Alexander O. Govorov

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

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.

Generating heat with metal nanoparticles

We describe recent studies on photothermal effects using colloidal nanoparticles. Metal nanoparticles efficiently generate heat in the presence of electromagnetic radiation. This process becomes strongly enhanced under plasmon resonance and also depends on the shape and organization of the nanoparticles. In particular, the amount of generated heat and temperature increase depends on the number of nanoparticles in a complex. Metal nanoparticles may induce phase transformations when they are in thermal contact with a polymer or a solid matrix, such as ice. This suggests new possibilities for measuring heat release at the nanoscale.

Spectroscopy of nanoscopic semiconductor rings

Making use of self-assembly techniques, we realize nanoscopic semiconductor quantum rings in which the electronic states are in the true quantum limit. We employ two complementary spectroscopic techniques to investigate both the ground states and the excitations of these rings. Applying a magnetic field perpendicular to the plane of the rings, we find that, when approximately one flux quantum threads the interior of each ring, a change in the ground state from angular momentum l = 0 to l = -1 takes place. This ground state transition is revealed both by a drastic modification of the excitation spectrum and by a change in the magnetic-field dispersion of the single-electron charging energy.

Gold nanoparticle ensembles as heaters and actuators: melting and collective plasmon resonances

We describe the peculiar conditions under which optically driven gold nanoparticles (NPs) can significantly increase temperature or even melt a surrounding matrix. The heating and melting processes occur under light illumination and involve the plasmon resonance. For the matrix, we consider water, ice, and polymer. Melting and heating the matrix becomes possible if a nanoparticle size is large enough. Significant enhancement of the heating effect can appear in ensembles of NPs due to an increase of a volume of metal and electric-field amplification.

Semiconductor-Metal Nanoparticle Molecules: Hybrid Excitons and the Nonlinear Fano Effect

Modern nanotechnology opens the possibility of combining nanocrystals of various materials with very different characteristics in one superstructure. Here we study theoretically the optical properties of hybrid molecules composed of semiconductor and metal nanoparticles. Excitons and plasmons in such a hybrid molecule become strongly coupled and demonstrate novel properties. At low incident light intensity, the exciton peak in the absorption spectrum is broadened and shifted due to incoherent and coherent interactions between metal and semiconductor nanoparticles. At high light intensity, the absorption spectrum demonstrates a surprising, strongly asymmetric shape. This shape originates from the coherent internanoparticle Coulomb interaction and can be viewed as a nonlinear Fano effect which is quite different from the usual linear Fano resonance.

Experimental and Theoretical Studies of Light-to-Heat Conversion and Collective Heating Effects in Metal Nanoparticle Solutions

We perform a set of experiments on photoheating in a water droplet containing gold nanoparticles (NPs). Using photocalorimetric methods, we determine efficiency of light-to-heat conversion (eta) which turns out to be remarkably close to 1, (0.97 < eta < 1.03). Detailed studies reveal a complex character of heat transfer in an optically stimulated droplet. The main mechanism of equilibration is due to convectional flow. Theoretical modeling is performed to describe thermal effects at both nano- and millimeter scales. Theory shows that the collective photoheating is the main mechanism. For a large concentration of NPs and small laser intensity, an averaged temperature increase (at the millimeter scale) is significant (approximately 7 degrees C), whereas on the nanometer scale the temperature increase at the surface of a single NP is small (approximately 0.02 degrees C). In the opposite regime, that is, a small NP concentration and intense laser irradiation, we find an opposite picture: a temperature increase at the millimeter scale is small (0.1 degrees C) but a local, nanoscale temperature has strong local spikes at the surfaces of NPs (approximately 3 degrees C). These studies are crucial for the understanding of photothermal effects in NPs and for their potential and current applications in nano- and biotechnologies.

Plasmonic Circular Dichroism of Chiral Metal Nanoparticle Assemblies

We describe from the theoretical point of view a plasmonic mechanism of optical activity in chiral complexes composed of metal nanoparticles (NPs). In our model, the circular dichroism (CD) signal comes from the Coulomb interaction between NPs. We show that the CD spectrum is very sensitive to the geometry and composition of a chiral complex and also has typically both positive and negative bands. In our calculations, the strongest CD signals were found for the helix geometry resembling helical structures of many biomolecules. For chiral tetramers and pyramids, the symmetry of a frame of a complex is very important for the formation of a strong CD response. Chiral natural molecules (peptides, DNA, etc.) often have strong CD signals in the UV range and typically show weak CD responses in the visible range of photon energies. In contrast to the natural molecules, the described mechanism of plasmonic CD is able to create strong CD signals in the visible wavelength range. This plasmonic mechanism offers a unique possibility to design colloidal and other nanostructures with strong optical chirality.

Theory of Circular Dichroism of Nanomaterials Comprising Chiral Molecules and Nanocrystals: Plasmon Enhancement, Dipole Interactions, and Dielectric Effects

Our calculations show that a nonchiral nanocrystal is able to dramatically change the circular dichroism (CD) of a chiral molecule when the nanocrystal and molecule form a complex and couple via dipole and multipole Coulomb interactions. Plasmon resonances of metal nanocrystals in the nanocrystal-molecule complex result in both the resonant enhancement of CD signals of molecules and the appearance of new spectral structures. Two mechanisms, in which a nanocrystal can influence the CD effect, have been identified. The first mechanism is the plasmon-induced change in the electromagnetic field inside the chiral molecule. The second is the optical absorption of the nanocrystal-molecule complex due to the chiral currents inside the metal nanocrystal induced by the dipole of the chiral molecule. The first mechanism creates a change in the angle between the effective electric and magnetic dipoles of the molecule. This mechanism can lead to symmetry breaking and to a plasmon-induced CD signal of the nonchiral molecule. Both mechanisms create interesting Fano-like shapes in the CD spectra. Importantly, the second mechanism gives the main contribution to the CD signal at the plasmon frequency when the absorption band of the chiral molecule is far from the plasmon resonance. This may happen in many cases since many biomolecules are optically active in the UV range, whereas plasmon resonances in commonly used nanometals are found at longer wavelengths. As concrete examples, the paper describes alpha-helix and calixarene ligand molecules coupled with metal nanocrystals. The above results are also applied to complexes incorporating semiconductor nanocrystals. The results obtained here can be used to design a variety of hybrid nanostructures with enhanced and tailored optical chirality in the visible wavelength range.

Reconfigurable 3D plasmonic metamolecules

A reconfigurable plasmonic nanosystem combines an active plasmonic structure with a regulated physical or chemical control input. There have been considerable efforts on integration of plasmonic nanostructures with active platforms using top-down techniques. The active media include phase-transition materials, graphene, liquid crystals and carrier-modulated semiconductors, which can respond to thermal, electrical and optical stimuli. However, these plasmonic nanostructures are often restricted to two-dimensional substrates, showing desired optical response only along specific excitation directions. Alternatively, bottom-up techniques offer a new pathway to impart reconfigurability and functionality to passive systems. In particular, DNA has proven to be one of the most versatile and robust building blocks for construction of complex three-dimensional architectures with high fidelity. Here we show the creation of reconfigurable three-dimensional plasmonic metamolecules, which execute DNA-regulated conformational changes at the nanoscale. DNA serves as both a construction material to organize plasmonic nanoparticles in three dimensions, as well as fuel for driving the metamolecules to distinct conformational states. Simultaneously, the three-dimensional plasmonic metamolecules can work as optical reporters, which transduce their conformational changes in situ into circular dichroism changes in the visible wavelength range.

Plasmonic Circular Dichroism of Peptide-Functionalized Gold Nanoparticles

Nature is remarkable at tailoring the chirality of different biomolecules to suit specific functions. Chiral molecules can impart optical activity to achiral materials in the form of the particles electronic transition frequency. Herein, we used peptides of differing secondary structures (random coil and α-helix) to artificially create optically active chiral gold nanoparticles through peptide-nanoparticle interactions as observed by circular dichroism (CD) spectroscopy. This interaction produces a CD signal at the plasmon resonance frequency (∼520 nm) of the chiral peptide-nanoparticle complex. Aggregation of the peptide-coated nanoparticles using metal ions results in a red-shifted plasmonic CD response. Our results suggest that chiroptical properties of nanomaterials can be engineered using peptides.