Plasmonic gold-cellulose nanofiber aerogels.

Assembly of plasmonic nanomaterials into a low refractive index medium, such as an aerogel, holds a great promise for optical metamaterials, optical sensors, and photothermal energy converters. However, conventional plasmonic aerogels are opaque and optically isotropic composites, impeding them from being used as low-loss or polarization-dependent optical materials. Here we demonstrate a plasmonic-cellulose nanofiber composite aerogel that comprises of well-dispersed gold nanorods within a cellulose nanofiber network. The cellulose aerogel host is highly transparent owing to the small scattering cross-section of the nanofibers and forms a nematic liquid crystalline medium with strong optical birefringence. We find that the longitudinal surface plasmon resonance peak of gold nanorods shows a dramatic shift when probed for the cellulose aerogel compared with the wet gels. Simulations reveal the shift of surface plasmon resonance peak with gel drying can be attributed to the change of the effective refractive index of the gels. This composite material may provide a platform for three- dimensional plasmonic devices ranging from optical sensors to metamaterials.

Electric switching of visible and infrared transmission using liquid crystals co-doped with plasmonic gold nanorods and dichroic dyes.

Smart windows and many other applications require synchronous or alternating facile electric switching of transmitted light intensity in visible and near infrared spectral ranges, but most electrochromic devices suffer from slow, nonuniform switching, high power consumption and limited options for designing spectral characteristics. Here we develop a guest-host mesostructured composite with rod-like dye molecules and plasmonic nanorods spontaneously aligned either parallel or orthogonally to the director of the liquid crystal host. This composite material enables fast, low-voltage electric switching of electromagnetic radiation in visible and infrared ranges, which can be customized depending on the needs of applications, like climate-dependent optimal solar gain control in smart windows.

A supramolecular hydrogel prepared from a thymine-containing artificial nucleolipid: study of assembly and lyotropic mesophases.

An artificial nucleolipid containing thymine, a triazole-ring, and phosphatidylcholine (TTPC) moieties was prepared by copper catalyzed azide alkyne cycloaddition (CuAAC) under aqueous conditions. The resulting TTPC molecules assembled in situ into a fibrous aggregation. The study of the TTPC fiber assembly using XRD and NMR spectroscopy revealed that the formation of fibers was driven by the unique combination of the lipid and nucleobase moieties in the structure of TTPC. At a critical TTPC concentration, entanglement of the fibers resulted in the formation of a supramolecular hydrogel. Investigation of the lyotropic mesophases in the TTPC supramolecular hydrogel showed the presence of multiple phases including two liquid crystal phases (i.e., nematic and lamellar), which have a certain degree of structural order and are promising templates for constructing functional biomaterials.

Self-assembly of predesigned optical materials in nematic codispersions of plasmonic nanorods.

Optical metamaterials and other nanostructured metal-dielectric composites hold great potential for designing and practically realizing novel types of light-matter interactions. Here we develop an approach to fabricate composites with tunable pre-engineered properties via self-assembly of anisotropic nanoparticles codispersed in a nematic liquid crystal host. Orientations of plasmonic nanorods of varying aspect ratios are controlled to align parallel or perpendicular to the nematic director and retain this relative orientation during a facile electric switching. The ensuing dynamic reconfigurability of the surface plasmon resonances of a composite enables a previously inaccessible means of controlling light and may enable tunable plasmonic filters and polarizers.

Morphological and Orientational Controls of Self-Assembly of Gold Nanorods Directed by Evaporative Microflows.

Evaporative self-assembly of noble metal nanoparticles into ordered structures holds great promise for fabricating optical and plasmonic devices by virtue of its low cost, high efficiency, and ease of operation. However, poor control of Marangoni flows is one of the challenges accounting for realizing a well-defined assembly. Herein, based on the theoretical analysis of the influence of evaporative intensity on the assembly, two simple but reliable flow-field-confinement platforms are designed to control the evaporative microflows and to work concurrently with depletion forces to enable the regulated self-assembly of gold nanorods. Orientationally ordered assemblies are realized by the designed strong unidirectional microflow in a capillary, and a device-scale assembly of monolayer membrane is obtained by the created weak convection in homemade glass cells. Morphologically diversified superstructure assemblies, such as spherulite-like, boundary-twisted, chiral spiral assemblies, and merging membranes with a π-twisted domain wall, are obtained due to the spontaneous symmetry breaking or in the presence of defects, such as surface steps and screw dislocations. Optical anisotropy and polarization-dependent behaviors of these assemblies are further revealed, implying the potential applications in plasmonic coupling devices and optoelectronic components. An understanding of the entropy-driven assembly behaviors and control of evaporative microflows to guide the self-assembly of gold nanorods provides insights into the general bottom-up approach that is helpful for constructing complex yet robust nanosuperstructures.

Plasmonic Metamaterial Gels with Spatially Patterned Orientational Order via 3D Printing.

Optical properties can be programmed on mesoscopic scales by patterning host materials while ordering their nanoparticle inclusions. While liquid crystals are often used to define the ordering of nanoparticles dispersed within them, this approach is typically limited to liquid crystals confined in classic geometries. In this work, the orientational order that liquid crystalline colloidal hosts impose on anisotropic nanoparticle inclusions is combined with an additive manufacturing method that enables engineered, macroscopic three-dimensional (3D) patterns of co-aligned gold nanorods and cellulose nanocrystals. These gels exhibit polarization-dependent plasmonic properties that emerge from the unique interaction between the host medium's anisotropic optical properties defined by orientationally ordered cellulose nanocrystals, from the liquid crystal's gold nanorod inclusions, and from the complexity of spatial patterns accessed with 3D printing. The gels' optical properties that are defined by the interplay of these effects are tuned by controlling the gels' order, which is tuned by adjusting the gels' cellulose nanocrystal concentrations. Lithe optical responsiveness of these composite gels to polarized radiation may enable unique technological applications like polarization-sensitive optical elements.

Tuning and Switching a Plasmonic Quantum Dot "Sandwich" in a Nematic Line Defect.

We study the quantum-mechanical effects arising in a single semiconductor core/shell quantum dot (QD) controllably sandwiched between two plasmonic nanorods. Control over the position and the "sandwich" confinement structure is achieved by the use of a linear-trap liquid crystal (LC) line defect and laser tweezers that "push" the sandwich together. This arrangement allows for the study of exciton-plasmon interactions in a single structure, unaltered by ensemble effects or the complexity of dielectric interfaces. We demonstrate the effect of plasmonic confinement on the photon antibunching behavior of the QD and its luminescence lifetime. The QD behaves as a single emitter when nanorods are far away from the QD but shows possible multiexciton emission and a significantly decreased lifetime when tightly confined in a plasmonic "sandwich". These findings demonstrate that LC defects, combined with laser tweezers, enable a versatile platform to study plasmonic coupling phenomena in a nanoscale laboratory, where all elements can be arranged almost at will.

Dynamics of topological solitons, knotted streamlines, and transport of cargo in liquid crystals.

Active colloids and liquid crystals are capable of locally converting the macroscopically supplied energy into directional motion and promise a host of new applications, ranging from drug delivery to cargo transport at the mesoscale. Here we uncover how topological solitons in liquid crystals can locally transform electric energy to translational motion and allow for the transport of cargo along directions dependent on frequency of the applied electric field. By combining polarized optical video microscopy and numerical modeling that reproduces both the equilibrium structures of solitons and their temporal evolution in applied fields, we uncover the physical underpinnings behind this reconfigurable motion and study how it depends on the structure and topology of solitons. We show that, unexpectedly, the directional motion of solitons with and without the cargo arises mainly from the asymmetry in rotational dynamics of molecular ordering in liquid crystal rather than from the asymmetry of fluid flows, as in conventional active soft matter systems.