Analysis of Hypodermic Needles and Syringes for the Presence of Blood and Polydimethylsiloxane (Silicone) Utilizing Microchemical Tests and Infrared Spectroscopy.

Suspect hypodermic needles and syringes were seized from an unlicensed individual who was allegedly injecting patients with silicone (polydimethylsiloxane [PDMS]) for cosmetic enhancement. Since control syringe barrels and needles often contain an interfering PDMS lubricant, a risk for false positives of foreign PDMS exists. The focus of this report was to minimize this risk and determine a quick and reliable test for the presence of blood in PDMS matrices. Using ATR-FT-IR spectroscopy, the risk for false-positive identification of foreign PDMS was reduced by (i) overfilling the sampling aperture to prevent spectral distortions and (ii) sampling a region of the suspect syringe/needle assembly where manufacturer-applied PDMS is not typically located. Analysis for blood indicated that the Teichman microchemical test was effective for detecting blood in the presence of PDMS. Overall, detecting PDMS established intent and detecting blood established that the needle containing the PDMS had been used for injection.

Simultaneous detection of two analytes using a spectroelectrochemical sensor.

Spectroelectrochemical sensors developed in our group achieve three modes of selectivity by combining electrochemistry, spectroscopy, and a chemically selective membrane in a single device. Analyte detection is based upon a change in the optical response due to the conversion of the analyte between two oxidation states that results from the cycling or stepping of the applied potential. We have demonstrated a novel approach to simultaneously detect two metals by combining optical stripping voltammetry for one metal (Pb(2+)) and the in situ ligand complexation in a film for the other metal (Fe(2+)). Using an indium tin oxide (ITO) sensor platform with a 50 nm Nafion film to preconcentrate the analytes, equimolar mixtures of Pb(2+) and Fe(2+) in 0.1 M sodium acetate buffer (pH 5) were detected. Pb(2+) was detected by optical stripping voltammetry, in which lead was deposited as metal on the ITO and detected by the optical change as it was removed by stripping. The ferrous ion was detected by the in situ ligand complexation method in which Fe(2+) was complexed with 2,2'-bipyridyl in the Nafion in the film to form an intense red complex that was detected by absorbance at 520 nm. Detection limits of 300 and 400 nM were obtained for Pb(2+) and Fe(2+), respectively. The presence of the film had no effect on the optical signal that results from the deposition and stripping of the Pb(2+). In addition, competition between the Pb(2+) and Fe(2+) for sites in the film and for the organic ligand was investigated.

Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 21. Selective chemical sensing using sulfonated polystyrene-block-poly(ethylene-ran-butylene)block-polystyrene thin films.

Spectroelectrochemical sensors combine three modes of selectivity in a single device (electrochemistry, spectroscopy, and selective partitioning). A thin polymer film is coated onto the sensing platform in order to facilitate chemically selective transport to the electrode. The film is an essential part of the sensor because it provides an increase in selectivity and sensitivity by selectively preconcentrating the analyte. Here, we report the next step in the characterization of partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)block-polystyrene (SSEBS) films for the purpose of chemical sensing by examining the selectivity of the sensor fabricated with this novel thin film material. Binary mixtures using model analytes were used to demonstrate the sensor's ability to detect an analyte in the presence of a direct interference. The binary mixtures consisted of Ru(bpy)(3)(2+)/Fe(CN)(6)(3-), Ru(bpy)(3)(2+)/Fe(bpy)(3)(2+), and Ru(bpy)(3)(2+)/Cu(bpy)(2)(2+). Demonstration of the selective partitioning mode using the Ru(bpy)(3)(2+)/Fe(CN)(6)(3-) mixture and absorption detection showed the SSEBS film's preference for Ru(bpy)(3)(2+) over Fe(CN)(6)(3-), and therefore, Fe(CN)(6)(3-) did not interfere with the sensor's response to Ru(bpy)(3)(2+). Furthermore, the importance of the use of three modes together was demonstrated by analysis of the Ru(bpy)(3)(2+)/Fe(bpy)(3)(2+) and the Ru(bpy)(3)(2+)/Cu(bpy)(2)(2+) test mixtures, where both selection of a specific wavelength for absorption and selection of a specific potential window were required to reduce or eliminate the signal from the interference. Finally, analysis of the Ru(bpy)(3)(2+)/Fe(bpy)(3)(2+) test mixture was also demonstrated using fluorescence detection.

Characterization of partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene thin films for spectroelectrochemical sensing.

The spectroelectrochemical sensor uses thin, solid polyelectrolyte films as an essential element in its operation. In this work we explored the potential of partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SSEBS) thin polymer films for chemical sensing. Spectroscopic ellipsometry was used to measure optical and surface properties of the air-dried and hydrated material. SSEBS incorporates a relatively small amount of water (overall change of 25%) mainly determined by the complex dynamics of the film. The decrease in the refractive index after complete hydration of the film can be predicted based on the magnitude of swelling using effective medium approximation models. Adhesion of the material on various surfaces (glass, indium tin oxide, gold) was evaluated with the tape peel-off method. The ability of the SSEBS material to preconcentrate cations was evaluated by cyclic voltammetry, absorbance, and luminescence measurements using model analytes (Ru(bpy)(3)(2+), phenosafranine, and rhodamine 6G). The detection limits of the sensor for Ru(bpy)(3)(2+) under unoptimized conditions can be significantly improved if luminescence is used as the detection modality (DL = 5 x 10(-10) M) instead of absorbance (DL = 5 x 10(-7) M). Overall, the results demonstrate the effectiveness of the SSEBS material for spectroelectrochemical sensing.

Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 17. Improvement in detection limits using ultrathin perfluorosulfonated ionomer films in conjunction with continuous sample flow.

We report herein an attenuated total reflectance (ATR) absorbance-based spectroelectrochemical sensor for tris(2,2'-bipyridyl)ruthenium(II) ion [Ru(bpy)(3)(2+)] that employs ultrathin (24-50 nm) Nafion films as the charge-selective layer. This film serves to sequester and preconcentrate the analyte at the optically transparent electrode surface such that it can be efficiently detected optically via electrochemical modulation. Our studies indicate that use of ultrathin films in tandem with continuous flow of sample solution through the cell compartment leads to a 100-500-fold enhancement in detection limit (10 nM) compared to earlier absorbance-based spectroelectrochemical sensors ( approximately 1-5 microM); markedly shorter analysis times also result. We report the dependence of the measured absorbance on sample flow rate and Nafion film thickness, and also provide calibration curves that illustrate the linear range and detection limits of the sensor using a 24 nm film at a constant sample flow rate of 0.07 mL/min.