Biomimetic Chiral Nanomaterials with Selective Catalysis Activity

Abstract

Chiral nanomaterials with unique chiral configurations and biocompatible ligands have been booming over the past decade for their interesting chiroptical effect, unique catalytical activity, and related bioapplications. The catalytic activity and selectivity of chiral nanomaterials have emerged as important topics, that can be potentially controlled and optimized by the rational biochemical design of nanomaterials. In this review, chiral nanomaterials synthesis, composition, and catalytic performances of different biohybrid chiral nanomaterials are discussed. The construction of chiral nanomaterials with multiscale chiral geometries along with the underlying principles for enhancing chiroptical responses are highlighted. Various biochemical approaches to regulate the selectivity and catalytic activity of chiral nanomaterials for biocatalysis are also summarized. Furthermore, attention is paid to specific chiral ligands, materials compositions, structure characteristics, and so on for introducing selective catalytic activities of representative chiral nanomaterials, with emphasis on substrates including small molecules, biological macromolecule, and in-site catalysis in living systems. Promising progress has also been emphasized in chiral nanomaterials featuring structural versatility and improved chiral responses that gave rise to unprecedented chances to utilize light for biocatalytic applications. In summary, the challenges, future trends, and prospects associated with chiral nanomaterials for catalysis are comprehensively proposed.

Keywords: biomimetic nanomaterials; chiroptical effects; selective catalysis activity.

Figure 1

A) CD spectra of chiral Au NPs with precise homochiral facets for chiral discrimination of L‐/D‐tryptophan. B) SEM images and corresponding geometric models of facets from D‐Cys, racemic Cys, and L‐Cys. g‐Factor spectra of chiral and achiral Au nanocrystals. C) SEM images of chiral trisoctahedral homochiral facets from D‐Cys, trisoctahedral from racemic Cys, and chiral trisoctahedral homochiral facets from L‐Cys, respectively. Upper scale bars: 200 nm, Downer scale 100 nm.^{[ 64 ]}

Figure 2

A) Schematic illustration of chiral CdTe nanoparticle, TEM, and high‐resolution TEM images of truncated tetrahedron‐shaped L‐Cys and D‐Cys CdTe nanoparticles, and their corresponding CD spectra.^{[ 116 ]} B) Schematic illustration of chiral semiconductor‐metal hetero‐nanorod and chiroptical properties.^{[ 124 ]} C,D) TEM images of D‐cys‐, or L‐cys‐CdSe@CdS nanorods C), and TEM of the D‐cys, D‐his CdSe@CdS‐Pt hetero‐nanorods (left) and L‐cys, L‐cys CdSe@CdS‐Pt hetero‐nanorods and the high‐resolution images D).

Figure 3

A) Schematic for the synthesis of chiral carbon dots and the TEM, high‐resolution TEM, and selected area electron diffraction pattern results. B) CD spectra and voltage‐dependent growth kinetics, and enantioselective catalytic activity of chiral carbon dots for DOPA enantiomers oxidation.^{[ 141 ]}

Figure 4

A) Schematic illustration of DNA functionalized Au NPs for the enantioselective oxidation of glucose enantiomers.^{[ 60 ]} B) Structure of Au NPs synthesized with D‐flga3 and L‐FlgA3, and corresponding Catalytic activity of D‐ and L‐peptide templated Au NPs for reduction of 4‐nitrophenol to 4‐aminophenol with catalysis selectivity.^{[ 59 ]} C) SEM images of the as‐synthesized D‐Cys‐Au and L‐Cys‐Au. D) The CD spectra. (E,F) The differential pulse voltammogram curves E) and selective catalytic oxidation of D‐Glu and L‐Glu in the presence of L‐ascorbic acid, urea, and chloride ions (F).^{[ 6 ]}

Figure 5

A) Schematic illustration for the synthesis of optically active gold core‐DNA‐silver shell NPs and their selective photocatalysis.^{[ 76 ]} B) The synthesis of a chiral encoded mesoporous bimetallic Pt‐Ir alloy supported on Ni foam. C) The corresponding asymmetric catalysis with chiral encoded Pt‐Ir alloy.^{[ 220 ].}

Figure 6

A) Representative structures of natural heme‐containing peroxidase (left) and yolk–shell‐structured artificial peroxidase (right), and the preparation procedures of the yolk–shell‐structured artificial peroxidase. B) The enantioselective oxidation of chiral tyrosinol catalyzed by Fe₃O₄@Poly(L‐/D‐Trp). C) TEM images of yolk–shell Fe₃O₄@Poly(L‐Trp), and Fe₃O₄@Poly(L‐Trp) NPs catalyze FITC‐L‐tyrosinol to label yeast cell (Scale bars: 10 mm).^{[ 102 ]} (D,E) Asymmetric biocatalysis of chiral alcohols by Fe₃O₄@helical multi‐walled carbon nanotubes and corresponding element mapping results (D). schematics of NADP+ hydrogenation by Fe²⁺ and Fe³⁺ on Fe₃O₄@ HCNTs. Batch reactions of NADP⁺ hydrogenation catalyzed by Fe₃O₄@HCNTs.^{[ 223 ]}

Figure 7

A) Structures of CuS nanotubes and the time‐dependent catalysis of chiral DOPA at 475 nm at 600 s intervals, and the mechanism of enantioselective oxidation of chiral DOPA by CuS.^{[ 37 ]} B) Schematic illustration for the sonication combined with ion intercalation for preparation of transition metal dichalcogenides chiral QDs, and the corresponding typical CD spectra.^{[ 48 ]}

Figure 8

A) The TEM and CD spectra of D‐/L‐penicillamine synthesized chiral copper sulfide QDs and the CPL triggered selective catalysis cleavage of BSA.^{[ 110 ]} B) Schematic illustration of CPL triggered chiral CdTe‐based specific DNA cleavage and the electrophoresis results of L‐Cys CdTe and D‐Cys CdTe nanoparticles with 1,839 bp DNA illuminated with 405 nm RCP/LCP for 2 h.^{[ 116 ]} C) Morphology and spectra characterization of chiral ZnS–Au supraparticles, the selective photocatalytic activity with L‐ZnS–Au SPs for different Tyr enantiomers and the corresponding binding frequency decreases in the order from D‐Pen‐D‐Tyr, L‐Pen‐L‐Tyr, L‐Pen‐D‐Tyr, to D‐Pen‐L‐Tyr.^{[ 25 ]}

Figure 9

A) The schematic illustration for chiral carbon Dots catalysis of plasmid DNA. B) The corresponding agarose gel electrophoresis for analysis of the selective catalysis of plasmid DNA.^{[ 229 ]}

Figure 10

A) Schematic illustration of the preparation process of MOF‐L(D)‐His Cu. The fabricated MOF‐L‐His‐Cu, chiral MOF‐L(D)‐His‐Cu as catechol oxidase mimic for chiral Dopa catalysis.^{[ 236 ]} B) Schematics of construction of a chiral COF nanozyme, which selectively catalyzed H₂O₂‐mediated oxidation of dopa enantiomers to corresponding dopachrome.^{[ 170 ]} C) Synthesis of Single 2D layer and crystal patterns of porphyrin‐containing COF‐Cu, Au@COF‐Cu, and Pd@COF‐Cu frameworks, and the corresponding TEM images (side and top views). The catalyzed model one‐pot asymmetric Henry reaction and catalyzed asymmetric coupling reactions.^{[ 245 ]}

Figure 11

A) Chiral ‐ITV framework with P4₁32 (top) or P4₃32 (bottom) enantiomorphic space groups show helicoidal spiral staircase‐like chain units of opposite handedness. The STEM analysis was employed to confirm the framework topology proposed, study the crystallinity of the materials, and provide additional information on the chirality of grupo de tamices moleculares‐3. B) Ring aperture of chiral trans‐stilbene oxide with 1‐hexanol giving inversion products. The enantiomeric excess of reactants increases with conversion, evidencing that one enantiomer reacts faster than the other.^{[ 247 ]}

Figure 12

A) Illustration of star‐like Ru‐Cu catalyst and the assembly with corresponding TEM mapping displayed circulation catalytic performance of Cat‐6 in asymmetric transfer hydrogenation of acetophenone.^{[ 85 ]} B) Schematic illustration of the fabrication of chiral Au NP films by utilizing Phe enantiomers as ligands. C) Photocatalytic activity evaluation of D‐Phe‐NP film or L‐Phe‐NP film for oxidation of glucose enantiomer.^{[ 188 ]}

Figure 13

A) Schematic illustration of the design of the chiral scaffolds for gold nanoparticles–lipid‐inspired peptide‐interdigitating amphiphiles by grafting an extended peptide domain to one alkyl tail of lipids either at the N‐ or C‐terminus of the domains. B) TEM images and schematic representation of supramolecular nanozymes. The changes of the UV/vis absorption intensity of the oxidation of L‐ or D‐DOPA as a function of time within the initial period.^{[ 248 ]}

Figure 14

Schematic illustration A) and results of the penicillamine‐modified Fe_xCu_ySe nanoparticles for the inhibition and disassembly of Aβ42 aggregation and mitigation of potential neurotoxicity in an AD mice model (B).^{[ 123 ]}

Figure 15

A) The preparation and intracellular catalysis activity of mesoporous silica‐Pd nanoparticles and structure characterizations. B–D) Targeted asymmetric transfer hydrogenation reaction catalyzed by mesoporous silica‐Pd nanoparticles for vivo anti‐inflammation. B) ROS imaging of lipopolysaccharide‐induced inflamed paws. C) Normalization of corresponding fluorescence intensities of ROS and prostaglandin E₂ level. D) Staining images of inflamed paws.^{[ 263 ]}