Chiral Symmetry Breaking in Colloidal Metal Nanoparticle Solutions by Circularly Polarized Light.

Shape symmetry breaking in the formation of inorganic nanostructures is of significant current interest. It was typically achieved through the growth of colloidal nanoparticles with adsorbed chiral molecules. Photochemical processes induced through asymmetric plasmon excitation by circularly polarized light in surface immobilized nanostructures also led to symmetry breaking.

Collective chiroptical activity through the interplay of excitonic and charge-transfer effects in localized plasmonic fields.

The collective light-matter interaction of chiral supramolecular aggregates or molecular ensembles with confined light fields remains a mystery beyond the current theoretical description. Here, we programmably and accurately build models of chiral plasmonic complexes, aiming to uncover the entangled effects of excitonic correlations, intra- and intermolecular charge transfer, and localized surface plasmon resonances. The intricate interplay of multiple chirality origins has proven to be strongly dependent on the site-specificity of chiral molecules on plasmonic nanoparticle surfaces spanning the nanometer to sub-nanometer scale.

Helitwistacenes-Combining Lateral and Longitudinal Helicity Results in Solvent-Induced Inversion of Circularly Polarized Light.

Helicity is expressed differently in ortho- and para-fused acenes-helicenes and twistacenes, respectively. While the extent of helicity is constant in helicenes, it can be tuned in twistacenes, and the handedness of flexible twistacenes is often determined by more rigid helicenes. Here, we combine helicenes with rigid twistacenes consisting of a tunable degree of twisting, forming helitwistacenes.

The effect of axial and helical chirality on circularly polarized luminescence: lessons learned from tethered twistacenes.

The effect of axial and helical twisting on the circularly polarized luminescence of acenes was studied both experimentally and computationally, using four series of tethered twisted acenes. We find that the combination of axial and helical chirality yields the highest anisotropy factors, and that the ratio between the absorption and emission anisotropy factors is an intrinsic property for twistacenes.

Circularly polarized and total luminescence as probes of nucleation and growth in chiral nanocrystals.

Nucleation of crystals as well as their growth is difficult to study experimentally. We have recently demonstrated that chiral Eu -doped terbium phosphate nanocrystals are an interesting system for studying nanocrystal formation mechanisms and chiral symmetry breaking, occurring during their formation, directed by chiral ligands, such as tartaric acid. In this paper, we show how simultaneous, in situ monitoring of both total emission intensity and circularly polarized luminescence magnitude and sign versus time during nanocrystal formation provides considerable information on the mechanisms of nanocrystal nucleation and growth.

Metal nanowires grown on polymeric fibres for electronic textiles.

A key aspect of the use of conventional fabrics as smart textiles and wearable electronics is to incorporate a means of electrical conductivity into single polymer fibres. We present the transformation of thin polymer fibres and fabrics into conductive materials by growth of a thin, optically transparent gold-silver nanowire (NW) mesh with a relatively low metal loading directly on the surface of polymer fibres. Demonstrating the method on poly(lactic--glycolic) acid and nylon microfibres, we show that the NW network morphology depends on the diameter of the polymer fibres, where at small diameters (1-2 μm), the NWs form a randomly oriented network, but for diameters above several micrometers, the NWs wrap around the fibres transversally.

A Kinetic Isotope Effect in the Formation of Lanthanide Phosphate Nanocrystals.

Mechanisms of nucleation and growth of crystals are still attracting a great deal of interest, in particular with recent advances in experimental techniques aimed at studying such phenomena. Studies of kinetic isotope effects in various reactions have been useful for elucidating reaction mechanisms, and it is believed that the same may apply for crystal formation kinetics. In this work, we present a kinetic study of the formation of europium-doped terbium phosphate nanocrystals under acidic conditions, including a strong H/D isotope effect.

Chiral Photomelting of DNA-Nanocrystal Assemblies Utilizing Plasmonic Photoheating.

Chiral plasmonic nanostructures exhibit anomalously strong chiroptical signals and offer the possibility to realize asymmetric photophysical and photochemical processes controlled by circularly polarized light. Here, we use a chiral DNA-assembled nanorod pair as a model system for chiral plasmonic photomelting. We show that both the enantiomeric excess and consequent circular dichroism can be controlled with chiral light.

Time-resolved circularly polarized luminescence of Eu -based systems.

Chiral Eu -based systems are frequently studied via circularly polarized luminescence spectroscopy. The emission lifetimes of each circular polarization, however, are virtually always ignored, because in a homogeneous sample of emitters, there should be no difference between the two. However, we show that in less robust Eu complex structures, as in the chiral complex Eu (facam) , a difference in the lifetimes of the two circularly polarized emission components arises due to heterogeneity of the complexes.

Enantiomeric Control of Intrinsically Chiral Nanocrystals.

The chiral aspect of inorganic crystals that crystallize in chiral space groups has been largely ignored until recently, partly due to difficulties in characterizing the chiroptical properties of bulk crystals, and also due to the difficulty in separating (sub)micrometer-scale chiral crystal enantiomers. In recent years, the colloidal synthesis of intrinsically chiral nanocrystals (NCs) of several chiral inorganic compounds with significant enantiomeric excess has been demonstrated. This is achieved through the use of chiral molecular ligands, which bind to the atomic/ionic components of the crystals, preferentially forming one crystal enantiomorph.

Spontaneous and directed symmetry breaking in the formation of chiral nanocrystals.

Symmetry plays a crucial part in our understanding of the natural world. Mirror symmetry breaking is of special interest as it is related to life as we know it. Studying systems which display chiral amplification, therefore, could further our understanding of symmetry breaking in chemical systems, in general, and thus also of the asymmetry in Nature.

Contact-free conductivity probing of metal nanowire films using THz reflection spectroscopy.

We utilize time-domain Terahertz (THz) reflectivity measurements for characterizing the surface conductivity of Polyethylene-terephthalate coated with nanowire (NW) films to form novel transparent electrodes (TE). We find good correspondence between the film conductivity and the THz-field reflectivity that provide uniquely desirable means for non-destructive, contactless conductivity measurements of large area NW-based-TEs. We demonstrate the robustness of THz reflectivity measurements to deviations invoked on NW film composition and film uniformity.

Determination of Handedness in a Single Chiral Nanocrystal via Circularly Polarized Luminescence.

The occurrence of biological homochirality is attributed to symmetry-breaking mechanisms which are still debatable. Studies of symmetry breaking require tools for monitoring the population ratios of individual chiral nano-objects, such as molecules, polymers, or nanocrystals. Moreover, mapping their spatial distributions may elucidate on their symmetry-breaking mechanism.

Circular dichroism enhancement in plasmonic nanorod metamaterials.

Optical activity is a fundamental phenomenon originating from the chiral nature of crystals and molecules. While intrinsic chiroptical responses of ordinary chiral materials to circularly polarized light are relatively weak, they can be enhanced by specially tailored nanostructures. Here, nanorod metamaterials, comprising a dense array of vertically aligned gold nanorods, is shown to provide a significant enhancement of the circular dichroism response of an embedded material.

Patterning Metal Nanowire-Based Transparent Electrodes by Seed Particle Printing.

This article describes a unique combination of inkjet printing of functional materials with an intricate self-assembly process. Gold-silver nanowire (NW) mesh films were produced by a sequential deposition process, in which small metal seed nanoparticle film was deposited at desired areas by inkjet printing, followed by coating with a thin film of NW growth solution. Two different types of NW growth solutions were used: the first, based on benzylhexadecyldimethylammonium chloride, exhibited a bulk solution growth mode and was thus suitable for coverage of large uniform areas.

Probing the Interaction of Quantum Dots with Chiral Capping Molecules Using Circular Dichroism Spectroscopy.

Circular dichroism (CD) induced at exciton transitions by chiral ligands attached to single component and core/shell colloidal quantum dots (QDs) was used to study the interactions between QDs and their capping ligands. Analysis of the CD line shapes of CdSe and CdS QDs capped with l-cysteine reveals that all of the features in the complex spectra can be assigned to the different excitonic transitions. It is shown that each transition is accompanied by a derivative line shape in the CD response, indicating that the chiral ligand can split the exciton level into two new sublevels, with opposite angular momentum, even in the absence of an external magnetic field.

Tracking the Verwey Transition in Single Magnetite Nanocrystals by Variable-Temperature Scanning Tunneling Microscopy.

Variable-temperature scanning tunneling spectroscopy revealed a sharp Verwey transition in individual ∼10 nm magnetite nanocrystals prepared by the coprecipitation technique and embedded in the surface of a gold film. The transition was observed as a significant change in the electronic structure around the Fermi level, with an apparent band gap of ∼140-250 meV appearing below the transition temperature and a pseudogap of ∼75 ± 10 meV appearing above it. The transition temperature was invariably observed around 101 ± 2 K for different nanocrystals, as opposed to 123 K typically reported for stoichiometric bulk crystals.

Relation between 2D/3D chirality and the appearance of chiroptical effects in real nanostructures.

The optical activity of fabricated metallic nanostructures is investigated by complete polarimetry. While lattices decorated with nanoscale gammadia etched in thin metallic films have been described as two dimensional, planar nanostructures, they are better described as quasi-planar structures with some three dimensional character. We find that the optical activity of these structures arises not only from the dissymmetric backing by a substrate but, more importantly, from the selective rounding of the nanostructure edges.

Self-assembled metallic nanowire-based vertical organic field-effect transistor.

We report on in situ, self-assembly, solution-processing of metallic (Au/Ag) nanowire-based transparent electrodes integrated to vertical organic field-effect transistors (VOFETs). In the VOFET architecture, the nanowires' microstructure facilitates current modulation by the gate across the otherwise shielding sandwiched source electrode. We show N-type VOFETs operation with on/off ratio ∼1 × 10(5) and high current density (>1 mA cm(-2) at VDS = 5 V).

Enantioselective control of lattice and shape chirality in inorganic nanostructures using chiral biomolecules.

A large number of inorganic materials form crystals with chiral symmetry groups. Enantioselectively synthesizing nanostructures of such materials should lead to interesting optical activity effects. Here we report the synthesis of colloidal tellurium and selenium nanostructures using thiolated chiral biomolecules.

Complete polarimetry on the asymmetric transmission through subwavelength hole arrays.

Dissymmetric, periodically nanostructured metal films can show non-reciprocal transmission of polarized light, in apparent violation of the Lorentz reciprocity theorem. The wave vector dependence of the extraordinary optical transmission in gold films with square and oblique subwavelength hole arrays was examined for the full range of polarized light input states. In normal incidence, the oblique lattice, in contrast to square lattice, showed strong asymmetric, non-reciprocal transmission of circularly polarized light.

The stabilization of a single domain in free-standing ferroelectric nanocrystals.

High resolution electron microscopy, electron diffraction and electron holography were used to study individual free-standing ∼ 30 nm barium titanate nanocrystals. Large unidirectional variations in the tetragonal distortion were mapped across the smaller nanocrystals, peaking to anomalously large values of up to 4% at the centers of the nanocrystals. This indicated that the nanocrystals consist of highly strained single ferroelectric domains.

Chirality and chiroptical effects in inorganic nanocrystal systems with plasmon and exciton resonances.

This paper reviews the recent advances in experiment and theory of the induction of chiroptical effects, primarily circular dichroism (CD), at the plasmonic and excitonic resonances of achiral inorganic nanocrystals (NCs) capped and/or formed with chiral molecules. It also addresses stronger chiroptical effects obtained in intrinsically chiral inorganic nanostructures obtained from growing enantiomeric excess of intrinsically chiral NCs or arranging achiral plasmonic particles in chiral configurations. The accumulated experimental data and theory on various CD induction mechanisms provide an extended set of tools to properly analyze and understand the electromagnetic influence of chiral molecules on inorganic particles and obtain new general insights into the interaction of capping molecules with inorganic NCs.

Amplification of chiroptical activity of chiral biomolecules by surface plasmons.

Chiral molecules are shown to induce circular dichroism (CD) at surface plasmon resonances of gold nanostructures when in proximity to the metal surface without direct bonding to the metal. By changing the molecule-Au separation, we were able to learn about the mechanism of plasmonic CD induction for such nanostructures. It was found that even two monolayers of chiral molecules can induce observable plasmonic CD, while without the presence of the plasmonic nanostructures their own CD signal is unmeasurable.