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.
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/m(3), 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.
Simplified lab-on-a-chip techniques are desirable for quick and efficient detection of analytes of interest in the field. The following work involves the use of deterministic pillar arrays on the micro-scale as a platform to separate compounds, and the use of Ag colloid within the arrays as a source of increased signal via surface enhanced Raman spectroscopy (SERS). One problem traditionally seen with SERS surfaces containing Ag colloid is oxidation; however, our platforms are superhydrophobic, reducing the amount of oxidation taking place on the surface of the Ag colloid. This work includes the successful separation and SERS detection of a fluorescent dye compounds (resorufin and sulforhodamine 640), fluorescent anti-tumor drugs (Adriamycin and Daunomycin), and purine and pyrimidine bases (adenine, cytosine, guanine, hypoxanthine, and thymine).
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.
Electrophoresis 2017, 38, 361–367. DOI: This graphical representation demonstrates our ability to separate and detect analytes with the use of our photolithographic deterministic pillar arrays in combination with surface enhanced Raman spectroscopy. The two spectra shown represent unique vibrational data for adenine (left) and thymine (right) and their structures. The chromatogram peaks shown indicate the ability to separate and detect separate bands with good efficiency. Enhancement of the Raman signal was provided by the silver colloid present throughout the bottom of the pillar array. Included is a scanning electron microscope image of the pillar arrays, in which the silver colloid can be observed.
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