Battling Chemical Weapons with Zirconium Hydroxide Nanoparticle Sorbent: Impact of Environmental Contaminants on Sarin Sequestration and Decomposition.

The promising reactive sorbent zirconium hydroxide (ZH) was challenged with common environmental contaminants (CO, SO, and NO) to determine the impact on chemical warfare agent decomposition. Several environmental adsorbates rapidly formed on the ZH surface through available hydroxyl species and coordinatively unsaturated zirconium sites. ZH decontamination effectiveness was determined using a suite of instrumentation including in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor sarin (GB) decomposition in real time and at ambient pressure.

Kinetics of Dimethyl Methylphosphonate Adsorption and Decomposition on Zirconium Hydroxide Using Variable Temperature In Situ Attenuated Total Reflection Infrared Spectroscopy.

The decomposition mechanisms of dimethyl methylphosphonate (DMMP), a widely used simulant for organophosphorus chemical warfare agents (CWAs), are relatively well understood from previous studies. However, there still lacks a quantitative description of DMMP decomposition kinetics under ambient conditions that is relevant for sequestration applications. We investigated adsorption and decomposition kinetics of DMMP on amorphous zirconium hydroxide (ZH) using variable-temperature in situ attenuated total reflection (ATR) infrared spectroscopy.

Silicon nanowire arrays for the preconcentration and separation of trace explosives vapors.

Silicon nanowire (SiNW) arrays are demonstrated as a suitable platform for the preconcentration of trace nitroaromatic compounds and subsequent desorption via Joule heating of the array. Arrays are fabricated from Si wafers containing an epitaxially grown layer of low conductivity intrinsic Si sandwiched between layers of high conductivity p-type Si. Passage of current through the nanowires results in nanowire temperatures in excess of 200 °C during heating of the arrays as verified by using the temperature-dependent shift of the Si Raman band at ˜520 cm.

Environmental Effects on Zirconium Hydroxide Nanoparticles and Chemical Warfare Agent Decomposition: Implications of Atmospheric Water and Carbon Dioxide.

Zirconium hydroxide (Zr(OH)) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) and toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness of Zr(OH) has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g.

Quantification of Efficient Plasmonic Hot-Electron Injection in Gold Nanoparticle-TiO Films.

Excitation of localized surface plasmons in metal nanostructures generates hot electrons that can be transferred to an adjacent semiconductor, greatly enhancing the potential light-harvesting capabilities of photovoltaic and photocatalytic devices. Typically, the external quantum efficiency of these hot-electron devices is too low for practical applications (<1%), and the physics underlying this low yield remains unclear. Here, we use transient absorption spectroscopy to quantify the efficiency of the initial electron transfer in model systems composed of gold nanoparticles (NPs) fully embedded in TiO or AlO films.

Surface plasmon polariton-induced hot carrier generation for photocatalysis.

Non-radiative plasmon decay in noble metals generates highly energetic carriers under visible light irradiation, which opens new prospects in the fields of photocatalysis, photovoltaics, and photodetection. While localized surface plasmon-induced hot carrier generation occurs in diverse metal nanostructures, inhomogeneities typical of many metal-semiconductor plasmonic nanostructures hinder predictable control of photocarrier generation and therefore reproducible carrier-mediated photochemistry. Here, we generate traveling surface plasmon polaritons (SPPs) at the interface between a noble metal/titanium dioxide (TiO) heterostructure film and aqueous solution, enabling simultaneous optical and electrochemical interrogation of plasmon-mediated chemistry in a system whose resonance may be continuously tuned via the incident optical excitation angle.

Fabrication of metallic nanodisc hexagonal arrays using nanosphere lithography and two-step lift-off.

Nanosphere lithography (NSL) has been widely used as an inexpensive method to create periodic arrays of metallic nanoparticles or nanodiscs on substrates. However, most nanodisc arrays derived from a NSL template are restricted to hexagonally-ordered triangular arrays because the metal layer is deposited onto the interstices between the nanospheres. Metallic nanodisc arrays with the same arrangement as the original nanosphere array have been rarely reported.

The importance of correcting for variable probe-sample interactions in AFM-IR spectroscopy: AFM-IR of dried bacteria on a polyurethane film.

AFM-IR is a combined atomic force microscopy-infrared spectroscopy method that shows promise for nanoscale chemical characterization of biological-materials interactions. In an effort to apply this method to quantitatively probe mechanisms of microbiologically induced polyurethane degradation, we have investigated monolayer clusters of ∼200 nm thick Pseudomonas protegens Pf-5 bacteria (Pf) on a 300 nm thick polyether-polyurethane (PU) film. Here, the impact of the different biological and polymer mechanical properties on the thermomechanical AFM-IR detection mechanism was first assessed without the additional complication of polymer degradation.

Influence of inhomogeneous porosity on silicon nanowire Raman enhancement and leaky mode modulated photoluminescence.

Metal-assisted chemical etching (MACE) offers an inexpensive, massively parallel fabrication process for producing silicon nanowires (SiNWs). These nanowires can possess a degree of porosity depending on etch conditions. Because the porosity is often spatially inhomogeneous, there is a need to better understand its nature if applications exploiting the porosity are to be pursued.

The impact of culture medium on the development and physiology of biofilms of Pseudomonas fluorescens formed on polyurethane paint.

Microbial biofilms cause the deterioration of polymeric coatings such as polyurethanes (PUs). In many cases, microbes have been shown to use the PU as a nutrient source. The interaction between biofilms and nutritive substrata is complex, since both the medium and the substratum can provide nutrients that affect biofilm formation and biodeterioration.

Quantitative LSPR imaging for biosensing with single nanostructure resolution.

Localized surface plasmon resonance (LSPR) imaging has the potential to map complex spatio-temporal variations in analyte concentration, such as those produced by protein secretions from live cells. A fundamental roadblock to the realization of such applications is the challenge of calibrating a nanoscale sensor for quantitative analysis. Here, we introduce a new, to our knowledge, LSPR imaging and analysis technique that enables the calibration of hundreds of individual gold nanostructures in parallel.

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.

Periodically porous top electrodes on vertical nanowire arrays for highly sensitive gas detection.

Nanowires of various materials and configurations have been shown to be highly effective in the detection of chemical and biological species. In this paper, we report a novel, nanosphere-enabled approach to fabricating highly sensitive gas sensors based on ordered arrays of vertically aligned silicon nanowires topped with a periodically porous top electrode. The vertical array configuration helps to greatly increase the sensitivity of the sensor while the pores in the top electrode layer significantly improve sensing response times by allowing analyte gases to pass through freely.

Vapor detection performance of vertically aligned, ordered arrays of silicon nanowires with a porous electrode.

Vertically aligned, ordered arrays of silicon nanowires capped with a porous top electrode are used to detect gas phase ammonia and nitrogen dioxide in humidified air. The sensors had very fast response times and large signal-to-noise ratios. Calibration curves were created using both an initial slope method and a fixed-time point method.

Controllable redox reaction of chemically purified DNA-single walled carbon nanotube hybrids with hydrogen peroxide.

We report for the first time the controllable redox reaction of chemically purified ssDNA-HiPco SWNT hybrids with hydrogen peroxide. Compared with the suspensions before separation, the purified SWNT suspensions become inert with hydrogen peroxide which may serve as a platform for further chemical manipulation. In the presence of thiocyanate ions, the reaction of SWNTs with hydrogen peroxide is initiated and accelerated at the earlier reaction stage, accompanied with the near-infrared spectral suppression.

Recoverable solution reaction of HiPco carbon nanotubes with hydrogen peroxide.

There is increasing interest in developing single-walled carbon nanotubes (SWNTs)-based optical biosensors for remote or in vitro and in vivo sensing because the near-IR optical properties of SWNTs are very sensitive to surrounding environmental changes. Many enzyme-catalyzed reactions yield hydrogen peroxide (H(2)O(2)) as a product. To our knowledge, there is no report on the interaction of H(2)O(2) with SWNTs from the optical sensing point of view.

Aggregation effects on the Raman spectroscopy of dielectrophoretically deposited single-walled carbon nanotubes.

The effect of aggregation on surfactant-suspended individual single-walled carbon nanotube (SWNT) Raman spectroscopy has been explored in the context of dielectrophoretic separation. The Raman spectra of individual surfactant-suspended HiPco SWNTs deposited on a substrate and the same suspension deposited via dielectrophoresis were compared as a function of iterative aggregation states. The evolution of the samples' radial breathing modes and tangential modes at multiple excitation wavelengths (514, 633, and 785 nm) illustrates a direct correlation between changes in the Raman spectra and a broadening and downshifting of resonance transition energies.

Optically sensing additional sonication effects on dispersed HiPco nanotubes in aerated water.

Ultrasonication is a necessary process to make single-walled carbon nanotubes (SWNTs) soluble in aqueous solution with surfactants such as sodium dodecyl sulfate (SDS). However, an understanding of the sonication effects on the electronic and optical properties of SWNTs in aqueous solution is still lacking. Here, we have observed that sonication-induced pH changes suppress the optical transitions of the first interband transition pair (S11) in the density of states of semiconducting SWNTs while other possible intermediates induced by sonication contribute less significantly to the observed spectral changes without the involvement of sonication-induced pH decrease.

Phenylphosphonic acid functionalization of indium tin oxide: surface chemistry and work functions.

The work function of indium tin oxide (ITO) substrates was modified with phosphonic acid molecular films. The ITO surfaces were treated prior to functionalization with a base cleaning procedure. The film growth and coverage were quantified by contact angle goniometry and XPS.

Optical pH response of DNA wrapped HiPco carbon nanotubes.

Solubilization of single-walled carbon nanotubes in aqueous solution by surface functionalization is of great interest for biosensor applications and separation of individual nanotubes. Here we have observed that HiPco nanotubes can be stably dispersed into double-stranded DNA aqueous solutions. Interestingly, the first optical interband transitions of the DNA wrapped semiconducting HiPco nanotubes possess a unique pH dependence, a phenomenon observed in SDS-encased and carboxylic group functionalized single-walled carbon nanotubes.

Solubilization of single-wall carbon nanotubes by supramolecular encapsulation of helical amylose.

We have developed a simple, efficient process for solubilization of single-wall carbon nanotubes (SWNTs) with amylose in aqueous DMSO. This process requires two important conditions, presonication of SWNTs and subsequent amylose treatment in an optimum mixture of DMSO/H2O. The former step separates SWNT bundles, and the latter step provides a maximum cooperative interaction of SWNTs with amylose, leading to the immediate and complete solubilization.

Water-soluble and optically pH-sensitive single-walled carbon nanotubes from surface modification.

There is great interest in using single-walled carbon nanotubes (SWNTs) as nanoscale probes and sensors in biological electronics and optical devices because the electronic and optical properties of SWNTs are extremely sensitive to the surrounding environments. A well-controlled modification of SWNT surfaces may provide unique interfaces that are sensitive to the biological variables such as pH, glucose, various ions and proteins. In this paper, we report a facile chemical routine to prepare water-soluble SWNTs that still retain their van Hove singularities after acid oxidative treatment.