Nitrogen carrier gas for the separation of trace explosives on CI-GC/MS.

Fluctuations in ultra high purity (UHP) helium supply has the potential to negatively impact critical research efforts. Disruptions have increased significantly with suppliers prioritizing delivery to medical facilities. Due to the greater demand for helium, supply issues are likely to continue through the coming years.

Opioid cutting agents for use as internal standards in ion mobility spectrometry (IMS).

Opioids have become a serious public health concern over the last decade. These compounds are commonly found mixed, or cut, with safer compounds to make the opioids appear unadulterated while also enhancing the psychoactive effect on the user. Commercial benchtop and handheld IMS devices are capable of detection but published reduced ion mobility (K) values, used to identify the target analytes with IMS instrumentation, have shown variability.

Tailoring Amphiphilic Copolymers for Improved Aqueous Foam Stability.

Amphiphilic copolymers of various-molecular-weight (MW) poly(ethylene glycol) (PEG) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The first PEG series, poly(ethylene glycol)monomethacrylate (PEGMA, average Mn 200 and 400 MW), contained an -OH terminal group, and the second series, poly(ethylene glycol) monomethyl ether monomethacrylate (PEGMMA, average Mn 200, 400, and 1000 MW), possessed an -OCH terminal group. A total of five PEG-functionalized copolymers contained the same hydrophobic monomer, butyl acrylate (BA), and were successfully reproduced via a one-pot synthesis.

Copolymer Reversible Addition-Fragmentation Chain Transfer Synthesis of Polyethylene Glycol (PEG) Functionalized with Hydrophobic Acrylates: A Study of Surface and Foam Properties.

A series of amphiphilic statistical copolymers involving poly(ethylene glycol) monomethacrylate (PEGMA, -OH terminated, average Mn 200 molecular weight) and various hydrophobic acrylates were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The gradient copolymers were characterized by gel-permeation chromatography (GPC), H nuclear magnetic resonance (NMR), and attenuated total reflection Fourier transform infrared spectroscopy (FTIR-ATR). Solution properties of the copolymers were investigated utilizing surface tension measurement, dynamic light-scattering (DLS), as well as foam analysis using a dynamic foam analyzer (DFA).

Empirical determination of explosive vapor transport efficiencies.

The transport efficiency of 2,4-dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazinane (RDX) trace vapors through tubing materials that commonly constitute vapor handling infrastructures have been determined for a variety of tubing dimensions and sampling conditions. Using a programmable temperature vaporization inlet coupled with a gas chromatography mass spectrometer (PTV-GC-MS), the explosive vapors were quantified both with and without a length of tubing of a specific material in the sampling flow path. At vapor temperatures of 30 °C and 66 °C, minimal attenuations were observed for 2,4-DNT and TNT vapor concentrations when the tubing material was in-line with the sampling flow path, indicating that the transport is largely unaffected by interactions with the surface of the tubing materials.

Trace vapor generator for Explosives and Narcotics (TV-Gen).

The Trace Vapor Generator for Explosives and Narcotics (TV-Gen) is a portable and compact instrument designed to deliver a continuous source of trace-level vapors and vapor mixtures. It provides a tool to assist in the independent validation and verification of new materials and sensors under development for the vapor detection of explosives and narcotics. The design was conceived for use with a broad range of analytes, detection systems, materials, and sensors and to switch easily between the clean and analyte vapor streams.

Non-target analysis of vapor mixtures using silicon nanowire array sampling and thermal desorption.

This work presents and evaluates an algorithmic approach to deconvolving the elution profiles of chemical components of vapor mixtures that have been sampled and desorbed from a novel preconcentrator based on highly ordered silicon nanowire arrays. The arrays provide a medium for both preconcentration and partial chromatographic resolution, which is then further leveraged with multichannel detection. Here, mixtures of nitro aromatic vapors are sampled and then thermally desorbed from the device, at which point they are detected by a conventional mass selective detector.

Combined secondary electrospray and corona discharge ionization (SECDI) for improved detection of explosive vapors using drift tube ion mobility spectrometry.

Secondary electrospray corona discharge ionization (SECDI) combines the principles of secondary electrospray ionization (SESI) and corona discharge (CD) to achieve higher sensitivity, which is demonstrated through the detection of 2,4,6-trinitrotoluene (TNT) and 2,6-dinitrotoluene (2,6-DNT) vapors using ion mobility spectrometry (IMS). Using SECDI, enhancements in the IMS signal for TNT and 2,6-DNT vapors at trace concentrations are as much as 2-26 times that observed with CD or SESI alone. The enhancement in sensitivity is hypothesized to result from an increase in ionization efficiency driven by a higher number of reactant ions associated with SECDI compared to either technique individually.

Flow-Through Optical Chromatography in Combination with Confocal Raman Microspectroscopy: A Novel Label-Free Approach To Detect Responses of Live Macrophages to Environmental Stimuli.

Flow-through optical chromatography (FT-OC), an advanced mode of optical chromatography, achieved baseline separation of a mixture of silica microparticles (SiO, 1.00 and 2.50 μm) and a mixture of polystyrene microparticles (PS, 1.

Part per quadrillion quantitation of pentaerythritol tetranitrate vapor using online sampling gas chromatography-mass spectrometry.

The development of an online sampling method using programmable temperature vaporization gas chromatography with a mass spectrometer detector (PTV-GC/MS) for the analysis of trace pentaerythritol tetranitrate (PETN) vapor is presented. PETN degradation was minimized by optimizing the temperature and flow rates of the vapor sampling infrastructure. Validation of the online method was done using a previously published technique, vapor sampling with Tenax-TA thermal desorption tubes followed by analysis with a thermal desorption system coupled to a programmable temperature vaporization gas chromatograph with a micro-electron capture detector (TDS-PTV-GC/μECD).

Silicon nanowire arrays for the preconcentration and separation of trace explosives vapors.

Silicon nanowire (SiNW) arrays are demonstrated as a suitable platform for the preconcentration of trace nitroaromatic compounds and subsequent desorption via Joule heating of the array. Arrays are fabricated from Si wafers containing an epitaxially grown layer of low conductivity intrinsic Si sandwiched between layers of high conductivity p-type Si. Passage of current through the nanowires results in nanowire temperatures in excess of 200 °C during heating of the arrays as verified by using the temperature-dependent shift of the Si Raman band at ˜520 cm.

Micellar Electrokinetic Chromatography.

Micellar electrokinetic chromatography (MEKC) is a mode of capillary electrophoresis that allows for the separation of neutral molecules in an electric field. Typically, neutral molecules move with electroosmotic flow (EOF) or bulk flow during electrophoretic separations resulting in no temporal resolution between mixtures of neutral analytes. Inclusion of surfactant micelles in the separation buffer allows for the separation of neutral analytes from one another through association with the micelle.

Mixed Vapor Generation Device for delivery of homemade explosives vapor plumes.

While there is a large body of research on the properties and detection of traditional military high explosives and propellant low explosives, there is a dearth of research on homemade explosive (HME) materials, though they are prevalent today. The safety of working with these materials in the laboratory is the greatest limiting factor preventing HME research. A vapor delivery tool, the Mixed Vapor Generation Device (MV-Gen), was designed to safely contain the individual solid or liquid components that often compose homemade explosives vapor plumes and deliver the mixed component vapors for instrumental sampling and analysis.

Preconcentration and partial separation of nitroaromatic vapors using a methyltrimethoxysilane-based sol-gel.

Typical trace vapor analysis involves sorbent trapping, followed by desorption and chromatographic separation. This communication describes a method for streamlining this process by combining sorbent sampling/preconcentration with partial separation achieved through temperature-programmed thermal desorption. A novel sorbent trap was formulated in which tubular glass liners for a programmable-temperature gas chromatograph inlet were coated with a sol-gel based polymer stationary phase synthesized from methyltrimethoxysilane precursor and installed into the inlet, which was directly connected to a mass-selective detector by a fused silica capillary transfer line.

Trace explosives sensor testbed (TESTbed).

A novel vapor delivery testbed, referred to as the Trace Explosives Sensor Testbed, or TESTbed, is demonstrated that is amenable to both high- and low-volatility explosives vapors including nitromethane, nitroglycerine, ethylene glycol dinitrate, triacetone triperoxide, 2,4,6-trinitrotoluene, pentaerythritol tetranitrate, and hexahydro-1,3,5-trinitro-1,3,5-triazine. The TESTbed incorporates a six-port dual-line manifold system allowing for rapid actuation between a dedicated clean air source and a trace explosives vapor source. Explosives and explosives-related vapors can be sourced through a number of means including gas cylinders, permeation tube ovens, dynamic headspace chambers, and a Pneumatically Modulated Liquid Delivery System coupled to a perfluoroalkoxy total-consumption microflow nebulizer.

Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry.

As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane (i-CH) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer.

Trace Explosives Vapor Generation and Quantitation at Parts per Quadrillion Concentrations.

The generation of trace 2,4,6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), and pentaerythritol tetranitrate (PETN) vapors using a pneumatically modulated liquid delivery system (PMLDS) coupled to a polytetrafluoroethylene (PTFE) total-consumption micronebulizer is presented. The vapor generator operates in a continuous manner with final vapor concentrations proportional to the explosive concentration in aqueous solution delivered through the nebulizer and the diluent air flow rate. For quantitation of concentrations in the parts per billionvolume (ppbv) to parts per trillionvolume (pptrv) range, Tenax-TA thermal desorption tubes were used for vapor collection with subsequent analysis on a thermal-desorption system programmable-temperature vaporization gas chromatograph (TDS-PTV-GC) with a μ-ECD detector.

Minimizing thermal degradation in gas chromatographic quantitation of pentaerythritol tetranitrate.

An analytical method for establishing calibration curves for the quantitation of pentaerythriol tetranitrate (PETN) from sorbent-filled thermal desorption tubes by gas chromatography with electron capture detection (TDS-GC-ECD) was developed. As PETN has been demonstrated to thermally degrade under typical GC instrument conditions, peaks corresponding to both PETN degradants and molecular PETN are observed. The retention time corresponding to intact PETN was verified by high-resolution mass spectrometry with a flowing atmospheric pressure afterglow (FAPA) ionization source, which enabled soft ionization of intact PETN eluting the GC and subsequent accurate-mass identification.

Quantitative detection of trace explosive vapors by programmed temperature desorption gas chromatography-electron capture detector.

The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive vapor samples. The direct liquid deposition method yields a higher fidelity between the analysis of vapor samples and the analysis of solution standards than using separate injection methods for vapors and solutions, i.e.

Continuous flow, explosives vapor generator and sensor chamber.

A novel liquid injection vapor generator (LIVG) is demonstrated that is amenable to low vapor pressure explosives, 2,4,6-trinitrotoluene and hexahydro-1,3,5-trinitro-1,3,5-triazine. The LIVG operates in a continuous manner, providing a constant and stable vapor output over a period of days and whose concentration can be extended over as much as three orders of magnitude. In addition, a large test atmosphere chamber attached to the LIVG is described, which enables the generation of a stable test atmosphere with controllable humidity and temperature.

Dynamic headspace generation and quantitation of triacetone triperoxide vapor.

Two methods for quantitation of triacetone triperoxide (TATP) vapor using a programmable temperature vaporization (PTV) inlet coupled to a gas chromatography/mass spectrometer (GC/MS) have been demonstrated. The dynamic headspace of bulk TATP was mixed with clean humid air to produce a TATP vapor stream. Sampling via a heated transfer line to a PTV inlet with a Tenax-TA™ filled liner allowed for direct injection of the vapor stream to a GC/MS for vapor quantitation.

Direct liquid deposition calibration method for trace cyclotrimethylenetrinitramine using thermal desorption instrumentation.

A simple method for establishing calibration curves with sorbent-filled thermal desorption tubes has been demonstrated for nitroaromatic and nitramine vapor samples using a thermal desorption system with a cooled inlet system (TDS-CIS), which was coupled to a gas chromatograph (GC) with an electron capture detector (ECD). The method relies upon the direct liquid deposition of standard solutions onto the glass frit at the head of sorbent-filled thermal desorption tubes. Linear calibration results and ideal system conditions for the TDS-CIS-GC-ECD were established for mixtures containing both cyclotrimethylenetrinitramine, a.

On-line sample pre-concentration in microfluidic devices: a review.

On-line sample preconcentration is an essential tool in the development of microfluidic-based separation platforms. In order to become more competitive with traditional separation techniques, the community must continue to develop newer and more novel methods to improve detection limits, remove unwanted sample matrix components that disrupt separation performance, and enrich/purify analytes for other chip-based actions. Our goal in this review is to familiarize the reader with many of the options available for on-chip concentration enhancement with a focus on those manuscripts that, in our assessment, best describe the fundamental principles that govern those enhancements.

Characterization of thermal desorption instrumentation with a direct liquid deposition calibration method for trace 2,4,6-trinitrotoluene quantitation.

The use of thermal desorption systems for the analysis of trace vapors typically requires establishing a calibration curve from vapors generated with a permeation tube. The slow equilibration time of permeation tubes causes such an approach to become laborious when covering a wide dynamic range. Furthermore, many analytes of interest, such as explosives, are not available as permeation tubes.

Direct injection of seawater for the analysis of nitroaromatic explosives and their degradation products by micellar electrokinetic chromatography.

Practical considerations for the injection and separation of nitroaromatic explosives in seawater sample matrices are discussed. The use of high surfactant concentrations and long electrokinetic injections allows for improved detection limits. Sensitivity was enhanced by two mechanisms, improved stacking at the detector-side of the sample plug and desorption of analyte from the capillary wall by surfactant-containing BGE from the inlet side of the sample plug.