Masuyuki Sugiyama

Development of a portable mass spectrometer characterized by discontinuous sample gas introduction, a low-pressure dielectric barrier discharge ionization source, and a vacuumed headspace technique.

The present study has attempted to downscale a mass spectrometer in order to make it portable and enable onsite analysis with it. The development of a small mass spectrometer required the use of a compact pump whose displacement was small, decreasing the sensitivity of that spectrometer. To get high sensitivity with a small mass spectrometer, we have integrated novel techniques: a highly sensitive ionization source and efficient extraction of sample vapor. The low-pressure dielectric barrier discharge ionization (LP-DBDI) source made it possible to increase the conductance between the source and the mass analyzer, compared with ambient ionization sources, enhancing the efficiency of the ion transfer from the ionization source to the mass analyzer. We have also developed a vacuumed headspace method efficiently transporting the sample vapor to the ionization source. The sensitivity was further enhanced by also using a discontinuous sample gas introduction technique. A prototype portable mass spectrometer using those novel techniques was found to be sensitive enough to detect 0.1 ppm methamphetamine, 1 ppm amphetamine, 1 ppm 3,4-methylenedioxymethamphetamine, and 10 ppm cocaine in liquid.

High-throughput walkthrough detection portal for counter terrorism: detection of triacetone triperoxide (TATP) vapor by atmospheric-pressure chemical ionization ion trap mass spectrometry.

With the aim of improving security, a high-throughput portal system for detecting triacetone triperoxide (TATP) vapor emitted from passengers and luggage was developed. The portal system consists of a push-pull air sampler, an atmospheric-pressure chemical ionization (APCI) ion source, and an explosives detector based on mass spectrometry. To improve the sensitivity of the explosives detector, a novel linear ion trap mass spectrometer with wire electrodes (wire-LIT) is installed in the portal system. TATP signals were clearly obtained 2 s after the subject under detection passed through the portal system. Preliminary results on sensitivity and throughput show that the portal system is a useful tool for preventing the use of TATP-based improvised explosive devices by screening persons in places where many people are coming and going.

High-Throughput Walkthrough Detection Portal as a Measure for Counter Terrorism: Design of a Vapor Sampler for Detecting Triacetone Triperoxide Vapor by Atmospheric-Pressure Chemical-Ionization Ion-Trap Mass Spectrometry

Aiming to prevent terrorist attacks in places where many people are coming and going, we have been developing a “high-throughput detection portal system.” The portal system consists of a vapor sampler, an atmospheric-pressure chemical-ionization ion source, and an explosives detector based on ion-trap mass spectrometry. The vapor sampler was designed to be installed in an automated ticket gate of a train station. By optimizing the shape of the nozzle that controls the air flow of the vapor sampler, triacetone triperoxide (TATP) vapor could be detected at a high throughput, i.e., 1200 persons/hour. The false-positive rate of the detection portal system for TATP was evaluated by a field test performed at a train station. A multi-marker logic to determine whether TATP existed or not was adopted, and no false-positive alarms were obtained for over 3000 passengers during the field test. However, acetone, which is an inflammable liquid, was accidentally detected from the passengers during the field test. It is concluded from this detection result that this detection portal system is useful for detecting dangerous chemicals that have high vapor pressure (such as TATP and inflammable liquids) in places where many people are coming and going.

Mass-selective axial ejection from a linear ion trap with a direct current extraction field

We have developed a new mass-selective axial ejection method from a linear ion trap (LIT). In this method, a set consisting of a trap wire lens and an extraction wire lens positioned orthogonally to each other was placed between quadrupole rods. The trap wire lens confines the ions inside the trap, and the extraction wire axially extracts ions from the trap. Ions introduced into the LIT are trapped between the inlet lens and the trap wire lens. In addition to the wire lenses, a set of excitation lenses, which are aligned orthogonally to the trap wire lens, are inserted between rods. The ions are resonantly excited in the direction perpendicular to the trap wire lens by applying a supplemental alternating current (AC) to the excitation lenses. Excited ions with a large motion pass over the trap wire lens, while unexcited ions remain trapped inside. Ions that have passed over the trap wire lens are then extracted by the extraction wire lens. The characteristics of the mass-selective ejection with a direct current (DC) extraction field were investigated by both simulation and experiment. A mass resolving power of m/Deltam = 1300 was achieved at a scan rate of 500 Th/s. The dependence of the ejection efficiency on trap wire lens bias was measured, and an ejection efficiency of 20% at a scan rate of 500 Th/s was achieved by optimizing the DC bias on the trap wire lens.

Sensitive low‐pressure dielectric barrier discharge ion source

RATIONALE We developed a novel highly sensitive soft ionization method: a low-pressure dielectric barrier discharge ionization (LP-DBDI) source. In this configuration, samples pass through the inside of a dielectric barrier discharge (DBD). Since samples pass through a DBD and its plasma jet, high ionization efficiency is expected. Furthermore, high transmission efficiency from the ion source to the mass spectrometer is also expected since the ion source is placed in a vacuum. METHODS Mass spectrometric detection was carried out in positive ion mode using an ion trap mass spectrometer. The LP-DBDI source or a conventional atmospheric pressure chemical ionization (APCI) source was attached to the mass spectrometer. Samples were vaporized and sent to ion sources with air flowing at a constant flow rate of 1.5 L/min. The LP-DBDI source was compared with a conventional APCI source. RESULTS Mass spectra of methyl salicylate, 2-undecanone and methamphetamine were acquired using the LP-DBDI source. Protonated molecules were mainly observed in the mass spectra. The sensitivities for methyl salicylate and 2-undecanone obtained using the LP-DBDI source were 44 times and 39 times higher, respectively, than those obtained using an APCI source. CONCLUSIONS LP-DBDI is a soft ionization method characterized by only minor fragmentation, similar to APCI. The sensitivity of the LP-DBDI source was found to be about 40 times higher than that of the conventional APCI source.

Mass spectra separation for explosives detection by using probabilistic latent component analysis

We propose a new method to separate mass spectra into components of each chemical compound for explosives detection. In mass spectra, all components have no negative values. However, conventional factor analyses for basis decomposition use no constraints of non-negativity, and we can not apply these methods to mass spectra. The proposed method is based on probabilistic latent component analysis (PLCA). The constraints of non-negativity always hold in PLCA, so that the method is effective for mass spectra. In addition, PLCA is defined in a statistical framework, thus PLCA makes it possible to utilize additional a priori information. Therefore, we introduce sparseness assumptions in the domain of mass spectrometry to PLCA in order to estimate the components more accurately. Experimental results indicate that the proposed method outperforms existing methods.

Probe Heating Method for the Analysis of Solid Samples Using a Portable Mass Spectrometer

We previously reported on the development of a portable mass spectrometer for the onsite screening of illicit drugs, but our previous sampling system could only be used for liquid samples. In this study, we report on an attempt to develop a probe heating method that also permits solid samples to be analyzed using a portable mass spectrometer. An aluminum rod is used as the sampling probe. The powdered sample is affixed to the sampling probe or a droplet of sample solution is placed on the tip of the probe and dried. The probe is then placed on a heater to vaporize the sample. The vapor is then introduced into the portable mass spectrometer and analyzed. With the heater temperature set to 130°C, the developed system detected 1 ng of methamphetamine, 1 ng of amphetamine, 3 ng of 3,4-methylenedioxymethamphetamine, 1 ng of 3,4-methylenedioxyamphetamine, and 0.3 ng of cocaine. Even from mixtures consisting of clove powder and methamphetamine powder, methamphetamine ions were detected by tandem mass spectrometry. The developed probe heating method provides a simple method for the analysis of solid samples. A portable mass spectrometer incorporating this method would thus be useful for the onsite screening of illicit drugs.

ICA-based acceleration of probabilistic latent component analysis for mass spectrometry-based explosives detection

We propose a new method to separate mass spectra into components of each chemical compound for explosives detection. The conventional method based on probabilistic latent component analysis (PLCA) is effective because the method can solve the problems of non-negativity and non-orthogonality by using sparsity of the domain of explosives detection. However, the convergence of the method is slow, and the calculation time is long. In order to solve this problem, the proposed method makes use of independent component analysis (ICA) in the initialization process. Experimental results indicate that the convergence of the proposed method is accelerated, and total calculation time is decreased.