Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps: errata.

We correct a nomenclature error for the plasmon ruler equation used to fit the simulation data in Fig. 2(d) [Opt. Express24, 27360 (2016)].

Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps.

We created centimeter-scale area metasurfaces consisting of a quasi-hexagonally close packed monolayer of gold nanospheres capped with alkanethiol ligands on glass substrates using a directed self-assembly approach. We experimentally characterized the morphology and the linear and nonlinear optical properties of metasurfaces. We show these metasurfaces, with interparticle gaps of 0.

Toward high throughput optical metamaterial assemblies.

Optical metamaterials have unique engineered optical properties. These properties arise from the careful organization of plasmonic elements. Transitioning these properties from laboratory experiments to functional materials may lead to disruptive technologies for controlling light.

A technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates.

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface.

Virus-templated plasmonic nanoclusters with icosahedral symmetry via directed self-assembly.

The assembly of plasmonic nanoparticles with precise spatial and orientational order may lead to structures with new electromagnetic properties at optical frequencies. The directed self-assembly method presented controls the interparticle-spacing and symmetry of the resulting nanometer-sized elements in solution. The self-assembly of three-dimensional (3D), icosahedral plasmonic nanosclusters (NCs) with resonances at visible wavelengths is demonstrated experimentally.

Molecular sensing: modulating molecular conduction through intermolecular interactions.

We observe changes in the molecular conductivity of individual oligophenylene-vinylene (OPV) molecules due to interactions with small aromatic molecules. Fluorescence experiments were correlated with scanning tunneling microscopy measurements in order to determine the origin of the observed effect. Both nitrobenzene and 1,4-dinitrobenzene decreased fluorescence intensity and molecular conductivity, while toluene had no effect.

Biotemplating rod-like viruses for the synthesis of copper nanorods and nanowires.

Background: In the past decade spherical and rod-like viruses have been used for the design and synthesis of new kind of nanomaterials with unique chemical positioning, shape, and dimensions in the nanosize regime. Wild type and genetic engineered viruses have served as excellent templates and scaffolds for the synthesis of hybrid materials with unique properties imparted by the incorporation of biological and organic moieties and inorganic nanoparticles. Although great advances have been accomplished, still there is a broad interest in developing reaction conditions suitable for biological templates while not limiting the material property of the product.

Tuning mechanical properties of liquid crystalline nanoparticles.

We report the synthesis of colloidal nanoparticles with an internal structure forming a gel-like matrix. These nanoparticles are composed of low molecular weight liquid crystal (LC) 4-pentyl-4-cyanobiphenyl (5CB) encapsulated in an LC-based polymer network. Using nanoscopic mechanical analysis, we demonstrate the ability to independently tune the shape anisotropy and stiffness by varying, respectively, the 5CB concentration and the extent of the polymer cross-linking.

Role of hexahistidine in directed nanoassemblies of tobacco mosaic virus coat protein.

A common challenge in nanotechnology is the fabrication of materials with well-defined nanoscale structure and properties. Here we report that a genetically engineered tobacco mosaic virus (TMV) coat protein (CP), to which a hexahistidine (His) tag was incorporated, can self-assemble into disks, hexagonally packed arrays of disks, stacked disks, helical rods, fibers, and elongated rafts. The insertion of a His tag to the C-terminus of TMV-CP was shown to significantly affect the self-assembly in comparison to the wild type, WT-TMV-CP.

Strain analysis of a chiral smectic-A elastomer.

We present a detailed analysis of the molecular packing of a strained liquid crystal elastomer composed of chiral mesogens in the smectic-A phase. X-ray diffraction patterns of the elastomer collected over a range of orientations with respect to the x-ray beam were used to reconstruct the three-dimensional scattering intensity as a function of tensile strain. We show that the smectic domain order is preserved in these strained elastomers.

Molecular electronics based nanosensors on a viral scaffold.

Assembling and interconnecting the building blocks of nanoscale devices and being able to electronically address or measure responses at the molecular level remains an important challenge for nanotechnology. Here we show the usefulness of bottom-up self-assembly for building electronic nanosensors from multiple components that have been designed to interact in a controlled manner. Cowpea mosaic virus was used as a scaffold to control the positions of gold nanoparticles.

Critical field strength in an electroclinic liquid crystal elastomer.

We elucidate the polymer dynamics of a liquid crystal elastomer based on the time-dependent response of the pendent liquid crystal mesogens. The molecular tilt and switching time of mesogens are analyzed as a function of temperature and cross-linking density upon application of an electric field. We observe an unexpected maximum in the switching time of the liquid crystal mesogens at intermediate field strength.

Virus hybrids as nanomaterials for biotechnology.

The current review describes advances in the field of bionanotechnology in which viruses are used to fabricate nanomaterials. Viruses are introduced as protein cages, scaffolds, and templates for the production of biohybrid nanostructured materials where organic and inorganic molecules are incorporated in a precise and a controlled fashion. Genetic engineering enables the insertion or replacement of selected amino acids on virus capsids for uses from bioconjugation to crystal growth.

Spectral tuning of organic nanocolloids by controlled molecular interactions.

The controlled self-assembly of molecules and interactions between them remain a challenge in creating tunable and functional organic nanostructures. One class of molecular systems that has proven useful for incorporating tunable functionality at different length scales is liquid crystals (LCs) due to its ability to inherently self-organize. Here we present a novel approach to utilize the self-assembly of polymerizable liquid crystals to control the molecular aggregation of stable fluorescent chromophores and create a unique class of organic fluorescent nanocolloids.

Cowpea mosaic virus nanoscaffold as signal enhancement for DNA microarrays.

Previous studies have shown that a functionalized viral nanoparticle can be used as a fluorescent signal-generating element and enhance detection sensitivity for immunoassays and low density microarrays. In this study, we further tested this ability in commercial DNA microarrays, including Affymetrix high density resequencing microarray. Optimum conditions for NeutrAvidin and dye coupling to a double-cysteine mutant of cowpea mosaic virus (CPMV) were found to be comparable to the commonly used streptavidin-phycoerythrin (SAPE) for high density resequencing microarray.

"Smart dust" biosensors powered by biomolecular motors.

The concept of a microfabricated biosensor for environmental and biomedical monitoring applications which is composed of environmentally benign components is presented. With a built-in power source (the biological fuel ATP) and driven by biological motors (kinesin), sensing in the microdevice can be remotely activated and the presence of a target molecule or toxin remotely detected. The multifaceted progress towards the realization of such a device is described.

Nanoparticle networks as chemoselective sensing devices.

We theoretically analyzed transport properties of a molecular network constructed of gold nanoparticles linked with oligophenylenevinulene (OPV) molecules. We showed that the conductance of such system was strongly reduced when trinitrotoluene (TNT) became attached to the OPV linkers in the network. The reported results are based on the ab initio electronic structure calculations.

Role of surfactant in the stability of liquid crystal-based nanocolloids.

We examine the dependence of liquid crystalline nanocolloid formation and stability on surfactant. Nanocolloids composed of polymerizable liquid crystal mesogens and cross-linking agents and capped with either ionic or nonionic surfactants are prepared via the miniemulsion technique. Colloids synthesized with anionic surfactant were stable and displayed 2D hexagonal packing when deposited via slow vertical pulling of the silicon substrate from an aqueous suspension.

Quantum dot fluorescence as a function of alkyl chain length in aqueous environments.

In this work, we examine the dependence of the fluorescence quantum yield of water-soluble CdSe/ZnS quantum dots on the local environment. The hydrophobicity of the local environment was modified by using different alkyl chain lengths in a set of oligo-ethylene glycols. Our results show that the quantum yield of CdSe/ZnS quantum dots is highest for the longest alkyl chain length, suggesting that a more hydrophobic environment is beneficial for generating bright, water-soluble quantum dots.

Toward single molecule detection of staphylococcal enterotoxin B: mobile sandwich immunoassay on gliding microtubules.

An immunoassay based on gliding microtubules (MTs) is described for the detection of staphylococcal enterotoxin B. Detection is performed in a sandwich immunoassay format. Gliding microtubules carry the antigen-specific "capture" antibody, and bound analyte is detected using a fluorescent viral scaffold as the tracer.

Long term storage of virus templated fluorescent materials for sensing applications.

Wild type, mutant, and chemically modified Cowpea mosaic viruses (CPMV) were studied for long term preservation in the presence and absence of cryoprotectants. Viral complexes were reconstituted and tested via fluorescence spectroscopy and a UV/vis-based RNase assay for structural integrity. When viruses lyophilized in the absence of cryoprotectant were rehydrated and RNase treated, UV absorption increased, indicating that the capsids were damaged.

Electronic properties of molecular memory circuits on a nanoscale scaffold.

Significant challenges exist in assembling and interconnecting the building blocks of a nanoscale device and being able to electronically address or measure responses at the molecular level. Here we demonstrate the usefulness of engineered proteins as scaffolds for bottom-up self-assembly for building nanoscale devices out of multiple components. Using genetically engineered cowpea mosaic virus, modified to express cysteine residues on the capsid exterior, gold nanoparticles were attached to the viral scaffold in a specific predetermined pattern to produce specific interparticle distances.

An engineered virus as a bright fluorescent tag and scaffold for cargo proteins--capture and transport by gliding microtubules.

We have demonstrated substantial capture and transport of fluorescently-labeled engineered cowpea mosaic virus (CPMV) using Drosophila kinesin-driven microtubules (MTs). The capture occurred through both NeutrAvidin (NA)-biotin and antibody (IgG)-antigen interactions. The MTs were derivatized with rabbit anti-chicken IgG or biotin, and the virus was conjugated with chicken IgG or NA.

Fluorescent signal amplification of carbocyanine dyes using engineered viral nanoparticles.

We report enhancement in the fluorescent signal of the carbocyanine dye Cy5 by using an engineered virus as a scaffold to attach >40 Cy5 reporter molecules at fixed locations on the viral capsid. Although cyanine dye loading is often accompanied by fluorescence quenching, our results demonstrate that organized spatial distribution of Cy5 reporter molecules on the capsid obviates this commonly encountered problem. In addition, we observe energy transfer from the virus to adducted dye molecules, resulting in a highly fluorescent viral nanoparticle.