Tunable Chiroptical Properties from the Plasmonic Band to Metal–Ligand Charge Transfer Band of Cysteine‐Capped Molybdenum Oxide Nanoparticles

Li, Yiwen; Cheng, Jiaji; Li, Jiagen; Zhu, Xi; He, Tingchao; Chen, Rui; Tang, Zikang

doi:10.1002/anie.201806093

Cited by 60 publications

(45 citation statements)

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“…[8] Chiral inorganic NPs have triggered great interest due to their easy synthesis and their tremendous applications including chiral sensing, [9] chiral separation, enantioselective catalysis,a nd advanced photonic devices. [10] Recently,c hiral metal oxides (Co 3 O 4 NPs, [11] MoO 3 NPs, [12] and WO 3Àx NPs [13] ), which exhibited intense optical activities in the visible range,h ave been synthesized using chiral ligands.S ome chiral metal sulfide nanomaterials such as HgS [14] and CdS [15] have also been prepared. These chiral NPs with deformations of the crystal lattices may be extended to other nanomaterials with tailorable chiroptical properties.Nanocrystalline copper sulfide (Cu 2Àx S) is ap -type semiconductor and am aterial of particular interest due to its promising applications in biomedicine, [16] and optoelectronic conversion (photovoltaics,p hotocatalysis,a nd thermoelectrics).…”

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Chiral Semiconductor Nanoparticles for Protein Catalysis and Profiling

et al. 2019

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In this study,v ia as imple one-step method, chiral copper sulfide quantum dots (d/l-QDs) were prepared using d-/l-penicillamine (d-/l-Pen). The anisotropyfactor of d/l-QDs was as high as 0.01. The d/l-QDs can be used as photocatalysts to cleave proteins.N otably,t he l-QDs displayed the highest catalytic performance under left-circularly polarized light irradiation. Mechanistic investigations indicate the generation of hydroxylr adicals as the reactive species that cause the cutting of proteins.Chirality,which is usually based on organic molecules, [1] has been extended to inorganic nanomaterials such as metal nanoparticles (NPs), [2] carbon NPs, [3] semiconductor NPs, [4] ZnO films, [5] metaphotonic nanostructures, [6] NP assemblies with chiral geometries, [7] and so on. [8] Chiral inorganic NPs have triggered great interest due to their easy synthesis and their tremendous applications including chiral sensing, [9] chiral separation, enantioselective catalysis,a nd advanced photonic devices. [10] Recently,c hiral metal oxides (Co 3 O 4 NPs, [11] MoO 3 NPs, [12] and WO 3Àx NPs [13] ), which exhibited intense optical activities in the visible range,h ave been synthesized using chiral ligands.S ome chiral metal sulfide nanomaterials such as HgS [14] and CdS [15] have also been prepared. These chiral NPs with deformations of the crystal lattices may be extended to other nanomaterials with tailorable chiroptical properties.Nanocrystalline copper sulfide (Cu 2Àx S) is ap -type semiconductor and am aterial of particular interest due to its promising applications in biomedicine, [16] and optoelectronic conversion (photovoltaics,p hotocatalysis,a nd thermoelectrics). [17] Endowing chirality to Cu 2Àx Sn anomaterials could enable aw ider range of potential applications for chiral Cu 2Àx Si nb iology,c hemistry,a nd physics.H owever, to date,n op ublications are available on the synthesis and application of chiral Cu 2Àx Snanomaterials.Circularly polarized light (CPL), one of the most attractive chiral sources,has been used to activate chiral assemblies to probe metal ions, [18] trigger photochemical reactions, [19] and fabricate chiral nanostructures. [20] Kotov et al. reported the use of right-(left-) handed CPL to assemble racemic CdTe

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Chiral Semiconductor Nanoparticles for Protein Catalysis and Profiling

et al. 2019

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“…For the first mechanism, due to the microscopic feature, the most common way to treat it is to use atomistic calculations, for example, density function theory (DFT) in which the molecular chirality is transferred to the excitons in NCs through the orbital hybridization effect between the electronic states of the NCs and orbital wavefunctions of the chiral molecule. [12,27,28] While for the Coulomb interactions, as Figure 1. Inorganic nanostructures with chirality: A) intrinsically chiral NCs or lattice, B) nanostructures with chiral shape, C) chiral arrangement of achiral nanoparticles, and D) achiral nanoparticle capped with chiral molecules on the surface.…”

Section: Chirality Theory In Tmo Nanostructuresmentioning

confidence: 99%

Chiral Transition Metal Oxides: Synthesis, Chiral Origins, and Perspectives

Wang

Miao³

et al. 2020

Advanced Materials

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to inorganic nanocrystals (NCs) whose unique physicochemical properties could be easily tuned by altering their size, shape, or ingredient, providing a powerful platform for exploring enhanced chiroptical effects, chirogenesis, and potentials in which chiral inorganic NCs could provide to interdisciplinary fields such as optical and biosensing, [2,3] chiral bioimaging, [4] and polarization-based display devices. [5] In general, chirality in inorganic NCs can be obtained from: [6,7] 1) intrinsic chirality formed by chiral crystals, lattice distortions, and defects, [8-10] 2) chiral shape with subwavelength dimensions, [11] 3) chirality transfer via chiral assembled nanostructures of achiral NCs, [5,12] and 4) chiral interactions of achiral NCs with chiral molecules [13] as depicted in Figure 1. The most famous property of chiral nanostructure is the optical activity which refers to the ability of a chiral unit to rotate the plane of plane polarized light. [14] In modern optics, this property is associated to the circular dichroism (CD) phenomenon, which concerns the absorption difference between left and right circularly polarized (LCP and RCP) light, therefore CD-based spectroscopies are generally regarded as powerful tools to detect chirality of a measured sample. With rapid development, a number of cutting-edge work concerning on chiral metal nanoparticles (NPs), chiral semiconductor NCs, chiral ceramics, and metal coordinate systems has been investigated recently. [6] Among them, chiral transition metal oxides (TMOs) are a newly discovered area attracting tremendous attentions because of their striking feature for nonstoichiometry even though great challenges on establishing systematic control over the synthesis and theoretical supports for chirality induction mechanisms still remain. Since the nature of metal-oxygen bonding in TMOs can vary from nearly ionic to covalent or metallic, the physicochemical properties of TMOs are strongly related to their outer d electrons. [15] When combined with chiral molecules, the overlap of the orbital of chiral molecules with the density of states of TMOs or formation of chiral surfaces can bring in tunable chirality for TMOs from UV-visible to near infrared region, endowing fascinating chiroptical properties. Therefore, herein, we emphasize recent progress on chiral TMOs in terms of their synthesis, CD effects, and possible mechanisms of induced optical chirality. In Section 2, theoretical background on the origin of induced chirality in TMOs nanostructures is briefly introduced. Section 3 will show recent progress of chiral TMOs with their synthetic Transition metal oxides (TMOs) consist of a series of solid materials, exhibiting a wide variety of structures with tunability and versatile physicochemical properties. Such a statement is undeniably true for chiral TMOs since the introduction of chirality brings in not only active optical activities but also geometrical anisotropy due to the symmetry-breaking effect. Although progressive investigations have been made for accu...

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“…The 2D nanomaterials are characterized by strong in‐plane covalent bonding and weak non‐covalent bonding (van der Waals forces) between layers . Among all of the studied 2D materials, transition metal oxides/sulfides as the active species have been explored for various optoelectronic applications, further modified atomically thin or defective active‐site nanomaterials have presented excellent electronic, mechanical and optical properties, which are totally different from their bulk counterparts . More importantly, the flexible 2D structures can be easily integrated into other systems, or stacked layer by layer in a precise way to form heterostructures with desired functionalities…”

Section: Figurementioning

confidence: 99%