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.

The unique properties associated with beryllium metal ensures the continued use in many industries despite the documented health and environmental risks. While engineered safeguards and personal protective equipment can reduce risks associated with working with the metal, it has been mandated by the Environmental Protection Agency (EPA) and Occupational Safety and Health Administration (OSHA) that the workplace air and surfaces must be monitored for toxic levels. While many methods have been developed to monitor levels down to the low μg/m3, the complexity and expense of these methods have driven the investigation into alternate methodologies. Herein, we use a combination of the previously developed fluorescence Be(II) ion detection reagent, 10-hydroxybenzo[h]quinoline (HBQ), with an optical field enhanced silicon nanopillar array, creating a new surface immobilized (si-HBQ) platform. The si-HBQ platform allows the positive control of the reagent for demonstrated reusability and a pillar diameter based tunable enhancement. Furthermore, native silicon nanopillars are overcoated with thin layers of porous silicon oxide to develop an analytical platform capable of a 0.0006 μg/L limit of detection (LOD) using sub-μL sample volumes. Additionally, we demonstrate a method to multiplex the introduction of the sample to the platform, with minimal 5.2% relative standard deviation (RSD) at 0.1 μg/L, to accommodate the potentially large number of samples needed to maintain industrial compliance. The minimal sample and reagent volumes and lack of complex and highly specific instrumentation, as well as positive control and reusability of traditionally consumable reagents, create a platform that is accessible and economically advantageous.

Silicon nanopillars are important building elements for innovative nanoscale systems with unique optical, wetting, and chemical separation functionalities. However, technologies for creating expansive pillars arrays on the submicron scale are often complex and with practical time, cost, and method limitations. Herein we demonstrate the rapid fabrication of nanopillar arrays using the thermal dewetting of Pt films with thicknesses in the range from 5 to 19 nm followed by anisotropic reactive ion etching (RIE) of the substrate materials. A second level of roughness on the sub-30 nm scale is added by overcoating the silicon nanopillars with a conformal layer of porous silicon oxide (PSO) using room temperature plasma enhanced chemical vapor deposition (PECVD). This technique produced environmentally conscious, economically feasible, expansive nanopillar arrays with a production pathway scalable to industrial demands. The arrays were systematically analyzed for size, density, and variability of the pillar dimensions. We show that these stochastic arrays exhibit rapid wicking of various fluids and, when functionalized with a physiosorbed layer of silicone oil, act as a superhydrophobic surface. We also demonstrate high brightness fluorescence and selective transport of model dye compounds on surfaces of the implemented nanopillar arrays with two-tier roughness. The demonstrated combination of functionalities creates a platform with attributes inherently important for advanced separations and chemical analysis.Keywords: capillary flow wicking; enhanced fluorescence; nanopillars; porous silicon oxide; selective transport; superhydrophobic

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.

A simple and rapid fluorescence sensing platform based on the MIL-53(Fe) MOF was developed for fast, highly selective and ultrasensitive direct determination of MeHg+.

A method for hyphenating surface enhanced Raman scattering (SERS) and thin-layer chromatography (TLC) is presented that employs silver–polymer nanocomposites as an interface. Through the process of conformal blotting, analytes are transferred from TLC plates to nanocomposite films before being imaged via SERS. A procedure leading to maximum blotting efficiency was established by investigating various parameters such as time, pressure, and type and amount of blotting solvent. Additionally, limits of detection were established for test analytes malachite green isothiocyanate, 4-aminothiophenol, and Rhodamine 6G (Rh6G) ranging from 10–7 to 10–6 M. Band broadening due to blotting was minimal (∼10%) as examined by comparing the spatial extent of TLC-spotted Rh6G via fluorescence and then the SERS-based spot size on the nanocomposite after the blotting process. Finally, a separation of the test analytes was carried out on a TLC plate followed by blotting and the acquisition of distance × wavenumber × intensity three-dimensional TLC-SERS plots.

The importance of fluorescent detection in many fields is well established. While advancements in instrumentation and the development of brighter fluorophore have increased sensitivity and lowered the detection limits of the method, additional gains can be made by manipulating the local electromagnetic field. Herein we take advantage of silicon nanopillars that exhibit optical resonances and field enhancement on their surfaces and demonstrate their potential in improving performance of biomolecular fluorescent assays. We use electron beam lithography and wafer scale processes to create silicon nanoscale pillars with dimensions that can be tuned to maximize fluorescence enhancement in a particular spectral region. Performance of the nanopillar based fluorescent assay was quantified using two model bioaffinity systems (biotin-streptavidin and immunoglobulin G-antibody) as well as covalent binding of fluorescently tagged bovine serum albumin (BSA). The effects of pillar geometry and number of pillars in arrays were evaluated. Color specific and pillar diameter dependent enhancement of fluorescent signals is clearly demonstrated using green and red labels (FITC, DyLight 488, Alexa 568, and Alexa 596). The ratios of the on pillar to off pillar signals normalized by the nominal increase in surface area due to nanopillars were found to be 43, 75, and 292 for the IgG-antibody assay, streptavidin-biotin system, and covalently attached BSA, respectively. Applicability of the presented approaches to the detection of small numbers of molecules was evaluated using highly diluted labeled proteins and also control experiments without biospecific analytes. Our analysis indicates that detection of fewer than 10 tagged proteins is possible.

Unlike HPLC, there has been sparse advancement in the stationary phases used for planar chromatography. Nevertheless, modernization of planar chromatography platforms can further highlight the technique’s ability to separate multiple samples simultaneously, utilize orthogonal separation formats, image (detect) separations without rigorous temporal demands, and its overall simplicity. This paper describes the fabrication and evaluation of ordered pillar arrays that are chemically modified for planar chromatography and inspected by fluorescence microscopy to detect solvent development and analyte bands (spots). Photolithography, in combination with anisotropic deep reactive ion etching, is used to produce uniform high aspect ratio silicon pillars. The pillar heights, diameters, and pitch variations are approximately 15–20 μm, 1–3 μm, and 2–6 μm, respectively, with the total pillar array size typically 1 cm × 3 cm. The arrays are imaged using scanning electron microscopy in order to measure the pillar diameter and pitch as well as analyze the pillar sidewalls after etching and stationary phase functionalization. These fluidic arrays will enable exploration of the impact on mass transport and chromatographic efficiency caused by altering the pillar array morphology. A C18 reverse stationary phase (RP), common RP solvents that are transported by traditional but uniquely rapid capillary flow, and Rhodamine 6G (R6G) as the preliminary analyte are used for this initial evaluation. The research presented in this article is aimed at understanding and overcoming the unique challenges in developing and utilizing ordered pillar arrays as a new platform for planar chromatography: focusing on fabrication of expansive arrays, studies of solvent transport, methods to create compatible sample spots, and an initial evaluation of band dispersion.

Numerous studies have addressed the challenges of implementing miniaturized microfluidic platforms for chemical and biological separation applications. However, the integration of real time detection schemes capable of providing valuable sample information under continuous, ultra low volume flow regimes has not fully been addressed. In this report we present a chip based chromatography system comprising of a pillar array separation column followed by a reagent channel for passive mixing of a silver colloidal solution into the eluent stream to enable surface enhanced Raman spectroscopy (SERS) detection. Our design is the first integrated chip based microfluidic device to combine pressure driven separation capability with real time SERS detection. With this approach we demonstrate the ability to collect distinctive SERS spectra with or without complete resolution of chromatographic bands. Computational fluidic dynamic (CFD) simulations are used to model the diffusive mixing behaviour and velocity profiles of the two confluent streams in the microfluidic channels. We evaluate the SERS spectral band intensity and chromatographic efficiency of model analytes with respect to kinetic factors as well as signal acquisition rates. Additionally, we discuss the use of a pluronic modified silver colloidal solution as a means of eliminating contamination generally caused by nanoparticle adhesion to channel surfaces.

Silicon nanowire and nanopillar structures have drawn increased attention in recent years due in part to their unique optical properties. Herein, electron beam lithography combined with reactive-ion etching is used to reproducibly create individual silicon nanopillars of various sizes, shapes, and heights. Finite difference time domain analysis predicts local field intensity enhancements in the vicinity of appropriately sized and coaxially illuminated silicon nanopillars of approximately 2 orders of magnitude. While this level of enhancement is modest when compared to plasmonic systems, the unique advantage of the silicon nanopillar resonators is that they enhance optical fields in substantially larger volumes. By analyzing experimentally measured strength of the silicon Raman phonon line (500 cm–1), it was determined that nanopillars produced local field enhancements that are consistent with these predictions. Additionally, we demonstrate that a thin layer of Zn phthalocyanine on the nanopillar surface with a total amount of <30 attomoles produced prominent Raman spectra, yielding enhancement factors (EFs) better than 2 orders of magnitude. Finally, silicon nanopillars of cylindrical and elliptical shapes were labeled with different fluorophors and evaluated for their surface-enhanced fluorescence (SEF) capability. The EFs derived from analysis of the acquired fluorescence microscopy images indicate that silicon nanopillar structures can provide enhancements comparable or even stronger than those typically achieved using plasmonic SEF structures without the limitations of the metal-based substrates, such as fluorescence quenching and an insufficiently large probe volume. It is anticipated that dense arrays of silicon nanopillars will enable SEF assays with extremely high sensitivity, while a broader impact of the reported phenomena is anticipated in photovoltaics, subwavelength light focusing, and fundamental nanophotonics.Keywords: axial illumination; FDTD analysis; fundamental HE11 mode; large local field enhancement; SEF; SERS; silicon nanopillars

This communication describes a simple method that uses a thin film of octafluorocyclobutane (OFCB) polymer for efficient nanoscale transfer printing (nTP). Plasma polymerization of OFCB produces a Teflon-like fluoropolymer which strongly adheres and conformally covers a 3-D inorganic stamp. The inherently low surface energy of in situ deposited OFCB polymer on nanoscale silicon features is demonstrated as a unique nanocomposite stamp to fabricate various test structures with improved nTP feature resolution down to sub-100 nm.

In this work, geometrical optimizations of Ag disc on pillar (DOP) hybrid plasmonic nanostructures were conducted and allowed us to achieve reproducible average enhancement factors of 1 × 109 and greater.

Pressure driven liquid chromatography (LC) is a powerful and versatile separation technique particularly suitable for differentiating species present in extremely small quantities. This paper briefly reviews main historical trends and focuses on more recently developed technological approaches in miniaturization and on-chip integration of LC columns. The review emphasizes enabling technologies as well as main technological challenges specific to pressure driven separations and highlights emerging concepts that could ultimately overcome fundamental limitations of conventional LC columns.

Due to the difficulty of reliably producing sealed 3-D structures, few researchers have tackled the challenges of creating pillar beds suitable for miniaturized liquid phase separation systems. Herein, we describe an original processing sequence for the fabrication of enclosed pillar arrays integrated on a fluidic chip which, we believe, will further stimulate interest in this field. Our approach yields a mechanically robust enclosed pillar system that withstands mechanical impacts commonly incurred during processing, sealing and operation, resulting in a design particularly suitable for the research environment. A combination of a wafer-level fabrication sequence with chip-level elastomer bonding allows for chip reusability, an attractive and cost efficient advancement for research applications. The characteristic features in the implemented highly ordered pillar arrays are scalable to submicron dimensions. The proposed fluidic structures are suitable for handling picolitre sample volumes and offer prospects for substantial improvements in separation efficiency and permeability over traditional packed and monolithic columns. Our experimental observations indicate plate heights as low as 0.76 μm for a 10 mm long pillar bed. Theoretical calculations confirm that ordered pillar arrays with submicron pore sizes combine superior analysis speed, picolitre sample volumes, high permeability and reasonably large plate numbers on a small footprint. In addition, we describe a fluidic interface that provides streamlined coupling of the fabricated structures with off-chip fluidic components.

Novel nanostructured microcantilever (MC) surfaces were developed by modifying the active side of the MCs with aluminum oxide nanoparticles (AONP) for purposes of enhancing sensitivity in nanomechanical-based sensing. Uniform layers of AONP were spin coated and chemically immobilized on the surfaces of MCs with tetramethoxysilane (TMOS) as a cross-linker. Optimization studies on MC modification were performed for better surface uniformity and higher surface area, based on scanning electron microscope (SEM) images. The AONP-modified MC array (MCA) were subsequently functionalized by being immersed in parallel configured capillaries filled with different reagents for immobilizing chemical or biological receptors onto the MC surfaces. A MCA prepared for chemical sensing was exposed to the samples made of headspace vapor of different volatile organic compounds (VOCs). The characteristic response signatures for each gas phase VOC analyte showed substantial diversity. Immersion time in the capillary and the chemical nature of the reagents used for functionalization were both optimized to achieve the highest sensitivity and long-term reproducibility in nanomechanical responses to the test analytes. A second MCA functionalized with two different immunological receptors was prepared and exposed to three biological analytes in the liquid phase, with a highly selective response obtained for each analyte. Fluorescence microscope images and FT-IR spectra were used in this work to validate the controlled, variable chemical nature of the MC surfaces.

The present paper discusses the ability to separate chemical species using high-aspect-ratio, silicon oxide-enclosed pillar arrays. These miniaturized chromatographic systems require smaller sample volumes, experience less flow resistance, and generate superior separation efficiency over traditional packed bed liquid chromatographic columns, improvements controlled by the increased order and decreased pore size of the systems. In our distinctive fabrication sequence, plasma-enhanced chemical vapor deposition (PECVD) of silicon oxide is used to alter the surface and structural properties of the pillars for facile surface modification while improving the pillar mechanical stability and increasing surface area. The separation behavior of model compounds within our pillar systems indicated an unexpected hydrophobic-like separation mechanism. The effects of organic modifier, ionic concentration, and pressure-driven flow rate were studied. A decrease in the organic content of the mobile phase increased peak resolution while detrimentally effecting peak shape. A resolution of 4.7 (RSD = 3.7%) was obtained for nearly perfect Gaussian shaped peaks, exhibiting plate heights as low as 1.1 and 1.8 μm for fluorescein and sulforhodamine B, respectively. Contact angle measurements and DART mass spectrometry analysis indicate that our employed elastomeric soft bonding technique modifies pillar properties, creating a fortuitous stationary phase. This discovery provides evidence supporting the ability to easily functionalize PECVD oxide surfaces by gas-phase reactions.

Landfill biogases are being utilized more frequently as a new source of fuel energy. Volatile siloxane compounds usually contained in landfill biogases will form siloxane residues when the gases are burned, which significantly increases abrasion of combustion engines. Research on detection of siloxanes in landfill gas has been active during recent years with the principal analytical technique being gas chromatography/mass spectrometry (GC/MS). In our present work, we introduce a less expensive, compact methodology that employs microcantilever (MC) arrays for sensitive nanomechanical-based gas-phase sensing of the siloxanes. The cantilevers on the MC array were differentially coated on the active, nanostructured side with different responsive phases, and composite responses (magnitude of siloxane-induced MC bending) for four siloxanes were collected that exhibited selective signatures to aid in recognizing each siloxane. Limits of detection (LODs) derived from linear calibration plots were down to the sub-parts-per-million range, a sensitivity that is comparable with that of GC/MS reported by other researchers. Studies were performed in rather inert helium environment and a realistic matrix, and the overall response profiles and LODs were similar for both matrixes. A 5 week long-term reproducibility study illustrates the stability of the MC array. Moreover, the portable character of the MC array setup makes our method a very promising way to facilitate in-field detection of siloxanes in landfill gas in the future.

The development of new and better substrates is a major focus of research aimed at improving the analytical capabilities of surface-enhanced Raman spectroscopy (SERS). Perhaps the most common type of SERS substrate, one consistently exhibiting large enhancements, is simple colloidal gold or silver nanoparticles in the 10−150 nm size range. The colloidal systems that are used most for ultrasensitive detection are generally aggregated clusters that possess “hot spot(s)” within some of the aggregates. A significant limitation of these synthetic substrates is that the “hot” aggregates are extremely difficult to create consistently or predict. Electron beam lithography (EBL) along with combinatorial spectral mapping can be used to overcome this limitation. Our previous work, and that of other researchers, invokes the special capabilities of EBL to design and fabricate periodic, highly ordered nanoparticle arrays for SERS. Building on this work, EBL, in conjunction with ancillary fabrication steps, can be used to create complex patterns that mimic random aggregates. These aggregates, unlike those created by colloidal deposition methods, can be uniquely reproduced within the resolution limits of EBL. In the work reported herein, we use a unique approach to create substrates containing a large number of randomly generated cells with different morphologies that are arrayed on silicon wafers. Instead of isolated metal nanoparticles, these structures resemble the aggregates of colloid. By spectral mapping, we investigate the SERS activity of the combinatorial arrays of cells using probe analytes. Two general categories of shapes are randomly designed in different sizes and densities into several hundred different 5 μm square cells. Following fabrication, it is shown that a SERS performance contrast of more than a factor of 44 is achieved among these cells and that the best performing cells can be cloned into uniformly high performing macropatterns of lithographically defined nanoaggregates (LDNAs). In this manner, extended LDNA surfaces with uniform 5 × 108 enhancement factors are created. Furthermore, the LDNAs can be further dissected and studied in an effort to increase the SERS enhancement per unit geometric substrate area.Keywords: electron beam lithography; microscopy; nanofabrication; nanoparticle aggregates; surface-enhanced Raman spectroscopy

The development of biosensors is vital in many areas of biotechnology and biomedical research. A prominent new class of label-free biosensors are those based on ligand-induced nanomechanical responses of microcantilevers (MCs). The interaction between biologically significant ligands with bioreceptors (e.g., antibodies or nuclear receptor proteins) immobilized on one side of the MC surface causes an apparent surface stress, resulting in static bending of the MC, which can be detected by an optical beam bending technique. The three key performance metrics of sensitivity, selectivity, and reversibility are foci of the work reported herein. The nature of the MC surface and the method by which the bioreceptor is immobilized influence these performance metrics and, hence, optimization studies involving these were conducted. In our work, the gold surface on one side of the MC is first activated via self-assembled monolayer formation with amino ethane thiol (AET) then reacted with glutaraldehyde (GA) as a crosslinker before finally functionalizing with the protein receptor. We report the effect of concentration, reaction time, and pH for these reagents on the magnitude of the nanomechanical responses using an anti-immunoglobulin G (anti-IgG) receptor: IgG ligand test system. By vapor depositing an alloy of silver and gold and then etching away the former, a nanostructured “dealloyed” MC surface is created that outperforms a smooth gold MC in terms of nanomechanical responses. Optimization of the dealloying parameters (thickness, metal ratio) is also reported herein using the aforementioned anti-IgG–IgG system. Maximum response was obtained with these conditions: 150 nm dealloyed surface, 1 mM aqueous solution of AET-incubation time 1 h, 1% GA solution in 10 mM pH 8 phosphate buffered saline (PBS)-incubation time 3 h, and 0.5 mg mL−1 of receptor protein solution in 10 mM pH 7 PBS-incubation time 1 h. Additionally, surprising results are reported when Protein A is immobilized first to properly orient the bioreceptor IgG molecules. We also report the application of optimum and non-optimum conditions to detect thyroid disrupting chemicals (TDCs) using MCs functionalized with the transport protein thyroxine-binding globulin. Selectivity patterns are reported for several TDCs and sensitive detection of thyroxin at sub-nM levels is demonstrated.

The development of quantitative, highly sensitive surface-enhanced Raman spectroscopy (SERS) substrates requires control over size, shape, and position of metal nanoparticles. Despite the fact that SERS has gained the reputation as an information-rich spectroscopy for detection of many classes of analytes, in some isolated instances down to the single molecule detection limit, its future development depends critically on techniques for nanofabrication. Herein, an unconventional nanofabrication approach is used to produce efficient SERS substrates. Metallic nanopatterns of silver disks are transferred from a stamp onto poly(dimethysiloxane) (PDMS) to create nanocomposite substrates with regular periodic morphologies. The stamp with periodic arrays of square, triangular, and elliptical pillars is created via electron beam lithography (EBL) of ma-N 2403 resist. A modified cyclodextrin is thermally evaporated onto the stamp to overcome the adhesive nature of the EBL resist and to function as a releasing layer. Subsequently, Ag is physically vapor deposited onto the stamp at a controlled rate and thickness and used directly for nanotransfer printing (nTP). Stamps, substrates, and the efficiency of the nTP process were explored by scanning electron microscopy. Transferred Ag nanodisk−PDMS substrates are studied by SERS using Rhodamine 6G as the probe analyte. There are observed optimal conditions involving both Ag and cyclodextrin thickness. The SERS response of metallic nanodisks of various shapes and sizes on the original stamp is compared to the corresponding nTP created substrates with similar trends observed. Limits of detection for crystal violet and Mitoxantrone are approximately 10−8 and 10−9 M, respectively. As an innovative feature of this approach, we demonstrate that physical manipulation of the PDMS post-nTP can be used to alter morphology, e.g., to change internanodisk spacing. Additionally, stamps are shown to be reusable after the nTP process, adding the potential to scale-up regular morphology substrates by a stamp-and-repeat methodology.Keywords: electron beam lithography; metal–polymer nanocomposites; nanotransfer printing; poly(dimethylsiloxane); SEM; SERS

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-α) and estrogen receptor beta (ER-β), 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-β is diethylstilbestrol (DES) > 17-β-estradiol > 17-α-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-β-estradiol, 17-α-estradiol, and 2-OH-estrone, with ER-β and ER-α 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-β-estradiol Ab show responses in the range of 1 × 10−11 through 1 × 10−7 M for 17-β-estradiol with a linear portion extending over two orders of magnitude in concentration.

In the present work, we have performed analyte species and concentration identification using an array of ten differentially functionalized microcantilevers coupled with a back-propagation artificial neural network pattern recognition algorithm. The array consists of ten nanostructured silicon microcantilevers functionalized by polymeric and gas chromatography phases and macrocyclic receptors as spatially dense, differentially responding sensing layers for identification and quantitation of individual analyte(s) and their binary mixtures. The array response (i.e. cantilever bending) to analyte vapor was measured by an optical readout scheme and the responses were recorded for a selection of individual analytes as well as several binary mixtures. An artificial neural network (ANN) was designed and trained to recognize not only the individual analytes and binary mixtures, but also to determine the concentration of individual components in a mixture. To the best of our knowledge, ANNs have not been applied to microcantilever array responses previously to determine concentrations of individual analytes. The trained ANN correctly identified the eleven test analyte(s) as individual components, most with probabilities greater than 97%, whereas it did not misidentify an unknown (untrained) analyte. Demonstrated unique aspects of this work include an ability to measure binary mixtures and provide both qualitative (identification) and quantitative (concentration) information with array-ANN-based sensor methodologies.

Successful development of chemical sensors and multi-sensor arrays critically depends on the availability of appropriate coatings. In the present studies, we synthesized hydrophobic and thermally stable cyclodextrin (CD) derivatives and, using a physical vapor deposition method, successfully deposited them on surfaces as thin films. NMR and FT-IR spectroscopy verified that while heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-methyl)cyclomaltoheptaose (DMe-CD) remained chemically intact after the deposition, heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-acetyl)cyclomaltoheptaose (DAc-CD) showed some variations. The hydrophobicity and refractive indices of the prepared thin films were determined using, respectively, contact angle measurements and ellipsometry. Selectivity patterns of the prepared CD films with respect to a series of analytes were defined using surface plasmon resonance. Because the chemical structure of the DAc-CD derivatives is compromised during the PVD process and any structural change may affect the selectivity of these thin films, additional attention should be given to the PVD process. In addition, thin films of the DMe-CD derivative were tested as protective coatings on silver island films for sensors based on surface enhanced Raman spectroscopy (SERS). The observed kinetics of SERS signals indicates that medium molecular weight analytes are able to rapidly diffuse through the CD films and reach the underlying silver islands.

In an effort to impart selectivity to chemical sensors based on micro-machined silicon cantilevers, thin films of polymeric chromatographic stationary phases (SP-2340 and OV-25) were applied to one side of the cantilever surface using a spin coating procedure. These coatings influenced the response of the micro-cantilever to vapor phase test analytes of varying chemical compositions. For the SP-2340 coated micro-cantilevers, the effects of both polymeric film thickness and cantilever structure thickness on response characteristics were investigated. Sensitivity improved as both film thickness and cantilever leg thickness were decreased. The selectivity, as indicated by differences in relative responses to the test analytes, were different for the two phases which differed significantly in polarity. The SP-2340 coated cantilevers exhibited response characteristics that are fairly similar to that expected for adsorption of the test analytes onto silica. Responses are shown to be proportional to analyte concentration. Response characteristics are shown to be consistent with predictions based on a gas chromatographic stationary phase classification scheme.

A chemical sensor based on the deflection of a surface modified silicon micro-cantilever is presented. A thin film of sol-gel was applied to one side of the micro-cantilever surface using a spin coating procedure. The sensor has been shown to give different responses to vapor phase analytes of varying chemical composition, as well as to varying concentrations of a given analyte. Ethanol, a highly polar molecule, exhibits a strong affinity for the polar sol-gel coating resulting in a large response; pentane, a non-polar hydrocarbon, shows very little response. The sol-gel coating has also been shown to function as a backbone for the immobilization of chemically selective phases on the cantilever surface. Reaction of the sol-gel film with chlorotriethoxysilane and subsequent capping of the remaining reactive surface silanols with hexamethyldisilizane increases the non-polar nature of the film. This results in an increase in the response of the sensor to non-polar analytes. The effects of film thickness and cantilever structure thickness on response were also investigated.

In this work, geometrical optimizations of Ag disc on pillar (DOP) hybrid plasmonic nanostructures were conducted and allowed us to achieve reproducible average enhancement factors of 1 × 109 and greater.

A simple and rapid fluorescence sensing platform based on the MIL-53(Fe) MOF was developed for fast, highly selective and ultrasensitive direct determination of MeHg+.