Facile Mechanochemical Functionalization of Hydrophobic Substrates for Single-Walled Carbon Nanotube Based Optical Reporters of Hydrolase Activity.

Single walled carbon nanotubes (SWCNT) have recently been demonstrated as modular, near-infrared (nIR) probes for reporting hydrolase activity; however, these have been limited to naturally amphipathic substrate targets used to noncovalently functionalize the hydrophobic nanoparticles. Many relevant substrate targets are hydrophobic (such as recalcitrant biomass) and pose a challenge for modular functionalization. In this work, a facile mechanochemistry approach was used to couple insoluble substrates, such as lignin, to SWCNT using l-lysine amino acid as a linker and tip sonication as the mechanochemical energy source.

Charge-Transfer Complexes: Fundamentals and Advances in Catalysis, Sensing, and Optoelectronic Applications.

Supramolecular assemblies, formed through electronic charge transfer between two or more entities, represent a rich class of compounds dubbed as charge-transfer complexes (CTCs). Their distinctive formation pathway, rooted in charge-transfer processes at the interface of CTC-forming components, results in the delocalization of electronic charge along molecular stacks, rendering CTCs intrinsic molecular conductors. Since the discovery of CTCs, intensive research has explored their unique properties including magnetism, conductivity, and superconductivity.

Lipid-Functionalized Single-Walled Carbon Nanotubes as Probes for Screening Cell Wall Disruptors.

Membrane-active molecules are of great importance to drug delivery and antimicrobials applications. While the ability to prototype new membrane-active molecules has improved greatly with the advent of automated chemistries and rapid biomolecule expression techniques, testing methods are still limited by throughput, cost, and modularity. Existing methods suffer from feasibility constraints of working with pathogenic living cells and by intrinsic limitations of model systems.

Single-Walled Carbon Nanotube Probes for the Characterization of Biofilm-Degrading Enzymes Demonstrated against Extracellular Matrices.

Hydrolase co-therapies that degrade biofilm extracellular polymeric substances (EPS) allow for a better diffusion of antibiotics and more effective treatment; current methods for quantitatively measuring the enzymatic degradation of EPS are not amendable to high-throughput screening. Herein, we present biofilm EPS-functionalized single-walled carbon nanotube (SWCNT) probes for rapid screening of hydrolytic enzyme selectivity and activity on EPS. The extent of biofilm EPS degradation is quantified by monitoring the quenching of the SWCNT fluorescence.

Salt Mediated Self-Assembly of Poly(ethylene glycol)-Functionalized Gold Nanorods.

Although challenging, assembling and orienting non-spherical nanomaterials into two- and three-dimensional (2D and 3D) ordered arrays can facilitate versatile collective properties by virtue of their shape-dependent properties that cannot be realized with their spherical counterparts. Here, we report on the self-assembly of gold nanorods (AuNRs) into 2D films at the vapor/liquid interface facilitated by grafting them with poly(ethylene glycol) (PEG). Using surface sensitive synchrotron grazing incidence small angle X-ray scattering (GISAXS) and specular X-ray reflectivity (XRR), we show that PEG-AuNRs in aqueous suspensions migrate to the vapor/liquid interface in the presence of salt, forming a uniform monolayer with planar-to-surface orientation.

Massive Enhancement of Optical Transmission across a Thin Metal Film via Wave Vector Matching in Grating-Coupled Surface Plasmon Resonance.

We demonstrate how distinct surface plasmon resonance modes on opposite sides of a metal-coated grating can be coupled across the metal film. This coupling occurs by matching the resonance conditions on each side of the grating by tuning the refractive index directly adjacent to the metal film. In the first example, we deposited a high refractive index layer of tin oxide on top of the grating to red-shift the front side surface plasmon until it coupled with the backside surface plasmon across a semitransparent ∼45 nm thin silver grating.

Solution-Processed Bismuth Halide Perovskite Thin Films: Influence of Deposition Conditions and A-Site Alloying on Morphology and Optical Properties.

Bismuth-based halide perovskites have been proposed as a potential nontoxic alternative to lead halide perovskites; however, they have not realized suitable performance. Their poor performance has been attributed to substandard film morphologies and too wide of a band gap for many applications. Herein we used a two-step deposition procedure to convert BiI thin films into ABiI (A = FA, MA, Cs, or Rb), which resulted in a substantial improvement in film morphology, a larger band gap, and greater compositional tunability compared toresults when using aconventional single-step deposition technique.

Experimental analysis of waveguide-coupled surface-plasmon-polariton cone properties.

Experimental data for waveguide-coupled surface-plasmon-polariton (SPP) cones generated from dielectric waveguides is presented. The results demonstrate a simpler route to collect plasmon waveguide resonance (i.e.

A phase-change thin film-tuned photonic crystal device.

This paper reports a tunable photonic device that incorporates a thin layer of phase-change material, GeSbTe (GST), in a photonic crystal (PC) structure. The PC structure is based on a one-dimensional grating waveguide with a metal cladding. The metal-cladded PC structure supports a guided-mode resonance (GMR) that selectively absorbs light at a particular wavelength.

Templating Colloidal Crystal Growth Using Chirped Surface Relief Gratings.

We report a method for controlling the lattice geometry of monodisperse colloidal crystals formed by confined convective self-assembly on a substrate patterned with a chirped surface relief grating. Chirped gratings were fabricated using laser interference lithography and a curved mirror reflector to create photoresist patterns with pitch values ranging from ∼500 to >10 000 nm spread over a planar surface. These surface nanostructures are shown to guide the formation of various lattice geometries not normally found via colloidal assembly on planar surfaces.

Creating metamaterial building blocks with directed photochemical metallization of silver onto DNA origami templates.

DNA origami can be used to create a variety of complex and geometrically unique nanostructures that can be further modified to produce building blocks for applications such as in optical metamaterials. We describe a method for creating metal-coated nanostructures using DNA origami templates and a photochemical metallization technique. Triangular DNA origami forms were fabricated and coated with a thin metal layer by photochemical silver reduction while in solution or supported on a surface.

A strain-tunable nanoimprint lithography for linear variable photonic crystal filters.

This paper presents the fabrication methodology of a linear variable photonic crystal (PC) filter with narrowband reflection that varies over a broad spectral range along the length of the filter. The key component of the linear variable PC filter is a polymer surface-relief grating whose period changes linearly as a function of its position on the filter. The grating is fabricated using a nanoreplica molding process with a wedge-shaped elastomer mold.

One-step sol-gel imprint lithography for guided-mode resonance structures.

Guided-mode resonance (GMR) structures consisting of sub-wavelength periodic gratings are capable of producing narrow-linewidth optical resonances. This paper describes a sol-gel-based imprint lithography method for the fabrication of submicron 1D and 2D GMR structures. This method utilizes a patterned polydimethylsiloxane (PDMS) mold to fabricate the grating coupler and waveguide for a GMR device using a sol-gel thin film in a single step.

Multipitched Diffraction Gratings for Surface Plasmon Resonance-Enhanced Infrared Reflection Absorption Spectroscopy.

We demonstrate the application of metal-coated diffraction gratings possessing multiple simultaneous pitch values for surface enhanced infrared absorption (SEIRA) spectroscopy. SEIRA increases the magnitude of vibrational signals in infrared measurements by one of several mechanisms, most frequently involving the enhanced electric field associated with surface plasmon resonance (SPR). While the majority of SEIRA applications to date have employed nanoparticle-based plasmonic systems, recent advances have shown how various metals and structures lead to similar signal enhancement.

Reducing optical losses in organic solar cells using microlens arrays: theoretical and experimental investigation of microlens dimensions.

The performance of organic photovoltaic devices is improving steadily and efficiencies have now exceeded 10%. However, the incident solar spectrum still largely remains poorly absorbed. To reduce optical losses, we employed a microlens array (MLA) layer on the side of the glass substrate facing the incident light; this approach does not interfere with the processing of the active-layer.

Epitaxially grown collagen fibrils reveal diversity in contact guidance behavior among cancer cells.

Invasion of cancer cells into the surrounding tissue is an important step during cancer progression and is driven by cell migration. Cell migration can be random, but often it is directed by various cues such as aligned fibers composed of extracellular matrix (ECM), a process called contact guidance. During contact guidance, aligned fibers bias migration along the long axis of the fibers.

Angle-tunable enhanced infrared reflection absorption spectroscopy via grating-coupled surface plasmon resonance.

Surface enhanced infrared absorption (SEIRA) spectroscopy is an attractive method for increasing the prominence of vibrational modes in infrared spectroscopy. To date, the majority of reports associated with SEIRA utilize localized surface plasmon resonance from metal nanoparticles to enhance electromagnetic fields in the region of analytes. Limited work has been performed using propagating surface plasmons as a method for SEIRA excitation.

High rate detection of volatile products using differential electrochemical mass spectrometry: combining an electrode-coated membrane with hydrodynamic flow in a wall-tube configuration.

We present an experimental system that combines differential electrochemical mass spectrometry with hydrodynamic flow consisting of an impinging jet in a wall-tube configuration. This assembly allows simultaneous detection of electrochemical signals along with monitoring of dissolved gas species using differential electrochemical mass spectrometry under well-defined hydrodynamic conditions and over a wide range of mass transfer rates. The working electrode is deposited directly onto a thin, hydrophobic membrane, which also serves as the inlet to the mass spectrometer.

Use of dispersion imaging for grating-coupled surface plasmon resonance sensing of multilayer Langmuir-Blodgett films.

We report grating-coupled surface plasmon resonance measurements involving the use of dispersion images to interpret the optical response of a metal-coated grating. Optical transmission through a grating coated with a thin, gold film exhibits features characteristic of the excitation of surface plasmon resonance due to coupling with the nanostructured grating surface. Evidence of numerous surface plasmon modes associated with coupling at both front (gold/air) and back (gold/substrate) grating interfaces is observed.

Atom probe tomography characterization of thin copper layers on aluminum deposited by galvanic displacement.

″Ultrathin″ metallization layers on the order of nanometers in thickness are increasingly used in semiconductor interconnects and other nanostructures. Aqueous deposition methods are attractive methods to produce such layers due to their low cost, but formation of ultrathin layers has proven challenging, particularly on oxide-coated substrates. This work focused on the formation of thin copper layers on aluminum, by galvanic displacement from alkaline aqueous solutions.

Resonance quenching and guided modes arising from the coupling of surface plasmons with a molecular resonance.

In this paper, we describe experimental and modeling results that illucidate the nature of coupling between surface plasmon polaritons in a thin silver film with the molecular resonance of a zinc phthalocyanine dye film. This coupling leads to several phenomena not generally observed when plasmons are coupled to transparent materials. The increased absorption coefficient near a molecular resonance leads to a discontinuity in the refractive index, which causes branching of the plasmon resonance condition and the appearance of two peaks in the p-polarized reflectance spectrum.

Diffraction-based tracking of surface plasmon resonance enhanced transmission through a gold-coated grating.

Surface plasmon resonance enhanced transmission through metal-coated nanostructures represents a highly sensitive yet simple method for quantitative measurement of surface processes and is particularly useful in the development of thin film and adsorption sensors. Diffraction-induced surface plasmon excitation can produce enhanced transmission at select regions of the visible spectrum, and wavelength shifts associated with these transmission peaks can be used to track adsorption processes and film formation. In this report, we describe a simple optical microscope-based method for monitoring the first-order diffracted peaks associated with enhanced transmission through a gold-coated diffraction grating.

Three-dimensional atom probe tomography of oxide, anion, and alkanethiolate coatings on gold.

We have used three-dimensional atom probe tomography to analyze several nanometer-thick and monomolecular films on gold surfaces. High-purity gold wire was etched by electropolishing to create a sharp tip suitable for field evaporation with a radius of curvature of <100 nm. The near-surface region of a freshly etched gold tip was examined with the atom probe at subnanometer spatial resolution and with atom-level composition accuracy.

Combined electrochemical surface plasmon resonance for angle spread imaging of multielement electrode arrays.

A surface plasmon resonance imaging system combined with a multielement electrode array is described. An optical system with shaping optics is used to direct a wedge of light onto a gold-coated sample. The reflected light is detected in the form of an angle-spread image of the surface, with one direction denoting a variable incident angle and the other showing a span of locations along one lateral direction of the sample surface.

Wavelength tunable surface plasmon resonance-enhanced optical transmission through a chirped diffraction grating.

We report the construction and testing of a chirped diffraction grating, which serves as a substrate for surface plasmon-enhanced optical transmission. This grating possesses a spatial variation in both pitch and amplitude along its surface. It was created by plasma oxidation of a curved poly(dimethoxysilane) sheet, which resulted in nonuniform buckling along the polymer surface.