The soft ionization mechanism of helium-based plasma seems to be understood while it still remains challenging in argon-based plasma, although many studies have used argon plasmas as a soft ...ionization source with good ionization efficiencies. In this study, helium, argon, krypton, and xenon were fed into the same discharge geometry, a flexible micro-tube plasma (FµTP), to determine the ionization mechanisms. The FµTPs operated with the named noble gases obtained comparable ionization efficiencies by MS measurements. The optical emission results showed that N2+ were the dominant ions within the helium-FµTP and noble gas ions were dominant for the other plasmas. These ions support the development of excitation and eventually stop at the end of the capillary. Therefore, Penning ionization and charge transfer between plasma and ambient air/analytes in the open atmosphere have been proven not to be the primary soft ionization mechanism. Furthermore, it was found that photoionization played a minor role in soft ionization. Using helium as a diagnosis gas in front of the discharge capillary nozzle of the FµTP, where the sample is usually positioned, shows that helium can be ignited by all of these FµTPs. This demonstrates that the excitation of a diagnosis gas as well as the ionization of analytes is independent of the type of the discharge gas. An alternative mechanism that a transient potential created by the ions is responsible for the soft ionization is subsequently proposed.The soft ionization mechanism of helium-based plasma seems to be understood while it still remains challenging in argon-based plasma, although many studies have used argon plasmas as a soft ionization source with good ionization efficiencies. In this study, helium, argon, krypton, and xenon were fed into the same discharge geometry, a flexible micro-tube plasma (FµTP), to determine the ionization mechanisms. The FµTPs operated with the named noble gases obtained comparable ionization efficiencies by MS measurements. The optical emission results showed that N2+ were the dominant ions within the helium-FµTP and noble gas ions were dominant for the other plasmas. These ions support the development of excitation and eventually stop at the end of the capillary. Therefore, Penning ionization and charge transfer between plasma and ambient air/analytes in the open atmosphere have been proven not to be the primary soft ionization mechanism. Furthermore, it was found that photoionization played a minor role in soft ionization. Using helium as a diagnosis gas in front of the discharge capillary nozzle of the FµTP, where the sample is usually positioned, shows that helium can be ignited by all of these FµTPs. This demonstrates that the excitation of a diagnosis gas as well as the ionization of analytes is independent of the type of the discharge gas. An alternative mechanism that a transient potential created by the ions is responsible for the soft ionization is subsequently proposed.
Miniature DBD has been obtaining more and more attention. A recently developed miniature flexible micro-tube plasma (FμTP) has proved to be an excellent soft ionization source for mass spectrometry ...and ion mobility spectrometry. In this paper, the optical characterization of the novel FμTP ionization source was carried out, aiming to cast light on the plasma propagation mechanism in one discharge cycle. To provide a clean environment for investigating the plasma propagation, the plasma was totally sustained in a capillary tube. It was found that in one discharge cycle, three discharge developments, namely two dielectric guided discharges in both positive and negative half cycle, and a negative glow discharge in the negative half cycle. Compared with the conventional dielectric barrier discharge, there is no formation of a dissociative plasma, which improves the soft ionization capacity of the present source. In addition to the whole light emission from 200 nm to 1100 nm, the lines related to the reactive species including He 706 nm, N2+ 391 nm, and O 777 nm were investigated spatially and temporally. Due to the effect of the attached charges, the plasma of the negative half cycle propagates faster than that of the positive half cycle. It was also found that the plasma in the positive half cycle propagates more discretely than that of the negative one, while the negative one has a larger emission intensity due to the overlap of the signal in both temporal and spatial scales. Further on, the electric field distribution was proved to be in Gaussian shape along the diameter of the capillary, while the negative one has a flat shape. By changing the concentration of N2 in He, the electron collision and penning ionization for generating N2+ were experimentally proved and identified. This study identifies the typical discharge process of the FμTP in one discharge cycle, indicating the plasma is indeed a dielectric guided discharge.
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•The plasma development in one discharge cycle for the FμTP ionization source was optically characterized.•The charges attached on the inner wall of the tube in positive half cycle act as “virtual electrode” in the negative one.•The electron collision and penning ionization for generating N2+ is experimentally identified.•The FμTP is indeed a dielectric guided discharge.
In order to find an explanation for the mechanism in a plasma operated with an alternating voltage, or rather a square wave voltage, such a plasma was investigated. It was found that Penning ...ionization, charge transfer, and photoionization played a minor or even no role in the soft ionization mechanism of a FµTP. If the collision of plasma gases with air does not contribute to soft ionization, it should also be possible to use a separated plasma for soft ionization. Preliminary investigations show that it is possible to ignite a diagnosis gas with a plasma gas even when there is a barrier such as glass between those gases. A temporally and locally limited potential must be produced at the outer surface to achieve this. This potential should be sufficient to ionize the environment softly and to be able to use this so-called closed µ-tube plasma as a new ionization source.In order to find an explanation for the mechanism in a plasma operated with an alternating voltage, or rather a square wave voltage, such a plasma was investigated. It was found that Penning ionization, charge transfer, and photoionization played a minor or even no role in the soft ionization mechanism of a FµTP. If the collision of plasma gases with air does not contribute to soft ionization, it should also be possible to use a separated plasma for soft ionization. Preliminary investigations show that it is possible to ignite a diagnosis gas with a plasma gas even when there is a barrier such as glass between those gases. A temporally and locally limited potential must be produced at the outer surface to achieve this. This potential should be sufficient to ionize the environment softly and to be able to use this so-called closed µ-tube plasma as a new ionization source.
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•Innovative coupling of laser desorption to GC – ion mobility spectrometry (GC/IMS).•Rapid, sensitive and mobile detection.•Comprehensive characterisation of liquid samples based on ...volatiles.•Additional analysis of semi- and non-volatiles.•GC/IMS analysis of olive oil.
The investigation of volatile compounds in the headspace of liquid samples can often be used for detailed and non-destructive characterisation of the sample. This has great potential for process control or the characterisation of food samples, such as olive oil. We investigated, for the first time, the plume of substances released from olive oil droplets by laser desorption in a feasibility study and applied ion mobility spectrometry coupled to rapid GC pre-separation to enhance selectivity. Our investigation demonstrated that significantly more substances can be detected and quantified via laser desorption than in the usual headspace, enabling a rapid (5–10 min), sensitive (low ng/g range) and comprehensive analysis of the sample, with the potential for quality control and fraud identification. Therefore, laser desorption provides a useful sampling tool for characterising liquids in many applications, requiring only a few µL of sample.
The present study investigated the potential for solvent-assisted laser desorption coupled with flexible microtube plasma ionization mass spectrometry (SALD-FμTP-MS) as a rapid analytical technique ...for direct analysis of surface-deposited samples. Paper was used as the demonstrative substrate, and an infrared hand-held laser was employed for sample desorption, aiming to explore cost-effective sampling and analysis methods. SALD-FμTP-MS offers several advantages, particularly for biofluid analysis, including affordability, the ability to analyze low sample volumes (<10 μL), expanded chemical coverage, sample and substrate stability, and in situ analysis and high throughput potential. The optimization process involved exploring the use of viscous solvents with high boiling points as liquid matrices. This approach aimed to enhance desorption and ionization efficiencies. Ethylene glycol (EG) was identified as a suitable solvent, which not only improved sensitivity but also ensured substrate stability during analysis. Furthermore, the addition of cosolvents such as acetonitrile/water (1:1) and ethyl acetate further enhanced sensitivity and reproducibility for a standard solution containing amphetamine, imazalil, and cholesterol. Optimized conditions for reproducible and sensitive analysis were determined as 1000 ms of laser exposure time using a 1 μL solvent mixture of 60% EG and 40% acetonitrile (ACN)/water (1:1). A mixture of 60% EG and 40% ACN/water (1:1) resulted in signal enhancements and relative standard deviations of 12, 20, and 13% for the evaluated standards, respectively. The applicability of SALD-FμTP-MS was further evaluated by successfully analyzing food, water, and biological samples, highlighting the potential of SALD-FμTP-MS analysis, particularly for thermolabile and polarity diverse compounds.
An ambient air laser desorption, plasma ionization imaging method is developed and presented using a microsecond pulsed laser diode for desorption and a flexible microtube plasma for ionization of ...the neutral desorbate. Inherent parameters such as the laser repetition rate and pulse width are optimized to the imaging application. For the desorption substrate, copper spots on a copper-glass sandwich structure are used. This novel design enables imaging without ablating the metal into the mass spectrometer. On this substrate, fixed calibration markers are used to decrease the positioning error in the imaging process, featuring a 3D offset correction within the experiment. The image is both screened spot-by-spot and per line scanning at a constant speed, which allows direct comparison. In spot-by-spot scanning, a novel algorithm is presented to unfold and to reconstruct the imaging data. This approach significantly decreases the time required for the imaging process, which allows imaging even at decreased sampling rates and thus higher mass resolution. After the experiment, the raw data is automatically converted and interpreted by a second algorithm, which allows direct visualization of the image from the data, even on low-intensity signals. Mouse liver microtome cuts have been screened for dehydrated cholesterol, proving good agreement of the unfolded data with the morphology of the tissue. The method optically resolves 30 μm, with 30 μm diameter copper spots and a 10 μm gap. No conventional chemical matrices or vacuum conditions are required.
Ionization mechanisms of different lipid classes and other hydrophobic compounds have been evaluated in an ambient air laser-desorption flexible microtube plasma ionization (LD-FμTPi) setup, without ...sample manipulation. Lipids require a minimum laser fluency of 27 W/mm2 for efficient desorption and detection, providing the possibility for temperature-programmed laser desorption of different lipid classes. The flexible microtube plasma (FμTP) produces oxygen addition to double bonds, even to polyunsaturated molecules. The characteristic fragmentation pattern of phospholipids consisting of the neutral loss of the phosphocholine head group was verified. The formation of dimers due to hydrogen bonding and dispersion forces was observed as well. In this sense, soft ionization capabilities of the FμTP were proven in both ion modes. Ambient air mass spectrometry methods often suffer from decreased reproducibility, for instance, due to changing atmospheric conditions or sensitive positioning of the ion source. It was shown that neutrals become increasingly unstable above a distance of 7 ± 1 mm to the spectrometer’s inlet, providing estimates for the free volume in LD-FμTPi MS. In this sense, no guided transport is required. The ion plume ejected from the plasma can be altered by applying a bias voltage to the copper substrate. Ions can be detected at −950 V, 300 V (negative ion mode) and −400 V, 900 V (positive ion mode), respectively. The ions are guided through an internal electric field gradient of the FμTP that arises from charged capillary walls, ideal for ion detection. In conclusion, this makes the method fast, robust, and flexible.
Non-thermal plasma-based ionization sources have been widely used and shown excellent soft ionization performance in mass spectrometry. Despite their extensive application, the ionization mechanisms ...of these sources are of great interest for further exploring their full potential. A controlled atmosphere can provide a clean and controllable ionization environment and is beneficial for studying the ionization mechanism. The plasma source itself also has a significant impact on the ionization mechanism of the analyte, and the voltage waveform is one of the key parameters for controlling the plasma source. In this paper, a miniature flexible micro-tube plasma (FμTP) ionization source was sustained using both square and sine-wave voltage. The ionization processes of typical semi-fluorinated n-alkanes (SFAs) were investigated in the controlled atmosphere filled with 80% N2 and 20% O2. The main mass peaks using both square and sine-wave voltages are found to be M-mH+ and M-mH+nO+ (m = 1, 3; n = 0, 1, 2). However, for the square-wave voltage, the M-H+O+ species are the most abundant while M−H+ species are dominant for the sine-wave voltage, showing that the plasma generated with sine-wave voltage is somewhat “softer” than the one with square-wave voltage for SFAs. With the assistance of optical spectroscopy, the plasma developments in one discharge cycle for both voltage waveforms were obtained. Only one discharge can be found in each half cycle for square-wave voltage while several for the sine-wave voltage. These would be responsible for the different ionization behaviors in these two cases. This work provides more insight into the ionization mechanism of SFAs and more understanding of plasma-based soft ionization. In addition, the analytical performance was evaluated to be comparable when using these two voltage generators with a big difference in cost, which will benefit the instrumental development.
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•SFAs was analyzed using mass spectrometry with miniature FμTP as ionization source in controlled atmosphere.•The ionization mechanism of SFAs was found to be the same while different pathways for square- and sine-wave voltage.•Square- and sine-wave voltage sustained FμTP ionization sources give high-sensitive and comparable analytical performance.•The ionization source sustained by sine-wave voltage is somewhat “softer” than that by square-wave voltage for SFAs.
This study introduced sandwich-structured copper-glass substrates for standardization of laser desorption and plasma ionization. For standardized quantitative analysis, cavities were constructed ...which allow better reproducibility in droplet deposition and for laser application. Applying the diode laser, molten substrate material is incorporated into the glass, being trapped inside. Therefore, this method can be separated from laser ablation, achieving high ion signals without ablating material from the surface. Flexible microtube plasma (FμTP) was selected as the ionization source, this being the first time that laser desorption and FμTP ionization are coupled. This laser–plasma interface was applied to the detection of cholesterol, which showed a significantly improved limit of detection of 0.46 ng and linear dynamic range of 3 orders of magnitude in positive ion mode compared to other (ambient air mass spectrometry) methods. The main reason was the change of phase on the copper surface. The dehydrated molecule M-H2O+H+ was the base peak of the spectrum and no further dissociation or fragmentation was observed. Blood plasma was spiked with cholesterol. In a 1:100 chloroform dilution, the presence of the plasma was neglectable and led to the same detection limits and linear dynamic range as in the cholesterol standard. No sample preparation or internal standards were needed for calibration. The physical effects of the surface modification were investigated, including the calculation of the laser beam waist to simplify the comparison and reproducibility of results.
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