helical plasmonic nanorods (HPNRs) with strong and tailorable plasmonic circular dichroism (PCD) responses, deriving from the zwitterionic interactions between the -NH3+ and -COO- groups of the cysteine molecules (Cys). The influence of structural parameters of HPNRs on PCD responses was analyzed systematically by theoretical simulations. Among the different structural parameters, the pitch depth was found to have the greatest impact on the PCD signals, in agreement with the experimental results. Moreover, the obtained HPNRs with the strong, tunable, and stable chiroptical properties were found to be able to induce circularly polarized luminescence of achiral luminophores. Due to the generality of this effect, this chiral plasmonic nanostructure may have great potential for use in the fields of chiral sensors, chiral catalysis, and displays.

Jiaqi Chen

Papers

Bottom-Up Synthesis of Helical Plasmonic Nanorods and Their Application in Generating Circularly Polarized Luminescence.