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Quantitative determination and in situ monitoring of molecular chirality at extremely low concentrations is still challenging with simple optics because of the molecular-scale mismatch with the incident light wavelength. Advances in spectroscopy1-4 and nanophotonics have successfully lowered the detection limit in enantioselective sensing, as it can bring the microscopic chiral characteristics of molecules into the macroscopic scale5-7 or squeeze the chiral light into the subwavelength scale8-17. Conventional nanophotonic approaches depend mainly on the optical helicity density8,9 by localized resonances within an individual structure, such as localized surface plasmon resonances (LSPRs)10-16 or dielectric Mie resonances17. These approaches use the local chiral hotspots in the immediate vicinity of the structure, whereas the handedness of these hotspots varies spatially. As such, these localized resonance modes tend to be error-prone to the stochasticity of the target molecular orientations, vibrations and local concentrations18,19. Here we identified enantioselective characteristics of collective resonances (CRs)20 arising from assembled 2D crystals of isotropic, 432-symmetric chiral gold nanoparticles (helicoids)21,22. The CRs exhibit a strong and uniform chiral near field over a large volume above the 2D crystal plane, resulting from the collectively spinning, optically induced dipoles at each helicoid. Thus, energy redistribution by molecular back action on the chiral near field shifts the CRs in opposite directions, depending on the handedness of the analyte, maximizing the modulation of the collective circular dichroism (CD).
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Molecular chirality is represented as broken mirror symmetry in the structural orientation of constituent atoms and plays a pivotal role at every scale of nature. Since the discovery of the chiroptic property of chiral molecules, the characterization of molecular chirality is important in the fields of biology, physics, and chemistry. Over the centuries, the field of optical chiral sensing was based on chiral light-matter interactions between chiral molecules and polarized light. Starting from simple optics-based sensing, the utilization of plasmonic materials that could control local chiral light-matter interactions by squeezing light into molecules successfully facilitated chiral sensing into noninvasive, ultrasensitive, and accurate detection. In this Review, the importance of plasmonic materials and their engineering in chiral sensing are discussed based on the principle of chiral light-matter interactions and the theory of optical chirality and chiral perturbation; thus, this Review can serve as a milestone for the proper design and utilization of plasmonic nanostructures for improved chiral sensing.
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Chiral plasmonic nanostructures have facilitated a promising method for manipulating the polarization state of light. While a precise structural modification at the nanometer-scale-level could offer chiroptic responses at various wavelength ranges, a system that allows fast response control of a given structure has been required. In this study, we constructed uniformly arranged chiral gold helicoids with cobalt thin-film deposition that exhibited a strong chiroptic response with magnetic controllability. Tunable circular dichroism (CD) values from 0.9° to 1.5° at 550 nm wavelength were achieved by reversing the magnetic field direction. In addition, a magnetic circular dichroism (MCD) study revealed that the gap structure and size-related surface plasmon resonance induced MCD peaks. We demonstrated the transmitted color modulation, where the color dynamically changed from green-to-red, by controlling the field strength and polarizer axis. We believe current work broadens our understanding of magnetoplasmonic nanostructure and expands its potential applicability in optoelectronics or optical-communications.
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Ouro , Ressonância de Plasmônio de Superfície , Ouro/química , Ressonância de Plasmônio de Superfície/métodos , Dicroísmo Circular , Campos Magnéticos , CobaltoRESUMO
Linear optical methods of determining the chirality of organic and inorganic materials have relied on weak chiral optical (chiroptical) effects. Nonlinear chiroptical characterization holds the potential of much greater sensitivity and smaller interaction volumes. However, suitable materials on which to perform measurements have been lacking for decades. Here, we present the first nonlinear chiroptical characterization of crystallographic chirality in gold helicoids (≈150 nm size) and core/shell helicoids with the newly discovered hyper-Rayleigh scattering optical activity (HRS OA) technique. The observed chiroptical signal is, on average, originating from between ≈0.05 and ≈0.13 helicoids, i.e., less than a single nanoparticle. The measured HRS OA ellipticities reach ≈3°, for a concentration ≈109 times smaller than that of chiral molecules with similar nonlinear chiroptical response. These huge values indicate that the helicoids are excellent candidates for future nonlinear chiroptical materials and applications.
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Over the last two decades, nanophotonics, including plasmonics and metamaterials, have promised compelling opportunities for exotic control over light-matter interactions. The strong chiral light-matter interaction is a representative example. Three-dimensional (3D) chirality has existed naturally only in organic molecules and bio-organisms, but a negligible chiroptic effect was attained with these naturally occurring materials because of their small absorption cross sections. However, inspired by biological chirality, nanophotonic chiral materials have greatly expanded the design space of accessible chiroptic effects (e.g., pushing the chiral light-matter interaction to an exceptional regime, such as a broad-band circular polarizer, negative refractive index, and sensitive chiral sensing). Nevertheless, it is still a challenge to achieve precisely defined and dynamically reconfigurable chiral morphologies that further increase the chiroptic effect. Biological systems continue to inspire approaches to the design and synthesis of precisely defined 3D nanostructures. In particular, a living organism can program the evolutionary pathway of highly complexed 3D chiral morphology precisely from the molecular scale to the macroscopic scale while simultaneously enabling dynamic reconfiguration of their chirality. What if we could harness the power of biological selectivity and evolutionary capability in synthesizing chiral plasmonic materials? We envisioned that platform technology mimicking biological principles would enable control of 3D chiral structures for effective plasmonic interactions with polarized light and further impart the concept of time-dependent evolution (3D + 1D = 4D) to bring about responsive and dynamic changes in chiral plasmonics. In this Account, we review our efforts to develop the biomolecule-based synthesis of 3D chiral plasmonic materials and share the vision that as in biological systems, chirality can be programmed at the molecular level and hierarchically transferred at multiple scales to develop macroscopic chirality. Accompanied by a biomimetic time-dependent chirality of singular plasmonic nanometals, we also summarize recent achievements in the chemistry and nanophotonics communities pursuing 4D plasmonics that are closely related to our research. The biomimetic and bioinspired approaches discussed in this Account will provide new synthetic insights into implementing chiral nanomaterials and extend the range of accessible nanophotonic design. We hope that the molecular encoding approach will be useful to achieve dynamic light-matter interactions at unprecedented dimensions, time scales, and chirality.
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Biomimética/métodos , EstereoisomerismoRESUMO
Chiral optical metamaterials with delicate structures are in high demand in various fields because of their strong light-matter interactions. Recently, a scalable strategy for the synthesis of chiral plasmonic nanoparticles (NPs) using amino acids and peptides has been reported. Reported herein, 3D chiral gold NPs were synthesized using dipeptide γ-Glu-Cys and Cys-Gly and analyzed crystallographically. The γ-Glu-Cys-directed NPs present a cube-like outline with a protruding chiral wing. In comparison, the NPs synthesized with Cys-Gly exhibited a rhombic dodecahedron-like outline with curved edges and elliptical cavities on each face. Morphology analysis of intermediates indicated that γ-Glu-Cys generated an intermediate concave hexoctahedron morphology, while Cys-Gly formed a concave rhombic dodecahedron. NPs synthesized with Cys-Gly are named 432 helicoidâ V because of their unique morphology and growth pathway.
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The fundamental challenge in designing transparent pressure sensors is the ideal combination of high optical transparency and high pressure sensitivity. Satisfying these competing demands is commonly achieved by a compromise between the transparency and usage of a patterned dielectric surface, which increases pressure sensitivity, but decreases transparency. Herein, a design strategy for fabricating high-transparency and high-sensitivity capacitive pressure sensors is proposed, which relies on the multiple states of nanoparticle dispersity resulting in enhanced surface roughness and light transmittance. We utilize two nanoparticle dispersion states on a surface: (i) homogeneous dispersion, where each nanoparticle (≈500 nm) with a size comparable to the visible light wavelength has low light scattering; and (ii) heterogeneous dispersion, where aggregated nanoparticles form a micrometer-sized feature, increasing pressure sensitivity. This approach is experimentally verified using a nanoparticle-dispersed polymer composite, which has high pressure sensitivity (1.0 kPa-1 ), and demonstrates excellent transparency (>95%). We demonstrate that the integration of nanoparticle-dispersed capacitor elements into an array readily yields a real-time pressure monitoring application and a fully functional touch device capable of acting as a pressure sensor-based input device, thereby opening up new avenues to establish processing techniques that are effective on the nanoscale yet applicable to macroscopic processing.
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The assembly of micro- and nanomaterials is a key issue in the development of potential bottom-up construction of building blocks, but creating periodic arrays of such materials in an efficient and scalable manner still remains challenging. Here, we show that a cymatic assembly approach in which micro- and nanomaterials in a liquid medium that resonate at low-frequency standing waves can be used for the assembly in a spatially periodic and temporally stationary fashion that emerges from the wave displacement antinodes of the standing wave. We also show that employing a two-dimensional liquid, rather than a droplet, with a coffee-ring effect yields a result that exhibits distinct lattice equivalents comprising the materials. The crystallographic parameters, such as the lattice parameters, can be adjusted, where the parameters along the x- and y-axes are controlled by the applied wave frequencies, and the one along z-axis is controlled by a transparent layer as a spacer to create three-dimensional crystal equivalents. This work represents an advancement in assembling micro- and nanomaterials into macroscale architectures on the centimeter-length scale, thus establishing that a standing wave can direct micro- and nanomaterial assembly to mimic plane and space lattices.
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The development of subunit vaccines that mimic the molecular complexity of attenuated vaccines has been limited by the difficulty of intracellular co-delivery of multiple chemically diverse payloads at controllable concentrations. We report on hierarchical hydrogel depots employing simple poly(propylene sulfone) homopolymers to enable ratiometric loading of a protein antigen and four physicochemically distinct adjuvants in a hierarchical manner. The optimized vaccine consisted of immunostimulants either adsorbed to or encapsulated within nanogels, which were capable of noncovalent anchoring to subcutaneous tissues. These 5-component nanogel vaccines demonstrated enhanced humoral and cell-mediated immune responses compared to formulations with standard single adjuvant and antigen pairing. The use of a single simple homopolymer capable of rapid and stable loading and intracellular delivery of diverse molecular cargoes holds promise for facile development and optimization of scalable subunit vaccines and complex therapeutic formulations for a wide range of biomedical applications.
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Chiral metal oxide nanostructures have received tremendous attention in nanotechnological applications owing to their intriguing chiroptical and magnetic properties. Current synthetic methods mostly rely on the use of amino acids or peptides as chiral inducers. Here, we report a general approach to fabricate chiral metal oxide nanostructures with tunable magneto-chiral effects, using block copolymer (BCP) inverse micelle and R/S-mandelic acid (MA). Diverse chiral metal oxide nanostructures are prepared by the selective incorporation of precursors within micellar cores followed by the oxidation process, exhibiting intense chiroptical properties with a g-factor up to 7.0 × 10-3 in the visible-NIR range for the Cr2O3 nanoparticle multilayer. The BCP inverse micelle is found to inhibit the racemization of MA, allowing MA to act as a chiral dopant that imparts chirality to nanostructures via hierarchical chirality transfer. Notably, for paramagnetic nanostructures, magneto-chiroptical modulation is realized by regulating the direction of the external magnetic field. This BCP-driven approach can be extended to the mass production of chiral nanostructures with tunable architectures and optical activities, which may provide insights into the development of chiroptical functional materials.
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Quantitative analysis of chiral molecules in various solvents is essential. However, there are still many challenges to enhancing the sensitivity in precisely determining both concentration and chirality. Here, we built an algorithmic methodology to predict and optimally design the chiroptical response of chiral plasmonic sensors for a specific target chiral analyte with the aid of deep learning. Based upon the analytic and intuitive understanding of the Born-Kuhn type plasmonic nanodimer, we designed and trained the neural networks that can successfully predict the chiroptical properties and further inversely design the plasmonic structure to achieve the intended circular dichroism. The developed algorithm could identify the optimum structure exhibiting the maximum sensitivity for the given specific analytes. Surprisingly, we discovered that sensitivity strongly depends on the various conditions of analytes and can be finely tuned with the structural parameters of plasmonic nanodimers. We envision that this study can provide a general platform to develop ultrasensitive chiral plasmonic sensors whose structure and sensitivity have been evolved algorithmically for adoption in specific applications.
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Identifying the three-dimensional (3D) crystal plane and strain-field distributions of nanocrystals is essential for optical, catalytic, and electronic applications. However, it remains a challenge to image concave surfaces of nanoparticles. Here, we develop a methodology for visualizing the 3D information of chiral gold nanoparticles ≈ 200 nm in size with concave gap structures by Bragg coherent X-ray diffraction imaging. The distribution of the high-Miller-index planes constituting the concave chiral gap is precisely determined. The highly strained region adjacent to the chiral gaps is resolved, which was correlated to the 432-symmetric morphology of the nanoparticles and its corresponding plasmonic properties are numerically predicted from the atomically defined structures. This approach can serve as a comprehensive characterization platform for visualizing the 3D crystallographic and strain distributions of nanoparticles with a few hundred nanometers, especially for applications where structural complexity and local heterogeneity are major determinants, as exemplified in plasmonics.
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Nanopartículas Metálicas , Nanopartículas Metálicas/química , Ouro/química , Difração de Raios X , CatáliseRESUMO
While plasmonic particles can provide optical resonances in a wide spectral range from the lower visible up to the near-infrared, often, symmetry effects are utilized to obtain particular optical responses. By breaking certain spatial symmetries, chiral structures arise and provide robust chiroptical responses to these plasmonic resonances. Here, we observe strong chiroptical responses in the linear and nonlinear optical regime for chiral L-handed helicoid-III nanoparticles and quantify them by means of an asymmetric factor, the so-called g-factor. We calculate the linear optical g-factors for two distinct chiroptical resonances to -0.12 and -0.43 and the nonlinear optical g-factors to -1.45 and -1.63. The results demonstrate that the chirality of the helicoid-III nanoparticles is strongly enhanced in the nonlinear regime.
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The quantitative detection of circularly polarized light (CPL) is necessary in next-generation optical communication carrying high-density information and in phase-controlled displays exhibiting volumetric imaging. In the current technology, multiple pixels of different wavelengths and polarizers are required, inevitably resulting in high loss and low detection efficiency. Here, we demonstrate a highly efficient CPL-detecting transistor composed of chiral plasmonic nanoparticles with a high Khun's dissymmetry (g-factor) of 0.2 and a high mobility conducting oxide of InGaZnO. The device successfully distinguished the circular polarization state and displayed an unprecedented photoresponsivity of over 1 A/W under visible CPL excitation. This observation is mainly attributed to the hot electron generation in chiral plasmonic nanoparticles and to the effective collection of hot electrons in the oxide semiconducting transistor. Such characteristics further contribute to opto-neuromorphic operation and the artificial nervous system based on the device successfully performs image classification work. We anticipate that our strategy will aid in the rational design and fabrication of a high-performance CPL detector and opto-neuromorphic operation with a chiral plasmonic structure depending on the wavelength and circular polarization state.
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Precise control of morphology and optical response of 3-dimensional chiral nanoparticles remain as a significant challenge. This work demonstrates chiral gold nanoparticle synthesis using single-stranded oligonucleotide as a chiral shape modifier. The homo-oligonucleotide composed of Adenine nucleobase specifically show a distinct chirality development with a dissymmetric factor up to g ~ 0.04 at visible wavelength, whereas other nucleobases show no development of chirality. The synthesized nanoparticle shows a counter-clockwise rotation of generated chiral arms with approximately 200 nm edge length. The molecular dynamics and density functional theory simulations reveal that Adenine shows the highest enantioselective interaction with Au(321)R/S facet in terms of binding orientation and affinity. This is attributed to the formation of sequence-specific intra-strand hydrogen bonding between nucleobases. We also found that different sequence programming of Adenine-and Cytosine-based oligomers result in chiral gold nanoparticles' morphological and optical change. These results extend our understanding of the biomolecule-directed synthesis of chiral gold nanoparticles to sequence programmable deoxyribonucleic acid and provides a foundation for programmable synthesis of chiral gold nanoparticles.
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Ouro , Nanopartículas Metálicas , Adenina , Ouro/química , Nanopartículas Metálicas/química , OligonucleotídeosRESUMO
A novel combination of machine learning algorithms is proposed for the differentiation of distinct spectra in a large electron energy loss spectroscopy spectrum image (EELS-SI) dataset. For clustering of the EEL spectra including similar fine structures in an efficient space, linear and nonlinear dimensionality reduction methods are used to project the EEL spectra onto a low-dimensional space. Then, a density-based clustering algorithm is applied to distinguish the meaningful data clusters. By applying this strategy to various experimental EELS-SI datasets, differentiation of several groups of EEL spectra representing specific fine structures was achieved. It is possible to investigate particular fine structures by averaging all of the spectra in each cluster. Also, the spatial distributions of each cluster in the scanning regions can be observed, which enables investigation of the locations of different fine structures in materials. This method does not require any prior knowledge, i.e., it is a data-driven analysis; therefore, it can be applied to any hyperspectral image.
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Chiral inorganic nanomaterials have revealed opportunities in various fields owing to their strong light-matter interactions. In particular, chiral metal oxide nanomaterials that can control light and biochemical reactions have been highlighted due to their catalytic activity and biocompatibility. In this study, we present the synthesis of chiral cobalt oxide nanoparticles with a g-factor of 0.01 in the UV-visible region using l- and d-Tyr-Tyr-Cys ligands. The conformation of the Tyr-Tyr-Cys peptide on the nanoparticle surfaces was identified by 2D NMR spectroscopy analysis. In addition, the sequence effect of Tyr-Tyr-Cys developing chiral nanoparticles was analyzed. The revealed peptide structure, along with the experimental results, demonstrate the important role of the thiol group and carboxyl group of the Tyr-Tyr-Cys ligand in chirality evolution. Importantly, due to the magnetic properties of chiral cobalt oxide nanoparticles and their strong absorption in the UV region, the circular dichroism (CD) responses can be dramatically modulated under an external magnetic field.
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Nanopartículas , Cobalto , Conformação Molecular , Óxidos , PeptídeosRESUMO
Chirality is a basic property of nature and has great importance in photonics, biochemistry, medicine, and catalysis. This importance has led to the emergence of the chiral inorganic nanostructure field in the last two decades, providing opportunities to control the chirality of light and biochemical reactions. While the facile production of 3D nanostructures has remained a major challenge, recent advances in nanocrystal synthesis have provided a new pathway for efficient control of chirality at the nanoscale by transferring molecular chirality to the geometry of nanocrystals. Interestingly, this discovery stems from a purely crystallographic outcome: chirality can be generated on high-Miller-index surfaces, even for highly symmetric metal crystals. This is the starting point herein, with an overview of the scientific history and a summary of the crystallographic definition. With the advance of nanomaterial synthesis technology, high-Miller-index planes can be selectively exposed on metallic nanoparticles. The enantioselective interaction of chiral molecules and high-Miller-index facets can break the mirror symmetry of the metal nanocrystals. Herein, the fundamental principle of chirality evolution is emphasized and it is shown how chiral surfaces can be directly correlated with chiral morphologies, thus serving as a guide for researchers in chiral catalysts, chiral plasmonics, chiral metamaterials, and photonic devices.
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The process of memory and learning in biological systems is multimodal, as several kinds of input signals cooperatively determine the weight of information transfer and storage. This study describes a peptide-based platform of materials and devices that can control the coupled conduction of protons and electrons and thus create distinct regions of synapse-like performance depending on the proton activity. We utilized tyrosine-rich peptide-based films and generalized our principles by demonstrating both memristor and synaptic devices. Interestingly, even memristive behavior can be controlled by both voltage and humidity inputs, learning and forgetting process in the device can be initiated and terminated by protons alone in peptide films. We believe that this work can help to understand the mechanism of biological memory and lay a foundation to realize a brain-like device based on ions and electrons.
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Materiais Biomiméticos/química , Memória/fisiologia , Peptídeos/química , Prótons , Biomimética , Eletroquímica , Elétrons , Umidade , Aprendizagem/fisiologia , Sinapses/fisiologia , Transistores Eletrônicos , Tirosina/químicaRESUMO
Synthesis of chiral plasmonic materials has been highlighted for the last decades with their optical properties and versatile potential applications. Recently reported aqueous-based amino acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles with 432 point-group symmetry shows exceptionally high chiroptic response within 100 nm scales. Despite its already excellent chiroptic response, a single-nanoparticle dark field scattering study revealed that full chiroptic potential of chiral gold nanoparticle is limited with its overall synthetic uniformity. Based on this knowledge, we present a multi-chirality-evolution step synthesis method for the enhancement of chiroptic response through an increase in particle uniformity. Detailed time variant study and interrelationship study of reaction parameters allowed the systematic construction of design principles for chiral nanoparticles with exceptional chiroptic response. With the application of precisely controlled growth kinetic to two distinct growth regimes, modified chiral gold nanoparticles showed significantly improved uniformity, achieving an improved dissymmetry factor of g = 0.31. We expect that our strategy will aid in precise morphology and property control for chiral nanomaterials, which can be used in various plasmonic metamaterial applications.