Matter structured on a length scale comparable to or smaller than the wavelength of light can exhibit unusual optical properties. Particularly promising components for such materials are metal nanostructures, where structural alterations provide a straightforward means of tailoring their surface plasmon resonances and hence their interaction with light. But the top-down fabrication of plasmonic materials with controlled optical responses in the visible spectral range remains challenging, because lithographic methods are limited in resolution and in their ability to generate genuinely three-dimensional architectures. Molecular self-assembly provides an alternative bottom-up fabrication route not restricted by these limitations, and DNA- and peptide-directed assembly have proved to be viable methods for the controlled arrangement of metal nanoparticles in complex and also chiral geometries. Here we show that DNA origami enables the high-yield production of plasmonic structures that contain nanoparticles arranged in nanometre-scale helices. We find, in agreement with theoretical predictions, that the structures in solution exhibit defined circular dichroism and optical rotatory dispersion effects at visible wavelengths that originate from the collective plasmon-plasmon interactions of the nanoparticles positioned with an accuracy better than two nanometres. Circular dichroism effects in the visible part of the spectrum have been achieved by exploiting the chiral morphology of organic molecules and the plasmonic properties of nanoparticles, or even without precise control over the spatial configuration of the nanoparticles. In contrast, the optical response of our nanoparticle assemblies is rationally designed and tunable in handedness, colour and intensity-in accordance with our theoretical model.

https://www.softmatter.physik.uni-muenchen.de/publications/liedl/nature-483-2012.pdf

DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response

Supramolecular Chirality in Self-Assembled Systems

Metamaterials enable the tailoring of properties like dielectric permittivity and magnetic permeability. Electromagnetic excitations of metamaterial constituents and their interactions are reviewed, as well as promising future directions. Despite the extraordinary degree of interest in optical metamaterials in recent years, the hoped-for devices and applications have, in large part, yet to emerge. It is becoming clear that the first generation of metamaterial-based devices will most probably arise from their two-dimensional equivalents — metasurfaces. In this Review, we describe recent progress in the area of metasurfaces formed from plasmonic meta-atoms. In particular, we approach the subject from the perspective of the fundamental excitations supported by the meta-atoms and the interactions between them. We also identify some areas ripe for future research and indicate likely avenues for future device development.

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Plasmonic meta-atoms and metasurfaces

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.

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

Deep-learning framework has significantly impelled the development of modern machine learning technology by continuously pushing the limit of traditional recognition and processing of images, speech, and videos. In the meantime, it starts to penetrate other disciplines, such as biology, genetics, materials science, and physics. Here, we report a deep-learning-based model, comprising two bidirectional neural networks assembled by a partial stacking strategy, to automatically design and optimize three-dimensional chiral metamaterials with strong chiroptical responses at predesignated wavelengths. The model can help to discover the intricate, nonintuitive relationship between a metamaterial structure and its optical responses from a number of training examples, which circumvents the time-consuming, case-by-case numerical simulations in conventional metamaterial designs. This approach not only realizes the forward prediction of optical performance much more accurately and efficiently but also enables one to i...

Deep-Learning-Enabled On-Demand Design of Chiral Metamaterials.

The spectroscopic analysis of large biomolecules is important in applications such as biomedical diagnostics and pathogen detection, and spectroscopic techniques can detect such molecules at the nanogram level or lower. However, spectroscopic techniques have not been able to probe the structure of large biomolecules with similar levels of sensitivity. Here, we show that superchiral electromagnetic fields, generated by the optical excitation of plasmonic planar chiral metamaterials, are highly sensitive probes of chiral supramolecular structure. The differences in the effective refractive indices of chiral samples exposed to left- and right-handed superchiral fields are found to be up to 10(6) times greater than those observed in optical polarimetry measurements, thus allowing picogram quantities of adsorbed molecules to be characterized. The largest differences are observed for biomolecules that have chiral planar sheets, such as proteins with high β-sheet content, which suggests that this approach could form the basis for assaying technologies capable of detecting amyloid diseases and certain types of viruses.

/pdf/ultrasensitive-detection-and-characterization-of-4vm2e080ni.pdf

Ultrasensitive detection and characterization of biomolecules using superchiral fields

Ultraviolet and X-ray photoelectron spectroscopies are used to probe the chemical and electronic structure of an amorphous, 2–20 nm-thick shell that encases the crystalline core in core–shell nanoribbons of TaS3. The shell is chemically heterogeneous, containing elemental sulfur and a with a notable (S2)2− deficiency over the crystalline TaS3 core. We find nanoribbon stability to be substrate-dependent; whilst the ribbons are stable on the native oxide of a silicon surface, mass transport of sulfur species between the amorphous shell and a gold substrate leads to a significant change in the electronic properties of the nanomaterials. Our observations may have general implications for the incorporation of nanostructured transition metal chalcogenides into electronic devices.

M. Popland

Papers

Ultrasensitive detection and characterization of biomolecules using superchiral fields

Probing the chemical and electronic properties of the core-shell architecture of transition metal trisulfide nanoribbons.