Discontinuous Atmospheric Pressure Interface Research Articles

Discontinuous Atmospheric Pressure Interface in-Trap Single Photon Ionization Ion Trap Mass Spectrometry (DAPI in-Trap SPI ITMS)

A compact in-trap single photon ionization (SPI) system, termed discontinuous atmospheric pressure interface (DAPI) ion trap mass spectrometry (ITMS), for the rapid determination of trace volatile organic compounds (VOCs). DAPI enables the maintenance of high analyte pressure in the SPI source while preserving the vacuum. Utilizing vacuum ultraviolet (VUV) lamp as the ion source, we ionize the analyte within an enclosed miniature 3D ion trap for efficient analysis. Experimental findings demonstrate that the system achieves a mass resolution of less than 0.5 atomic mass units for full width at half maxima (FWHM), providing unit resolution. For the response for benzene, the system achieves almost instantaneous response, with rise and fall times of only 2 s, which is a significant advantage compared to the membrane inlet (MI) approach necessary for on-site detection. Additionally, tandem mass spectrometry (MS/MS) with unit m/z isolation window was achieved and resolved dimethyl disulfide and phenol with similar molecular weights. Our results demonstrate that the system provides excellent performance and we anticipate its application in rapidly determining VOCs.

Development and characterization of discontinuous atmospheric pressure interface - Dual pressure chamber miniature mass spectrometer

Miniaturized mass spectrometers have become increasingly prevalent for real-time detection and analysis, owing to their compact size and portability. The pursuit of performance enhancement in these instruments is a pivotal objective within the domain of mass spectrometry miniaturization. This study introduces a novel miniature mass spectrometer featuring a discontinuous atmospheric pressure interface and a dual pressure chamber. Compared to conventional single-chamber, discontinuous sampling interface mass spectrometers, the newly developed instrument demonstrates a more than tenfold improvement in detection efficiency. This significant enhancement is achieved without the need for complex control of switch coupling time series, thereby streamlining the circuit design and improving the instrument's fault tolerance. Furthermore, by capitalizing on the benefits of discontinuous sampling, the instrument reduces the operational pressure relative to traditional continuous sampling in differential pressure vacuum chambers. It accommodates larger inlet capillary (0.38 mm) and skimmer (0.5 mm) diameters, leading to a ninefold increase in response strength for risperidone and lowering the detection limit to 0.5 ppb. The instrument's capacity for rapid drug detection, along with enhanced resolution and detection limits, underscores its potential utility. Additionally, it facilitates the use of smaller mechanical pumps, significantly diminishing both the instrument's volume and power consumption. This presents a promising avenue for further miniaturization of mass spectrometers.

Development of a handheld mass spectrometer driven by the sinusoidal frequency scanning technique

The rapid chemical identifications are critical when treating poisoning patients in hospitals. Conventional liquid chromatography-MS techniques would consume hours of valuable rescue time, even without considering sample transfer time. A diagnostic device readily available in emergency room would help doctors make quick treatment plan and greatly save rescue time. Over the past two decades, several key technologies have been developed for mass spectrometer miniaturization. As a first attempt, three complementary technologies (discontinuous atmospheric pressure interface, sinusoidal frequency scanning ion trap driving and Faraday detection) were integrated together, which enables the construction of a handheld mass spectrometer. The whole device weights 5.2 kg and could work for 2 h on battery. It has dimensions of 21 by 21.6 by 12.3 cm, which is able to be held by one hand. Different types of ionization sources could be coupled with the mass spectrometer to facilitate different sample analysis. This MS device has mass resolution: up to 900; limit of detection: 0.1 μg/mL. With acceptable analytical performances, this device could potentially be used in field or conventional hospitals for emergency management of poisonings. The capability of detecting drug of abuse and warfare agents/simulants were demonstrated.

Triboionization in Discontinuous Atmospheric Pressure Inlet for a Miniature Ion Trap Mass Spectrometer.

Discontinuous atmospheric pressure interface (DAPI) consisting of a pinch valve, a silicone tube, and two metal capillaries has been widely used in miniature mass spectrometry. It is interesting that clear ion signals could be observed even when the extra ionization source was turned off. In-depth analysis suggested that this new ionization phenomenon known as triboionization is based on the surface friction on the inner surface of the silicone tube during the on/off of the pinch valve. In this study, triboionization in the DAPI of a miniature ion trap mass spectrometer was investigated. It was discovered that the signal intensity depended greatly on the material and the roughness of the silicone tube used in the DAPI. By rubbing the inner surface of the silicone tube, for example, the signal intensity can increase by nearly 20 times. Two connected pinch valves were developed to study the effects of the discharge pressure, the number, and the frequency of on/off of the pinch valve on triboionization, which were verified to have a large impact on the product ions. In addition, the humidity of the inner surface of the silicone tube impacted the signal intensity of product ions and the mass spectrum patterns, where the product ions were typically protonated ions. As the humidity increases, the signal intensity of analytes with high proton affinity increases accordingly. This triboionization source, which does not require heat, light, radiation, auxiliary gas, or solution, has been preliminarily proved to have potential for surface detection after continuous enrichment.

Enhanced Sensitivity and Precision of Portable Mass Spectrometry (MS) with a Discontinuous Atmospheric Pressure Interface by Multiple Ion Injection

The detection limit is one of the most important performance characteristics for portable mass spectrometers (MS). To significantly reduce the size and the weight, small vacuum pumps are used in portable MS which leads to the use of a discontinuous atmospheric pressure interface (DAPI). Multiple ion injections (M-DAPI), which accumulates ions through opening the DAPI pinch valve several times during the ion injection period while maintaining a radio frequency (RF) voltage continuously on the trap, was shown to improve the sensitivity of DAPI-based portable MS. A systematic investigation of the optimization of M-DAPI was performed. The primary parameters affecting the performance of M-DAPI were optimized and sensitivity and stability improvements are reported. An 11.6-fold improvement in sensitivity was achieved by M-DAPI compared to the single ion injection DAPI operation for 1 μg/mL enrofloxacin. A more than 10-fold reduction in the limit of detection (LOD) to 0.01 μg/mL was also obtained. In addition, the stability was improved by M-DAPI with a relative standard deviation of 14.4% compared to 4.6% for DAPI.

On-Demand Mass Spectrometry Analysis by Miniature Mass Spectrometer.

Electrospray ionization (ESI) has become a powerful tool for the analysis of biomolecules by mass spectrometry (MS). The process of ESI is difficult to control, and side reactions such as electrochemical reactions can occur during the ESI process because of the high voltages applied. Herein, a novel on-demand MS analysis method was developed based on discontinuous ion injection-induced ESI on a miniature MS system. Highly efficient ionization was enabled under low voltages (<300 V) using a discontinuous atmospheric pressure interface. On-demand ionization showed comparable sensitivity with regular nanoESI for the analyses of a series of compounds. It was found to be softer than regular ESI or nanoESI methods for ionization of proteins such as myoglobin and cytochrome C. As the ionization finished as soon as the interface was closed, the sample consumption was observed to reduce significantly for MS analysis, allowing single-cell analysis with multiple MS and MS/MS measurements.

Rapid Screening of Trace Volatile and Nonvolatile Illegal Drugs by Miniature Ion Trap Mass Spectrometry: Synchronized Flash-Thermal-Desorption Purging and Ion Injection.

The increasing demand for rapid and sensitive roadside identification of trace illegal drugs drives the development of high-performance miniature mass spectrometric instrumentation and methodology. Here, we report a synchronized flash-thermal-desorption purging and ion injection (SFTDPI) method to increase the sensitive and rapid screening of volatile and nonvolatile illegal drugs for miniature ion trap mass spectrometry (ITMS). The flash-thermal desorption could reach 290 °C in 2.5 s, which could achieve efficient vaporization of nonvolatile noscapine with boiling point at 565 °C. ITMS using discontinuous atmospheric pressure interface (DAPI) has an ion utilization ratio of less than 1%, the synchronized purging for flash-thermal desorption and ion injection with DAPI could accurately control the time interval along with the desorption, gas purging, ionization and ion injection, and the sample utilization ratio increases more than five times. The miniature SFTDPI-ITMS presents good performance: (1) more than 60 times improvement in sensitivity was achieved compared to the previously reported thermal-desorption acetone-assisted photoionization ion trap mass spectrometer for nonvolatile drugs, and the minimum detectable quantity reaches 50 pg for fentanyl. (2) Ten kinds of mixing drugs with boiling point difference of 300 °C can be simultaneously identified within 3 s under a single analysis. SFTDPI-ITMS was deployed at the roadside checkpoint of Sino-Burmese border; fentanyl in the captured encapsulated powder and the suspected opiate had been successfully identified.

Rapid On-Site Detection of Illegal Drugs in Complex Matrix by Thermal Desorption Acetone-Assisted Photoionization Miniature Ion Trap Mass Spectrometer.

Illegal drug smugglings and crimes have long been a global concern, and an apparatus which can identify drugs on-the-spot is urgently demanded by law enforcement. A thermal desorption acetone-assisted photoionization miniature ion trap mass spectrometer was developed for on-site and rapid identification of illegal drugs at checkpoints. Acetone was chosen for dopant-assisted photoionization, and the sensitivity of selected drugs was further enhanced with protonated analyte molecular ions [M + H]+. For example, the sensitivity of ephedrine was improved by as high as 22-fold. The mass discrimination effect, which was usually considered as a shortcoming of ion trap mass analyzer, was ingeniously utilized to eliminate the protonated acetone reagent ions and maximize the trapping efficiency of analyte ions in mass analyzer. Twenty-seven drugs were analyzed, and the limits of detection (LODs) of selected illegal drugs were at the nanogram level with analysis time of 2 s. Analyte/dopant ion peak intensity ratios in mass spectra could be used for quantitation to improve the quantitative analysis performance of miniature ion trap mass spectrometer equipped with a discontinuous atmospheric pressure interface (DAPI) with the prerequisite that dopant ions and analyte ions could be simultaneously and effectively trapped by the ion trap. The RSD of signal intensity was reduced from 25.3% to 8.5%, and the linear range was extended from 0.5-25 to 0.5-100 ng/μL for methamphetamine. A temperature-resolved thermal desorption sampling strategy was developed and used to distinguish illegal drug components in plant-based drug samples and drinks containing illegal drugs.

Tandem Analysis by a Dual-Trap Miniature Mass Spectrometer.

Miniature mass spectrometers are of an increasing interest for in-situ analyses, and their coupling with the ambient ionization sources is a valid path for direct analysis of complex samples. In this study, a miniature mass spectrometer using discontinuous atmospheric pressure interface was developed with a dual-LIT (linear ion trap) configuration. The comprehensive scan modes were enabled for tandem mass spectrometry analysis, which are critical for high-quality qualitative and quantitative analysis. A real-time pressure control was implemented to facilitate the ion transfer and collision induced dissociation (CID). Beam-type CID could be performed for tandem analysis at a high number of stages. In-trap CID at high q could also be performed with the fragment ions accumulated in a second trap. A precursor ion scan mode for analyzing target analytes has also been demonstrated.

Recent developments of miniature ion trap mass spectrometers

With outstanding analytical performance and portability, miniature mass spectrometer is one of the most powerful tools for in-situ analysis. The miniaturization of mass spectrometers has lasted for more than ten years, during which a number of miniature mass spectrometers employing different techniques have been developed. Small-in-size, working at relatively high pressure region and capable of performing tandem mass spectrometry, ion trap is the most widely used mass analyzer in miniature mass spectrometer systems. The recent development of miniature ion trap mass spectrometer systems in the last ten years was reviewed in this paper. These instruments adopt different atmospheric pressure interfaces (APIs), which are membrane inlets (MIs), discontinuous atmospheric pressure interface (DAPI) and continuous atmospheric pressure interface (CAPI). This review emphasizes on the mini mass spectrometry (MS) system that can be handheld by one person, but not the field-able ones that are too large to be hand-portable.

Developing a Vacuum Electrospray Source To Implement Efficient Atmospheric Sampling for Miniature Ion Trap Mass Spectrometer.

The performance of a miniature mass spectrometer in atmospheric analysis is closely related to the design of its sampling system. In this study, a simplified vacuum electrospray ionization (VESI) source was developed based on a combination of several techniques, including the discontinuous atmospheric pressure interface, direct capillary sampling, and pneumatic-assisted electrospray. Pulsed air was used as a vital factor to facilitate the operation of electrospray ionization in the vacuum chamber. This VESI device can be used as an efficient atmospheric sampling interface when coupled with a miniature rectilinear ion trap (RIT) mass spectrometer. The developed VESI-RIT instrument enables regular ESI analysis of liquid, and its qualitative and quantitative capabilities have been characterized by using various solution samples. A limit of detection of 8 ppb could be attained for arginine in a methanol solution. In addition, extractive electrospray ionization of organic compounds can be implemented by using the same VESI device, as long as the gas analytes are injected with the pulsed auxiliary air. This methodology can extend the use of the proposed VESI technique to rapid and online analysis of gaseous and volatile samples.

Discontinuous atmospheric pressure interface for mass spectrometry using a solenoid pulse valve.

For the development of on-site mass spectrometry for security and safety, point-of-care analysis, etc., the gas volume introduced into the vacuum should be reduced to a minimum. To cope with this demand, a discontinuous atmospheric pressure interface using a solenoid pulse valve was developed. The sample gas was introduced discontinuously into the ionization cell with a volume of 0.17cm(3) . The sampled gas in the cell was ionized by an alternating current (ac) corona discharge. The generated ions were sampled through a 0.25mm i.d. and 12mm long nickel capillary into the vacuum of a time-of-flight mass spectrometer. A gas flow rate of ~25mL/min was achieved with the 1Hz pulse valve operation and 20ms valve opening time. Sub-ng limits of detection for less volatile compounds such as explosives and drugs were obtained. Due to its compact size and low gas load to the vacuum, this new interface may be useful for applications in miniaturized mass spectrometry. Copyright © 2016 John Wiley & Sons, Ltd.

Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer.

An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0μg/m(3) to 6.3μg/m(3). Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80W) and weight (<13kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection. Graphical Abstract ᅟ.

Probe electrospray ionization (PESI) mass spectrometry with discontinuous atmospheric pressure interface (DAPI).

Probe electrospray ionization (PESI) using a 0.2 mm outside diameter titanium wire was performed and the generated ions were introduced into the mass spectrometer via a discontinuous atmospheric pressure interface using a pinch valve. Time-lapse PESI mass spectra were acquired by gradually increasing delay time for the pinch valve opening with respect to the start of each electrospray event when a high voltage was applied. The opening time of the pinch valve was 20 ms. Time-resolved PESI mass spectra showed marked differences for 10 mM NaCl, 10(-5) M gramicidin S and insulin in H(2)O/CH(3)OH/CH(3)COOH/CH(3)COONH(4) (65/35/1) with and without the addition of 10 mM CH(3)COONH(4). This was ascribed to the pH change of the liquid attached to the needle caused by electrochemical reactions taking place at the interface between the metal probe and the solution. NaCl cluster ions appeared only after the depletion of analytes. For the mixed solution of 10(-5) M cytochrome c, insulin, and gramicidin S in H(2)O/CH(3)OH/CH(3)COOH (65/35/1), a sequential appearance of analyte ions in the order of cytochrome c→insulin→gramicidin S was observed. The present technique was applied to three narcotic samples; methamphetamine, morphine and codeine. Limits of detection for these compounds were 10 ppb in H(2)O/CH(3)OH (1/1) for the single sampling with a pinch valve opening time of 200 ms.

Development and characterizations of a miniature capillary electrophoresis mass spectrometry system.

A miniature capillary electrophoresis mass spectrometry (CE/MS) system has been developed in this work. A 100% electrical driven miniaturized CE device was integrated with a miniature MS instrument, which has a discontinuous atmospheric pressure interface (DAPI) for coupling with atmospheric pressure ionization sources. A nanoelectrospray ionization (nano-ESI) source was developed with a sheath liquid interface for coupling the miniature CE and the MS system. A systematic characterization and optimization of the analytical performance have been done. The analysis of isobaric peptides and avoiding charge competition effects in nano-ESI sources have been demonstrated.

Design of portable mass spectrometers with handheld probes: aspects of the sampling and miniature pumping systems.

Miniature mass spectrometry analytical systems of backpack configuration fitted with sampling probes could potentially be of significant interest for in-field, real-time chemical analysis. In this study, various configurations were explored in which a long narrow tube was used to connect the turbo and backing pumps used to create and maintain vacuum. Also, for the first time we introduced two new types of pumps for miniature mass spectrometers, the Creare 130 g drag pump and Creare 350 g scroll backing pump. These pumps, along with another Creare 550 turbo pump and the commercially available Pfeiffer HiPace 10 turbo and KnF diaphragm backing pumps, were tested with the backpack configurations. The system performance, especially the scan time, was characterized when used with a discontinuous atmospheric pressure interface (DAPI) for ion introduction. The pumping performance in the pressure region above 1 mtorr is critical for DAPI operation. The 550 g turbo pump was shown to have a relatively higher pumping speed above 1 mtorr and gave a scan time of 300 ms, almost half the value obtained with the larger, heavier HiPace 10 often used with miniature mass spectrometers. The 350 g scroll pump was also found to be an improvement over the diaphragm pumps generally used as backing pumps. With a coaxial low temperature plasma ion source, direct analysis of low volatility compounds glass slides was demonstrated, including 1 ng DNP (2,4-Dinitrophenol) and 10 ng TNT (2,4,6-trinitrotoluene) with Creare 550 g turbo pump as well as 10 ng cocaine and 20 ng DNP with Creare 130 g drag pump.

Characterization of a DAPI-RIT-DAPI System for Gas-Phase Ion/Molecule and Ion/Ion Reactions

The discontinuous atmospheric pressure interface (DAPI) has been developed as a facile means for efficiently introducing ions generated at atmospheric pressure to an ion trap in vacuum [e.g., a rectilinear ion trap (RIT)] for mass analysis. Introduction of multiple beams of ions or neutral species through two DAPIs into a single RIT has been previously demonstrated. In this study, a home-built instrument with a DAPI-RIT-DAPI configuration has been characterized for the study of gas-phase ion/molecule and ion/ion reactions. The reaction species, including ions or neutrals, can be introduced from both ends of the RIT through the two DAPIs without complicated ion optics or differential pumping stages. The primary reactant ions were isolated prior to reaction and the product ions were mass analyzed after controlled reaction time period. Ion/molecule reactions involving peptide radical ions and proton-transfer ion/ion reactions have been carried out using this instrument. The gas dynamic effect due to the DAPI operation on internal energy deposition and the reactivity of peptide radical ions has been characterized. The DAPI-RIT-DAPI system also has a unique feature for allowing the ion reactions to be carried out at significantly elevated pressures (in 10(-1) Torr range), which has been found to be helpful to speed up the reactions. The viability and flexibility of the DAPI-RIT-DAPI system for the study of gas-phase ion reactions have been demonstrated.

Simulation of Rarefied Gas Flows in Atmospheric Pressure Interfaces for Mass Spectrometry Systems

The understanding of the gas dynamics of the atmospheric pressure interface is very important for the development of mass spectrometry systems with high sensitivity. While the gas flows at high pressure (>1Torr) and low pressure (<10(-3)Torr) stages are relatively well understood and could be modeled using continuum and molecular flows, respectively, the theoretical modeling or numeric simulation of gas flow through the transition pressure stage (1 to 10(-3)Torr) remains challenging. In this study, we used the direct simulation Monte Carlo (DMSC) method to develop the gas dynamic simulations for the continuous and discontinuous atmospheric pressure interfaces (API), with different focuses on the ion transfer by gas flows through a skimmer or directly from the atmospheric pressure to a vacuum stage, respectively. The impacts by the skimmer location in the continuous API and the temporal evolvement of the gas flow with a discontinuous API were characterized, which provide a solid base for the instrument design and performance improvement.

Ambient Aerodynamic Desorption/Ionization Method for Microparticle Mass Measurement

An ambient desorption/ionization method, named aerodynamic desorption (AD), was proposed for the in situ rapid mass measurement of microparticles. The AD method exploited the discontinuous atmospheric pressure interface (DAPI) to generate a pulsed airflow, which was used to desorb the microparticles under atmospheric pressure. Various microparticles, e.g., bacteria, cell, polystyrene, synthetic diamond, and silica particles, with different size and surface component were successfully desorbed. Similar to that in the conventional laser-induced acoustic desorption (LIAD) method, these microparticles were desorbed as precharged ions in the AD process and the charge number was largely relevant to the particle size. However, compared with LIAD, the sensitivity of the AD method was higher. A lower concentration of particles was required for the analysis. In addition, the construction and sampling process of AD source were much simpler. All types of liquid, solid, or/and gaseous samples can be directly sampled under ambient condition. As a demonstration of this AD method, the in situ mass analysis of red blood cells (RBCs) and E. coli bacteria were carried out using a homemade ambient AD mass spectrometer consisting of AD source, QIT mass analyzer, and charge detector. Their mass and mass distributions were obtained successfully.

Synchronized Discharge Ionization for Analysis of Volatile Organic Compounds Using a Hand-Held Ion Trap Mass Spectrometer

The sensitivity of mass analysis is highly dependent on the efficiencies of the sample introduction, analyte ionization, and subsequent ion transfer to the mass analyzer. For miniature mass spectrometry (MS) systems, it is highly desirable to maximize the amount of the samples that can be introduced at the pumping capability highly compromised and to have the MS analysis performed with simple electronics and robust in-vacuum components. In this study, a discharge ionization source synchronized with the sample introduction has been developed for hand-held mass spectrometers with discontinuous atmospheric pressure interfaces (DAPI). The flow rate of the sample introduced with a DAPI can be much higher than that allowed with a conventional continuous atmospheric pressure interface. The pressure variation associated with the DAPI operation was used to turn on and off the synchronized discharge ionization (SDI). For analysis of volatile organic compounds (VOCs) in air samples, the SDI has been shown to be soft and molecular ions of the VOCs have been observed as the major species. Since the ions could be transferred directly to the ion trap mass analyzer without a barrier for maintaining pressure differences, high sensitivity in chemical analysis was also achieved, with limits of detection (LODs) better than 1 ppbv obtained for PAHs (polycyclic aromatic hydrocarbons) in air.