New data is presented related to high-pressure underwater laser-induced breakdown spectroscopy measurements.

There is a growing need for standoff detection of nonvolatile threat contamination on surfaces. These threats include explosives in the form of improvised explosive devices (IEDs) as well as low volatility chemical agents and toxic industrial chemicals (TICs). The ability to assess surface hazards, even at standoff distances as short as 1 m, would provide an increased level of safety to those tasked with assessing sites with possible weapons of mass destruction (WMD). A number of optical spectroscopy techniques have been investigated to solve this problem. Laser-induced breakdown spectroscopy (LIBS), fluorescence, and Raman all show promise for meeting this challenge of surface detection, with each having both advantages and disadvantages. While most of the work to date has been on assessing these techniques individually, more emphasis is being placed on combining orthogonal detection techniques for improved probability of detection and the reduction in false positives.

Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) with a collinear laser beam orientation is shown for high-pressure bulk aqueous solutions (up to 50bar) along with bubble and plasma images. These investigations reveal that the emission plasma is quenched much more rapidly in solution requiring much shorter detector gate delays than for typical LIBS measurements in air. Also, the emission is inversely proportional to solution pressure, and the most intense emission at all pressures occurs when the laser-induced vapor bubble is at a maximum diameter. It is also shown that the laser-induced bubble grows initially at the same rate for all solution pressures, collapsing more quickly as the pressure is increased. Intense emission is best obtained for conditions where the laser-induced bubble formed by the first laser pulse is small and spherically shaped.

Several fluorinated and trifluoromethylated indanone, tetralone and naphthone derivatives have been prepared via Claisen condensations and selective fluorinations in yields ranging from 22–60%. In addition, we report the synthesis of new, selectively fluorinated bindones in yields ranging from 72–92%. Of particular interest is the fluorination and trifluoroacetylation regiochemistry observed in these fluorinated products. We also note unusual transformations including a novel one pot, dual trifluoroacetylation, trifluoroacetylnaphthone synthesis via a deacetylation as well as an acetyl-trifluoroacetyl group exchange. Solid-state structural features exhibited by these compounds were investigated using crystallographic methods. Crystallographic results, supported by spectroscopic data, show that trifluoroacetylated ketones prefer a chelated cis-enol form whereas fluorinated bindone products exist primarily as the cross-conjugated triketo form.

Fluorinated aryl β-diketones were prepared using Claisen and electrophilic fluorination methods. The keto–enol and enol–enol tautomerism of these compounds were examined in the solid state, as neat liquids and in polar, aprotic solution by crystallography and spectroscopy. Neat-liquid spectroscopic measurements as well as single crystal X-ray crystallographic results for selected electron-deficient aryl β-diketones suggest a single, chelated cis-enol isomer that is conjugated with the aryl ring. In polar aprotic solvents, nonfluorinated aryl β-diketones equilibrate rapidly from the chelated cis-enol form to a tautomeric mixture of cis-chelated enol and a substantial proportion of the diketone form, trifluoromethylated aryl β-diketones show only limited equilibration from the chelated cis-enol to the diketone form, with 2-fluoro-1-aryl β-diketones again displaying only the diketonic form.

Fielded surface detection systems rely on contact with either the liquid contamination itself or the associated chemical vapor above the contaminated surface and do not provide a standoff or remote detection capability. Conversely, standoff chemical vapor sensing techniques have not shown efficacy in detecting those contaminants as liquids or solids on surfaces. There are a number of optical or spectroscopic techniques that could be applied to this problem of standoff chemical detection on surfaces. The three techniques that have received the most interest and development are laser induced breakdown spectroscopy (LIBS), fluorescence, and Raman spectroscopy. Details will be presented on the development of these techniques and their applicability to detecting CBRNE contamination on surfaces.

The rapid detection and quantification of saxitoxin (STX) is reported using surface-enhanced Raman spectroscopy (SERS) with a colloidal hydrosol of silver nanoparticles. Under the conditions of our experiments, the limit of detection ( L D ) for STX using SERS is 3 nM, with a limit of quantification ( L Q ) of 20 nM. It is shown that the SERS method is rapid, with spectra being collected in as little as 5 seconds total integration time for a 40 nM STX sample. In order to improve the signal-to-noise ratio, SERS spectra were generally collected with a total integration time of 1 minute (6 accumulations of 10 seconds each), with no need for extensive sample work-up or substrate preparation. Based on these results, the SERS technique shows great promise for the future detection and quantification of STX molecules in aqueous solutions.

Raman measurements of two common gases are made using a simple multipass capillary Raman cell (MCC) coupled to an unfiltered 18 around 1 fiber-optic Raman probe. The MCC, which is fabricated by chemical deposition of silver on the inner walls of a 2 mm inner diameter glass capillary tube, gives up to 20-fold signal enhancements for nonabsorbing gases. The device is relatively small and suitable for remote and in situ Raman measurements with optical fibers. The optical behavior of the MCC is similar to previously described liquid-core waveguides and hollow metal-coated waveguides used for laser transmission, but unlike the former devices, the MCC is generally applicable to a very wide range of nonabsorbing gases.

The Raman analysis of common, non-absorbing gases was performed using an 18@1 fiber-optic probe coupled to a multi-pass capillary cell (MCC) for signal enhancement. The MCC is fabricated by metal-coating, using silver or other highly reflective metals, the inside of a 1-2 mm diameter glass capillary using commercially available silvering solutions and provides enhancements up to 30-fold over measurements using the fiber-optic probe alone. The design of the MCC is simple and the device is easy to incorporate into an experimental setup making it suitable for remote and in-situ analysis. Although the MCC is functionally similar to liquid-core waveguides that have been previously described in the literature, the MCC is not based on total internal reflection and so the refractive index of the analyte is not important to the operation of the device. The principle of operation of the MCC is similar to mirror-based multiple pass Raman cells, however, the MCC is not expensive, alignment is trivial and an optical path length up to several meters in length is possible. With our first-generation silver-coated MCCs, limits of detection were determined to be 0.02% and 0.2% for CH4 and CO2 respectively. In this talk we will discuss optimization of the MCC and issues involved in its use.

A simple Raman multipass capillary cell (MCC) is described that gives 12- to 30-fold signal enhancements for non-absorbing gases. The cell is made by coating the inside of 2-mm inner diameter silica capillary tubes with silver. The device is very small and suitable for remote and in situ Raman measurements with optical fibers. Application of the MCC is similar to previously described liquid core waveguides but, unlike the latter devices, the MCC is generally more applicable to a wide range of non-absorbing gases.

Autoinducer (AI) molecules are used by quorum sensing (QS) bacteria to communicate information about their environment and are critical to their ability to coordinate certain physiological activities. Studying how these organisms react to environmental stresses could provide insight into methods to control these activities. To this end, we are investigating spectroscopic methods of analysis that allow in situ measurements of these AI molecules under different environmental conditions. We found that for one class of AIs, N-acyl-homoserine lactones (AHLs), surface-enhanced Raman spectroscopy (SERS) is a method capable of performing such measurements in situ. SERS spectra of seven different AHLs with acyl chain lengths from 4 to 12 carbons were collected for the first time using Ag colloidal nanoparticles synthesized via both citrate and borohydride reduction methods. Strong SERS spectra were obtained in as little as 10 seconds for 80 μM solutions of AI that exhibited the strongest SERS response, whereas 20 seconds was typical for most AI SERS spectra collected during this study. Although all spectra were similar, significant differences were detected in the SERS spectra of C4-AHL and 3-oxo-C6-AHL and more subtle differences were noted between all AHLs. Initial results indicate a detection limit of ∼10−6 M for C6-AHL, which is within the limits of biologically relevant concentrations of AI molecules (nM–μM). Based on these results, the SERS method shows promise for monitoring AI molecule concentrations in situ, within biofilms containing QS bacteria. This new capability offers the possibility to “listen in” on chemical communications between bacteria in their natural environment as that environment is stressed.

In the work reported herein, we have combined a short-lived femtosecond laser-induced plasma (LIP) and a longer-lived nanosecond LIP in a collinear pulse configuration to examine the source(s) of atomic emission and signal-to-noise enhancement in dual-pulse laser-induced breakdown spectroscopy (LIBS). Initial studies indicate that the primary source of dual-pulse LIBS enhancement in the collinear configuration may in large part be a matter of pulse focus; focusing on the sample surface, for example, yields atomic emission enhancements whose lifetime correlates reasonably well with the femtosecond LIP emissive lifetime, suggesting that plasma–plasma coupling may play an important role at that pulse focus. At a second “optimal” focal position above the sample surface, alternatively, atomic emission and signal-to-noise enhancements correlate quite well with the nitrogen and oxygen atomic emission reductions previously seen following use of a femtosecond air spark and a nanosecond ablative pulse in the orthogonal dual-pulse configuration, suggesting that pressure or number density reductions due to femtosecond LIP formation in air may be significant at that pulse focus.

Initial results demonstrating the ability to classify surface-enhanced Raman (SERS) spectra of chemical and biological warfare agent simulants are presented. The spectra of two endospores ( B. subtilis and B. atrophaeus), two chemical agent simulants (dimethyl methylphosphonate (DMMP) and diethyl methylphosphonate (DEMP)), and two toxin simulants (ovalbumin and horseradish peroxidase) were studied on multiple substrates fabricated from colloidal gold adsorbed onto a silanized quartz surface. The use of principal component analysis (PCA) and hierarchical clustering were used to evaluate the efficacy of identifying potential threat agents from their spectra collected on a single substrate. The use of partial least squares–discriminate analysis (PLS-DA) and soft independent modeling of class analogies (SIMCA) on a compilation of data from separate substrates, fabricated under identical conditions, demonstrates both the feasibility and the limitations of this technique for the identification of known but previously unclassified spectra.

Initial results which demonstrate the ability to classify surface enhanced Raman (SERS) spectra of chemical and biological warfare agent simulants are presented. The spectra of 2 endospores (B. subtilis, B. atrophaeus); 2 chemical agent simulants (Dimethyl methylphosphonate (DMMP), Diethyl methylphosphonate (DEMP)); and 2 toxin simulants (Ovalbumin, Horseradish peroxidase) were collected on multiple substrates fabricated from colloidal gold adsorbed onto a silanized quartz surface. The use of principle component analysis (PCA) and Hierarchical Clustering was used as a method of determining the reproducibility of the individual spectra collected from a single substrate. Additionally, the use of partial least squares-discriminate analysis (PLS-DA) and soft independent modeling of class analogies (SIMCA) on a compilation of data from separate substrates, fabricated under identical conditions, demonstrates the feasibility of this technique for the identification of known but previously unclassified spectra.

As much as tenfold atomic emission enhancements have been observed in experiments combining nanosecond (ns) and femtosecond (fs) laser pulses in an orthogonal dual-pulse configuration for laser-induced breakdown spectroscopy (ns-fs orthogonal dual-pulse LIBS). In the examination of one of several potential sources of these atomic emission enhancements (sample heating by a ns air spark), minor reductions in atomic emission and as much as 15-fold improvements in mass removal have been observed for fs single-pulse LIBS of heated brass and aluminum samples. These results suggest that, although material removal with a high-powered, ultrashort fs pulse is temperature dependent, sample heating by the ns air spark is not the source of the atomic emission enhancements observed in ns-fs orthogonal dual-pulse LIBS.

Nanosecond and femtosecond laser pulses were combined in an orthogonal preablation spark dual-pulse laser-induced breakdown spectroscopy (LIBS) configuration. Even without full optimization of interpulse alignment, ablation focus, large signal, signal-to-noise ratio, and signal-to-background ratio enhancements were observed for both copper and aluminum targets. Despite the preliminary nature of this study, these results have significant implications in the attempt to explain the sources of dual-pulse LIBS enhancements.

Use of dual-pulse laser-induced breakdown spectroscopy with an orthogonal spark orientation is presented as a technique for trace metal analysis in bulk aqueous solutions. Two separate Q-switched Nd:YAG lasers operating at their fundamental wavelengths are used to form a subsurface, laser-induced plasma in a bulk aqueous solution that is spectroscopically analyzed for the in situ detection of Ca, Cr, and Zn. Optimizing the key experimental parameters of proper spark alignment, gate delay (td), gate width (tb), and interpulse timing (deltaT) allowed experimentally determined detection limits of the order of micrograms per milliliter and submicrograms per milliliter. We present supporting evidence of a sampling mechanism that involves the formation of a cavitation bubble with the first pulse (E1) followed by analysis of that bubble with a second pulse (E2). The plasma created by E2 contains the analytically relevant information from the aqueous sample and often represents >250-fold enhancement over a single laser pulse with energy equal to E1 alone.

The Journal of Popular CultureVolume 17, Issue 3 p. 75-83 A Profile of Antique Collectors Aida K. Tomeh, Aida K. Tomeh Aida K. Tomeh is Professor in the Sociology Department at Bowling Green State University, Bowling Green, Ohio.Search for more papers by this authorWilliam Pearman, William Pearman William Pearman, is Dean of School of Humanities and Social Sciences, Millerville State College, Pennsylvania.Search for more papers by this authorJohn Schnabel, John Schnabel John Schnabel, is Professor of Sociology at West Virginia University, Morgantown, West Virginia.Search for more papers by this author Aida K. Tomeh, Aida K. Tomeh Aida K. Tomeh is Professor in the Sociology Department at Bowling Green State University, Bowling Green, Ohio.Search for more papers by this authorWilliam Pearman, William Pearman William Pearman, is Dean of School of Humanities and Social Sciences, Millerville State College, Pennsylvania.Search for more papers by this authorJohn Schnabel, John Schnabel John Schnabel, is Professor of Sociology at West Virginia University, Morgantown, West Virginia.Search for more papers by this author First published: Winter 1983 https://doi.org/10.1111/j.0022-3840.1983.1703_75.xCitations: 1AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume17, Issue3Winter 1983Pages 75-83 RelatedInformation