We report on a new sensor strategy that integrates molecularly imprinted polymers (MIPs) with surface enhanced Raman scattering (SERS). The sensor was developed to detect the explosive, 2,4,6-trinitrotoluene (TNT). Micron thick films of sol gel-derived xerogels were deposited on a SERS-active surface as the sensing layer. Xerogels were molecularly imprinted for TNT using non-covalent interactions with the polymer matrix. Binding of the TNT within the polymer matrix results in unique SERS bands, which allow for detection and identification of the molecule in the MIP. This MIP-SERS sensor exhibits an apparent dissociation constant of (2.3 ± 0.3) × 10−5 M for TNT and a 3 μM detection limit. The response to TNT is reversible and the sensor is stable for at least 6 months. Key challenges, including developing a MIP formulation that is stable and integrated with the SERS substrate, and ensuring the MIP does not mask the spectral features of the target analyte through SERS polymer background, were successfully met. The results also suggest the MIP-SERS protocol can be extended to other target analytes of interest.

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Detection and quantification of analytes in clinical settings (e.g., routine blood testing), at home (e.g., glucose monitoring), in the field (e.g., environmental monitoring, war fighter protection, homeland security), and in the factory (e.g., worker health, beverage and food safety) is exceedingly challenging. Chemical sensors and biosensors have attracted considerable attention because of their perceived ability to meet these challenges. Chemical sensors exploit a recognition element in concert with a transduction strategy. When the recognition element is biological (e.g., antibody, aptamer, enzyme), the sensor is termed a biosensor. There is substantial literature on biosensing; however, there are compelling reasons for developing inexpensive, robust, and reusable alternatives for the expensive or unstable biorecognition elements. This Account summarizes recent research on designing and producing analyte-responsive materials based on molecularly imprinted xerogels.

The United States Army and the first responder community are evaluating optical detection systems for the trace detection of hazardous energetic materials. Fielded detection systems must be evaluated with the appropriate material concentrations to accurately identify the residue in theater. Trace levels of energetic materials have been observed in mutable polymorphic phases and, therefore, the systems being evaluated must be able to detect and accurately identify variant sample phases observed in spectral data. In this work, we report on the novel application of drop-on-demand technology for the fabrication of standardized trace 1,3,5-trinitro-1,3,5-triazine (RDX) samples. The drop-on-demand sample fabrication technique is compared both visually and spectrally to the more commonly used drop-and-dry technique. As the drop-on-demand technique allows for the fabrication of trace level hazard materials, concerted efforts focused on characterization of the polymorphic phase changes observed with low concentrations of RDX commonly used in drop-on-demand processing. This information is important when evaluating optical detection technologies using samples prepared with a drop-on-demand inkjet system, as the technology may be "trained" to detect the common bulk α phase of the explosive based on its spectral features but fall short in positively detecting a trace quantity of RDX (β-phase). We report the polymorphic shifts observed between α- and β-phases of this energetic material and discuss the conditions leading to the favoring of one phase over the other.