Surface-enhanced Raman spectroscopy substrate composed of chemically modified gold colloid particles immobilized on magnetic microparticles.

In this paper, immobilization of gold colloidal particles onto amine-modified magnetic microparticles is demonstrated. Once immobilized, the gold was then reacted with pentachlorothiophenol (PCTP) to form a self-assembled monolayer. The PCTP-gold colloid on magnetic microparticles was then used to extract naphthalene from aqueous samples. A magnet was used to concentrate the microparticles onto the side of the sample vial, allowing detection of naphthalene by surface-enhanced Raman spectroscopy. Using the PCTP-gold colloid on magnetic microparticles the limit of detection for naphthalene achieved was 0.3 microg mL(-1). Multiple extractions can be done with the PCTP-gold colloid on magnetic microparticles to further lower the detection limit.

The role of hydrogen bonding in the selectivity of L-cysteine methyl ester (CYSM) and L-cysteine ethyl ester (CYSE) for chloride ion.

The interaction of cysteamine (CY), L-cysteine methyl ester (CYSM), and L-cysteine ethyl ester (CYSE) with nitrate, sulfate, perchlorate, dihydrogen phosphate, and chloride ions was investigated using surface enhanced Raman spectroscopy (SERS). CYSM and CYSE are chemical derivatives of CY. These thiols have a quaternary ammonium group to attract the anions to the SERS surface. Dihydrogen phosphate did not interact with these cationic thiols. The CY interaction with perchlorate, nitrate, and sulfate is stronger than the interaction with chloride. However, replacing a hydrogen on the carbon adjacent to the quaternary ammonium group with either a methyl or ethyl ester group results in stronger complexation with chloride ion than with either sulfate or nitrate ion. In the case of CYSM, the chloride interaction is five times stronger than the interaction with perchlorate. Molecular modeling indicates that the high selectivity of CYSM/CYSE for chloride is due to hydrogen bonding between the chloride ion and the hydrogen of the CH3 moeities of adjacent ester groups.

Detection of lead derived from automotive scrap residue using a direct push fiber-optic laser-induced breakdown spectroscopy metal sensor.

At Naval Base Point Loma in San Diego, California, a canyon had been filled with construction debris and automotive scrap residue (ASR), the latter of which included lead acid batteries. A magnetic survey and induced potential (IP)/DC resistivity survey showed the presence of anomalies at the western end of the site where historic records indicated that the ASR had been placed. Lead concentration depth profiles were obtained in situ and in real time at the site using a direct push fiber-optic laser-induced breakdown spectroscopy (FO-LIBS) sensor probe. Lead, along with strontium and titanium, was detected at depths of 7 to 8 m bgs. These results provided confirmation that the magnetic/IP anomalies at the site are due to ASR.

Detection of anions by normal Raman spectroscopy and surface-enhanced Raman spectroscopy of cationic-coated substrates.

The use of normal Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) of cationic-coated silver and gold substrates to detect polyatomic anions in aqueous environments is examined. For normal Raman spectroscopy, using near-infrared excitation, linear concentration responses were observed. Detection limits varied from 84 ppm for perchlorate to 2600 ppm for phosphate. In general, detection limits in the ppb to ppm concentration range for the polyatomic anions were achieved using cationic-coated SERS substrates. Adsorption of the polyatomic anions on the cationic-coated SERS substrates was described by a Frumkin isotherm. The SERS technique could not be used to detect dichromate, as this anion reacted with the coatings to form thiol esters. A competitive complexation method was used to evaluate the interaction of chloride ion with the cationic coatings. Hydrogen bonding and pi-pi interactions play significant roles in the selectivity of the cationic coatings.

Use of fluorescently labeled phage in the detection and identification of bacterial species.

Phages are viruses whose hosts are bacterial cells. They identify their hosts by specific receptor molecules on the outside of the host cell. Once the phages find their specific receptors, they bind to the bacterial cell and inject their nucleic acid inside the cell. The binding between phage and host can be so specific that only certain strains of a single species can be infected. In this communication, the specificity of phage P22 for Salmonella typhimurium LT2 is exploited to allow the detection of Salmonella in the presence of other bacterial species. In particular, the dsDNA of P22 is bound to SYBR gold, a highly sensitive, fluorescent nucleic acid stain. When multiple phages infect the same cell, the fluorescence emissions of the phage DNA inside the cell allow it to be imaged using an epifluorescence microscope. The advantages of using phages as the bacterial recognition element in a sensor over antibodies are discussed.

Field demonstrations of a direct push FO-LIBS metal sensor.

A direct push, FO-LIBS sensor probe for real-time, in-situ measurement of metals in soils has been built and its capabilities demonstrated at three sites. The response of the FO-LIBS sensor is affected by the soil matrix conditions of grain size, composition, and water content. For each site, uncontaminated soil was collected and spiked with known quantities of the metal under investigation. These calibration standards were used to generate a site-specific calibration curve, which compensates for variations in soil matrix conditions of grain size, composition, porosity, etc. To compensate for moisture content, extra laser pulses are used to volatilize the water, higher power densities and/or shortened acquisition delay times are used. The LIBS experiment inherently exhibits poor precision since it is a point measurement. When multiple spectra are taken of a single, homogenized soil sample, there is a significant amount of variability in the peak intensities. There is no internal standard available to correct for this variability. In this communication, it is shown that normalizing the peak areas under the spectral curves to one effectively corrects for variation due to differences in the plasma volume. Because the LIBS technique is essentially a point measurement the FO-LIBS sensor is used as a semiquantitative field screening tool and not as a quantitative analytical method. In the field demonstrations reported in this communication, remarkably good agreement between the in-situ FO-LIBS results and ICP lab results were obtained.