Effect of membrane properties on the odor emanating from training aids for explosive-detecting canines.

Canines are widely used for real-time detection of explosives and have proven to be on par with instrumental methods. Canines are thought to rely largely upon detection of volatile chemical constituents of the explosives, though not necessarily the explosive itself. Hence, it is crucial to understand the odor available to them as generated by training aids. Previous studies have established that the Training Aid Delivery Device (TADD) developed by SciK9 is a reliable training aid that reduces cross-contamination and doubles as a storage device. A TADD comprises a standardized container, a synthetic membrane, a membrane holder, and a lid. In the work presented, activated charcoal strips were placed above and below the TADD membrane to determine the relative amounts of volatiles emitted by dynamite (i.e., ethylene glycol dinitrate (EGDN) and trinitroglycerin (NG)). The strips were eluted and the extracts tested using gas chromatography-mass spectrometry in negative ion chemical ionization mode. A series of t-tests at 95% confidence level were performed to determine any differences in vapor composition above and below the membranes. Nine synthetic membranes and six glass fiber membranes were tested in this study. It was expected that the relative concentration of volatiles would remain the same on both sides of the membrane; however, selective removal of nitroglycerin by some membranes was observed. Synthetic membranes with larger pore sizes showed no alteration in the vapor composition. Both synthetic and glass fiber membranes did not show a significant change in relative concentration of the other volatile compound in dynamite, i.e., EGDN. Out of all the membranes tested, three synthetic membranes and four glass fiber membranes showed selective alteration in odor availability of nitroglycerin in dynamite. For training purposes, membranes that do not alter the vapor composition should be used in the training aid.

Enhancing Nonfouling and Sensitivity of Surface-Enhanced Raman Scattering Substrates for Potent Drug Analysis in Blood Plasma via Fabrication of a Flexible Plasmonic Patch.

Surface-enhanced Raman scattering (SERS) is an ultrasensitive analytical technique, which is capable of providing high specificity; thus, it can be used for toxicological drug assay (detection and quantification). However, SERS-based drug analysis directly in human biofluids requires mitigation of fouling and nonspecificity effects that commonly appeared from unwanted adsorption of endogenous biomolecules present in biofluids (e.g., blood plasma and serum) onto the SERS substrate. Here, we report a bottom-up fabrication strategy to prepare ultrasensitive SERS substrates, first, by functionalizing chemically synthesized gold triangular nanoprisms (Au TNPs) with poly(ethylene glycol)-thiolate in the solid state to avoid protein fouling and second, by generating flexible plasmonic patches to enhance SERS sensitivity via the formation of high-intensity electromagnetic hot spots. Poly(ethylene glycol)-thiolate-functionalized Au TNPs in the form of flexible plasmonic patches show a twofold-improved signal-to-noise ratio in comparison to triethylamine (TEA)-passivated Au TNPs. Furthermore, the plasmonic patch displays a SERS enhancement factor of 4.5 ×107. Utilizing the Langmuir adsorption model, we determine the adsorption constant of drugs for two different surface ligands and observe that the drug molecules display stronger affinity for poly(ethylene glycol) ligands than TEA. Our density functional theory calculations unequivocally support the interaction between drug molecules and poly(ethylene glycol) moieties. Furthermore, the universality of the plasmonic patch for SERS-based drug detection is demonstrated for cocaine, JWH-018, and opioids (fentanyl, despropionyl fentanyl, and heroin) and binary mixture (trace amount of fentanyl in heroin) analyses. We demonstrate the applicability of flexible plasmonic patches for the selective assay of fentanyl at picogram/milliliter concentration levels from drug-of-abuse patients' blood plasma. The fentanyl concentration calculated in the patients' blood plasma from SERS analysis is in excellent agreement with the values determined using the paper spray ionization mass spectrometry technique. We believe that the flexible plasmonic patch fabrication strategy would be widely applicable to any plasmonic nanostructure for SERS-based chemical sensing for clinical toxicology and therapeutic drug monitoring.

Instrumental and chemometric analysis of opiates via gas chromatography-vacuum ultraviolet spectrophotometry (GC-VUV).

Since its introduction, gas chromatography (GC) coupled to vacuum ultraviolet spectrophotometry (VUV) has been shown to complement mass spectrometry (MS) for materials such as petrochemicals, explosives, pesticides, and drugs. In forensic chemistry, opioids are commonly encountered but rarely are the samples pure. This work focuses on GC-VUV analysis applied to naturally occurring (e.g., morphine), semi-synthetic (e.g., heroin), and synthetic (fentanyl) opioids as well as common adulterants and diluents (e.g., lidocaine and quinine). The specificity of the VUV spectra were examined visually as well as via descriptive statistical methods (e.g., correlation coefficients and sums of square residuals). Multivariate pattern recognition techniques (principal component analysis and discriminant analysis (DA)) were used to prove the opioid spectra can be reliably differentiated. The accuracy of the DA model was 100% for a test set of VUV spectra. Finally, three "street" heroin samples were analyzed to show "real-world" performance for forensic analyses. These samples contained adulterants such as caffeine, as well as by-products of heroin manufacture.

Fabrication of a self-assembled and flexible SERS nanosensor for explosive detection at parts-per-quadrillion levels from fingerprints.

Apart from high sensitivity and selectivity of surface-enhanced Raman scattering (SERS)-based trace explosive detection, efficient sampling of explosive residue from real world surfaces is very important for homeland security applications. Herein, we demonstrate an entirely new SERS nanosensor fabrication approach. The SERS nanosensor was prepared by self-assembling chemically synthesized gold triangular nanoprisms (Au TNPs), which we show display strong electromagnetic field enhancements at the sharp tips and edges, onto a pressure-sensitive flexible adhesive film. Our SERS nanosensor provides excellent SERS activity (enhancement factor = ∼6.0 × 106) and limit of detection (as low as 56 parts-per-quadrillions) with high selectivity by chemometric analyses among three commonly military high explosives (TNT, RDX, and PETN). Furthermore, the SERS nanosensors present excellent reproducibility (<4.0% relative standard deviation at 1.0 µM concentration) and unprecedentedly high stability with a "shelf life" of at least 5 months. Finally, TNT and PETN were analyzed and quantified by transferring solid explosive residues from fingerprints left on solid surfaces to the SERS nanosensor. Taken together, the demonstrated sensitivity, selectivity, and reliability of the measurements as well as with the excellent shelf life of our SERS nanosensors obviate the need for complicated sample processing steps required for other analytical techniques, and thus these nanosensors have tremendous potential not only in the field of measurement science but also for homeland security applications to combat acts of terror and military threats.

Optimization of total vaporization solid-phase microextraction (TV-SPME) for the determination of lipid profiles of Phormia regina, a forensically important blow fly species.

A new method has been developed for the determination of fatty acids, sterols, and other lipids which naturally occur within pupae of the blow fly Phormia regina. The method relies upon liquid extraction in non-polar solvent, followed by derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) w/ 1% trimethylchlorsilane (TMCS) carried out inside the sample vial. The analysis is facilitated by total vaporization solid-phase microextraction (TV-SPME), with gas chromatography-mass spectrometry (GC-MS) serving as the instrumentation for analysis. The TV-SPME delivery technique is approximately a factor of five more sensitive than traditional liquid injection, which may alleviate the need for rotary evaporation, reconstitution, collection of high performance liquid chromatography fractions, and many of the other pre-concentration steps that are commonplace in the current literature. Furthermore, the ability to derivatize the liquid extract in a single easy step while increasing sensitivity represents an improvement over current derivatization methods. The most common lipids identified in fly pupae were various saturated and unsaturated fatty acids ranging from lauric acid (12:0) to arachinoic acid (20:4), as well as cholesterol. The concentrations of myristic acid (14:0), palmitelaidic acid (16:2), and palmitoleic acid (16:1) were the most reliable indicators of the age of the pupae. Graphical abstract Blow fly pupae were extracted prior to emerging as adults. The extracts were analyzed via total vaporization solid-phase microextraction (TV-SPME), revealing a complex mixture of lipids that could be associated with the age of the insect. This information may assist in determining a post-mortum interval (PMI) in a death investigation.

Endothelial disruptive proinflammatory effects of nicotine and e-cigarette vapor exposures.

The increased use of inhaled nicotine via e-cigarettes has unknown risks to lung health. Having previously shown that cigarette smoke (CS) extract disrupts the lung microvasculature barrier function by endothelial cell activation and cytoskeletal rearrangement, we investigated the contribution of nicotine in CS or e-cigarettes (e-Cig) to lung endothelial injury. Primary lung microvascular endothelial cells were exposed to nicotine, e-Cig solution, or condensed e-Cig vapor (1-20 mM nicotine) or to nicotine-free CS extract or e-Cig solutions. Compared with nicotine-containing extract, nicotine free-CS extract (10-20%) caused significantly less endothelial permeability as measured with electric cell-substrate impedance sensing. Nicotine exposures triggered dose-dependent loss of endothelial barrier in cultured cell monolayers and rapidly increased lung inflammation and oxidative stress in mice. The endothelial barrier disruptive effects were associated with increased intracellular ceramides, p38 MAPK activation, and myosin light chain (MLC) phosphorylation, and was critically mediated by Rho-activated kinase via inhibition of MLC-phosphatase unit MYPT1. Although nicotine at sufficient concentrations to cause endothelial barrier loss did not trigger cell necrosis, it markedly inhibited cell proliferation. Augmentation of sphingosine-1-phosphate (S1P) signaling via S1P1 improved both endothelial cell proliferation and barrier function during nicotine exposures. Nicotine-independent effects of e-Cig solutions were noted, which may be attributable to acrolein, detected along with propylene glycol, glycerol, and nicotine by NMR, mass spectrometry, and gas chromatography, in both e-Cig solutions and vapor. These results suggest that soluble components of e-Cig, including nicotine, cause dose-dependent loss of lung endothelial barrier function, which is associated with oxidative stress and brisk inflammation.

Design and optimization of a total vaporization technique coupled to solid-phase microextraction.

Solid-phase microextraction (SPME) is a popular sampling technique in which chemical compounds are collected with a sorbent-coated fiber and then desorbed into an analytical instrument such as a liquid or gas chromatograph. Typically, this technique is used to sample the headspace above a solid or liquid sample (headspace SPME), or to directly sample a liquid (immersion SPME). However, this work demonstrates an alternative approach where the sample is totally vaporized (total vaporization SPME or TV-SPME) so that analytes partition directly between the vapor phase and the SPME fiber. The implementation of this technique is demonstrated with polydimethylsiloxane-divinylbenzene (PDMS-DVB) and polyacrylate (PA) coated SPME fibers for the collection of nicotine and its metabolite cotinine in chloroform extracts. The most important method parameters were optimized using a central composite design, and this resulted in an optimal extraction temperature (96 °C), extraction time (60 min), and sample volume (120 µL). In this application, large sample volumes up to 210 µL were analyzed using a volatile solvent such as chloroform at elevated temperatures. The sensitivity of TV-SPME is nearly twice that of liquid injection for cotinine and nearly 6 times higher for nicotine. In addition, increased sampling selectivity of TV-SPME permits detection of both nicotine and cotinine in hair as biomarkers of tobacco use where in the past the detection of cotinine has not been achieved by conventional SPME.

"Fooling fido"--chemical and behavioral studies of pseudo-explosive canine training aids.

Genuine explosive materials are traditionally employed in the training and testing of explosive-detecting canines so that they will respond reliably to these substances. However, challenges arising from the acquisition, storage, handling, and transportation of explosives have given rise to the development of "pseudo-explosive" training aids. These products attempt to emulate the odor of real explosives while remaining inert. Therefore, a canine trained on a pseudo-explosive should respond to its real-life analog. Similarly, a canine trained on an actual explosive should respond to the pseudo-explosive as if it was real. This research tested those assumptions with a focus on three explosives: single-base smokeless powder, 2,4,6-trinitrotoluene (TNT), and a RDX-based plastic explosive (Composition C-4). Using gas chromatography-mass spectrometry with solid phase microextraction as a pre-concentration technique, we determined that the volatile compounds given off by pseudo-explosive products consisted of various solvents, known additives from explosive formulations, and common impurities present in authentic explosives. For example, simulated smokeless powders emitted terpenes, 2,4-dinitrotoluene, diphenylamine, and ethyl centralite. Simulated TNT products emitted 2,4- and 2,6-dinitrotoluene. Simulated C-4 products emitted cyclohexanone, 2-ethyl-1-hexanol, and dimethyldinitrobutane. We also conducted tests to determine whether canines trained on pseudo-explosives are capable of alerting to genuine explosives and vice versa. The results show that canines trained on pseudo-explosives performed poorly at detecting all but the pseudo-explosives they are trained on. Similarly, canines trained on actual explosives performed poorly at detecting all but the actual explosives on which they were trained.

Screening of volatiles from explosive initiators and plastic-bonded explosives (PBX) using headspace solid-phase microextraction coupled with gas chromatography - mass spectrometry (SPME/GC-MS).

The detection of explosives and explosive devices based on the volatile compounds they emit is a long-standing tool for law enforcement and physical security. Toward that end, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) has become a crucial analytical tool for the identification of volatiles emitted by explosives. Previous SPME studies have identified many volatile compounds emitted by common explosive formulations that serve as the main charge in explosive devices. However, limited research has been conducted on initiators like fuses, detonating cords, and boosters. In this study, a variety of SPME fiber coatings (i.e., polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), divinylbenzene/carboxin/polydimethylsiloxane (DVB/CAR/PDMS), and carboxin/polydimethylsiloxane (CAR/PDMS)) were employed for the extraction and analysis of volatiles from Composition C-4 (cyclohexanone, 2-ethyl-1-hexanol, and 2,3-dimethyl-2,3-dinitrobutane (DMNB)) and Red Dot double-base smokeless powder (nitroglycerine, phenylamine). The results revealed that a PDMS/DVB fiber was optimal. Then, an assortment of explosive items (i.e., detonation cord, safety fuse, slip-on booster, and shape charge) were analyzed with a PDMS/DVB fiber. A variety of volatile compounds were identified, including plasticizers (tributyl acetyl citrate, N-butylbenzenesulfonamide), taggants (DMNB), and degradation products (2-ethyl-1-hexanol).

Proteomic study of low-temperature responses in strawberry cultivars (Fragaria x ananassa) that differ in cold tolerance.

To gain insight into the molecular basis contributing to overwintering hardiness, a comprehensive proteomic analysis comparing crowns of octoploid strawberry (Fragaria × ananassa) cultivars that differ in freezing tolerance was conducted. Four cultivars were examined for freeze tolerance and the most cold-tolerant cultivar ('Jonsok') and least-tolerant cultivar ('Frida') were compared with a goal to reveal how freezing tolerance is achieved in this distinctive overwintering structure and to identify potential cold-tolerance-associated biomarkers. Supported by univariate and multivariate analysis, a total of 63 spots from two-dimensional electrophoresis analysis and 135 proteins from label-free quantitative proteomics were identified as significantly differentially expressed in crown tissue from the two strawberry cultivars exposed to 0-, 2-, and 42-d cold treatment. Proteins identified as cold-tolerance-associated included molecular chaperones, antioxidants/detoxifying enzymes, metabolic enzymes, pathogenesis-related proteins, and flavonoid pathway proteins. A number of proteins were newly identified as associated with cold tolerance. Distinctive mechanisms for cold tolerance were characterized for two cultivars. In particular, the 'Frida' cold response emphasized proteins specific to flavonoid biosynthesis, while the more freezing-tolerant 'Jonsok' had a more comprehensive suite of known stress-responsive proteins including those involved in antioxidation, detoxification, and disease resistance. The molecular basis for 'Jonsok'-enhanced cold tolerance can be explained by the constitutive level of a number of proteins that provide a physiological stress-tolerant poise.

The effects of season and soil type on microbial degradation of gasoline residues from incendiary devices.

The primary task of a fire debris chemist is to determine if there is an ignitable liquid present in a fire debris sample and, if so, to classify it according to its boiling point and carbon number range. However, in organic-rich substrates such as soil, the ignitable liquid residue is subject to microbial degradation due to the ease with which bacteria can metabolize the various hydrocarbons present. This is a rapid process which is problematic in many forensic laboratories as fire debris is often stored for extended periods of time due to case backlog. Although microbial degradation has been studied in laboratory samples, it has not been well-studied in "real-world" samples, which have not only been exposed to microbial degradation but have also suffered the effects of weathering due to the intense heat of the fire. In this work, the effects of microbial degradation of gasoline from an incendiary device have been evaluated over time. In addition to visually monitoring chromatographic changes, this work also utilizes multivariate statistical techniques to simplify the complex data set and elucidate trends that might not otherwise be observed. Results indicate a clear difference between glass samples, which suffered the loss of low boiling compounds, and soil, which suffered the loss of the normal alkanes and lesser substituted aromatics. Also, devices deployed on lawn soil and in the winter season appear to show the most extensive degradation of gasoline. Finally, while the ratio of the C(3)-alkylbenzenes is significantly altered in soil samples recovered from large devices, the overall chromatographic profile of gasoline recovered from smaller incendiary devices is significantly lower.

Characterization of an odor permeable membrane device for the storage of explosives and use as canine training aids.

The storage and use of explosives is regulated at the state and federal level, with a particular focus on physical security and rigorous accounting of the explosive inventory. For those working with explosives for the training and testing of explosive-detecting canines, cross-contamination is an important concern. Hence, explosives intended for use with canine teams must be placed into secondary storage containers that are new, clean, and airtight. A variety of containers meet these requirements and include screw-top glass jars (e.g., mason jars). However, an additional need from the explosive-detecting canine community is secondary containers that can also be used as training aids whereby the volatiles emitted by explosives are emitted in a predictable and stable manner. Currently, a generally accepted method for the storage of explosives and controlled emission of explosive vapor for canine detection does not exist. Ideally, such containers should allow odor to escape from the training aid but block external contaminates such as particulates or other volatiles. One method in use places the explosive inside a permeable cotton bag when in use for training and then stores the cotton bag inside an impermeable nylon bag for long-term storage. This paper describes the testing of an odor permeable membrane device (OPMD) as a new way to store and deploy training aids. We measured the evaporation rate and flux of various liquid explosives and volatile compounds that have been identified in the headspace of actual explosives. OPMDs were used in addition to traditional storage containers to monitor the contamination and degradation of 14 explosives used as canine training aids. Explosives were stored individually using traditional storage bags or inside an OPMD at two locations, one of which actively used the training aids. Samples from each storage type at both locations were collected at 0, 3, 6, and 9 months and analyzed using Fourier Transform Infrared (FTIR) Spectroscopy and Gas Chromatography-Mass Spectrometry (GC-MS) with Solid-Phase Microextraction (SPME). FTIR analyses showed no signs of degradation. GC-MS identified cross-contamination from ethylene glycol dinitrate (EGDN) and/or 2,3-dimethyl-2,3-dinitrobutane (DMNB) across almost all samples regardless of storage condition. The contamination was found to be higher among training aids that were stored in traditional ways and that were in active use by canine teams.

Superhydrophobic Surface Modification of Polymer Microneedles Enables Fabrication of Multimodal Surface-Enhanced Raman Spectroscopy and Mass Spectrometry Substrates for Synthetic Drug Detection in Blood Plasma.

Microneedles are widely used substrates for various chemical and biological sensing applications utilizing surface-enhanced Raman spectroscopy (SERS), which is indeed a highly sensitive and specific analytical approach. This article reports the fabrication of a nanoparticle (NP)-decorated microneedle substrate that is both a SERS substrate and a substrate-supported electrospray ionization (ssESI) mass spectrometry (MS) sample ionization platform. Polymeric ligand-functionalized gold nanorods (Au NRs) are adsorbed onto superhydrophobic surface-modified polydimethylsiloxane (PDMS) microneedles through the control of various interfacial interactions. We show that the chain length of the polymer ligands dictates the NR adsorption process. Importantly, assembling Au NRs onto the micrometer-diameter needle tips allows the formation of highly concentrated electromagnetic hot spots, which provide the SERS enhancement factor as high as 1.0 × 106. The micrometer-sized area of the microneedle top and high electromagnetic field enhancement of our system can be loosely compared with tip-enhanced Raman spectroscopy, where the apex of a plasmonic NP-functionalized sharp probe produces high-intensity plasmonic hot spots. Utilizing our NR-decorated microneedle substrates, the synthetic drugs fentanyl and alprazolam are analyzed with a subpicomolar limit of detection. Further analysis of drug-molecule interactions on the NR surface utilizing the Langmuir adsorption model suggests that the higher polarizability of fentanyl allows for a stronger interaction with hydrophilic polymer layers on the NR surface. We further demonstrate the translational aspect of the microneedle substrate for both SERS- and ssESI-MS-based detection of these two potent drugs in 10 drug-of-abuse (DOA) patient plasma samples with minimal preanalysis sample preparation steps. Chemometric analysis for the SERS-based detection shows a very good classification between fentanyl, alprazolam, or a mixture thereof in our selected 10 samples. Most importantly, ssESI-MS analysis also successfully identifies fentanyl or alprazolam in these same 10 DOA plasma samples. We believe that our multimodal detection approach presented herein is a highly versatile detection technology that can be applicable to the detection of any analyte type without performing any complicated sample preparation.

Quantitative analysis of smokeless powder particles in post-blast debris via gas chromatography/vacuum ultraviolet spectroscopy (GC/VUV).

Forensic analysis of smokeless powder particles recovered from the debris of an improvised explosive device can provide information about the type of smokeless powder used and can aid investigation efforts. In this study, quantitative methods were used to yield information about the difference in the chemical composition of the particles pre- and post-blast. The technique, gas chromatography/vacuum ultraviolet spectroscopy (GC/VUV), was able to quantify nitroglycerin, 2,4-dinitrotoluene, diphenylamine, ethyl centralite, and di-n-butyl phthalate in pre- and post-blast smokeless powder particles using heptadecane as an internal standard. Post-blast debris was obtained via controlled explosions with assistance from the Indiana State Police Bomb Squad. Two galvanized steel and two polyvinyl chloride pipe bombs were assembled. Two devices contained single-base smokeless powder and two contained double-base smokeless powder. 2,4-dinitrotoluene and diphenylamine were successfully quantified in the single-base smokeless powder post-blast debris while nitroglycerin, diphenylamine, and ethyl centralite were successfully quantified in the double-base smokeless powder post-blast debris. Compounds were detected at concentrations as low as 9 µg of 2,4-dinitrotoluene per mg, <3 µg of diphenylamine per mg, 131 µg of nitroglycerin per mg, and <3 µg of ethyl centralite per mg. Concentration changes between pre- and post-blast smokeless powder particles were determined as well as microscopic differences between pre- and post-blast debris for both smokeless powders in all devices. To our knowledge, this is the first use of GC/VUV for the quantification of explosives.

Studies into exfoliation and coating of Egyptian blue in methanol for application to the detection of latent fingermarks.

We have recently demonstrated that coated exfoliated Egyptian blue powder is effective for detecting latent fingermarks on a range of highly-patterned non-porous and semi-porous surfaces. In this extension of that work, we present our studies into an alternative approach to prepare exfoliated Egyptian blue coated with cetrimonium bromide and Tween® 20 using a simpler technique. The quality of the latent fingermarks developed with these exfoliated powders and the commercial powder were compared in acomprehensive study. Depletion series of natural fingermarks from a wide range of donors (12 males and females) deposited on non-porous (glass slides) and semi-porous (Australian banknotes) surfaces were used in this study. Enhancement in the performance of the coated exfoliated particles compared to the commercial powder was observed, particularly in the case of aged fingermarks and polymer banknotes as challenging substrates.

Thermal and spectroscopic analysis of nitrated compounds and their break-down products using gas chromatography/vacuum UV spectroscopy (GC/VUV).

Gas chromatography/vacuum UV spectroscopy (GC/VUV) was utilized to study various explosives and pharmaceuticals in the nitrate ester and nitramine structural classes. In addition to generating specific VUV spectra for each compound, VUV was used to indicate the onset of thermal decomposition based upon the appearance of break-down products such as nitric oxide, carbon monoxide, formaldehyde, water, and molecular oxygen. The effect of temperature on decomposition could be fit to a logistical function where the fraction of intact compound remaining decreased as the transfer line/flow cell temperature was increased from 200 °C to 300 °C. Utilizing this relationship, the decomposition temperatures for the nitrate ester and nitramine compounds were determined to range between 244 °C and 277 °C. It was also discovered that the decomposition temperature was dependent on the GC carrier gas flow rate and, therefore, the residence time of the compounds in the transfer line/flow cell. For example, the measured decomposition temperature of nitroglycerine ranged from 222 °C to 253 °C across four flow rates. Tracking the appearance/disappearance of decomposition products across this temperature range indicated that NO, CO, and H2CO are final decomposition products while O2 and H2O are intermediate products. The decomposition temperatures for all explosives were highly correlated to similar decomposition measurements taken by differential scanning calorimetry (DSC) (r = 0.91) and thermal gravimetric analysis (TGA) (r = 0.90-0.98). In addition, the decomposition temperatures for all explosives were negatively correlated to the heat of explosion at constant volume (r = -0.68) and strongly positively correlated to the oxygen balance (r = 0.92).

A systematic study of the absorbance of the nitro functional group in the vacuum UV region.

The nitro functional group (NO2) features strongly in compounds such as explosives, pharmaceuticals, and fragrances. However, its gas phase absorbance characteristics in the vacuum UV region (120-200 nm) have not been systematically studied. Gas chromatography/vacuum UV spectroscopy (GC/VUV) was utilized to study the gas phase VUV spectra of various nitrated compounds (e.g., nitrate esters (-R-O-NO2), nitramines (R-N-NO2), nitroaromatics (Ar-NO2), and nitroalkanes (R-NO2)). The nitro absorption maximum appeared over a wide range (170-270 nm) and its wavelength and intensity were highly dependent upon the structure of the rest of the molecule. For example, the nitroalkanes exhibited a trend in that the ratio of the relative absorption intensity between these two absorption features between the alkyl group (<150 nm) and the nitro group (200 nm) increases as the molecular weight increases. It was observed that the addition of multiple nitro functional groups on benzene or toluene resulted in an increase in intensity and blue shift from approximately 240 nm-210 nm. Nitrate esters exhibited an absorption between 170 nm and 210 nm and absorbance increased with increasing nitrogen content. The relative diversity of the spectra obtained was analyzed by Principal Component Analysis (PCA) and Linear Discriminant Analysis (LDA). These calculations revealed that the spectra of all the compounds analyzed could be reliably differentiated without any misclassifications.

Gas Chromatography-Mass Spectrometry Paired with Total Vaporization Solid-Phase Microextraction as a Forensic Tool.

Gas Chromatography - Mass Spectrometry (GC-MS) is a frequently used technique for the analysis of numerous analytes of forensic interest, including controlled substances, ignitable liquids, and explosives. GC-MS can be coupled with Solid-Phase Microextraction (SPME), in which a fiber with a sorptive coating is placed into the headspace above a sample or immersed in a liquid sample. Analytes are sorbed onto the fiber which is then placed inside the heated GC inlet for desorption. Total Vaporization Solid-Phase Microextraction (TV-SPME) utilizes the same technique as immersion SPME but immerses the fiber into a completely vaporized sample extract. This complete vaporization results in a partition between only the vapor phase and the SPME fiber without interference from a liquid phase or any insoluble materials. Depending upon the boiling point of the solvent used, TV-SPME allows for large sample volumes (e.g., up to hundreds of microliters). On-fiber derivatization may also be performed using TV-SPME. TV-SPME has been used to analyze drugs and their metabolites in hair, urine, and saliva. This simple technique has also been applied to street drugs, lipids, fuel samples, post-blast explosive residues, and pollutants in water. This paper highlights the use of TV-SPME to identify illegal adulterants in very small samples (microliter quantities) of alcoholic beverages. Both gamma-hydroxybutyrate (GHB) and gamma-butyrolactone (GBL) were identified at levels that would be found in spiked drinks. Derivatization by a trimethylsilyl agent allowed for conversion of the aqueous matrix and GHB into their TMS derivatives. Overall, TV-SPME is quick, easy, and requires no sample preparation aside from placing the sample into a headspace vial.

Optimization of the qualitative and quantitative analysis of cocaine and other drugs of abuse via gas chromatography - Vacuum ultraviolet spectrophotometry (GC - VUV).

Gas Chromatography-Vacuum UV Spectroscopy (GC-VUV) has seen increased attention in many areas, however, a statistical optimization of VUV method parameters has not been published. This article presents the first statistical optimization of parameters influencing analytes such as cocaine in the VUV flow-cell. Flow-cell temperature, make-up gas pressure, and carrier gas flow rate from the GC were examined and optimized for the detection of controlled substances. The accuracy, precision, linearity, and optimized detection limits for drugs such as cocaine (98.5%, 1.2%, 0.9998, 1.5 ng), heroin (99.3%, 0.94%, 0.9998, 2.0 ng), and fentanyl (98.5%, 1.7%, 0.9752, 9.7 ng) are reported. In general, the limits of detection for cocaine, heroin, fentanyl, and methamphetamine after optimization were comparable to gas chromatography-mass spectrometry (GC-MS) in "scan mode", which had detection limits of 1.1-38 ng on column. The VUV absorption spectra of cocaine, PCP, lorazepam, and HU-210 are also reported. And three samples of "real world" cocaine are analyzed to demonstrate applicability to forensic drug analysis.

Detection of ɣ-hydroxybutyric acid (GHB) and ɣ-butyrolactone (GBL) in alcoholic beverages via total vaporization solid-phase microextraction (TV-SPME) and gas chromatography-mass spectrometry.

Total Vaporization Solid-Phase Microextraction (TV-SPME) relies on the same technique as standard SPME but completely vaporizes a sample extract, and analytes are sorbed directly from the vapor phase. On-fiber derivatization may also be performed using TV-SPME, where the fiber is first exposed to the headspace of a vial containing the derivatization agent, then exposed to a new vial containing the sample. É£-Hydroxybutyric acid (GHB) and É£-butyrolactone (GBL) are drugs of concern in that they may be used in drug facilitated sexual assault by surreptitiously spiking them into a victim's beverage. These drugs cause sedation, memory loss, and are difficult to detect in biological samples. One challenge in their analysis is that they can interconvert in aqueous samples, which was demonstrated in samples allowed to stand at room temperature for long periods. A volume study of GBL in water was performed with volumes ranging from 1 to 10,000 µl to compare the efficacy of TV-SPME, headspace SPME, and immersion SPME. Lastly, water, beer, wine, liquor, and mixed drinks were spiked with either GHB or GBL with realistic concentrations (mg/ml) and microliter quantities were analyzed using a TV-SPME Gas Chromatography-Mass Spectrometry method. The GBL volume study demonstrated an increased sensitivity in GBL detection when TV-SPME was utilized. Additionally, GHB and GBL were identified in various beverages at realistic concentrations. Overall, TV-SPME is beneficial because it requires no sample preparation and uses smaller sample volumes than immersion and headspace SPME.