Evaluation of Porous Silicon Oxide on Silicon Microcantilevers for Sensitive Detection of Gaseous HF.

Sensitive detection of harmful chemicals in industrial applications is pertinent to safety. In this work, we demonstrate the use of a sensitive silicon microcantilever (MC) system with a porous silicon oxide layer deposited on the active side of the MCs that have been mechanically manipulated to increase sensitivity. Included is the evaluation of porous silicon oxide present on different geometries of MCs and exposed to varying concentrations of hydrogen fluoride in humid air. Profilometry and the signal generated by the stress-induced porous silicon oxide (PSO) coating and bending of the MC were used as methods of evaluation.

Synthesis of Half-Sphere/Half-Funnel-Shaped Silica Structures by Reagent Localization and the Role of Water in Shape Control.

Shape control of silica structures is demonstrated by localization of the reagents. A uniform dispersion of reagents provided straight silica rods, whereas localization of the reagents in the emulsion droplet periphery provided a new type of half-sphere/half-funnel structure. The effect of water concentration appeared to be related to the ease of diffusion of the silica precursor inside the emulsion droplet (i.e., the higher the water concentration, the lower the silica precursor diffusion).

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria.

Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

Step-by-Step Growth of Complex Oxide Microstructures.

The synthesis of complex and hybrid oxide microstructures is of fundamental interest and practical applications. However, the design and synthesis of such structures is a challenging task. A solution-phase process to synthesize complex silica and silica-titania hybrid microstructures was developed by exploiting the emulsion-droplet-based step-by-step growth featuring shape control. The strategy is robust and can be extended to the preparation of complex hybrid structures consisting of two or more materials, with each having its own shape.

Strong and electrically conductive graphene-based composite fibers and laminates.

Graphene is an ideal candidate for lightweight, high-strength composite materials given its superior mechanical properties (specific strength of 130 GPa and stiffness of 1 TPa). To date, easily scalable graphene-like materials in a form of separated flakes (exfoliated graphene, graphene oxide, and reduced graphene oxide) have been investigated as candidates for large-scale applications such as material reinforcement. These graphene-like materials do not fully exhibit all the capabilities of graphene in composite materials. In the current study, we show that macro (2 inch × 2 inch) graphene laminates and fibers can be produced using large continuous sheets of single-layer graphene grown by chemical vapor deposition. The resulting composite structures have potential to outperform the current state-of-the-art composite materials in both mechanical properties and electrical conductivities (>8 S/cm with only 0.13% volumetric graphene loading and 5 × 10(3) S/cm for pure graphene fibers) with estimated graphene contributions of >10 GPa in strength and 1 TPa in stiffness.

Control of membrane permeability in air-stable droplet interface bilayers.

Air-stable droplet interface bilayers (airDIBs) on oil-infused surfaces are versatile model membranes for synthetic biology applications, including biosensing of airborne species. However, airDIBs are subject to evaporation, which can, over time, destabilize them and reduce their useful lifetime compared to traditional DIBs that are fully submerged in oil. Here, we show that the lifetimes of airDIBs can be extended by as much as an order of magnitude by maintaining the temperature just above the dew point. We find that raising the temperature from near the dew point (which was 7 °C at 38.5% relative humidity and 22 °C air temperature) to 20 °C results in the loss of hydrated water molecules from the polar headgroups of the lipid bilayer membrane due to evaporation, resulting in a phase transition with increased disorder. This dehydration transition primarily affects the bilayer electrical resistance by increasing the permeability through an increasingly disordered polar headgroup region of the bilayer. Temperature and relative humidity are conveniently tunable parameters for controlling the stability and composition of airDIB membranes while still allowing for operation in ambient environments.

Optically transparent and environmentally durable superhydrophobic coating based on functionalized SiO2 nanoparticles.

Optical surfaces such as mirrors and windows that are exposed to outdoor environmental conditions are susceptible to dust buildup and water condensation. The application of transparent superhydrophobic coatings on optical surfaces can improve outdoor performance via a 'self-cleaning' effect similar to the Lotus effect. The contact angle (CA) of water droplets on a typical hydrophobic flat surface varies from 100° to 120°. Adding roughness or microtexture to a hydrophobic surface leads to an enhancement of hydrophobicity and the CA can be increased to a value in the range of 160°-175°. This result is remarkable because such behavior cannot be explained using surface chemistry alone. When surface features are on the order of 100 nm or smaller, they exhibit superhydrophobic behavior and maintain their optical transparency. In this work we discuss our results on transparent superhydrophobic coatings that can be applied across large surface areas. We have used functionalized silica nanoparticles to coat various optical elements and have measured the CA and optical transmission between 190 and 1100 nm on these elements. The functionalized silica nanoparticles were dissolved in a solution of the solvents, while the binder used was a polyurethane clearcoat. This solution was spin-coated onto a variety of test glass substrates, and following a curing period of about 30 min, these coatings exhibited superhydrophobic behavior with a static CA ≥ 160°.

Superhydrophobic analyte concentration utilizing colloid-pillar array SERS substrates.

The ability to detect a few molecules present in a large sample is of great interest for the detection of trace components in both medicinal and environmental samples. Surface enhanced Raman spectroscopy (SERS) is a technique that can be utilized to detect molecules at very low absolute numbers. However, detection at trace concentration levels in real samples requires properly designed delivery and detection systems. The following work involves superhydrophobic surfaces that have as a framework deterministic or stochastic silicon pillar arrays formed by lithographic or metal dewetting protocols, respectively. In order to generate the necessary plasmonic substrate for SERS detection, simple and flow stable Ag colloid was added to the functionalized pillar array system via soaking. Native pillars and pillars with hydrophobic modification are used. The pillars provide a means to concentrate analyte via superhydrophobic droplet evaporation effects. A ≥ 100-fold concentration of analyte was estimated, with a limit of detection of 2.9 × 10(-12) M for mitoxantrone dihydrochloride. Additionally, analytes were delivered to the surface via a multiplex approach in order to demonstrate an ability to control droplet size and placement for scaled-up uses in real world applications. Finally, a concentration process involving transport and sequestration based on surface treatment selective wicking is demonstrated.

Synthesis of very small diameter silica nanofibers using sound waves.

Silica nanofibers of an average diameter ≈30 nm and length ≈100 µm have been synthesized using an unprecedented strategy: sound waves. A new phenomenon, spinning off the nanofibers at silica rod tips, is also observed.

Air-stable droplet interface bilayers on oil-infused surfaces.

Droplet interface bilayers are versatile model membranes useful for synthetic biology and biosensing; however, to date they have always been confined to fluid reservoirs. Here, we demonstrate that when two or more water droplets collide on an oil-infused substrate, they exhibit noncoalescence due to the formation of a thin oil film that gets squeezed between the droplets from the bottom up. We show that when phospholipids are included in the water droplets, a stable droplet interface bilayer forms between the noncoalescing water droplets. As with traditional oil-submerged droplet interface bilayers, we were able to characterize ion channel transport by incorporating peptides into each droplet. Our findings reveal that droplet interface bilayers can function in ambient environments, which could potentially enable biosensing of airborne matter.

Synthesis of segmented silica rods by regulation of the growth temperature.

The control of the diameter of colloidal structures is of fundamental interest and practical importance. We synthesized segmented silica rods by regulating the reaction temperature while the rods were growing. With higher growth temperatures, the segment diameter became smaller. Longer incubation times gave longer segments at the same temperature. Similarly, high temperature for the same incubation time gave longer segments. It appears that the correlation between temperature and diameter results from the relation between temperature and the size of the emulsion droplet, that is, the higher the temperature, the smaller the emulsion droplet.

Role of hydrogen in chemical vapor deposition growth of large single-crystal graphene.

We show that graphene chemical vapor deposition growth on copper foil using methane as a carbon source is strongly affected by hydrogen, which appears to serve a dual role: an activator of the surface bound carbon that is necessary for monolayer growth and an etching reagent that controls the size and morphology of the graphene domains. The resulting growth rate for a fixed methane partial pressure has a maximum at hydrogen partial pressures 200-400 times that of methane. The morphology and size of the graphene domains, as well as the number of layers, change with hydrogen pressure from irregularly shaped incomplete bilayers to well-defined perfect single layer hexagons. Raman spectra suggest the zigzag termination in the hexagons as more stable than the armchair edges.

Electrical and thermal conductivity of low temperature CVD graphene: the effect of disorder.

In this paper we present a study of graphene produced by chemical vapor deposition (CVD) under different conditions with the main emphasis on correlating the thermal and electrical properties with the degree of disorder. Graphene grown by CVD on Cu and Ni catalysts demonstrates the increasing extent of disorder at low deposition temperatures as revealed by the Raman peak ratio, IG/ID. We relate this ratio to the characteristic domain size, La, and investigate the electrical and thermal conductivity of graphene as a function of La. The electrical resistivity, ρ, measured on graphene samples transferred onto SiO2/Si substrates shows linear correlation with La(-1). The thermal conductivity, K, measured on the same graphene samples suspended on silicon pillars, on the other hand, appears to have a much weaker dependence on La, close to K∼La1/3. It results in an apparent ρ∼K3 correlation between them. Despite the progressively increasing structural disorder in graphene grown at lower temperatures, it shows remarkably high thermal conductivity (10(2)-10(3) W K(-1) m(-1)) and low electrical (10(3)-3×10(5) Ω) resistivities suitable for various applications.

Differentially ligand-functionalized microcantilever arrays for metal ion identification and sensing.

A microcantilever array sensor with cantilevers differentially functionalized with self-assembled monolayers (SAMs) of thiolated ligands is prepared by simultaneous capillary coating. This array is described for the detection of metal ions including Li+, Cs+, Cu2+, Co2+, Fe3+, and Al3+. Binding of the charged metal cations to the surface of the microcantilever sensors produces surface stress that causes bending of the cantilevers that is detected as tip deflection using an array of vertical cavity surface emitting lasers and a position-sensitive detector. Optimization studies of the nanostructured dealloyed surface were performed for SAMs based on their response to Cu2+ cations. Sensor performance experiments demonstrate good sensitivity toward metal ions, with limits of detection as low as 10(-8) molar. A multiplex capillary coating method for cantilever array creation is demonstrated and validated based on surface-enhanced Raman spectra obtained from adjacent cantilevers that were functionalized with different thiolated SAMs. The cantilever array coated with a range of thiolated ligands was exposed to the group of metal ions. The response characteristics of each metal ion show substantial diversity, varying not only in response magnitude, but response kinetics. A pattern recognition algorithm based on a combination of independent component analysis and support vector machines was able to validate that the sensor array response profiles produced enough information content that metal ions could be reliably classified with probabilities as high as 89%.

Development of a nanomechanical biosensor for analysis of endocrine disrupting chemicals.

A nanomechanical transducer is developed to detect and screen endocrine disrupting chemicals (EDCs) combining fluidic sample injection and delivery with bioreceptor protein functionalized microcantilevers (MCs). The adverse affects of EDCs on the endocrine system of humans, livestock, and wildlife provides strong motivation for advances in analytical detection and monitoring techniques. The combination of protein receptors, which include estrogen receptor alpha (ER-alpha) and estrogen receptor beta (ER-beta), as well as monoclonal antibodies (Ab), with MC systems employing modified nanostructured surfaces provides for excellent nanomechanical response sensitivity and the inherent selectivity of biospecific receptor-EDC interactions. The observed ranking of binding interaction of the tested EDCs with ER-beta is diethylstilbestrol (DES) > 17-beta-estradiol > 17-alpha-estradiol > 2-OH-estrone > bisphenol A > p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) with measurements exhibiting intra-day RSDs of about 3%. A comparison of responses of three EDCs, which include 17-beta-estradiol, 17-alpha-estradiol, and 2-OH-estrone, with ER-beta and ER-alpha illustrates which estrogen receptor subtype provides the greatest sensitivity. Antibodies specific to a particular EDC can also be used for analyte specific screening. Calibration plots for a MC functionalized with anti-17-beta-estradiol Ab show responses in the range of 1 x 10(-11) through 1 x 10(-7) M for 17-beta-estradiol with a linear portion extending over two orders of magnitude in concentration.

Independent component analysis of nanomechanical responses of cantilever arrays.

The ability to detect and identify chemical and biological elements in air or liquid environments is of far reaching importance. Performing this task using technology that minimally impacts the perceived environment is the ultimate goal. The development of functionalized cantilever arrays with nanomechanical sensing is an important step towards this goal. This report couples the feature extraction abilities of independent component analysis (ICA) and the classification techniques of neural networks to analyze the signals produced by microcantilever-array-based nanomechanical sensors. The unique capabilities of this analysis unleash the potential of this sensing technology to accurately identify chemical mixtures and concentrations. Furthermore, it is demonstrated that the knowledge of how the sensor array reacts to individual analytes in isolation is sufficient information to decode mixtures of analytes--a substantial benefit, significantly increasing the analytical utility of these sensing devices.

Facile hyphenation of gas chromatography and a microcantilever array sensor for enhanced selectivity.

The very simple coupling of a standard, packed-column gas chromatograph with a microcantilever array (MCA) is demonstrated for enhanced selectivity and potential analyte identification in the analysis of volatile organic compounds (VOCs). The cantilevers in MCAs are differentially coated on one side with responsive phases (RPs) and produce bending responses of the cantilevers due to analyte-induced surface stresses. Generally, individual components are difficult to elucidate when introduced to MCA systems as mixtures, although pattern recognition techniques are helpful in identifying single components, binary mixtures, or composite responses of distinct mixtures (e.g., fragrances). In the present work, simple test VOC mixtures composed of acetone, ethanol, and trichloroethylene (TCE) in pentane and methanol and acetonitrile in pentane are first separated using a standard gas chromatograph and then introduced into a MCA flow cell. Significant amounts of response diversity to the analytes in the mixtures are demonstrated across the RP-coated cantilevers of the array. Principal component analysis is used to demonstrate that only three components of a four-component VOC mixture could be identified without mixture separation. Calibration studies are performed, demonstrating a good linear response over 2 orders of magnitude for each component in the primary study mixture. Studies of operational parameters including column temperature, column flow rate, and array cell temperature are conducted. Reproducibility studies of VOC peak areas and peak heights are also carried out showing RSDs of less than 4 and 3%, respectively, for intra-assay studies. Of practical significance is the facile manner by which the hyphenation of a mature separation technique and the burgeoning sensing approach is accomplished, and the potential to use pattern recognition techniques with MCAs as a new type of detector for chromatography with analyte-identifying capabilities.

Characterization of ligand-functionalized microcantilevers for metal ion sensing.

A sensor for metal cations is demonstrated using single and binary mixtures of different thiolated ligands as self-assembled monolayers (SAMs) functionalized on silicon microcantilevers (MCs) with gold nanostructured surfaces. Binding of charged metal ions to the active surface of a cantilever induces an apparent surface stress, thereby causing static bending of the MC that is detected in this work by a beam-bending technique. A MC response mechanism based on changes in surface charge is discussed. The monodentated ligands arranged as SAMs on the MC surface are not expected to fully satisfy the coordination sphere of the detected metals. This leads to lower binding constants than would be expected for chelating ligands, but reversible responses. The modest binding constants are compensated in terms of the magnitudes of responses by the inherent higher sensitivity of the nanostructured approach as opposed to more traditional smooth surface MCs. Response characteristics are optimized in terms of SAM formation time, concentration of ligand solution, and pH of working buffer solution. Limits of detection for the tested mono-, di-, and trivalent metal ions are in low to submicromolar range. The results indicated that shapes and magnitudes of response profiles are characteristics of the metal ions and type of SAM. The response factors for a given SAM with the tested metal ions, or for a given metal with the tested SAMs, varied by roughly 1 order of magnitude. While the observed selectivity is not large, it is anticipated that sufficient ionic recognition contrast is available for selective metal ion identification when differentially functionalized arrays of MCs (different ligands on different cantilevers in the array) are used in conjunction with pattern recognition techniques.

Detection of anthrax simulants with microcalorimetric spectroscopy: Bacillus subtilis and Bacillus cereus spores.

Recent advances in the development of ultrasensitive micromechnical thermal detectors have led to the advent of novel subfemtojoule microcalorimetric spectoscopy (CalSpec). On the basis of principles of photothermal IR spectroscopy combined with efficient thermomechanical transduction, CalSpec provides acquisition of vibrational spectra of microscopic samples and absorbates. We use CalSpec as a method of identifying nanogram quantities of biological micro-organisms. Our studies focus on Bacillus subtilis and Bacillus cereus spores as simulants for Bacillus anthracis spores. Using CalSpec, we measured IR spectra of B. subtilis and B. cereus spores present on surfaces in nanogram quantities (approximately 100-1,000 spores). The spectra acquired in the wavelength range of 690-4000 cm(-1) (2.5-14.5 microm) contain information-rich vibrational signatures that reflect the different ratios of biochemical makeup of the micro-organisms. The distinctive features in the spectra obtained for the two types of microorganism can be used to distinguish between the spores of the Bacillus family. As compared with conventional IR and Fourier-transform IR microscopic spectroscopy techniques, the advantages of the present technique include significantly improved sensitivity (at least a full order of magnitude), absence of expensive IR detectors, and excellent potential for miniaturization.