Chiral plasmonic sensing: From the perspective of light-matter interaction.

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.

Nanoscopic Observation of Chiro-Optical Force.

Nanoscopic observation of chiro-optical phenomena is essential in wide scientific areas but has measurement difficulties; hence, its physics is still unknown. To obtain a full understanding of the physics of chiro-optical systems and derive the full potentials, it is essential to perform an in situ observation of the chiro-optical effect from the individual parts because the macroscopic chiro-optical effect cannot be translated directly into microscopic effects. In the present study, we observed the chiro-optical responses at the nanoscale level by detecting the chiro-optical forces, which were generated by illumination of the material-probe system with circularly polarized light. The induced optical force was dependent on the handedness and wavelength of the incident circularly polarized light and was well correlated to the electromagnetically simulated differential intensity of the longitudinal electric field. Our results facilitate the clarification of chiro-optical phenomena at the nanoscale level and could innovate chiro-optical nanotechnologies.

Optical gradient force on chiral particles.

When a chiral nanoparticle is optically trapped using a circularly polarized laser beam, a circular polarization (CP)-dependent gradient force can be induced on the particle. We investigated the CP-dependent gradient force exerted on three-dimensional chiral nanoparticles. The experimental results showed that the gradient force depended on the handedness of the CP of the trapping light and the particle chirality. The analysis revealed that the spectral features of the CP handedness-dependent gradient force are influenced not only by the real part of the refractive index but also by the electromagnetic field perturbed by the chiral particle resonant with the incident light. This is in sharp contrast to the well-known behavior of the gradient force, which is governed by the real part of the refractive index. The extended aspect of the chiral optical force obtained here can provide novel methodologies on chirality sensing, manipulation, separation, enantioselective biological reactions, and other fields.

γ-Glutamylcysteine- and Cysteinylglycine-Directed Growth of Chiral Gold Nanoparticles and their Crystallographic Analysis.

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 helicoid V because of their unique morphology and growth pathway.

Uniform Chiral Gap Synthesis for High Dissymmetry Factor in Single Plasmonic Gold Nanoparticle.

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.

Cysteine-encoded chirality evolution in plasmonic rhombic dodecahedral gold nanoparticles.

Chiral plasmonic nanostructures have opened up unprecedented opportunities in optical applications. We present chirality evolution in nanoparticles focusing on the crystallographic aspects and elucidate key parameters for chiral structure formation. From a detailed understanding of chirality formation, we achieved a morphology (432 Helicoid IV) of three-dimensionally controlled chiral plasmonic nanoparticles based on the rhombic dodecahedral shape. The role of the synthesis parameters, seed, cysteine, cetyltrimethylammonium bromide and ascorbic acid on chiral formation are studied, and based on this understanding, the systematic control of the chiral structure is presented. The relation between the modulated chiral structure factors and optical response is further elucidated by electromagnetic simulation. Importantly, a new optical response is achieved by assembling chiral nanoparticles into a film. This comprehensive study of chiral nanoparticles will provide valuable insight for the further development of diverse chiral plasmonic nanostructures with fascinating properties.

Chiral Surface and Geometry of Metal Nanocrystals.

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.

Bioinspired Toolkit Based on Intermolecular Encoder toward Evolutionary 4D Chiral Plasmonic Materials.

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.

Size-controllable and uniform gold bumpy nanocubes for single-particle-level surface-enhanced Raman scattering sensitivity.

Gold nanocubes modified to form roughened structures, namely, gold bumpy nanocubes (Au BNCs), with very strong and uniform single-particle surface-enhanced Raman scattering (SERS) intensity were developed. The Au BNCs were synthesized by controlled regrowth, competing with 4-aminothiophenol during gold nanocube growth. Under controlled conditions, Au BNCs of various sizes were successfully generated while maintaining a cubic outline. As the bumpy surfaces of the Au BNCs increased the number of hot spots on a single cubic nanoparticle, these nanoparticles exhibited 15-times stronger SERS than normal cubic nanoparticles. We expect that this unique nanostructure will be applicable in versatile fields as an ultrasensitive SERS nanoprobe or nanoantenna owing to its cubic outline and high uniformity, as well as the ease of particle size adjustment.

Highly Selective Active Chlorine Generation Electrocatalyzed by Co3O4 Nanoparticles: Mechanistic Investigation through in Situ Electrokinetic and Spectroscopic Analyses.

The reaction mechanism of electrochemical chloride oxidation at neutral pH is different from that at acidic pH, in which a commercial chlor-alkali process has been developed. Different proton concentrations and accelerated hydrolysis of the generated chlorine into hypochlorous acid at high pH can change the electrokinetics and stability of reaction intermediates. We have investigated a unique reaction mechanism of Co3O4 nanoparticles for chloride oxidation at neutral pH. In contrast with water oxidation, the valency of cobalt was not changed during chloride oxidation. Interestingly, a new intermediate of Co-Cl was captured spectroscopically, distinct from the reaction intermediate at acidic pH. In addition, Co3O4 nanoparticles exhibited high selectivity for active chlorine generation at neutral pH, comparable to commercially available RuO2-based catalysts. We believe that this study provides insight into designing efficient electrocatalysts for active chlorine generation at neutral pH, which can be practically applied to electrochemical water treatment coupled to hydrogen production.

Hierarchical carbon-silicon nanowire heterostructures for the hydrogen evolution reaction.

Silicon nanowires (SiNWs) opened up exciting possibilities in a variety of research fields due to their unique anisotropic morphologies, facile tuning capabilities, and accessible fabrication methods. The SiNW-based photoelectrochemical (PEC) conversion has recently been known to provide an efficiency superior to that of various photo-responsive semiconductor heterostructures. However, a challenge still remains in designing optimum structures to minimize photo-oxidation and photo-corrosion of the Si surface in a liquid electrolyte. Here, we report a simple method to synthesize hierarchically branched carbon nanowires (CNWs) on SiNWs utilizing copper vapor as the catalyst in a chemical vapor deposition (CVD) process, which exhibits outstanding photocatalytic activities for hydrogen generation along with excellent chemical stability against oxidation and corrosion. Thus, we believe that the CNW-SiNW photoelectrodes would provide a new route to developing high-performing cost-effective catalysts essential for advanced energy conversion and storage technologies.

Amino-acid- and peptide-directed synthesis of chiral plasmonic gold nanoparticles.

Understanding chirality, or handedness, in molecules is important because of the enantioselectivity that is observed in many biochemical reactions 1 , and because of the recent development of chiral metamaterials with exceptional light-manipulating capabilities, such as polarization control2-4, a negative refractive index 5 and chiral sensing 6 . Chiral nanostructures have been produced using nanofabrication techniques such as lithography 7 and molecular self-assembly8-11, but large-scale and simple fabrication methods for three-dimensional chiral structures remain a challenge. In this regard, chirality transfer represents a simpler and more efficient method for controlling chiral morphology12-18. Although a few studies18,19 have described the transfer of molecular chirality into micrometre-sized helical ceramic crystals, this technique has yet to be implemented for metal nanoparticles with sizes of hundreds of nanometres. Here we develop a strategy for synthesizing chiral gold nanoparticles that involves using amino acids and peptides to control the optical activity, handedness and chiral plasmonic resonance of the nanoparticles. The key requirement for achieving such chiral structures is the formation of high-Miller-index surfaces ({hkl}, h ≠ k ≠ l ≠ 0) that are intrinsically chiral, owing to the presence of 'kink' sites20-22 in the nanoparticles during growth. The presence of chiral components at the inorganic surface of the nanoparticles and in the amino acids and peptides results in enantioselective interactions at the interface between these elements; these interactions lead to asymmetric evolution of the nanoparticles and the formation of helicoid morphologies that consist of highly twisted chiral elements. The gold nanoparticles that we grow display strong chiral plasmonic optical activity (a dis-symmetry factor of 0.2), even when dispersed randomly in solution; this observation is supported by theoretical calculations and direct visualizations of macroscopic colour transformations. We anticipate that our strategy will aid in the rational design and fabrication of three-dimensional chiral nanostructures for use in plasmonic metamaterial applications.

Plasmon Enhanced Fluorescence Based on Porphyrin-Peptoid Hybridized Gold Nanoparticle Platform.

A porphyrin-peptoid-hybridized silica-coated gold nanoparticle is developed, which is inspired by the protein-chlorophyll ensemble found in photosynthetic antenna. In the natural antenna, chlorophylls are integrated into dense assemblies that are supported by frameworks of proteins, which ensure optimal pigment arrangement for effective light harvesting. In the subject platform, porphyrins are conjugated to the peptoid helix scaffold in a structurally well-defined alignments and subsequently immobilized on the surface of nanoparticles. This prevents intermolecular aggregation among porphyrins and allows high resolution analysis of the effect of porphyrin configuration on the optical properties of the system. Interestingly, under the influence of plasmon from the gold nanoparticle core, the fluorescence of porphyrin is enhanced up to 24-fold at the wavelength where the plasmon resonance matches the porphyrin excitation wavelength. In addition, differences in porphyrin configuration result in spectral modification of their fluorescence emissions. Particularly, the peptoid bearing two porphyrins at a distance of 6 Å shows the most significant alteration in fluorescence. The platform can facilitate extensive studies on the relationship between porphyrin arrangement design and their photophysical interaction in antenna complexes.

Double-Layer Graphene Outperforming Monolayer as Catalyst on Silicon Photocathode for Hydrogen Production.

Photoelectrochemical cells are used to split hydrogen and oxygen from water molecules to generate chemical fuels to satisfy our ever-increasing energy demands. However, it is a major challenge to design efficient catalysts to use in the photoelectochemical process. Recently, research has focused on carbon-based catalysts, as they are nonprecious and environmentally benign. Interesting advances have also been made in controlling nanostructure interfaces and in introducing new materials as catalysts in the photoelectrochemical cell. However, these catalysts have as yet unresolved issues involving kinetics and light-transmittance. In this work, we introduce high-transmittance graphene onto a planar p-Si photocathode to produce a hydrogen evolution reaction to dramatically enhance photon-to-current efficiency. Interestingly, double-layer graphene/Si exhibits noticeably improved photon-to-current efficiency and modifies the band structure of the graphene/Si photocathode. On the basis of in-depth electrochemical and electrical analyses, the band structure of graphene/Si was shown to result in a much lower work function than Si, accelerating the electron-to-hydrogen production potential. Specifically, plasma-treated double-layer graphene exhibited the best performance and the lowest work function. We electrochemically analyzed the mechanism at work in the graphene-assisted photoelectrode. Atomistic calculations based on the density functional theory were also carried out to more fully understand our experimental observations. We believe that investigation of the underlying mechanism in this high-performance electrode is an important contribution to efforts to develop high-efficiency metal-free carbon-based catalysts for photoelectrochemical cell hydrogen production.

Biomimetic whitlockite inorganic nanoparticles-mediated in situ remodeling and rapid bone regeneration.

Bone remodeling process relies on complex signaling pathway between osteoblasts and osteoclasts and control mechanisms to achieve homeostasis of their growth and differentiation. Despite previous achievements in understanding complicated signaling pathways between cells and bone extracellular matrices during bone remodeling process, a role of local ionic concentration remains to be elucidated. Here, we demonstrate that synthetic whitlockite (WH: Ca18Mg2(HPO4)2(PO4)12) nanoparticles can recapitulate early-stage of bone regeneration through stimulating osteogenic differentiation, prohibiting osteoclastic activity, and transforming into mechanically enhanced hydroxyapatite (HAP)-neo bone tissues by continuous supply of PO43- and Mg2+ under physiological conditions. In addition, based on their structural analysis, the dynamic phase transformation from WH into HAP contributed as a key factor for rapid bone regeneration with denser hierarchical neo-bone structure. Our findings suggest a groundbreaking concept of 'living bone minerals' that actively communicate with the surrounding system to induce self-healing, while previous notions about bone minerals have been limited to passive products of cellular mineralization.

Concave Rhombic Dodecahedral Au Nanocatalyst with Multiple High-Index Facets for CO2 Reduction.

A concave rhombic dodecahedron (RD) gold nanoparticle was synthesized by adding 4-aminothiophenol (4-ATP) during growth from seeds. This shape is enclosed by stabilized facets of various high-indexes, such as (331), (221), and (553). Because it is driven thermodynamically and stabilized by 4-ATP ligands, the concave RD maintains its structure over a few months, even after rigorous electrochemical reactions. We discussed the mechanism of the shape evolution controlled by 4-ATP and found that both the binding energy of Au-S and the aromatic geometry of 4-ATP are major determinants of Au atom deposition during growth. As a possible application, we demonstrated that the concave RD exhibits superior electrocatalytic performance for the selective conversion of CO2 to CO in aqueous solution.

Biofunctionalized ceramic with self-assembled networks of nanochannels.

Nature designs circulatory systems with hierarchically organized networks of gradually tapered channels ranging from micrometer to nanometer in diameter. In most hard tissues in biological systems, fluid, gases, nutrients and wastes are constantly exchanged through such networks. Here, we developed a biologically inspired, hierarchically organized structure in ceramic to achieve effective permeation with minimum void region, using fabrication methods that create a long-range, highly interconnected nanochannel system in a ceramic biomaterial. This design of a synthetic model-material was implemented through a novel pressurized sintering process formulated to induce a gradual tapering in channel diameter based on pressure-dependent polymer agglomeration. The resulting system allows long-range, efficient transport of fluid and nutrients into sites and interfaces that conventional fluid conduction cannot reach without external force. We demonstrate the ability of mammalian bone-forming cells placed at the distal transport termination of the nanochannel system to proliferate in a manner dependent solely upon the supply of media by the self-powering nanochannels. This approach mimics the significant contribution that nanochannel transport plays in maintaining living hard tissues by providing nutrient supply that facilitates cell growth and differentiation, and thereby makes the ceramic composite "alive".

Phase transformation from hydroxyapatite to the secondary bone mineral, whitlockite.

Whitlockite (WH: Ca18Mg2(HPO4)2(PO4)12) is the second most abundant mineral in hard tissues, but its precipitation mechanism or role in the body system is poorly understood. Here, using a newly discovered synthetic method for WH, we investigated the kinetic mechanism for the precipitation of WH under physiologically similar conditions, excluding any effects of toxic ions. Based on systematically classified stages in the precipitation process of WH, we monitored the transformation of calcium phosphate phases from neutral pH to acidic pH with the addition of H3PO4. The study revealed that at 70 °C, hydroxyapatite (HAP: Ca10(PO4)6(OH)2) transforms into dicalcium phosphate dihydrate (DCPD: CaHPO4·2H2O) and then into WH in the presence of Mg2+ ions as the pH decreases. The transformation process involves multiple intermediates, the stability of which depends on the cation (Ca and Mg) activities and the solution pH. WH is the most stable calcium phosphate compound below pH 4.2, whereas HAP is the most stable around neutral pH. We also found that Mg2+ ions, which are known to block the growth of HAP, can play a key role in WH formation. This study provides a new insight into the interplay of biologically important calcium phosphate compounds.

Virus templated gold nanocube chain for SERS nanoprobe.

A M13 virus based SERS nanoprobe is presented. Gold nanocubes closely aligned into chains along the length of the virus intensify Raman signals of various reporter molecules serving as specific labels. An antibody is expressed at one end to detect the analyte. This new SERS nanoprobe holds promise for infinitesimal and multiplexed detection of any antigen.