The concept of chirality arises from the lack of superimposability between an object and its mirror image, a consequence of the inverted symmetry inherent in the material's eigenvalue. This phenomenon can be likened to the inability of left and right hands to align perfectly through rotations or translations alone[1]. The term“enantiomer”refers to each pair of chemically identical mirror compounds. At the molecular level, the term chirality refers to bonding geometry in molecular structure, which possesses a sp3 - hybridized C center connected to four different substituents forming a tetrahedron[2]. The carbon atom is referred to as the“chirality center”, denoting its connection to four distinct atoms or groups of atoms, resulting in enantiomers that possess identical chemical formulas but exhibit contrasting configurations (Fig. 1A). The identification of chiral inorganic crystals in crystallography relies on the observation of their lattice structures exhibiting handedness, which arises from the absence of mirror and inversion symmetries, as well as other roto-inversion symmetries (Fig. 1B) [3]. Such as the mineral quartz SiO2 exhibits geometric asymmetry in both left- and right-handed variants, which depend on the orientation of structural helices. In addition, the common (2131) trigonal scalenohedral form of calcite exhibits adjacent crystal faces with enantiomorphic surface structures. The detection of chirality has always been a crucial aspect of studying chiral compounds.
Among various chirality detection methods, circular dichroism (CD) spectroscopy stands out as a promising and appealing technique due to its ability to reveal distinct chiroptical effects exhibited by enantiomers[4-6]. The CD signals of chiral molecules originating from enantiomers exhibit differences in the absorption of left-handed circularly polarized light (LCP) and right- handed circularly polarized light (RCP), and the working principle of CD spectroscopy is as follows (Fig. 1C). The incident unpolarized light is linearly polarized by passing through a linear polarizer, resulting in the generation of linearly polarized light (LPL). Subsequently, the LPL undergoes modulation using a rapid switchable photo - elastic modulator that introduces a phase retardation of π/2 to either of its two components, thereby producing LCP or RCP light. LCP/RCP light interacts with the sample and reaches the detector, resulting in the differential absorption of LCP/RCP lights. After calculating and processing the absorption difference, the CD spectral image is ultimately generated as output. CD spectroscopy methods have been widely employed in chemistry, biology, pharmacy, and photonics[7-15]. Notably, biomolecules' chirality can extend to increasingly complex structures, including peptides and proteins with secondary structure α-helix. Despite being structurally mirror-image molecules sharing similar physical and chemical properties, they can conversely affect chemical and biological functions[16]. Therefore, sensing the chirality of molecules plays a pivotal role in diverse domains such as the pharmaceutical industry, enantioselective synthesis, toxicology, and biomedicine.
The chiroptical properties of inorganic chiral plasmonic nanomaterials present intriguing characteristics, rendering them promising contenders for biosensing applications[17-24]. The generation of plasmonic chirality can be categorized into four distinct mechanisms, contributing to the diversity of plasmon-based chirality[25-31]. The first mechanism involves the fabrication of discrete chiral plasmonic structures that possess inherent geometric chirality, leveraging the rapid advancements in top - down lithography techniques such as direct laser writing. These techniques have been successfully employed to achieve intrinsically chiral plasmonic nanostructures. It presented a square array consisting of individual 3D gold helices fabricated through the integration of direct laser writing and electrochemical deposition techniques, exhibiting exceptional circular polarizing properties (Fig. 2A) [32]. Besides, there are numerous similar methods used for constructing intrinsically chiral plasmonic nanoparticles (NPs) [33-34]. The second mechanism is the self-assembly of achiral plasmonic NPs with chiral molecules serving as templates, resulting in the formation of chiral superstructures that exhibit highly intense CD signals within the visible and near - IR spectral regions[35-41]. Notably, Liedl and colleagues employed the DNA origami technique to fabricate gold helices assembled by NPs with a diameter of 16 nm, which exhibited a distinct CD signal at 545 nm (Fig. 2B) [42]. Following theoretical predictions, they observe well - defined CD and optical rotatory dispersion (ORD) effects at visible wavelengths in the solution structures, which arise from the precise positioning of NPs with an accuracy surpassing two nanometers and their collective plasmon-plasmon interactions. Third, the plasmon nanostructures with intrinsic chiral morphology can also be synthesized via a wet chemical method during crystal growth facilitated by the presence of chiral molecules[41, 43-55]. Nam and co-workers employed small chiral amino acids as chiral inducers to direct the growth of Au NPs with chiral surfaces exhibiting high Miller indices (321) facets (Fig. 2C) [43]. This approach resulted in the formation of twist sites and the breaking of crystal symmetry through the 432 point group symmetry, ultimately leading to the development of chiral structures. The experimental results demonstrated that chiral molecules of cysteine (Cys) can effectively induce the growth of Au nanocubes, leading to the formation of perfectly mirrored symmetry and exhibiting superior chiroptical responses. The last mechanism is to generate chiral plasmon Au with template worm-like micelles by combining typical surfactants and chiral ligands[56-60]. Liz-Marzán and coworkers demonstrated the formation of chiral micelles that adopted quasihelical structures upon complete adsorption onto the surface of Au NRs, thereby directing the growth of chiral Au NRs with distinct morphology and optical chirality (Fig. 2D) [57]. Chiral, worm-like micelles were formed by combining conventional surfactants (CTAC, quaternary alkylammonium chloride) with chiral ligands (BINOL, 1, 1' - bi(2 - naphthol)), as illustrated in Fig. 2D. In comparison to the biomolecule- mediated growth of chiral plasmonic NPs, the micelledirected chiral growth method relies more on the capability of chiral co - surfactants for directing the formation of helical micelles. In summary, the development of chiral inorganic nanomaterials establishes a robust foundation for their utilization in biosensing applications.
Chirality is a universal phenomenon in nature and plays a pivotal role in biological systems. Comprehending and synthesizing chiral molecules is not only conducive to the development of life science but also holds immense significance for the progress of chiral recogni- tion[61-63]. Compared with other traditional chiral biosensing recognition methods, electrochemical and enzyme-mimicked biosensing technologies possess unique advantages. The electrochemical methods have garnered significant attention due to their inherent advantages of rapid recognition, simplified operation, and heightened sensitivity. Similarly, the enzymemimicked approach has gained widespread favor owing to its distinctive attributes encompassing exceptional stability, recyclability, controllable activity, and facile large-scale production[5, 64-66]. Irrespective of the method employed, chiral recognition necessitates the involvement of a chiral selector that provides either a chiral microenvironment or a chiral center. In general, chiral selectors can be categorized into two groups: chiral inducer induction and intrinsic chiral NPs. The chiral recognition mechanism of the two types of selectors can generate intermolecular forces with chiral molecules, including electrostatic attraction, electrostatic repulsion, hydrogen bonding, hydrophobic interaction, π-π force, etc. Additionally, the precise homochiral facets of chiral NPs contribute to enantioselective surface chemistry. The schematic representation of chiral electrochemical and enzyme-mimicked biosensing is depicted in Fig. 3.
The chiral biomolecular sensing technology holds a prominent and indispensable position in the field of biomedical engineering, serving as a leading and fundamental technology with significant implications for research advancements[22]. Many effects and attempts have been made in recent years in this field to continue promoting this technology's development by scientists. This review presents the fundamentals of chiral nanocatalysts, including chiral inducer mechanisms and intrinsically chiral nanostructures. Furthermore, we review the application of chiral nanocatalysts in electrochemical and enzyme - mimicking catalytic biosens- ing, respectively. Finally, we provide an outlook on the challenges and opportunities of using chiral nanoprobes for emerging biosensing applications. By rational design of the chiral nanoprobes, we envisioned that biosensing with increasing sensitivity and resolution toward the single - molecule level can be achieved, which will substantially promote sensing applications in many emerging interdisciplinary areas.
Amino acids serve as the fundamental building blocks of proteins, with all amino acids except glycine exhibiting optical activity. Consequently, they establish a chiral environment essential for fabricating electrochemical chiral sensing interfaces during the construction of electrochemical chiral sensors[67-69]. Chiral amino acids, such as phenylalanine and tryptophan, are commonly utilized as chiral selectors. The recognition mechanism primarily relies on enantioselective forces between the chiral amino acids and the L/D substrate. Kuang and colleagues have developed a method where nanoporous films comprising self - assembled multilayers of L - phenylalanine - modified gold NPs exhibited high sensitivity to circular polarization, as light-induced polarization is dependent on the accumulation of ions at the particle interface (Fig. 4A)[70]. Notably, the photocurrent generated by the chiral Au NP films under right-handed CPL was 2.41 times higher than that under left-handed CPL. This study reveals a distinct difference in the optical response of Au NPs to the handedness of CPL and phenylalanine-induced assembly, highlighting the potential for biosensing applications. Wang and co - workers have developed a facile strategy wherein CuO/CoO nanofibers serve as the activity center, and chiral Cys acts as the chiral recognition inducer, resulting in the construction of nitrogen - doped chiral CuO/CoO nanofibers (N - CuO/CoO nanofibers) that exhibit both enzyme activity and electrochemical luminescence performance, enabling enantioselective catalysis and sensitive recognition of dihydroxyphenylalanine (DOPA) enantiomers (Fig. 4B) [71]. This approach provides a robust pathway for the discrimination and detection of chiral molecules.
Plasmonic NPs with intrinsically chiral surfaces play a crucial role as nanocatalysts in enantioselective heterogeneous processes, which are essential for asymmetric electrochemical biosensing. Fig. 5A illustrates that the structure of chiral surfaces is formed by the terraces, steps, and kinks of microplates derived from bulk crystal planes with low Miller indices (111), (110), and (100) [72]. The handedness of these surfaces can be determined by the sense of rotation (clockwise or anticlockwise) of the low - Miller - index microfacets around the kink. Intrinsically chiral metal surfaces have demonstrated a wide variety of enantiospecific interactions of adsorption energies and orientations with chiral molecules. Fig. 5B presents hard sphere models of the theoretically determined adsorption structures of D- and L-Cys on Au (17 11 9)S [73]. The results demonstrate chiral hetero-recognition between the amino acid molecules and the chiral Au surface, supported by density functional theory (DFT) calculation. This is also the theoretical basis for electrochemical biosensing by chiral NPs. This also serves as the theoretical foundation for electrochemical biosensing applications utilizing chiral NPs, which enhance selectivity and sensitivity in the detection of target analytes through their unique enantioselective properties.
The electroreduction of CO2 into multicarbon biomolecules is critically important for understanding natural systems and promoting CO2 capture technologies. Recently, Che and colleagues reported a novel process employing chiral Cu films (CCFs) to synthesize C3+ amino acids through electrocatalytic conversion of CO2 and NH3 [74]. As shown in Fig. 6A, the enantioselective formation of serine (Ser) occurs on chiral copper surfaces compared to achiral copper surfaces. This work opens unique avenues for further research into the enantioselectivity of chiral inorganic surfaces in various biologically relevant catalytic reactions. By enhancing the efficiency of these syntheses, this approach underscores the potential of chiral catalysts to facilitate complex biochemical transformations. Au surfaces with intrinsic chirality also play an essential role in enantioselective catalysis and biosensing[75-79]. Niu and co-workers reported that the remarkable enantioselective recognition properties of chiral Au surfaces enable an efficient electrochemical method for the chiral discrimination of L -/D -tryptophan (Fig. 6B) [80]. The insights gained from these findings lay a robust groundwork for in-depth investigations into the fundamental mechanisms underlying heterogeneous enantioselective catalytic processes. Our group demonstrated that the excellent catalytic activity and selectivity of chiral Au NPs for the electrocatalytic oxidation of enantiomers stem from the inherently chiral geometry of their high - energy surfaces. Additionally, we found that the generation of chiral Au NPs with a concave cubic structure, achieved by adding Cu²⁺, can significantly enhance catalytic activity (Fig. 6C)[47]. In addition to amino acid enantiomers, electrochemical biosensing can also be effectively used to detect carbohydrate enantiomers, demonstrating its versatility in applications such as food quality assessment and biomedical research. Nam and co-workers reported that the 432 helicoid Ⅲ, featuring chiral kink atoms on high-index facets, enabled the stereoselective oxidation of hydroxyl groups on various sugar molecules (Fig. 6D)[81]. They further characterized the crystal orientation and atom density of the kinked sites, investigating their specific interactions with glucose molecules, which are influenced by the morphological structure and surface electrostatic potential. Those results indicated that the NPs with chiral surfaces on inorganic metals represent a promising platform for the efficient catalysis of chiral biosensing applications.
Nanozymes serve as a quintessential representation of a new generation of artificial enzymes, facilitating biocatalysis through the utilization of nanomaterials[82-90]. This innovative approach enables the development of novel biocatalytic systems with improved stability, specificity, and efficiency. Since Yan and co - workers first discovered that Fe3O4 NPs possessed peroxidase - like activity in 2007, this breakthrough has opened the door for the development of nanozymes, which have emerged as a crucial intersection of nanotechnology, catalysis, and biomedicine in the past decade (Fig. 7A) [82]. Wei and co - workers developed an integrated cascade nanozyme, designated MSe1, which demonstrates both superoxide dismutase and glutathione peroxidase - like activities. This advanced nanozyme effectively mitigates the aging of human umbilical vein endothelial cells (HUVEC) by safeguarding DNA from oxidative damage (Fig. 7B)[91]. This study not only highlights the significant potential of cascade nanozymes in anti-senescence therapies for atheroscle- rosis but also demonstrates their promising applications in enzyme-mimicked biosensing.
Most naturally occurring amino acids are chiral, and this stereospecificity enables natural enzymes to exhibit enantiomeric selectivity. Therefore, the incorporation of chiral amino acids as chiral ligands presents a promising avenue for the development of enzymemimicked biosensing platforms[92-95]. Qu and co-workers synthesized a chiral nanozyme, designated Cys@ AuNPs-EMSN, by using Cys as a chiral ligand on Au NPs and loading them into an expanded mesoporous silica (EMSN) carrier (Fig. 8A) [96]. The results suggest that the D - Cys@AuNPs - EMSN nanozyme was more likely to catalyze the oxidation of L-DOPA, while the L- Cys@AuNPs - EMSN nanozyme was more efficient for the oxidation of D-DOPA, indicating the enantioselective catalytic activity of this chiral nanozyme platform. The researchers attributed the observed enantioselectivity of the L/D-Cys@AuNPs-EMSN nanozyme to the enhanced hydrogen bonding interactions between the matching enantiomeric pairs, i.e., L-Cys and L-DOPA or D-Cys and D-DOPA. This increased binding affinity between the chiral ligand and substrate enantiomers subsequently reduced the catalytic efficiency, leading-ECL to the observed enantioselectivity of the nanozyme system. Additionally, the researchers noted that DNA is also commonly employed as a chiral inducer in such nanozyme platforms, as it can flexibly transform between various multi-stranded conformations in response to environmental conditions. Ding and co - workers synthesized Au-based nanozymes modified with diverse DNA sequences, which demonstrated distinct enantioselectivity in the catalytic oxidation of L - glucose (L-glu) and D-glucose (D-glu) (Fig. 8B)[97]. Specifically, the researchers found that nanozymes capped with randomly coiled DNA preferentially catalyzed the oxidation of L-glu, while the nanozymes functionalized with structured DNA exhibited higher catalytic activity toward the oxidation of D-glu. The results of this study provide a simple yet effective strategy for achieving reactive enantioselective catalysis using metal NPs. Furthermore, these findings promote a deeper understanding of the chiral interactions between nucleic acids and saccharides, which can inform the design of advanced chiral nanomaterials and catalysts. In addition to metal-based nanomaterials, chiral metal-organic framework (MOF) materials hold great promise in enzyme-mimicked biosensing applications due to their molecular/atomic - level active sites, precisely tailored scaffolds, and tunable coordination microenvironments, which can be leveraged to achieve enhanced chiral recognition and catalytic performance. Zhu and co-workers developed a chiral MOF material by grafting a histidine (His)-coordinated copper (Cu) core onto a Zr-based MOF backbone, and the chiral MOF nano- material exhibited catechol oxidase-like catalytic activity (Fig. 8C)[98]. Specifically, the modification of the chiral His arm made the nanomaterial more catalytically selective towards chiral catechol substrates compared to natural enzymes. DFT calculations indicate that the enantioselectivity observed in the system is primarily attributed to the interactions between the active site and the reaction substrate, as well as the influence of stereoelectronic effects.
The plasmonic enhancement of catalytic activity in Au NPs is a well-researched area within photocatalysis, nanozyme catalysis, bio - photodynamic therapy, and various other fields. In the context of chiral plasmonic nanomaterials, Au NPs have shown significant promise as catalysts for enantioselective nanocatalysis[99-100]. The selective excitation of CPL on chiral plasmonic materials may exhibit distinct capabilities in inducing hot carriers during photocatalysis reactions, potentially influencing the enantioselectivity of the catalytic process. Govorov and co - workers developed a novel plasmon - based photocatalyst system by assembling Au and TiO2 onto chiral inorganic substrates, which exhibited polarization-dependent reactivity, offering a promising approach for enantioselective photocatalytic applications (Fig. 9A) [101]. The results revealed that CPL irradiation had a profound impact on photocatalytic degradation efficiency, with a notable chirality - dependent response. Specifically, the chiral SiO2@Au@TiO2 nanoribbons exhibited substantial photocatalytic activity only when excited with CPL that matched their inherent chirality, whereas relatively weak activity was observed when the same material was excited with oppositely polarized CPL. Furthermore, our previous work has demonstrated that CPL can effectively modulate the enzyme-mimicked catalytic activity of intrinsically chiral helical AuPd alloy NPs, highlighting the potential of CPL as a means to control and optimize the catalytic performance of these materials[102]. Notably, when the enzyme-mimicked reaction was performed, the L-AuPd alloy NPs exhibited a higher catalytic activity under LCP excitation compared to RCP light, and conversely, the R - AuPd NPs displayed enhanced activity when activated with RCP, as opposed to LCP, highlighting the chirality-dependent response of these materials to circularly polarized light (Fig. 9B). In contrast, achiral AuPd alloy NPs demonstrated negligible differences in catalytic activity between LCP and RCP excitations, underscoring the critical role of chirality in mediating the polarization-dependent response of these materials. In addition to noble metal NPs, carbon dots (CDs) are also a material with excellent enzyme - mimicked catalytic activity[103-105]. Yang and co-workers report that Cys-derived chiral CDs can mimic topoisomerase Ⅰ to mediate topological rearrangement of supercoiled DNA enanti- oselectively (Fig. 9C) [105]. The results indicated that D -CDs, in comparison to L - CDs, more effectively catalyzed the topological transformation of plasmid DNA from a superhelical structure to a notched open - loop structure. This enhanced catalytic efficiency is attributed to the distinct interactive binding forces with the DNA double helix. These findings underscore the promising potential of employing intrinsic chiral NPs as enzyme-mimicking biosensors.
Numerous reports have demonstrated that chiral amino acids can be incorporated into shell structures to achieve high-efficiency biosensing, suggesting their potential roles in living cells[106]. Qu and co-workers have developed a series of stereoselective nanozymes, utilizing Fe3O4 NPs yolks as the catalytic core and amino acid - appended chiral polymer shells as the chiral selectors, which exhibit artificial peroxidase activities with exceptional enantioselectivity[95]. Additionally, by fluorescently labeling fluorescein isothiocyanate (FITC)- tyrosine aminophenolL and RhB-tyrosinolD, these artificial peroxidase catalyzes green or red fluorescent chiral tyrosine, enabling the selective labeling of live yeast cells among yeast, S. aureus, E. coli, and B. subtilis bacterial cells (Fig. 10A). This work opens new doors for better design of stereoselective artificial enzymes. Chiral ligand NPs also have significant applications in cell analysis. Due to their sensitivity to the surrounding environment, the optical chirality of plasmon-molecular assemblies can distinguish between extracellular and intracellular states. Kotov and co-workers constructed DNA - bridged NP dimers that exhibit a real CD signal dependent on their localization, either intracellular or extracellular, for tracking NP internalization in mammalian cells (Fig. 10B) [107]. In the ensemble state, the electrostatic repulsion between the NPs changes markedly when the dimer transitions from the interstitial fluid to the cytosol, resulting in a spontaneous torsion around the NDA bridge, which results in the reversal of the plasma CD signal from negative to positive during the transmembrane transmission. This discovery not only advances spectral targeting of plasma nanomaterials but also holds great potential for photodynamic therapy of malignant tumors.
In recent years, chiral inorganic NPs have been extensively investigated for their applications in living cells and biomedical fields. This section primarily focuses on the biomedical applications of plasmon NPs with intrinsic chiral structures, emphasizing their enantioselective interactions with biological systems. Liu and co-workers utilized chiral nanooctopods (NOPs) to demonstrate that cell uptake efficiency is influenced by chiral morphology (Fig. 11A) [108]. It was observed that the uptake of D - GSH (glutathione) NOPs by GL261 and bEnd. 3 cells increased by more than 30% compared to L - GSH NOPs (racemic NOPs). Furthermore, Xu and co-workers illustrated the enantiomer-dependent immunological response to chiral Au NPs (Fig. 11B) [109]. They discovered that chiral Au NPs bind differentially to cluster - of - differentiation 97 (CD97) and epidermal growth factor - like module receptor 1 (EMR1) two proteins exhibited differentiation, leading to the activation of mechanosensitive potassium outflow channels, the formation of immune signaling complexes, and the maturation of mouse bone marrow-derived dendritic cells. The g-factor of chiral NPs was found to be sensitively correlated with immune responses both in vivo and in vitro, suggesting that nanoscale geometric chirality can be leveraged to regulate the maturation of immune cells. It breakthrough opens new avenues for the use of chiral NPs in immunological applications.
Due to the mismatch between the molecular scale and the wavelength of the incident light, quantitatively determining and in situ characterizing molecular chirality at extremely low concentrations in optical measurement schemes remain challenging. Nam and coworkers determined the enantioselectivity of collective CD generated by 2D crystals assembled by 432-symmetric chiral gold NPs with isotropic properties (Fig. 12)[110]. The previous approach in plasmonics relies on the optical helical density generated by LSPR on a single structure. However, this method faced challenges in controlling the distribution, orientation, and vibration of target molecules, limiting its ability to achieve strong coupling. In their work, a large-volume 2D crystal plane was prepared, where the optically induced dipole collective CD exhibited a strong and uniform chiral near-field due to the collective spin of each helical surface. Consequently, the molecular chiral reaction of the analyte and the energy redistribution of the chiral near-field shifted collective resonances in opposite directions, thereby maximizing the modulation of the collective CD. Additionally, they developed colorimetric sensors based on significant changes in collective CD values, which not only allowed for the intuitive quantification of molecular chirality but also demonstrated the versatility of the enantioselective biomolecular sensor platform[110]. Moreover, it is suggested that by further advancing the transformative application of enantioselective sensing, in situ monitoring of biomolecular conformational changes at molecular resolution can be realized in the future. A promising application direction includes monitoring changes in the secondary structure and folding status of membrane proteins. A promising application direction includes monitoring changes in the secondary structure and folding status of membrane proteins. Integrating a membrane with a 2D structure into the platform enables the detection of even the folding changes of individual proteins within the membrane. This work emphasizes NP-molecular interactions and plasmon - plasmon coupling, offering a novel perspective for improving chiral sensing capabilities.
In summary, this review presents the recent advances in the application of chiral inorganic nanocat- alysts in the field of biosensing. We focus on the elec- trochemical and enzyme-mimicking catalytic approach- es toward biosensing. The fundamentals of chiral nano- catalysts include chiral ligand-induced mechanism and intrinsically chiral nanostructures was first reviewed. We further systematically present the recent advance in the application of chiral nanocatalysts in electro- chemical and enzyme-mimicking catalytic biosensing, respectively. Finally, we provide an outlook on the challenges and opportunities of using chiral nano- probes for emerging biosensing applications. We envi- sioned that by rational design of the chiral nanoprobes, biosensing with increasing sensitivity and resolution toward the single-molecule level can be achieved, which will substantially promote sensing applications in many emerging interdisciplinary areas.
BENTLEY R. From optical-activity in quartz to chiral drugs-molecular handedness in biology and medicine[J]. Perspect. Biol. Med, 1995, 38(2): 188-229. doi: 10.1353/pbm.1995.0069
MEIERHENRICH U J. Amino acids and the asymmetry of life[J]. Eur. Rev., 2013, 21(2): 190-199. doi: 10.1017/S106279871200035X
HAZEN R M, SHOLL D S. Chiral selection on inorganic crystalline surfaces[J]. Nat. Mater., 2003, 2(6): 367-374. doi: 10.1038/nmat879
GOVOROV A O, FAN Z Y, HERNANDEZ P, SLOCIK J M, NAIK R R. Theory of circular dichroism of nanomaterials comprising chiral molecules and nanocrystals: Plasmon enhancement, dipole interactions, and dielectric effects[J]. Nano Lett., 2010, 10(4): 1374-1382. doi: 10.1021/nl100010v
ZHANG Q F, HERNANDEZ T, SMITH K W, JEBELI S A H, DAI A X, WARNING L, BAIYASI R, MCCARTHY L A, GUO H, CHEN D H, DIONNE J A, LANDES C F, LINK S. Unraveling the origin of chirality from plasmonic nanoparticle protein complexes[J]. Science, 2019, 365(6460): 1475.
FAN Z Y, GOVOROV A O. Chiral nanocrystals: Plasmonic spectra and circular dichroism[J]. Nano Lett., 2012, 12(6): 3283-3289. doi: 10.1021/nl3013715
AMDURSKY N, STEVENS M M. Circular dichroism of amino acids: Following the structural formation of phenylalanine[J]. ChemPhysChem, 2015, 16(13): 2768-2774. doi: 10.1002/cphc.201500260
YU Y, YANG G, ZHANG S, LIU M, XU S, WANG C, LI M, ZHANG S X A. Wide-range and highly sensitive chiral sensing by discrete 2D chirality transfer on confined surfaces of Au(Ⅰ)-thiolate nanosheets[J]. ACS Nano, 2021, 16(1): 148-159.
CHENG Q Q, YANG J, SUN L C, LIU C, YANG G Z, TAO Y L, SUN X H, ZHANG B B, XU H X, ZHANG Q F. Tuning the plexcitonic optical chirality using discrete structurally chiral plasmonic nanoparticles[J]. Nano Lett., 2023, 23(23): 11376-11384. doi: 10.1021/acs.nanolett.3c04265
SUN L C, TAO Y L, YANG G Z, LIU C, SUN X H, ZHANG Q F. Geometric control and optical properties of intrinsically chiral plasmonic nanomaterials[J]. Adv. Mater., 2023, : 2306297. doi: 10.1002/adma.202306297
YANG G, SUN L, ZHANG Q. Multicomponent chiral plasmonic hybrid nanomaterials: Recent advances in synthesis and applications[J]. Nanoscale Adv., 2024, 6(2): 318-336. doi: 10.1039/D3NA00808H
WANG C, LU D D, SUN L C, ZHANG Q F. Rational design of plasmonic nanoparticle molecule complexes for chirality sensing[J]. Chin. J. Chem., 2024, 42(8): 903-919. doi: 10.1002/cjoc.202300602
LIU P Z, BATTIE Y, OKAZAKI Y, RYU N, POUGET E, NLATE S, SAGAWA T, ODA R. Chiral optical scattering from helical and twisted silica nanoribbons[J]. Chem. Commun., 2021, 57(90): 12024-12027. doi: 10.1039/D1CC04200A
LV X L, WU F X, TIAN Y, ZUO P, LI F H, XU G B, NIU W X. Engineering the intrinsic chirality of plasmonic Au@Pd metamaterials for highly sensitive chiroplasmonic hydrogen sensing[J]. Adv. Mater., 2023, 35(51): 2305429. doi: 10.1002/adma.202305429
HAN B, SUN C, ZHOU Y L, GAO X Q. Geometry-modulated magnetoplasmonic circular dichroism of gold nanobipyramids[J]. J. Phys. Chem. C, 2022, 126(7): 3600-3605. doi: 10.1021/acs.jpcc.1c10808
WANG Y W, TAY A. Advances in enantiomer-dependent nanotherapeutics[J]. ACS Nano, 2023, 17(11): 9850-9869. doi: 10.1021/acsnano.3c02798
MA W, XU L G, DE MOURA A F, WU X L, KUANG H, XU C L, KOTOV N A. Chiral inorganic nanostructures[J]. Chem. Rev., 2017, 117(12): 8041-8093. doi: 10.1021/acs.chemrev.6b00755
WANG P P, YU S J, GOVOROV A O, OUYANG M. Cooperative expression of atomic chirality in inorganic nanostructures[J]. Nat. Commun., 2017, 8(4): 14312.
GAO Q, TAN L L, WEN Z H, FAN D D, HUI J F, WANG P P. Chiral inorganic nanomaterials: Harnessing chirality-dependent interactions with living entities for biomedical applications[J]. Nano Res., 2023, 16(8): 11107-11124. doi: 10.1007/s12274-023-5831-7
FU W L, TAN L L, WANG P P. Chiral inorganic nanomaterials for photo (electro) catalytic conversion[J]. ACS Nano, 2023, 17(17): 16326-16347. doi: 10.1021/acsnano.3c04337
ABBAS S U, LI J J, LIU X, SIDDIQUE A, SHI Y X, HOU M, YANG K, NOSHEEN F, CUI X Y, ZHENG G C, ZHANG Z C. Chiral metal nanostructures: Synthesis, properties and applications[J]. Rare Met., 2023, 42(8): 2489-2515. doi: 10.1007/s12598-023-02274-4
HAO C L, XU C L, KUANG H. Chiral probes for biosensing[J]. Chem. Commun., 2023, 59(87): 12959-12971. doi: 10.1039/D3CC03660J
ZHANG M J, WANG Y X, ZHOU Y J, YUAN H G, GUO Q, ZHUANG T T. Amplifying inorganic chirality using liquid crystals[J]. Nanoscale, 2022, 14(3): 592-601. doi: 10.1039/D1NR06036HyType=xml&restype=unixref&xml=|Polymer Degradation and Stability||158||102|2018|||
FENG Z Y, HE C L, XIE Y F, ZHANG C T, LI J H, LIU D D, JIANG Z F, CHEN X, ZOU G. Chiral biosensing at both interband transition and plasmonic extinction regions using twisted stacked nanowire arrays[J]. Nanoscale, 2022, 14(29): 10524-10530. doi: 10.1039/D2NR03357G
ZHENG G C, HE J J, KUMAR V, WANG S L, PASTORIZA-SANTOS I, PÉREZ-JUSTE J, LIZ-MARZÁN L M, WONG K Y. Discrete metal nanoparticles with plasmonic chirality[J]. Chem. Soc. Rev., 2021, 50(6): 3738-3754. doi: 10.1039/C9CS00765B
KNEER L M, ROLLER E M, BESTEIRO L V, SCHREIBER R, GOVOROV A O, LIEDL T. Circular dichroism of chiral molecules in DNA assembled plasmonic hotspots[J]. ACS Nano, 2018, 12(9): 9110-9115. doi: 10.1021/acsnano.8b03146
LIU W L, HAN H, WANG J Q. Recent advances in the 3D chiral plasmonic nanomaterials[J]. Small, 2023, 20(8): 2305725.
KIM Y, KIM H, YANG Y, BADLOE T, JEON N, RHO J. Three dimensional artificial chirality towards lowcost and ultra-sensitive enantioselective sensing[J]. Nanoscale, 2022, 14(10): 3720-3730. doi: 10.1039/D1NR05805C
LEE H E, KIM R M, AHN H Y, LEE Y Y, BYUN G H, IM S W, MUN J, RHO J, NAM K T. Cysteine-encoded chirality evolution in plasmonic rhombic dodecahedral gold nanoparticles[J]. Nat. Commun., 2020, 11(1): 263. doi: 10.1038/s41467-019-14117-x
SUN X H, SUN L C, LIN L F, GUO S Y, YANG Y M, ZHANG B B, LIU C, TAO Y L, ZHANG Q F. Tuning the geometry and optical chirality of pentatwinned Au nanoparticles with 5-fold rotational symmetry[J]. ACS Nano, 2024, 18(13): 9543-9556. doi: 10.1021/acsnano.3c12637
YANG L, MA Y C, LIN C, QU G P, BAI X P, HUANG Z F. Nanohelixinduced optical activity of liquid metal nanoparticles[J]. Small, 2022, 18(17): 2200620. doi: 10.1002/smll.202200620
GANSEL J K, THIEL M, RILL M S, DECKER M, BADE K, SAILE V, VON FREYMANN G, LINDEN S, WEGENER M. Gold helix photonic metamaterial as broadband circular polarizer[J]. Science, 2009, 325(5947): 1513-1515. doi: 10.1126/science.1177031
ESPOSITO M, TASCO V, CUSCUNà M, TODISCO F, BENEDETTI A, TARANTINI I, DE GIORGI M, SANVITTO D, PASSASEO A. Nanoscale 3D chiral plasmonic helices with circular dichroism at visible frequencies[J]. ACS Photonics, 2015, 2(1): 105-114. doi: 10.1021/ph500318p
JI C Y, CHEN S S, HAN Y, LIU X, LIU J, LI J F, YAO Y G. Artificial propeller chirality and counterintuitive reversal of circular dichroism in twisted meta molecules[J]. Nano Lett., 2021, 21(16): 6828-6834. doi: 10.1021/acs.nanolett.1c01802
LU J, XUE Y, BERNARDINO K, ZHANG N N, GOMES W R, RAMESAR N S, LIU S H, HU Z, SUN T M, DE MOURA A F, KOTOV N A, LIU K. Enhanced optical asymmetry in supramolecular chiroplasmonic assemblies with long range order[J]. Science, 2021, 371(6536): 1368. doi: 10.1126/science.abd8576
JUNG S H, JEON J, KIM H, JAWORSKI J, JUNG J H. Chiral arrangement of achiral Au nanoparticles by supramolecular assembly of helical nanofiber templates[J]. J. Am. Chem. Soc., 2014, 136(17): 6446-6452. doi: 10.1021/ja5018199
ZHANG N N, SHEN X X, LIU K, NIE Z H, KUMACHEVA E. Polymer-tethered nanoparticles: From surface engineering to directional self-assembly[J]. Acc. Chem. Res., 2022, 55(11): 1503-1513. doi: 10.1021/acs.accounts.2c00066
LU J, CHANG Y X, ZHANG N N, WEI Y, LI A J, TAI J, XUE Y, WANG Z Y, YANG Y, ZHAO L, LU Z Y, LIU K. Chiral plasmonic nanochains the self-assembly of gold nanorods and helical glutathione oligomers facilitated by cetyltrimethylammonium bromide micelles[J]. ACS Nano, 2017, 11(4): 3463-3475. doi: 10.1021/acsnano.6b07697
GONG Y J, CAO Z Z, ZHANG Z Z, LIU R J, ZHANG F H, WEI J J, YANG Z J. Chirality inversion in self assembled nanocomposites directed by curvature-mediated interactions[J]. Angew. Chem.-Int. Edit., 2022, 61(10): e202117406. doi: 10.1002/anie.202117406
PAN J H, WANG X Y, ZHANG J J, ZHANG Q, WANG Q B, ZHOU C. Chirally assembled plasmonic metamolecules from intrinsically chiral nanoparticles[J]. Nano Res., 2022, 15(10): 9447-9453. doi: 10.1007/s12274-022-4520-2
WANG S, ZHENG L H, CHEN W J, JI L K, ZHANG L, LU W S, FANG Z Y, GUO F C, QI L M, LIU M H. Helically grooved gold nanoarrows: Controlled fabrication, superhelix, and transcribed chiroptical switching[J]. CCS Chem., 2021, 3(9): 2473-2484. doi: 10.31635/ccschem.020.202000472
KUZYK A, SCHREIBER R, FAN Z Y, PARDATSCHER G, ROLLER E M, HÖGELE A, SIMMEL F C, GOVOROV A O, LIEDL T. DNAbased self-assembly of chiral plasmonic nanostructures with tailored optical response[J]. Nature, 2012, 483(7389): 311-314. doi: 10.1038/nature10889
LEE H E, AHN H Y, MUN J, LEE Y Y, KIM M, CHO N H, CHANG K, KIM W S, RHO J, NAM K T. Amino-acidand peptide-directed synthesis of chiral plasmonic gold nanoparticles[J]. Nature, 2018, 556(7701): 360. doi: 10.1038/s41586-018-0034-1
SUN X H, YANG J, SUN L C, YANG G Z, LIU C, TAO Y L, CHENG Q Q, WANG C, XU H X, ZHANG Q F. Tunable reversal of circular dichroism in the seed-mediated growth of bichiral plasmonic nanoparticles[J]. ACS Nano, 2022, 16(11): 19174-19186. doi: 10.1021/acsnano.2c08381
TAO Y L, SUN L C, LIU C, YANG G Z, SUN X H, ZHANG Q F. Siteselective chiral growth of anisotropic Au triangular nanoplates for tuning the optical chirality[J]. Small, 2023, 19(30): 2301218. doi: 10.1002/smll.202301218
YANG G Z, SUN L C, TAO Y L, CHENG Q Q, SUN X H, LIU C, ZHANG Q F. Chiral AuCu heterostructures with site specific geometric control and tailored plasmonic chirality[J]. Sci. China Chem., 2023, 66(11): 3280-3289. doi: 10.1007/s11426-023-1685-3
WAN J L, SUN L C, SUN X H, LIU C, YANG G Z, ZHANG B B, TAO Y L, YANG Y H, ZHANG Q F. Cu-dominated chirality transfer from chiral molecules to concave chiral Au nanoparticles[J]. J. Am. Chem. Soc., 2024, 146(15): 10640-10654. doi: 10.1021/jacs.4c00322
CHEN J Q, GAO X S, ZHENG Q, LIU J B, MENG D J, LI H Y, CAI R, FAN H Z, JI Y L, WU X C. Bottom-up synthesis of helical plasmonic nanorods and their application in generating circularly polarized luminescence[J]. ACS Nano, 2021, 15(9): 15114-15122. doi: 10.1021/acsnano.1c05489
ZHANG L L, CHEN Y L, ZHENG J P, LEWIS G R, XIA X Y, RINGE E, ZHANG W, WANG J F. Chiral gold nanorods with fivefold rotational symmetry and orientation-dependent chiroptical properties of their monomers and dimers[J]. Angew. Chem.-Int. Edit., 2023, 62(52): e202312615. doi: 10.1002/anie.202312615
KIM H, IM S W, KIM R M, CHO N H, LEE H E, AHN H Y, NAM K T. Chirality control of inorganic materials and metals by peptides or amino acids[J]. Mater. Adv., 2020, 1(4): 512-524. doi: 10.1039/D0MA00125B
ZHANG N N, SHEN Z L, GAO S Y, PENG F, CAO Z J, WANG Y, WANG Z Z, ZHANG W, YANG Y, LIU K, SUN T M. Synthesis and plasmonic chiroptical properties of double helical gold nanorod enantiomers[J]. Adv. Opt. Mater., 2023, 11(18): 2203119. doi: 10.1002/adom.202203119
ZHENG Y L, LI X Y, HUANG L P, LI X X, YANG S H, WANG Q, DU J X, WANG Y W, DING W Q, GAO B, CHEN H Y. Homochiral nanopropeller via chiral active surface growth[J]. J. Am. Chem. Soc., 2023, 146(1): 410-418.
ZHENG Y L, WANG Q, SUN Y W, HUANG J, JI J, WANG Z J, WANG Y W, CHEN H Y. Chiral active surface growth via glutathione control[J]. Adv. Opt. Mater., 2023, 11(18): 2202858. doi: 10.1002/adom.202202858
ZHANG N N, SUN H R, XUE Y, PENG F, LIU K. Tuning the chiral morphology of gold nanoparticles with oligomeric gold glutathione complexes[J]. J. Phys. Chem. C, 2021, 125(19): 10708-10715. doi: 10.1021/acs.jpcc.1c01641
WEN X, WANG S, LIU R L, DUAN R, HU S, JIAO T F, ZHANG L, LIU M H. Selenocystine and photo irradiation directed growth of helically grooved gold nanoarrows[J]. Small, 2021, 18(5): 2104301.
VAN GORDON K, BAÚLDE S, MYCHINKO M, HEYVAERT W, OBELLEIRO-LIZ M, CRIADO A, BALS S, LIZ-MARZÁN L M, MOSQUERA J. Tuning the growth of chiral gold nanoparticles through rational design of a chiral molecular inducer[J]. Nano Lett., 2023, 23(21): 9880-9886. doi: 10.1021/acs.nanolett.3c02800
GONZÁLEZ-RUBIO G, MOSQUERA J, KUMAR V, PEDRAZO-TARDAJOS A, LLOMBART P, SOLÍS D M, LOBATO I, NOYA E G, GUERRERO-MARTÍNEZ A, TABOADA J M, OBELLEIRO F, MACDOWELL L G, BALS S, LIZ-MARZÁN L M. Micelle-directed chiral seeded growth on anisotropic gold nanocrystals[J]. Science, 2020, 368(6498): 1472-1477. doi: 10.1126/science.aba0980
ZHUO X L, MYCHINKO M, HEYVAERT W, LARIOS D, OBELLEIRO-LIZ M, TABOADA J M, BALS S, LIZ-MARZÁN L M. Morphological and optical transitions during micelle seeded chiral growth on gold nanorods[J]. ACS Nano, 2022, 16(11): 19281-19292. doi: 10.1021/acsnano.2c08668
SPAETH P, ADHIKARI S, HEYVAERT W, ZHUO X L, GARCÍA I, LIZ-MARZÁN L M, BALS S, ORRIT M, ALBRECHT W. Photothermal circular dichroism measurements of single chiral gold nanoparticles correlated with electron tomography[J]. ACS Photonics, 2022, 9(12): 3995-4004. doi: 10.1021/acsphotonics.2c01457
HEYVAERT W, PEDRAZO-TARDAJOS A, KADU A, CLAES N, GONZÁLEZ-RUBIO G, LIZ-MARZÁN L M, ALBRECHT W, BALS S. Quantification of the helical morphology of chiral gold nanorods[J]. ACS Mater. Lett., 2022, 4(4): 642-649. doi: 10.1021/acsmaterialslett.2c00055
LI S, VEKSLER M, XU Z J, XU L G, XU C L, KOTOV N A. Selfassembly of earth-abundant supraparticles with chiral interstices for enantioselective photocatalysis[J]. ACS Energy Lett., 2021, 6(4): 1405-1412.
YUE X, LI S, LIN H, XU C, XU L. Heterogeneous agxcdys agcd nanoparticles with chiral bias for enhanced photocatalytic efficiency[J]. Adv. Funct. Mater., 2022, 33(4): 2210046.
TIAN Y, WU F X, LV X L, LUAN X X, LI F H, XU G B, NIU W X. Enantioselective surface enhanced Raman scattering by chiral Au nanocrystals with finely modulated chiral fields and internal standards[J]. Adv. Mater., 2024, 36(35): 2403373. doi: 10.1002/adma.202403373
NIU X H, YANG X, LI H X, LIU J, LIU Z Y, WANG K J. Application of chiral materials in electrochemical sensors[J]. Microchim. Acta, 2020, 187(12): 676. doi: 10.1007/s00604-020-04646-4
WANG S, SHI Y, HOU Y, SHAN S L, WANG H, LU J X. Electrocatalytic asymmetric reduction of ethyl benzoylformate on bimetallic Ag-Cu cathodes[J]. J. Appl. Electrochem., 2020, 50(9): 973-978. doi: 10.1007/s10800-020-01449-6
BUTCHA S, ASSAVAPANUMAT S, ITTISANRONNACHAI S, LAPEYRE V, WATTANAKIT C, KUHN A. Nanoengineered chiral Pt Ir alloys for high performance enantioselective electrosynthesis[J]. Nat. Commun., 2021, 12(1): 1314. doi: 10.1038/s41467-021-21603-8
HUANG L, LIN Q, LI Y X, ZHENG G C, CHEN Y T. Study of the enantioselectivity and recognition mechanism of sulfhydrylcompound functionalized gold nanochannel membranes[J]. Anal. Bioanal. Chem., 2019, 411(2): 471-478. doi: 10.1007/s00216-018-1464-1
ZHAO Q Q, ZHU W K, CAI W R, LI J Y, WU D T, KONG Y. TiO nanotubes decorated with CdSe quantum dots: A bifunctional electrochemiluminescent platform for chiral discrimination and chiral sensing[J]. Anal. Chem., 2022, 94(26): 9399-9406. doi: 10.1021/acs.analchem.2c01383
LIN H, MITOMO H, YONAMINE Y, GUO Z, IJIRO K. Coregapshell nanoparticles@polyaniline with tunable plasmonic chiroptical activities by pH and electric potential dual modulation[J]. Chem. Mater., 2022, 34(9): 4062-4072. doi: 10.1021/acs.chemmater.2c00313
CAI J R, ZHANG W, XU L G, HAO C L, MA W, SUN M Z, WU X L, QIN X, COLOMBARI F M, DE MOURA A F, XU J H, SILVA M C, CARNEIRO-NETO E B, GOMES W R, VALLÉE R A L, PEREIRA E C, LIU X G, XU C L, KLAJN R, KOTOV N A, KUANG H. Polarization-sensitive optoionic membranes from chiral plasmonic nanoparticles[J]. Nat. Nanotechnol., 2022, 17(4): 408. doi: 10.1038/s41565-022-01079-3
SONG Y X, LU S Y, HAI J, LIANG K, SUN S A, MENG G P, WANG B D. Nitrogen-doped chiral CuO/CoO nanofibers: An enhanced electrochemiluminescence sensing strategy for detection of 3, 4-dihydroxy-phenylalanine enantiomers[J]. Anal. Chem., 2021, 93(33): 11470-11478. doi: 10.1021/acs.analchem.1c01497
SHUKLA N, GELLMAN A J. Chiral metal surfaces for enantioselective processes[J]. Nat. Mater., 2020, 19(9): 939-945. doi: 10.1038/s41563-020-0734-4
GREBER T, SLJIVANCANIN Z, SCHILLINGER R, WIDER J, HAMMER B. Chiral recognition of organic molecules by atomic kinks on surfaces[J]. Phys. Rev. Lett., 2006, 96(5): 056103. doi: 10.1103/PhysRevLett.96.056103
FANG Y X, LIU X, LIU Z P, HAN L, AI J, ZHAO G, TERASAKI O, CUI C H, YANG J Z, LIU C Y, ZHOU Z Y, CHEN L W, CHE S A. Synthesis of amino acids by electrocatalytic reduction of Co on chiral Cu surfaces[J]. Chem, 2023, 9(2): 460-471. doi: 10.1016/j.chempr.2022.10.017
LI F H, WU F X, LUAN X X, YUAN Y L, ZHANG L, XU G B, NIU W X. Highly enantioselective electrochemical sensing based on helicoid Au nanoparticles with intrinsic chirality[J]. Sensors Actuator B-Chemical, 2022, 362: 131757. doi: 10.1016/j.snb.2022.131757
LI R Y, WANG X B, PENG Y F, XU P W, ZHU H Y, LI Z J, SUN X L. Synthesis of gold nanocrystals with chiral morphology, chiral ligand and more exposed high-index facets as electrocatalyst for the oxidation of glucose enantiomers with high enantioselectivity and catalytic activity[J]. Catal. Sci. Technol., 2022, 12(7): 2097-2105. doi: 10.1039/D1CY01764K
ZHOU Y L, ZOU Y, JIANG J. Synthesis of chorogi-like Au nanoparticles with chiral plasmonic response and enantioselective electrocatalytic activity[J]. Mater. Lett., 2023, 331: 133432. doi: 10.1016/j.matlet.2022.133432
WU F X, LI F H, TIAN Y, LV X L, LUAN X X, XU G B, NIU W X. Surface topographical engineering of chiral Au nanocrystals with chiral hot spots for plasmon enhanced chiral discrimination[J]. Nano Lett., 2023, 23(17): 8233-8240. doi: 10.1021/acs.nanolett.3c02385
WU F X, LI F H, LV X L, ZHANG Q X, XU G B, NIU W X. Heteroepitaxial growth of Au@Pd core-shell nanocrystals with intrinsic chiral surfaces for enantiomeric recognition[J]. Rare Met., 2023, 43(1): 225-235.
WU F X, TIAN Y, LUAN X X, LV X L, LI F H, XU G B, NIU W X. Synthesis of chiral Au nanocrystals with precise homochiral facets for enantioselective surface chemistry[J]. Nano Lett., 2022, 22(7): 2915-2922. doi: 10.1021/acs.nanolett.2c00094
CHOI S, LIU C, SEO D, IM S W, KIM R M, JO J, KIM J W, PARK G S, KIM M, BRINCK T, NAM K T. Kink-controlled gold nanoparticles for electrochemical glucose oxidation[J]. Nano Lett., 2024, 24(15): 4528-4536. doi: 10.1021/acs.nanolett.4c00413
GAO L Z, ZHUANG J, NIE L, ZHANG J B, ZHANG Y, GU N, WANG T H, FENG J, YANG D L, PERRETT S, YAN X. Intrinsic peroxidase like activity of ferromagnetic nanoparticles[J]. Nat. Nanotechnol., 2007, 2(9): 577-583. doi: 10.1038/nnano.2007.260
GAO L Z, WEI H, DONG S J, YAN X Y. Nanozymes[J]. Adv. Mater., 2024, 36(10): 2305249. doi: 10.1002/adma.202305249
CHEN J X, MA Q, LI M H, CHAO D Y, HUANG L, WU W W, FANG Y X, DONG S J. Glucose-oxidase like catalytic mechanism of noble metal nanozymes[J]. Nat. Commun., 2021, 12(1): 3375. doi: 10.1038/s41467-021-23737-1
SANG X Q, XIA S Y, CHENG L, WU F X, TIAN Y, GUO C X, XU G B, YUAN Y L, NIU W X. Deciphering the mechanisms of photoenhanced catalytic activities in plasmonic Pd-Au heteromeric nanozymes for colorimetric analysis[J]. Small, 2023, 20(3): 2305369.
WEI H, WANG E K. Nanomaterials with enzyme-like characteristics (nanozymes): Next-generation artificial enzymes[J]. Chem. Soc. Rev., 2013, 42(14): 6060-6093. doi: 10.1039/c3cs35486e
WANG Q Q, WEI H, ZHANG Z Q, WANG E K, DONG S J. Nanozyme: An emerging alternative to natural enzyme for biosensing and immunoassay[J]. TrAC Trend. Anal. Chem., 2018, 105: 218-224. doi: 10.1016/j.trac.2018.05.012
WU J J X, WANG X Y, WANG Q, LOU Z P, LI S R, ZHU Y Y, QIN L, WEI H. Nanomaterials with enzyme like characteristics (nanozymes): Next generation artificial enzymes(Ⅱ)[J]. Chem. Soc. Rev., 2019, 48(4): 1004-1076. doi: 10.1039/C8CS00457A
LIU C, ZHANG M, GENG H Q, ZHANG P, ZHENG Z, ZHOU Y L, HE W W. NIR enhanced peroxidase-like activity of Au@CeO2 hybrid nanozyme by plasmon-induced hot electrons and photothermal effect for bacteria killing[J]. Appl. Catal. B-Environ., 2021, 295: 120317. doi: 10.1016/j.apcatb.2021.120317
LIU C, YAN Y Y, ZHANG X W, MAO Y Y, REN X Q, HU C Y, HE W W, YIN J J. Regulating the proand anti-oxidant capabilities of bimetallic nanozymes for the detection of Fe and protection of pigments[J]. Nanoscale, 2020, 12(5): 3068-3075. doi: 10.1039/C9NR10135G
LIU W L, ZHANG Y H, WEI G, ZHANG M X, LI T, LIU Q Y, ZHOU Z J, DU Y, WEI H. Integrated cascade nanozymes with antisenescence activities for atherosclerosis therapy[J]. Angew. Chem.-Int. Edit., 2023, 62(33): e202304465. doi: 10.1002/anie.202304465
CHENG P, WANG H, SHI X H. The effect of phenylalanine ligands on the chiral-selective oxidation of glucose on Au (111)[J]. Nanoscale, 2020, 12(5): 3050-3057. doi: 10.1039/C9NR09506C
SUN Y H, ZHAO C Q, GAO N, REN J S, QU X G. Stereoselective nanozyme based on ceria nanoparticles engineered with amino acids[J]. Chem.-Eur. J., 2017, 23(72): 18146-18150. doi: 10.1002/chem.201704579
ZHOU Y, WEI Y, REN J S, QU X G. A chiral covalent organic framework (COF) nanozyme with ultrahigh enzymatic activity[J]. Mater. Horiz., 2020, 7(12): 3291-3297. doi: 10.1039/D0MH01535K
ZHOU Y, WEI W L, CUI F C, YAN Z Q, SUN Y H, REN J S, QU X G. Construction of a chiral artificial enzyme used for enantioselective catalysis in live cells[J]. Chem. Sci., 2020, 11(41): 11344-11350. doi: 10.1039/D0SC03082A
ZHOU Y, SUN H J, XU H C, MATYSIAK S, REN J S, QU X G. Mesoporous encapsulated chiral nanogold for use in enantioselective reactions[J]. Angew. Chem.-Int. Edit., 2018, 57(51): 16791-16795. doi: 10.1002/anie.201811118
ZHAN P F, WANG Z G, LI N, DING B Q. Engineering gold nanoparticles with DNA ligands for selective catalytic oxidation of chiral substrates[J]. ACS Catal., 2015, 5(3): 1489-1498. doi: 10.1021/cs5015805
SHA M, RAO L, XU W Q, QIN Y, SU R A, WU Y, FANG Q, WANG H J, CUI X W, ZHENG L R, GU W L, ZHU C Z. Amino-ligand-coor-dinated dicopper active sites enable catechol oxidase like activity for chiral recognition and catalysis[J]. Nano Lett., 2023, 23(2): 701709.
FANG Y X, LIU X, AI J, ZHAO G, CHEN L W, CHE S N, HAN L. Enantiospecific affinities of chiral Cu films for both D-ribose and L-amino acids[J]. Chem. Mater., 2023, 35(6): 2402-2407. doi: 10.1021/acs.chemmater.2c03534
RAO M, FAN C Y, JI J C, LIANG W T, WEI L L, ZHANG D J, YAN Z Q, WU W H, YANG C. Catalytic chiral photochemistry sensitized by chiral hosts grafted upconverted nanoparticles[J]. ACS Appl. Mater. Interfaces, 2022, 14(18): 21453-21460. doi: 10.1021/acsami.2c02313
NEGRÍN-MONTECELO Y, MOVSESYAN A, GAO J, BURGER S, WANG Z M, NLATE S, POUGET E, ODA R, COMESAÑA-HERMO M, GOVOROV A O, CORREA-DUARTE M A. Chiral generation of hot carriers for polarization sensitive plasmonic photocatalysis[J]. J. Am. Chem. Soc., 2022, 144(4): 1663-1671. doi: 10.1021/jacs.1c10526
LIU C, SUN L C, YANG G Z, CHENG Q Q, WANG C, TAO Y L, SUN X H, WANG Z X, ZHANG Q F. Chiral Au-Pd alloy nanorods with tunable optical chirality and catalytically active surfaces[J]. Small, 2023, 20(23): 2310353.
ZHANG M L, ZHANG W R, FAN X, MA Y R, HUANG H, WANG X T, LIU Y, LIN H P, LI Y Y, TIAN H, SHAO M W, KANG Z H. Chiral carbon dots derived from serine with well-defined structure and enantioselective catalytic activity[J]. Nano Lett., 2022, 22(17): 7203-7211. doi: 10.1021/acs.nanolett.2c02674
ZHANG M L, FAN X, DU X, MA Y R, WANG X T, HUANG H, LIU Y, LI Y Y, KANG Z H. Chiral carbon dots from glucose by room temperature alkali assisted synthesis for electrocatalytic oxidation of tryptophan enantiomers[J]. Nano Res., 2023, 16(7): 8929-8936. doi: 10.1007/s12274-023-5601-6
LI F, LI S, GUO X C, DONG Y H, YAO C, LIU Y P, SONG Y G, TAN X L, GAO L Z, YANG D Y. Chiral carbon dots mimicking topoisomerase Ⅰ to mediate the topological rearrangement of supercoiled DNA enantioselectively[J]. Angew. Chem.-Int. Edit., 2020, 59(27): 11087-11092. doi: 10.1002/anie.202002904
WENG Y, WANG Q, ZHANG C, HE Y, RAN X, KUANG Y, LIU R, GUO L. Near-infrared photothermal therapy of chiral Au helicoids with broadband optical absorption[J]. New J. Chem., 2023, 47(2): 882-890. doi: 10.1039/D2NJ03779C
SUN M Z, XU L G, BANHG J H, KUANG H, ALBEN S, KOTOV N A, XU C L. Intracellular localization of nanoparticle dimers by chirality reversal[J]. Nat. Commun., 2017, 8(1): 1847. doi: 10.1038/s41467-017-01337-2
ZHANG N N, SUN H R, LIU S, XING Y C, LU J, PENG F, HAN C L, WEI Z, SUN T, YANG B, LIU K. Gold nanoparticle enantiomers and their chiral-morphology dependence of cellular uptake[J]. CCS Chem., 2022, 4(2): 660-670. doi: 10.31635/ccschem.021.202000637
XU L G, WANG X X, WANG W W, SUN M Z, CHOI W J, KIM J Y, HAO C L, LI S, QU A H, LU M R, WU X L, COLOMBARI F M, GOMES W R, BLANCO A L, DE MOURA A F, GUO X, KUANG H, KOTOV N A, XU C L. Enantiomer dependent immunological response to chiral nanoparticles[J]. Nature, 2022, 601(7893): 366. doi: 10.1038/s41586-021-04243-2
KIM R M, HUH J H, YOO S, KIM T G, KIM C, KIM H, HAN J H, CHO N H, LIM Y C, IM S W, IM E, JEONG J R, LEE M H, YOON T Y, LEE H Y, PARK Q H, LEE S, NAM K T. Enantioselective sensing by collective circular dichroism[J]. Nature, 2022, 612(7940): 470. doi: 10.1038/s41586-022-05353-1
Figure 1 Concept of chirality and the detection method of chiral substances: (A) typical structure of chiral molecules of L/D-Cys; (B) left- and right-handed variants of quartz (SiO2) crystal, the trigonal scalenohedral crystal structure of calcite (CaCO3), and the surface CaO6 octahedra structure of the ($3\bar 1\bar 2$) face (upper) and the ($21 \overline{3}$) face (below)[3](Copyright 2003, Springer Nature); (C) CD spectrometer schematic
Figure 2 Construction of chiral nanostructures based on inorganic NPs: (A) an array of intrinsically chiral Au helices fabricated using direct laser writing that performs prominent transmittance difference between incident LCP and RCP[32] (Copyright 2009, AAAS); (B) DNA-directed chiral assembly of Au NPs with chiroptical activity (left) and CD spectra (right)[42] (Copyright 2012, Springer Nature); (C) CD spectra and SEM images of L-Cys (up) and D-Cys (down)[43] (Copyright 2018, Springer Nature); (D) chiral Au NRs with quasihelical surface patterns generated by the templating effect of chiral bi-surfactant micelles[57] (Copyright 2020, AAAS)
Figure 3 Chiral inorganic nanocatalysts for electrochemical and enzyme-mimicked biosensing
Figure 4 Inorganic nanocatalysts with chiral molecules for electrochemical biosensing: (A) schematic illustration of the electrochemical cell used in the study[70] (Copyright 2022, Springer Nature); (B) schematic illustration of the synthetic process of L-D-Cys@ N-CuO/CoO NFs and the enantioselective catalysis and detection of enantiomers by L-D-Cys@N-CuO/CoO NFs through electrogenerated chemiluminescence (ECL) signals[71] (Copyright 2021, American Chemical Society)
Figure 5 Surface atomic structures of chiral Au NPs: (A) stereographic projection (triangle) that enumerates all possible surface orientations of an fcc lattice with illustrations of the three high-symmetry, achiral, and low-Miller-index planes represented by the vertices of the triangle[72] (Copyright 2020, Springer Nature); (B) Three-dimensional images of the adsorption structures of D- and L-Cys[73] (Copyright 2006, American Physical Society)
Figure 6 Chiral nanocatalysts with intrinsic chirality for electrochemical biosensing: (A) selective synthesis diagram of Ser from the electrocatalytic reduction of CO2 with NH3 on chiral Cu surfaces (left) and Faraday efficiency and mass spectrum (right)[74] (Copyright 2023, Elsevier); (B) chiral Au nanocrystals exhibited remarkable enantioselective recognition properties of these homochiral surfaces (left) and efficient electrochemical performance for chiral discrimination of L-/D-tryptophan (right)[80] (Copyright 2022, American Chemical Society); (C) chiral electrocatalytic activities of concave chiral Vortex cube (VC) Au NPs toward the electrooxidation of the tryptophan (Trp) enantiomer[47] (Copyright 2024, American Chemical Society); (D) morphology features (left) and electrochemical characterization (right) of the 432 helicoid Ⅲ NPs (NPs) for the oxidation of glucose[81] (Copyright 2024, American Chemical Society)
Figure 7 Concept and applications of nanozyme: (A) schematic diagram of Fe3O4 magnetic nanoparticles (MNPs) catalyzing the oxidation of various peroxidase substrates in the presence of H2O2 to produce different color reactions[82] (Copyright 2007, Springer Nature); (B) schematic illustration of the MSe1 cascade nanozyme with antisenescence and antioxidant activities for atherosclerosis therapy[91] (Copyright 2023, Wiley VCH)
Figure 8 Inorganic nanocatalysts with chiral molecules for enzyme-mimicked catalytic biosensing: (A) enantioselective oxidation of chiral DOPA by D-Cys/L-Cys@AuNPs-EMSN (left), L-Cys and L-DOPA hydrogen bonds formation on a gold nanoparticle (orange) and L-Cys and D-DOPA hydrogen bond formation on a gold nanoparticle (middle), and absorbance change (right)[96] (Copyright 2018, Wiley VCH); (B) schematic illustration of chiral differentiation between the glu enantiomers by the catalytic DNA-capped AuNPs and hybridization-engineered chiral differentiation between the substrate enantiomers[97](Copyright 2015, American Chemical Society); (C) chiral His-coordinated copper core onto Zr-based MOF basic backbones to structurally mirror the bimetal active site for chiral recognition and catalysis (left) and linear relationship between L/D-DOPA and MOF-L-His-Cu (right)[98] (Copyright 2023, American Chemical Society)
Figure 9 Intrinsically chiral nanocatalysts for enzyme-mimicked catalytic biosensing: (A) schematic (left) and photodegradation profiles (right) of rhodamine B (RhB) in the presence of a chiral catalyst with circularly polarized light[101] (Copyright 2023, American Chemical Society); (B) regulation of intrinsically chiral helical AuPd alloy nanozyme activity by circularly polarized light[102] (Copyright 2024, Wiley VCH); (C) chiral CDs mimicking topoisomerase Ⅰ to mediate the topological rearrangement of supercoiled DNA enantioselectively[105] (Copyright 2020, Wiley VCH)
Figure 10 Inorganic nanocatalysts with chiral molecules for biomedical applications: (A) (left) confocal fluorescence microscopy and (right) flow cytometry analysis results of yeast cells treated with different conditions (Scale bar: 20 μm)[95] (Copyright 2020, Royal Society of Chemistry); (B) schematics of NP dimers in a model cell (left), schematics of dimers' geometry (middle), and simulated CD spectra of NP dimers (right)[107] (Copyright 2017, Springer Nature)
Figure 11 Intrinsically chiral nanocatalysts for biomedical applications: (A) schematic illustration of the chiral morphology⁃dependent cellular uptake for chiral Au NOPs (left) and the corresponding cellular uptake efficiencies (right)[108] (Copyright 2021, Chinese Chemical Society); (B) schematic illustration of the chirality⁃dependent interaction of chiral Au NPs with extracellular chiral chains of EGF⁃like domains on cellular AGPCR receptors (left) and binding affinity Ka (right)[109] (Copyright 2022, Springer Nature)
Figure 12 Biosensing using collective CD mode: (A) schematic illustration of enantioselective sensing using a 2D chiral Au helicoid crystal based on the collective CD; (B) schematic illustration of the optical setup for polarization colorimetry and chirality sensor based on the collective CD (left) and color transition paths of 2D helicoid crystals plotted in CIExy 1931 colour space (right)[110] (Copyright 2022, Springer Nature)
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