Understanding chirality, or handedness, in molecules is important because of the enantioselectivity that is observed in many biochemical reactions , and because of the recent development of chiral metamaterials with exceptional light-manipulating capabilities, such as polarization control, a negative refractive index and chiral sensing . Chiral nanostructures have been produced using nanofabrication techniques such as lithography and molecular self-assembly, 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 morphology. Although a few studies 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' sites 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.
Advances in ultrathin, skin-like electronics lead to wearable devices for continuous, noninvasive blood flow monitoring.
While Cu electrodes are a versatile material in the electrochemical production of desired hydrocarbon fuels, Cu binary alloy electrodes are recently proposed to further tune reaction directionality and, more importantly, overcome the intrinsic limitation of scaling relations. Despite encouraging empirical demonstrations of various Cu-based metal alloy systems, the underlying principles of their outstanding performance are not fully addressed. In particular, possible phase segregation with concurrent composition changes, which is widely observed in the field of metallurgy, is not at all considered. Moreover, surface-exposed metals can easily form oxide species, which is another pivotal factor that determines overall catalytic properties. Here, the understanding of Cu binary alloy catalysts for CO reduction and recent progress in this field are discussed. From the viewpoint of the thermodynamic stability of the alloy system and elemental mixing, possible microstructures and naturally generated surface oxide species are proposed. These basic principles of material science can help to predict and understand metal alloy structure and, moreover, act as an inspiration for the development of new binary alloy catalysts to further improve CO conversion and, ultimately, achieve a carbon-neutral cycle.
Wide-spread applications of nanoparticles require large-scale fabrication techniques. Being intrinsically scalable, bottom-up nanoparticle synthesis shows an ever-growing control over particle morphology, enabling even chirally selective shapes. Significant efforts have been undertaken to refine the synthesis in order to decrease the structural spread of the particles and to purify and maximize the resulting handedness. So far, imaging technologies such as electron microscopy are mostly used to investigate the quality of the synthesis. However, for nanophotonic and plasmonic applications, the optical properties are, in fact, key. In this work, we show that single particle chiral scatterometry holds great potential as a feedback to characterize the (chir-)optical quality of chemically synthesized nanoparticles. The spectra of single helicoid nanoparticles reveal a diverse set of chiroptical responses with hugely varying absolute chiral asymmetry in spite of the well-controlled morphology of the particles. Averaging over the single nanoparticles reproduces the solution ensemble measurement remarkably well. This demonstrates that the single particles, despite their morphological and consequently chiroptical differences, exhibit a clearly pronounced chiral spectral and structural feature. We find that the g-factor, that is, the degree of asymmetry of chiral light scattering of single nanoparticles can be up to 4 times larger than that for the ensemble. This proves that chiral scatterometry can be a highly important optical feedback for bottom-up nanoparticle synthesis as it reveals that the asymmetry of the ensemble solution can be further increased and maximized by appropriate refinement methods or by postfabrication purification.
New challenges for electrokinetic studies of CO2 reduction are addressed with the suggested reaction mechanisms of CO and HCOO− production.
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