Liying Peng

Fast Switching of CO3–(H2O)n and O2–(H2O)n Reactant Ions in Dopant-Assisted Negative Photoionization Ion Mobility Spectrometry for Explosives Detection

Ion mobility spectrometry (IMS) has become the most deployed technique for on-site detection of trace explosives, and the reactant ions generated in the ionization source are tightly related to the performances of IMS. Combination of multiform reactant ions would provide more information and is in favor of correct identification of explosives. Fast switchable CO3(-)(H2O)n and O2(-)(H2O)n reactant ions were realized in a dopant-assisted negative photoionization ion mobility spectrometer (DANP-IMS). The switching could be achieved in less than 2 s by simply changing the gas flow direction. Up to 88% of the total reactant ions were CO3(-)(H2O)n in the bidirectional mode, and 89% of that were O2(-)(H2O)n in the unidirectional mode. The characteristics of combination of CO3(-)(H2O)n and O2(-)(H2O)n were demonstrated by the detection of explosives, including 2,4,6-trinitrotoluene (TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), ammonium nitrate fuel oil (ANFO), and black powder (BP). For TNT, RDX, and BP, product ions with different reduced mobility values (K0) were observed with CO3(-)(H2O)n and O2(-)(H2O)n, respectively, which is a benefit for the accurate identification. For ANFO, the same product ions with K0 of 2.07 cm(2) V(-1) s(-1) were generated, but improved peak-to-peak resolution as well as sensitivity were achieved with CO3(-)(H2O)n. Moreover, an improved peak-to-peak resolution was also obtained for BP with CO3(-)(H2O)n, while the better sensitivity was obtained with O2(-)(H2O)n.

On-site Rapid Detection of Trace Non-volatile Inorganic Explosives by Stand-alone Ion Mobility Spectrometry via Acid-enhanced Evaporization

New techniques for the field detection of inorganic improvised explosive devices (IEDs) are urgently developed. Although ion mobility spectrometry (IMS) has been proved to be the most effective method for screening organic explosives, it still faces a major challenge to detect inorganic explosives owing to their low volatilities. Herein, we proposed a strategy for detecting trace inorganic explosives by thermal desorption ion mobility spectrometry (TD-IMS) with sample-to-sample analysis time less than 5 s based on in-situ acidification on the sampling swabs. The responses for typical oxidizers in inorganic explosives, such as KNO3, KClO3 and KClO4 were at least enhanced by a factor of 3000 and their limits of detection were found to be subnanogram. The common organic explosives and their mixtures with inorganic oxidizers were detected, indicating that the acidification process did not affect the detection of organic explosives. Moreover, the typical inorganic explosives such as black powders, firecrackers and match head could be sensitively detected as well. These results demonstrated that this method could be easily employed in the current deployed IMS for on-site sensitive detection of either inorganic explosives or organic ones.

Dopant-Assisted Positive Photoionization Ion Mobility Spectrometry Coupled with Time-Resolved Thermal Desorption for On-Site Detection of Triacetone Triperoxide and Hexamethylene Trioxide Diamine in Complex Matrices

Peroxide explosives, such as triacetone triperoxide (TATP) and hexamethylene trioxide diamine (HMTD), were often used in the terrorist attacks due to their easy synthesis from readily starting materials. Therefore, an on-site detection method for TATP and HMTD is urgently needed. Herein, we developed a stand-alone dopant-assisted positive photoionization ion mobility spectrometry (DAPP-IMS) coupled with time-resolved thermal desorption introduction for rapid and sensitive detection of TATP and HMTD in complex matrices, such as white solids, soft drinks, and cosmetics. Acetone was chosen as the optimal dopant for better separation between reactant ion peaks and product ion peaks as well as higher sensitivity, and the limits of detection (LODs) of TATP and HMTD standard samples were 23.3 and 0.2 ng, respectively. Explosives on the sampling swab were thermally desorbed and carried into the ionization region dynamically within 10 s, and the maximum released concentration of TATP or HMTD could be time-resolved from the matrix interference owing to the different volatility. Furthermore, with the combination of the fast response thermal desorber (within 0.8 s) and the quick data acquisition software to DAPP-IMS, two-dimensional data related to drift time (TATP: 6.98 ms, K0 = 2.05 cm(2) V(-1) s(-1); HMTD: 9.36 ms, K0 = 1.53 cm(2) V(-1) s(-1)) and desorption time was obtained for TATP and HMTD, which is beneficial for their identification in complex matrices.

Dopant titrating ion mobility spectrometry for trace exhaled nitric oxide detection

Ion mobility spectrometry (IMS) is a promising non-invasive tool for the analysis of exhaled gas and exhaled nitric oxide (NO), a biomarker for diagnosis of respiratory diseases. However, the high moisture in exhaled gas always brings about extra overlapping ion peaks and results in poor identification ability. In this paper, p-benzoquinone (PBQ) was introduced into IMS to eliminate the interference of overlapping ion peaks and realize the selective identification of NO. The overlapping ions caused by moisture were titrated by PBQ and then converted to hydrated PBQ anions (C6H4[Formula: see text](H2O)n). The NO concentration could be determined by quantifying gas phase hydrated nitrite anions (N[Formula: see text](H2O)n), product ions of NO. Under optimized conditions, a limit of detection (LOD) of about 1.4 ppbv and a linear range of 10-200 ppbv were obtained for NO even in 100% relative humidity (RH) purified air. Furthermore, this established method was applied to measure hourly the exhaled NO of eight healthy volunteers, and real-time monitoring the exhaled NO of an esophageal carcinoma patient during radical surgery. These results revealed the potential of the current dopant titrating IMS method in the measurement of exhaled NO for medical disease diagnosis.

Detection of Nitro-Based and Peroxide-Based Explosives by Fast Polarity-Switchable Ion Mobility Spectrometer with Ion Focusing in Vicinity of Faraday Detector

Ion mobility spectrometer (IMS) has been widely deployed for on-site detection of explosives. The common nitro-based explosives are usually detected by negative IMS while the emerging peroxide-based explosives are better detected by positive IMS. In this study, a fast polarity-switchable IMS was constructed to detect these two explosive species in a single measurement. As the large traditional Faraday detector would cause a trailing reactant ion peak (RIP), a Faraday detector with ion focusing in vicinity was developed by reducing the detector radius to 3.3 mm and increasing the voltage difference between aperture grid and its front guard ring to 591 V, which could remove trailing peaks from RIP without loss of signal intensity. This fast polarity-switchable IMS with ion focusing in vicinity of Faraday detector was employed to detect a mixture of 10 ng 2,4,6-trinitrotoluene (TNT) and 50 ng hexamethylene triperoxide diamine (HMTD) by polarity-switching, and the result suggested that [TNT-H]− and [HMTD+H]+ could be detected in a single measurement. Furthermore, the removal of trailing peaks from RIP by the Faraday detector with ion focusing in vicinity also promised the accurate identification of KClO4, KNO3 and S in common inorganic explosives, whose product ion peaks were fairly adjacent to RIP.

Online Measurement of Exhaled NO Concentration and Its Production Sites by Fast Non-equilibrium Dilution Ion Mobility Spectrometry.

Exhaled nitric oxide (NO) is one of the most promising breath markers for respiratory diseases. Its profile for exhalation and the respiratory NO production sites can provide useful information for medical disease diagnosis and therapeutic procedures. However, the high-level moisture in exhaled gas always leads to the poor selectivity and sensitivity for ion spectrometric techniques. Herein, a method based on fast non-equilibrium dilution ion mobility spectrometry (NED-IMS) was firstly proposed to directly monitor the exhaled NO profile on line. The moisture interference was eliminated by turbulently diluting the original moisture to 21% of the original with the drift gas and dilution gas. Weak enhancement was observed for humid NO response and its limit of detection at 100% relative humidity was down to 0.58 ppb. The NO concentrations at multiple exhalation flow rates were measured, while its respiratory production sites were determined by using two-compartment model (2CM) and Högman and Meriläinen algorithm (HMA). Last but not the least, the NO production sites were analyzed hourly to tentatively investigate the daily physiological process of NO. The results demonstrated the capacity of NED-IMS in the real-time analysis of exhaled NO and its production sites for clinical diagnosis and assessment.

Long-term sub second-response monitoring of gaseous ammonia in ambient air by positive inhaling ion mobility spectrometry

A real-time dynamic measurements of ammonia (NH3) is crucial for understanding the atmospheric nucleation process. A novel method was developed for on line monitoring at the sub-second time scale for the gaseous ammonia in ambient air for months, based on a positive inhaling ion mobility spectrometry (IMS) with a 63Ni ion source. The selective detection of NH3 was achieved using a high resolution IMS with an optimization of the drift tube temperature above 150°C. This method improved the peak-to-peak resolution significantly, thus avoided the interferences of the adjacent peaks to the quantitative analysis of NH3. The time resolution of the IMS was less than 0.1s at a data averaging of 10 times. The limit of detection (LOD) achieved at sub-ppb level while a linear response of peak intensity versus concentration of NH3 in the range of 10-60ppb and 60-400ppb were obtained. The relative standard deviations (RSD), the confidence level and the errors were 1.06%, 95% and ± 0.21ppb by measuring 100ppb NH3 for 100 times. The effect of ambient humidity could be greatly reduced by using the drift temperature of over 150°C. At last, the application of measuring the NH3 concentration evolutions of Dalian city was performed from June 19 to December 3 in 2015. The results illustrated a potential method of using IMS for a real-time measuring atmospheric NH3 at an unprecedented accuracy and sensitivity with long-term stability.

Dopant-assisted negative photoionization Ion mobility spectrometry coupled with on-line cooling inlet for real-time monitoring H2S concentration in sewer gas.

Malodorous hydrogen sulfide (H2S) gas often exists in the sewer system and associates with the problems of releasing the dangerous odor to the atmosphere and causing sewer pipe to be corroded. A simple method is in demand for real-time measuring H2S level in the sewer gas. In this paper, an innovated method based on dopant-assisted negative photoionization ion mobility spectrometry (DANP-IMS) with on-line semiconductor cooling inlet was put forward and successfully applied for the real-time measurement of H2S in sewer gas. The influence of moisture was effectively reduced via an on-line cooling method and a non-equilibrium dilution with drift gas. The limits of quantitation for the H2S in ≥60% relative humidity air could be obtained at ≤79.0ng L(-1) with linear ranges of 129-2064ng L(-1). The H2S concentration in a sewer manhole was successfully determined while its product ions were identified by an ion-mobility time-of-fight mass spectrometry. Finally, the correlation between sewer H2S concentration and the daily routines and habits of residents was investigated through hourly or real-time monitoring the variation of sewer H2S in manholes, indicating the power of this DANP-IMS method in assessing the H2S concentration in sewer system.

Quantitative Detection of Hexamethylene Triperoxide Diamine in Complex Matrix by Dopant-assisted Photoionization Ion Mobility Spectrometry

Abstract Hexamethylene triperoxide diamine (HMTD), a kind of novel organic peroxide explosives, is often used in terrorist attacks due to its easy synthesis from readily available starting materials. To counteract this new type of threat, a dopant-assisted positive photoionization ion mobility spectrometer was developed on the basis of a nonradioactive ionization source, i.e., vacuum ultraviolet (VUV) lamp, for the determination of HMTD. Toluene, acetone and 2-butanone were tested as dopants, with acetone finally chosen as the optimal dopant for the quantitative detection of HMTD in a perfume matrix. With mass spectrometry, the reactant ions of acetone and the product ions of HMTD were assigned. The reactant ions of acetone were proton dimer [(CH 3 ) 2 CO] 2 H + ( m / z 117), while the product ions of HMTD were proton molecular ion [HMTD + H] + ( m / z 209). With both the drift tube and the thermal desorber temperature under 120 °C, the HMTD standard samples were quantified with the maximum signal intensity and the 10 th second signal intensity, the measurement linear was in the range of 5−50 ng μL −1 and 5−100 ng μL −1 , and the limit of detection (LOD) was achieved at 0.2 and 0.3 ng μL −1 , respectively. Cosmetics such as perfume often interfere and inhibit the measurement of ion mobility spectrometry of the explosives. Therefore, the detection of HMTD in a perfume matrix for the rapid screening and detection of HMTD on-site was of realistic significance. These two quantitative methods were used for the quantitative detection of HMTD in three different brands of perfume samples. By comparison, the method using the 10 th second signal intensity of HMTD for the quantitative detection has a better recovery rate and accuracy for HMTD. This method was suitable for the accurate and rapid quantitative detection of HMTD in a complex matrix.

A thermal desorption ion mobility spectrometer for the measurement of anticoagulant rodenticide diphacinone in beverages via in situ acid-assisted conversion

Anticoagulant rodenticide diphacinone (DPN) with the common form of sodium diphacinone (SDPN), playing an important role in controlling field rodents and mice in homes, is harmful to both human beings and domestic animals while taken mistakenly or poisoned intentionally. In this work, we propose a simple and rapid method based on thermal desorption ion mobility spectrometry (TD-IMS) for detecting DPN and SDPN. SDPN, with ultra-low vapour pressure, was essentially measured in the form of DPN after its in situ conversion with the assistance of an acid. Under the optimal conditions, the limits of detection (S/N = 3) for SDPN and DPN were less than 0.15 ng μL−1 while their recoveries were 96% and 97%, respectively, and the relative standard deviation for five measurements was less than 6.15%. Finally, the current method was used to detect DPN and SDPN in beverages including green tea, cola, and coffee, demonstrating its capacity in the application for actual samples.