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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. We used this platform to screen 16 hydrolases with varying bond breaking selectivity against a panel of wild-type Pseudomonas aeruginosa and mutants deficient or altered in one or more EPS. Next, we performed concentration-dependent studies of six enzymes on two common strains found in cystic fibrosis (CF) environments and, for each enzyme, extracted three first-order rate constants and their relative contributions by fitting a parallel, multi-site degradation model, with a good model fit (R2 from 0.65 to 0.97). Reaction rates (turnover rates) are dependent on the enzyme concentration and range from 6.67 × 10-11 to 2.80 × 10-3 *s-1 per mg/mL of enzymes. Lastly, we confirmed findings from this new assay using an established crystal-violet staining assay for a subset of hydrolase panels. In summary, our work shows that this modular sensor is amendable to the high-throughput screening of EPS degradation, thereby improving the rate of discovery and development of novel hydrolases.
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Nanotubos de Carbono , Pseudomonas aeruginosa , Antibacterianos/metabolismo , Biopelículas , Matriz Extracelular/metabolismo , Pseudomonas aeruginosa/metabolismoRESUMEN
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 â¼45 nm thin silver grating. By shifting the resonance condition of the nearby surface plasmon, this high refractive index coating creates an effective matching of wave vectors across the metal film, allowing them to couple and enhance the optical response. A massive increase in the magnitude of enhanced transmission is observed, increasing from a 6-fold transmission enhancement through a bare silver grating to a near 100-fold enhancement after deposition of a tin oxide layer of appropriate thickness (â¼310 nm). This optical transmission enhancement is then probed through computational modeling and by experiments with liquids of various refractive index values. The matched system shows an increased amplitude sensitivity with respect to refractive index changes and a waveguide like behavior within the tin oxide film. As an alternative configuration, we also demonstrate coupling the front and back-side plasmon modes by using a lower refractive index substrate in order to blue-shift the back-side surface plasmon. Coupling between the two plasmon modes is then demonstrated by introducing aqueous solutions of various refractive index values. Under the proper conditions, this matched system also shows a substantial enhancement in transmission. This technique of wave vector matching provides a route to substantially increasing the plasmon enhanced optical transmission through metal gratings, which has potential application in improved plasmonic sensing, spectroscopy, and plasmon-based optical devices.
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This paper reports a tunable photonic device that incorporates a thin layer of phase-change material, Ge2Sb2Te5 (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. Inserting the GST material into the gating waveguide makes it possible to control the GMR mode. Here, the GST-PC device was numerically designed and optimized to obtain significant tuning of the GMR mode around 1550 nm. The tuning phenomena were experimentally demonstrated by the heat-induced phase change between crystalline and amorphous phases of the GST thin film. A spectral shift of the resonant wavelength from 1440 to 1610 nm was achieved via the crystallization process. The phase tuning of GST exhibits good repeatability as demonstrated by switching between amorphous and crystalline phases of GST for multiple cycles. The GST-PC device represents a new approach for tuning optical resonances with potential applications including but not limited to integrated photonic circuits, optical communications, and high-performance optical filters.
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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 â¼500 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. It is shown that when the pitch of the grating is much larger than the diameter of the colloidal particles, the grating trenches serve as compartments for deposition and the particles form close-packed, linear chains. Various ordered structures are observed as the dimensions of the grating pitch decrease and approach the diameter of the particles. The grating nanostructures guide the formation of various lattice geometries due to specific particle-surface and particle-particle interactions. Observed crystal lattices include square, hexagonal, and rhombic structures. The formation of these structures is explained in terms of the geometrical constraints imposed by the surface pattern and the particle diameter. These crystal lattices can be translated into large area samples when using corresponding single-pitch grating substrates. The initial monolayer lattice can also serve as a template for the growth of unique, bilayer structures that include rectangular lattices, chains of particle pairs or triplets, and graphitelike structured lattices. In addition, when coated with a thin silver layer, these various lattice configurations are shown to produce optical reflection features that are precisely controlled by the underlying structure as it varies from widely spaced particle chains to close-packed lattice geometries.
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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. The DNA origami template serves as a localized photosensitizer to facilitate reduction of silver ions directly from solution onto the DNA surface. The metallizing process is shown to result in a conformal metal coating, which grows in height to a self-limiting value with increasing photoreduction steps. Although this coating process results in a slight decrease in the triangle dimensions, the overall template shape is retained. Notably, this coating method exhibits characteristics of self-limiting and defect-filling growth, which results in a metal nanostructure that maps the shape of the original DNA template with a continuous and uniform metal layer and stops growing once all available DNA sites are exhausted.
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ADN/química , Conformación de Ácido Nucleico , Procesos Fotoquímicos , Plata/química , ADN/ultraestructura , Microscopía de Fuerza Atómica , Espectrofotometría UltravioletaRESUMEN
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. The top surface of the mold carries the grating pattern and the wedge is formed by a shallow angle between the top and bottom surfaces of the mold. During the replica molding process, a uniaxial force is applied to stretch the mold, resulting in a nearly linearly varying grating period. The period of the grating is determined using the magnitude of the force and the local thickness of the mold. The grating period of the fabricated device spans a range of 421.8-463.3 nm over a distance of 20 mm. A high refractive index dielectric film is deposited on the graded-period grating to act as the waveguide layer of the PC device. The resonance reflection feature of the device varies linearly in a range of 680.2-737.0 nm over the length of the grating.
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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. Recently, diffraction grating couplers have been demonstrated as a highly tunable platform for SEIRA. Indeed, gratings are an experimentally advantageous platform due to the inherently tunable nature of surface plasmon excitation at these surfaces since both the grating pitch and incident angle can be used to modify the spectral location of the plasmon resonance. In this work, we use laser interference lithography (LIL) to fabricate gratings possessing multiple pitch values by subjecting photoresist-coated glass slides to repetitive exposures at varying orientations. After metal coating, these gratings produced multiple, simultaneous plasmon peaks associated with the multipitched surface, as identified by infrared reflectance measurements. These plasmon peaks could then be coupled to vibrational modes in thin films to provide localized enhancement of infrared signals. We demonstrate the flexibility and tunability of this platform for signal enhancement. It is anticipated that, with further refinement, this approach might be used as a general platform for broadband enhancement of infrared spectroscopy.
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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. These aligned fibers of ECM are commonly composed of type I collagen, an abundant structural protein around tumors. In this paper, we epitaxially grew several different patterns of organized type I collagen on mica and compared the morphology and contact guidance behavior of two invasive breast cancer cell lines (MDA-MB-231 and MTLn3 cells). Others have shown that these cells randomly migrate in qualitatively different ways. MDA-MB-231 cells exert large traction forces, tightly adhere to the ECM, and migrate with spindle-shaped morphology and thus adopt a mesenchymal mode of migration. MTLn3 cells exert small traction forces, loosely adhere to the ECM, and migrate with a more rounded morphology and thus adopt an amoeboid mode of migration. As the degree of alignment of type I collagen fibrils increases, cells become more elongated and engage in more directed contact guidance. MDA-MB-231 cells perceive the directional signal of highly aligned type I collagen fibrils with high fidelity, elongating to large extents and migrating directionally. Interestingly, behavior in MTLn3 cells differs. While highly aligned type I collagen fibril patterns facilitate spreading and random migration of MTLn3 cells, they do not support elongation or directed migration. Thus, different contact guidance cues bias cell migration differently and the fidelity of contact guidance is cell type dependent, suggesting that ECM alignment is a permissive cue for contact guidance, but requires a cell to have certain properties to interpret that cue.
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Neoplasias de la Mama/patología , Colágenos Fibrilares/química , Silicatos de Aluminio/química , Línea Celular Tumoral , Movimiento Celular , Femenino , Colágenos Fibrilares/metabolismo , Humanos , Microscopía de Fuerza Atómica , Propiedades de SuperficieRESUMEN
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. We observed up to 10% enhancement in the short circuit current of poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl}):(6,6)-phenyl C71-butyric acid methyl ester (PTB7:PC71BM) OPV cells. Theoretically and experimentally investigating several MLA dimensions, we found that photocurrent increases with the ratio of the height to the pitch size of MLA. Simulations reveal the enhancement mechanisms: MLA focuses light, and also increases the light path within the active-layer by diffraction. Photocurrent enhancements increase for a polymer system with thinner active-layers, as demonstrated in poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT):PC71BM OPVs with 17% improvement in short circuit current.
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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. In this report, we demonstrate angle-tunable enhancement of vibrational stretching modes associated with a thin poly(methyl methacrylate) (PMMA) film that is coupled to a silver-coated diffraction grating. Gratings are fabricated using laser interference lithography to achieve precise surface periodicities, which can be used to generate surface plasmons that overlap with specific vibrational modes in the polymer film. Infrared reflection absorption spectra are presented for both bare silver and PMMA-coated silver gratings at a range of angles and polarization states. In addition, spectra were obtained with the grating direction oriented perpendicular and parallel to the infrared source in order to isolate plasmon enhancement effects. Optical simulations using the rigorous coupled-wave analysis method were used to identify the origin of the plasmon-induced enhancement. Angle-dependent absorption measurements achieved signal enhancements of more than 10-times the signal in the absence of the plasmon.
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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. Their more recently recognized semiconducting functionality has inspired recent developments in applications requiring organic semiconductors. In this context, CTCs offer a tuneable energy gap, unique charge-transport properties, tailorable physicochemical interactions, photoresponsiveness, and the potential for scalable manufacturing. Here, an updated viewpoint on CTCs is provided, presenting them as emerging organic semiconductors. To this end, their electronic and chemical properties alongside their synthesis methods are reviewed. The unique properties of CTCs that benefit various related applications in the realms of organic optoelectronics, catalysts, and gas sensors are discussed. Insights for future developments and existing limitations are described.
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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. The influence of wavelength and angle of incidence on plasmon coupling can be readily characterized via dispersion images, and the associated image features can be indexed to matching conditions associated with several diffracted orders at both the front and back of the grating. These features collapse onto a set of global dispersion curves when plotted as peak energy versus the grating wavevector, with feature locations clustered according to the refractive index values of the neighboring dielectric material, either air or polycarbonate. Coating of the grating with multilayer arachidic acid films via Langmuir-Blodgett deposition results in red-shifting of some, but not all, of the plasmon features. The magnitude of the shift is a function of the film thickness, wavelength, and angle of incidence. Dispersion images clearly depict the red-shifting and also broadening of the front side features with increasing film thickness. In contrast, little change is observed in features associated with the back-side of the grating. The nature and magnitude of the interaction between the plasmon modes appearing at the front and back sides of the grating are discussed and analyzed in terms of the predicted interactions determined via optical modeling calculations.
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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. This inlet provides extremely rapid mass detection as well as a high flux of products from the electrode surface into the mass spectrometer. The impinging jet is designed in a wall-tube configuration, in which the jet diameter is large compared to the electrode diameter, thus providing uniform and rapid mass transfer conditions over the entirety of the electrode surface. This combination of rapid detection and controllable flow conditions allows a wide range of hydrodynamic conditions to be accessed with simultaneous electrochemical and mass spectrometric detection of dissolved gas species, which is important in the analysis of a range of electrochemical reactions. The capabilities of this configuration are illustrated using a platinum-coated electrode and several electrochemical reactions, including ferrocyanide oxidation, proton reduction, and oxalic acid oxidation.
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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. Herein, we demonstrate an abiotic sensor that uses semiconducting single-walled carbon nanotubes (SWCNTs) as near-infrared fluorescent transducers to report membrane interactions. This sensor is composed of SWCNTs aqueously suspended in lipid, creating a cylindrical, bilayer corona; these SWCNT probes are very sensitive to solvent access (changes in permittivity) and thus report morphological changes to the lipid corona by modulation of fluorescent signals, where binding and disruption are reported as brightening and attenuation, respectively. This mechanism is first demonstrated with chemical and physical membrane-disruptive agents, including ethanol and sodium dodecyl sulfate, and application of electrical pulses. Known cell-penetrating and antimicrobial peptides are then used to demonstrate how the dynamic response of these sensors can be deconvoluted to evaluate different parallel mechanisms of interaction. Last, SWCNTs functionalized in several different bacterial lipopolysaccharides (Pseudomonas aeruginosa, Klebsiella pneumoniae, and Escherichia coli) are used to evaluate a panel of known membrane-disrupting antimicrobials to demonstrate that drug selectivity can be assessed by suspension of SWCNTs with different membrane materials.
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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. A gap exists between these peaks in the region of the spectrum associated with the molecular resonance and reflects quenching of the plasmon wave due to violation of the resonance condition. A second observation is the appearance of a peak in the s-polarized reflection spectra. The initial position of this peak corresponds to where the refractive index of the adsorbate achieves its largest value, which occurs at wavelengths just slightly larger than the maximum in the molecular resonance. Although this peak initially appears to be nondispersive, both experimental data and optical modeling indicate that increasing the film thickness shifts the peak position to longer wavelengths, which implies that this peak is not associated with the molecular resonance but, rather, is dispersive in nature. Indeed, modeling shows that this peak is due to a guided mode in the film, which appears in these conditions due to the abnormally high refractive index of the film near the absorbance maximum. Results also show that, with increasing film thickness, numerous additional guided modes appear and move throughout the visible spectrum for both s- and p-polarized light. Notably, these guided modes are also quenched near the location of the molecular resonance. The quenching of both the plasmon resonance and the guided modes can be explained by a large decrease in the in-plane wave propagation length that occurs near the molecular resonance, which is a direct result of the film's large absorption coefficient.
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â³Ultrathinâ³ 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. Analysis by atom probe tomography (APT) showed that continuous copper films of approximately 1 nm thickness were formed, apparently the first demonstration of deposition of ultrathin metal layers on oxidized substrates from aqueous solutions. The APT reconstructions indicate that deposited copper replaced a portion of the surface oxide film on aluminum. The results are consistent with mechanisms in which surface hydride species on aluminum mediate deposition, either by directly reducing cupric ions or by inducing electronic conduction in the oxide, thus enabling cupric ion reduction by Al metal.
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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. A Bertrand lens is used to focus the grating's diffraction image onto a CCD camera, and the spatial position of the diffracted peaks can be readily transformed into a spectral signature of the transmitted light without the use of a spectrometer. The surface plasmon peaks appear as a region of enhanced transmission when the sample is illuminated with p-polarized light, and the peak position reflects the local dielectric properties of the metal interface, including the presence of thin films. The ability to track the position of the plasmon peak and, thus, measure film thickness is demonstrated using the diffracted peaks for samples possessing thin films of silicon oxide. The experimental results are then compared with calculations of optical diffraction through a model, film-coated grating using the rigorously coupled wave analysis simulation method.
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Oro/química , Nanopartículas del Metal/química , Resonancia por Plasmón de Superficie/métodos , Adsorción , Luz , Metales/química , Óxidos/química , Compuestos de Silicona/químicaRESUMEN
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. A thin contaminant layer, primarily consisting of water and atmospheric gases, was observed on a fresh tip. This sample exhibited crystalline lattice spacings consistent with the interlayer spacing of {200} lattice planes of bulk gold. A thin oxide layer was created on the gold surface via plasma oxidation, and the thickness and composition of this layer was measured. Clear evidence of a nanometer-thick oxide layer was seen coating the gold tip, and the atomic composition of the oxide layer was consistent with the expected stoichiometry for gold oxide. Monomolecular anions layers of Br(-) and I(-) were created via adsorption from aqueous solutions onto the gold. Atom probe data verified the presence of the monomolecular anion layers on the gold surface, with ion density values consistent with literature values. A hexanethiolate monolayer was coated onto the gold tip, and atom probe analysis revealed a thin film whose ion fragments were consistent with the molecular composition of the monolayer and a surface coverage similar to that expected from literature. Details of the various coating compositions and structures are presented, along with discussion of the reconstruction issues associated with properly analyzing these thin-film systems.
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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. At the proper incident angle, the angle-spread image shows the complete surface plasmon resonance curve over a span of locations on the surface. This imaging system is combined with a sample configuration consisting of a series of gold microelectrode bands, each with independent electrochemical control. In solution, this system can be used to perform high-throughput and dynamic electrochemical experiments. Simultaneous measurement of electrochemical and surface plasmon resonance can be quantitatively performed on each of the electrode surfaces either by holding each electrode at a different potential value or by scanning the applied potential. The sensitivity of this configuration is demonstrated by monitoring oxide formation and removal at a gold electrode in an aqueous electrolyte. A second example, with the use of a thin poly(aniline) coating, illustrates the ability to monitor film changes, including thickness, dielectric properties, and associated electrochemically induced polymer oxidation/reduction on multiple electrodes. This represents a simple and compact method for combining the sensitivity of surface plasmon resonance into an array-based, high-throughput electrochemical system.
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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. A gold-coated replica of this surface elicited an optical response that consisted of a series of narrow, enhanced transmission peaks spread over the visible spectrum. The location and magnitude of these transmission peaks varied along the surface of the grating and coincided with conditions where surface plasmons were excited in the gold film via coupling to one or more of the grating's diffracted orders. A series of measurements were carried out using optical diffraction, atomic force microscopy, and normal incidence optical transmission to compare the grating topology to the corresponding optical response. In addition, the impact of a thin dielectric coating on the transmission response was determined by depositing a thin silicon oxide film over the grating surface. After coating, wavelength shifts were observed in the transmission peaks, with the magnitude of the shifts being a function of the film thickness, the local grating structure, and the diffracted order associated with each peak. These results illustrate the ability of this surface to serve as an information-rich optical sensor whose properties can be tuned by control of the local grating topology.