Increased sensitivity in proton transfer reaction mass spectrometry by incorporation of a radio frequency ion funnel

A drift tube capable of simultaneously functioning as an ion funnel is demonstrated in proton transfer reaction mass spectrometry (PTR-MS) for the first time. The ion funnel enables a much higher proportion of ions to exit the drift tube and enter the mass spectrometer than would otherwise be the case. An increase in the detection sensitivity for volatile organic compounds of between 1 and 2 orders of magnitude is delivered, as demonstrated using several compounds. Other aspects of analytical performance explored in this study include the effective E/N (ratio of electric field to number density of the gas) and dynamic range over which the drift tube is operated. The dual-purpose drift tube/ion funnel can be coupled to various types of mass spectrometers to increase the detection sensitivity and may therefore offer considerable benefits in PTR-MS work.     

Unambiguous identification of volatile organic compounds by proton-transfer reaction mass spectrometry coupled with GC/MS

Interest in on-line measurements of volatile organic compounds (VOCs) is increasing, as sensitive, compact, and affordable direct inlet mass spectrometers are becoming available. Proton-transfer reaction mass spectrometry (PTR-MS) distinguishes itself by its high sensitivity (low ppt range), high time resolution (200 ms), little ionization-induced fragmentation, and ionization efficiency independent of the compound to be analyzed. Yet, PTR-MS has a shortcoming. It is a one-dimensional technique that characterizes compounds only via their mass, which is not sufficient for positive identification. Here, we introduce a technical and analytical extension of PTR-MS, which removes this shortcoming, while preserving its salient and unique features. Combining separation of VOCs by gas chromatography (GC) with simultaneous and parallel detection of the GC effluent by PTR-MS and electron impact MS, an unambiguous interpretation of complex PTR-MS spectra becomes feasible. This novel development is discussed on the basis of characteristic performance parameters, such as resolution, linear range, and detection limit. The recently developed drift tube with a reduced reaction volume is crucial to exploit the full potential of the setup. We illustrate the performance of the novel setup by analyzing a complex food system.     

2,4,6-Trinitrotoluene detection by laser-photofragmentation-laser-induced fluorescence

Photofragmentation (PF) and subsequent nitric oxide (NO) laser-induced fluorescence (LIF) is being developed to measure the concentration of energetic materials (EM's) in soil and other media. Laser radiation near 226 nm photodissociates gas-phase EM to NO(2), which predissociates into NO that gives an intense luminescence. The EM concentration is inferred from the intensity of the NO fluorescence. We have studied the factors that affect the PF-LIF signal intensity, including the effect of buffer gas on the LIF spectrum of pure NO, the effect of 2,4,6-trinitrotoluene (TNT) pressure on the PF-LIF spectrum, the effect of buffer-gas pressure on the PF-LIF signal intensity of pure TNT, and the effect of temperature on the PF-LIF spectra of pure TNT and of TNT in simulated soil. Heating of the TNT sample above 343 K was found to increase the magnitude of the PF-LIF signal intensity significantly, but also was found to cause physical and chemical changes in the TNT sample. The effects of heating and evacuating on the TNT sample were investigated. TNT concentration calibration curves were obtained for TNT in simulated soil mixtures. The limit of detection of TNT in soil was estimated to be 40 parts in 10(9).     

Nanoporous organosilicas as preconcentration materials for the electrochemical detection of trinitrotoluene

We describe the use of nanoporous organosilicas for rapid preconcentration and extraction of trinitrotoluene (TNT) for electrochemical analysis and demonstrate the effect of template-directed molecular imprinting on TNT adsorption. The relative effects of the benzene (BENZ)- and diethylbenzene (DEB)-bridged organic-inorganic polymers, having narrow or broad pore size distributions, respectively, on electrochemical response and desorption behavior were examined. Sample volumes of 0.5-10 mL containing 5-1000 ppb TNT in a phosphate-buffered saline buffer were preconcentrated in-line before the detector using a microcolumn containing 10 mg of imprinted BENZ or DEB. Square-wave voltammetry was used to detect the first reduction peak of TNT in an electrochemical flow cell using a carbon working electrode and a Ag/AgCl reference electrode. Imprinted BENZ released TNT faster than imprinted DEB with considerably less peak tailing and displayed enhanced sensitivity and an improvement in the limit of detection (LOD) owing to more rapid elution of TNT from that material with increasing signal amplitude. For imprinted BENZ, the slope of signal versus concentration scaled linearly with increasing preconcentration volume, and for preconcentrating 10 mL of sample, the LOD for TNT was estimated to be 5 ppb. Template-directed molecularly imprinted DEB (TDMI-DEB) was 7-fold more efficient in adsorption of TNT from aqueous contaminated soil extract than nonimprinted DEB.     

Metallic nanoparticle-carbon nanotube composites for electrochemical determination of explosive nitroaromatic compounds

Metal nanoparticles (Pt, Au, or Cu) together with multiwalled and single-walled carbon nanotubes (MWCNT and SWCNT) solubilized in Nafion have been used to form nanocomposites for electrochemical detection of trinitrotoluene (TNT) and several other nitroaromatics. Electrochemical and surface characterization by cyclic voltammetry, AFM, TEM, SEM, and Raman spectroscopy confirmed the presence of metal nanoparticles on CNTs. Among various combinations tested, the most synergistic signal effect was observed for the nanocomposite modified glassy carbon electrode (GC) containing Cu nanoparticles and SWCNT solubilized in Nafion. This combination provided the best sensitivity for detecting TNT and other nitroaromatic compounds. Adsorptive stripping voltammetry for TNT resulted in a detection limit of 1 ppb, with linearity up to 3 orders of magnitude. Selectivity toward the number and position of the nitro groups in different nitroaromatics was very reproducible and distinct. Reproducibility of the TNT signal was within 7% (n = 8) from one electrode preparation to another, and the response signal was stable (+/-3.8% at 95% confidence interval) for 40 repeated analyses with 10 min of preconditioning. The Cu-SWCNT-modified GC electrode was demonstrated for analysis of TNT in tap water, river water, and contaminated soil.     

High-pressure gas phase femtosecond laser ionization mass spectrometry

We describe a novel ion source for analytical mass spectrometry based on femtosecond laser ionization at pressures at and above atmospheric and characterize its performance when coupled to a tandem quadrupole/time-of-flight mass spectrometer. We assess source saturation limits, ionization and sampling efficiencies, the effective ionization volume, and limits of detection. We demonstrate 100% efficient ionization for a set of organic compounds and show that the degree of ion fragmentation over a range of laser powers is favorable compared to electron impact ionization, especially in that a substantial parent ion signal is always observed. We show how collisional cooling plays a role in controlling fragmentation at high pressures and address how ion-molecule chemistry can be controlled or exploited. High-pressure femtosecond laser ionization will allow "universal" and efficient ionization, presenting a research direction that will broaden the options for gas phase analysis beyond the capabilities of electron impact ionization.     

A novel surface plasmon resonance immunosensor for 2,4,6-trinitrotoluene (TNT) based on indirect competitive immunoreaction: a promising approach for on-site landmine detection

A surface plasmon resonance (SPR) immunosensor for the determination of 2,4,6-trinitrotoluene (TNT) has been developed based on the principle of indirect competitive immunoreaction. 2,4,6-trinitrophenol-bovine serum albumin (TNP-BSA) conjugate was immobilized onto a SPR gold chip by means of simple physical adsorption. Binding of anti-TNP antibody with TNP-BSA conjugate was detected based on an increase in resonance angle due to antigen-antibody interaction. Preincubation of anti-TNP antibody with TNT suppresses its interaction with immobilized TNP-BSA conjugate, which leads to a decrease in resonance angle shift. Following the dependence of the resonance angle shift, concentration of TNT was detected. Pepsin solution was used for the regeneration of the sensing surface. The response time for TNT measurement is about 22 min. The immunosensor showed excellent sensitivity to TNT in a wide concentration range from 60 ppt to 1000 ppb with good selectivity, stability, and reproducibility. The proposed system is promising for future application for the on-site detection of landmines.     

Polygermole nanoaggregate chemical sensor for TNT: enhancement of photoluminescence efficiency by aggregation-induced emission

New photoluminescent and nanoscale polygermole nanoaggregates for the detection of 2,4,6-trinitrotoluene (TNT) were developed by using aggregation-induced emission property. Polygermole nanoaggregates displaying diameter of 40 nm exhibited that photoluminescence (PL) intensity of emission band was increased about 730% when the water fraction was increased to 90% by volume. Relative PL efficiency of polygermole nanoaggregates was exponentially increased to the percent of water fraction and particle diameter was dependent on solvent composition. Particle size of polygermole nanoaggregates was tuned by controlling the water fraction by volume. PL intensity of polygermole nanoaggregates was not changed over a month. This indicated that polygermole nanoaggregates showed neither further aggregation nor degradation. Detection of TNT was achieved from the measuring of quenching PL of polygermole nanoaggregates by adding the TNT A linear Stern-Volmer relationship was observed for the detection of TNT.     

Mass spectrometric analysis of DNA mixtures: instrumental effects responsible for decreased sensitivity with increasing mass

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has demonstrated great potential to replace gel electrophoresis for DNA sequence analysis. A current limitation in this method is, however, the decreased sensitivity with increasing mass of DNA molecules. In the present study, instrumental effects on the mass analysis of DNA molecules were investigated quantitatively using an equimolar DNA mixture. It is shown that detection efficiency, detector saturation, and ion beam divergence account for the entirety of the observed falloff in signal intensity with increasing mass. Although the present study focused upon the analysis of DNA mixtures, the instrumental effects observed apply equally to other macromolecular mixtures (e.g., proteins, polymers).     

Proton transfer reaction mass spectrometry, a tool for on-line monitoring of acrylamide formation in the headspace of maillard reaction systems and processed food

The formation of acrylamide was measured in real time during thermal treatment (120-170 degrees C) of potato as well as in Maillard model systems composed of asparagine and reducing sugars, such as fructose and glucose. This was achieved by on-line monitoring of acrylamide released into the headspace of the samples using proton transfer reaction mass spectrometry (PTR-MS). Unambiguous identification of acrylamide by PTR-MS was accomplished by gas chromatography coupled simultaneously to electron-impact MS and PTR-MS. The PTR-MS ion signal at m/z 72 was shown to be exclusively due to protonated acrylamide obtained without fragmentation. In model Maillard systems, the formation of acrylamide from asparagine was favored with increasing temperature and preferably in the presence of fructose. Maximum signal intensities in the headspace were obtained after approximately 2 min at 170 degrees C, whereas 6-7 min was required at 150 degrees C. Similarly, the level of acrylamide released into the headspace during thermal treatment of potato was positively correlated to temperature.     

Photodissociation followed by laser-induced fluorescence at atmospheric pressure and 24 degrees C: a unique scheme for remote detection of explosives

A unique scheme has been applied for sensitive remote detection of 2,4,6-trinitrotoluene (TNT) vapor trace amounts at atmospheric pressure and 24 degrees C. The detection concept is based on a single laser beam inducing a tandem process: photodissociation of TNT vapor followed by highly selective detection of its photofragments vibrationally excited NO, utilizing laser-induced fluorescence with the A2Sigma+(v' = 0) <-- X2Pi(v' = 2) transition. A detection sensitivity of at least 8 parts in 10(9) of TNT vapor with a signal-to-noise ratio of approximately 10 has been experimentally verified for an unfocused approximately 5-mJ laser beam, measured at a distance of approximately 15 cm from the TNT sample.     

Low Frequency Eddy Current Testing of Insulators and Composites

Eddy current testing (ECT), a non-destructive testing method widely used to evaluate defects within conductive materials, is explored in this study as it applies to insulators and non-uniformly conductive materials. Previous work has shown that at high frequencies, differences in electric permittivity can be detected with ECT. In this study, a new design of an ECT sensor that employs two resonance-tuned coils is evaluated. Results show that material inconsistencies in insulators are detectable due to spatial variations in permittivity and magnetic permeability, and that detection is possible at lower frequencies than previously demonstrated. In addition to determining signal dependence on individual electromagnetic parameters, sensitivity for defect detection in a carbon fiber-reinforced polymer (CFRP) composite is qualitatively determined. Although low signal-to-noise ratio is observed with a small-diameter coil, by increasing the coil diameter, the signal to noise ratio is increased while preserving adequate spatial resolution to detect defects in the sample. This study expands on previous studies of the application of ECT to insulators, and demonstrates that defect detection is possible in CFRPs.     

Highly sensitive and selective dynamic light-scattering assay for TNT detection using p-ATP attached gold nanoparticle

TNT is one of the most commonly used nitro aromatic explosives for landmines of military and terrorist activities. As a result, there is an urgent need for rapid and reliable methods for the detection of trace amount of TNT for screenings in airport, analysis of forensic samples, and environmental analysis. Driven by the need to detect trace amounts of TNT from environmental samples, this article demonstrates a label-free, highly selective, and ultrasensitive para-aminothiophenol (p-ATP) modified gold nanoparticle based dynamic light scattering (DLS) probe for TNT recognition in 100 pico molar (pM) level from ethanol:acetonitile mixture solution. Because of the formation of strong π-donor-acceptor interaction between TNT and p-ATP, para-aminothiophenol attached gold nanoparticles undergo aggregation in the presence of TNT, which changes the DLS intensity tremendously. A detailed mechanism for significant DLS intensity change has been discussed. Our experimental results show that TNT can be detected quickly and accurately without any dye tagging in 100 pM level with excellent discrimination against other nitro compounds.     

Separation and detection of explosives on a microchip using micellar electrokinetic chromatography and indirect laser-induced fluorescence

A new approach for sensitive detection on a microfabricated chip is presented. Indirect laser-induced-fluorescence (IDLIF) was used to detect explosive compounds after separation by micellar electrokinetic chromatography (MEKC). The detection setup was used in an epifluorescence configuration with excitation provided by a near-IR diode laser operating at 750 nm. To achieve indirect detection, a low concentration of a dye (5 microM Cy7) was added to the running buffer as a visualizing agent. Using this methodology, a sample containing 14 explosives (EPA 8330 mixture) was examined. Concentrations of 1 ppm of trinitrobenzene (TNB), trinitrotoluene (TNT), dinitrobenzene (DNB), tetryl, and 2,4-dinitrotoluene (2,4-DNT) could be detected with S/N ratios between 3 and 10. Analyses showing 10 peaks, with plate numbers on the order of 60000, were completed within 60 s using a 65 mm long separation channel. The three isomers of nitrotoluene (2-, 3-, and 4-nitrotoluene) were not resolved. Additionally, the two nitramines (HMX and RDX) could only be detected at much higher concentrations, likely due to the low fluorescence quenching efficiencies of these compounds. The analysis method was also used to separate and detect nitroaromatic compounds in extracts from spiked soil samples. The presence of 1 ppm (1 microg of analyte/1 g of soil) of TNB, DNB, TNT, tetryl, 2,4-DNT, 2,6-DNT, 2-NH2-4,6-DNT, and 4-NH2-2,6-DNT could readily be detected. In the interest of increasing the sensitivity of the analysis, various on-chip injection schemes were evaluated. It was found that a 250 microm double-T injector gave a 35% increase in peak signal compared to a straight-cross injector, which is less than expected based on injected volume.     

Effect of the water vapor density on the field dependence of the ion mobility increment for nitro compounds in air

The dependence of the ion mobility increment coefficient α on the electric field strength in the presence of a variable water vapor density C = (0.3?15) × 10¹⁶ cm^?3 in air has been studied for the ions of explosive nitro compounds including DNT (2,4-dinitrotoluene), TNT (2,4,6-trinitrotoluene), and their degradation products DNB (1,3-dinitrobenzene) and TNB (1,3,5-trinitrobenzene). The influence of the water vapor density C on the α value decreases in the following sequence: DNB > TNB > DNT > TNT. The obtained dependences can be used for the creation and exploitation of experimental and commercial analytical ionization devices used for the detection of explosive vapors.     

Control of ion distortion in field asymmetric waveform ion mobility spectrometry via variation of dispersion field and gas temperature

Field asymmetric waveform ion mobility spectrometry (FAIMS) has emerged as an analytical tool of broad utility, especially in conjunction with mass spectrometry. Of particular promise is the use of FAIMS and 2-D ion mobility methods that combine FAIMS with conventional IMS to resolve and characterize protein and other macromolecular conformers. However, FAIMS operation requires a strong electric field, and ions are inevitably heated by energetic collisions with buffer gas molecules. This may induce ion isomerization or dissociation, which distort the separation properties of FAIMS (and subsequent stages) or reduce instrumental sensitivity. As FAIMS employs a periodic waveform, whether those processes are controlled by ion temperature at maximum or average field intensity has been debated. Here we address this issue by measuring the unfolding of compact ubiquitin ion geometries as a function of waveform amplitude (dispersion field, E(D)) and gas temperature, T. The field heating is quantified by matching the dependences of structural transitions on E(D) and T: increasing E(D) from 12 to 16 or from 16 to 20 kV/cm is equivalent to heating the (N2) gas by approximately 15-25 degrees C. The magnitude of field heating for any E(D) can be estimated using the two-temperature theory, and raising E(D) by 4 kV/cm augments heating by approximately 15-30 degrees C for maximum and approximately 4-8 degrees C for average field in the FAIMS cycle. Hence, isomerization of ions in FAIMS appears to be determined by the excitation at waveform peaks.     

Investigation of two-photon-induced polarization spectroscopy of the a-X (1,0) transition in molecular nitrogen at elevated pressures

Two-photon-induced polarization spectroscopy of molecular nitrogen in the alpha 1IIg(nu' =) <-- X 1Sigma(g)+ (nu" =) system near 283 nm was performed, and its signal dependence investigated over the pressure range from 1.2 to 5 bars at 300 K. A significant increase of the signal intensity with pressure beyond the expected square law for a two-photon process was observed for pure nitrogen. Similar behavior was also found for a constant nitrogen partial pressure with increasing partial pressures of argon buffer gas. In both cases the spectral linewidth of the excited transitions increased dramatically with overall pressure. A possible explanation is given for the observed behavior in terms of contributions to the nonlinear susceptibility of the medium from the population of one-photon resonantly absorbing excited-state nitrogen and ground state N(2)(+) ions created in the multiphoton absorption process at the high laser intensities required.     

Mode-mismatched dual-beam differential thermal lensing with optical scheme design optimized using expert estimation for analytical measurements

The optimization of the optical scheme design of a mode-mismatched dual-beam thermal-lens spectrometer for differential (dual-cell) measurements in a far-field mode using diffraction thermal-lens theory is carried out. A criterion for an expert estimation of the quality of the spectrometer design for differential thermal-lens measurements in analytical chemistry (sensitivity, low limits of detection, and quantification) is also developed. The theoretical calculations agree well with previous papers on differential thermal lensing. Using the example of iron(II) tris-(1,10-phenanthrolinate), it is shown that the blank signal compensation in differential thermal lens spectrometry provides a decrease in the limit of detection by an order of magnitude compared to the decrease in single-cell measurements. Using an artificial two-component mixture of ferroin and potassium dichromate, it is shown that dual-beam differential thermal lens spectrometry makes it possible to determine trace components against 900-fold excess amounts of interfering substances.     

Multiple scattering from Chebyshev particles: Monte Carlo simulations for backscattering in lidar geometry

Lidar measurements are often interpreted on the basis of two fundamental assumptions: absence of multiple scattering and sphericity of the particles that make up the diffusing medium. There are situations in which neither holds true. We focus our interest on multiply-scattered returns from homogeneous layers of monodisperse, randomly oriented, axisymmetric nonspherical particles. T(2) Chebyshev particles have been chosen and their single-scattering properties have been reviewed. A Monte Carlo procedure has been employed to calculate the backscattered signal for several fields of view. Comparisons with the case of scattering from equivalent (equal-volume) spheres have been carried out (narrow polydispersions have been used to smooth the phase functions' oscillations). Our numerical effort highlights a considerable variability in the intensity of the multiply-scattered signal, which is a consequence of the strong dependence of the backscattering cross section on deformation of the particles. Even more striking effects have been noted for depolarization; peculiar behavior was observed at moderate optical depths when particles characterized by a large backscattering depolarization ratio were employed in our simulations. The sensitivity of depolarization to even small departures from sphericity, in spite of random orientation of the particles, has been confirmed. The results obtained with the Monte Carlo codes have been successfully checked with an analytical formula for double scattering.     

Trace-concentration detection of cobalt in a liquid flow cell by degenerate four-wave mixing using low-power off-resonant laser excitation.

Optical phase conjugation by degenerate four-wave mixing (D4WM) in an absorbing metal-ion solution using a low-power argon-ion laser as the excitation source is demonstrated. This nonlinear laser technique can be used as a sensitive analytical spectroscopic method for trace-concentration measurement of metal ions in a small-volume continuously flowing analyte cell. Several important characteristics are discussed, including the effects of solvent properties, excitation wave-length, laser intensity, and analyte absorptivity on signal intensity. Detection of 0.26 ng (4.4 pmol) of cobalt inside the laser probe volume of 0.14 microL is reported using an excitation wavelength that is 136 nm away from the maximum absorption wavelength of the analyte solution. The minimum absorbance measured in our D4WM experiment is 2.0 X 10(-5) without complex formation for cobalt. The D4WM detection sensitivity, in terms of the concentration-absorptivity product, is 4.05 X 10(-4) cm-1 for cobalt(II) in ethanol. Our preliminary detection sensitivity compares favorably with other laser-based spectrometric methods. This nonlinear laser technique is applicable to both fluorescing and nonfluorescing analytes.