Soft ionization mechanisms in flexible µ-tube plasma-elucidation of He-, Ar-, Kr-, and Xe-FµTP.

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.

Soft ionization mechanisms in flexible µ-tube plasma-from FµTP to closed µ-tube plasma.

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.

Solvent-Assisted Laser Desorption Flexible Microtube Plasma Mass Spectrometry for Direct Analysis of Dried Samples on Paper.

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.

Ionization of semi-fluorinated n-alkanes in controlled atmosphere using flexible micro-tube plasma (FµTP) ionization source with square- and sine-wave voltage.

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.

Pulsed Blue Laser Diode Thermal Desorption Microplasma Imaging Mass Spectrometry.

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.

Detection and Evaluation of Lipid Classes and Other Hydrophobic Compounds Using a Laser Desorption/Plasma Ionization Interface.

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.

Standardization of Sandwich-Structured Cu-Glass Substrates Embedded in a Flexible Diode Laser-Plasma Interface for the Detection of Cholesterol.

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.

Coupling laser desorption with gas chromatography and ion mobility spectrometry for improved olive oil characterisation.

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.

Medium Vacuum Electron Emitter as Soft Atmospheric Pressure Chemical Ionization Source for Organic Molecules.

An electron emitter as a soft atmospheric pressure chemical ionization source is presented, which operates at inner pressures of the device in the medium vacuum range (>10(-3) hPa). Conventional nonradioactive electron emitters require high vacuum (<10(-6) hPa) to prevent electrical sparkovers. The emitter presented here contains structural modifications of an existing setup, which inhibits electrical breakdowns up to 10(-2) hPa at 8 kV acceleration voltage. The increased inner pressure reduces the ionization efficiency until 10(-3) hPa-achievable without a turbomolecular pump-by 2% compared to high-vacuum conditions. This can be compensated with an increase of the electron source output. The functionality of this ion source is demonstrated with mass spectrometric and ion mobility measurements of acetone, eucalyptol, and diisopropyl methanephosphonate. Additional mass spectrometric measurements of 20 different organic compounds demonstrate the soft characteristics of this ionization source.

Time-resolved spectroscopy of a homogeneous dielectric barrier discharge for soft ionization driven by square wave high voltage.

Helium capillary dielectric barrier discharge driven by the square wave-shaped high voltage was investigated spatially and temporally by means of optical emission spectroscopy. The finding of the previous investigation conducted with the sinusoidal-like high voltage was confirmed, i.e., the plasma in the jet and the plasma in the capillary constitute two temporally separated events. The plasma in the jet occurs prior to the discharge in the capillary and exists only during the positive half period of the applied high voltage. The time delay of the capillary discharge with respect to the discharge in the jet depended on the high voltage, and it was between 2.4 and 8.4 µs for the voltage amplitude change in the range from 1.96 to 2.31 kV, respectively. It was found that, compared to sinusoidal-like voltage, application of the square wave high voltage results with stronger (~6 times) He line emission in the jet, which makes the latter more favorable for efficient soft ionization. The use of the square wave high voltage enabled comparison of the currents (~1 mA) flowing in the capillary during the positive and negative high voltage periods, which yielded the estimation for the charge dissipated in the atmosphere ((4 ± 20 %) × 10(-11) C) through the plasma jet.

Time- and spatially resolved emission spectroscopy of the dielectric barrier discharge for soft ionization sustained by a quasi-sinusoidal high voltage.

A helium capillary dielectric barrier discharge was investigated by means of time-resolved optical emission spectroscopy with the aim of elucidating the process of the formation of the plasma jet. The helium emission line at 706 nm was utilized to monitor spatial and temporal propagation of the excitation of helium atoms. The discharge was sustained with quasi-sinusoidal high voltage, and the temporal evolution of the helium atomic emission was measured simultaneously with the discharge current. The spatial development of the plasma was investigated along the discharge axis in the whole region, which covers the positions in the capillary between the electrodes as well as the plasma jet outside the capillary. The high voltage electrode was placed 2 mm from the capillary orifice, and the distance between the ground and high voltage electrode was 10 mm. The complete spatiotemporal grid of the development of the helium excitation has shown that during the positive half-period of the applied voltage, two independent plasmas, separated in time, are formed. First, the early plasma that constitutes the plasma jet is formed, while the discharge in the capillary follows subsequently. In the early plasma, the helium atom excitation propagation starts in the vicinity of the high voltage electrode and departs from the capillary towards the ground electrode as well as several millimeters outside of the capillary in the form of the plasma jet. After relatively slow propagation of the early plasma in the capillary and the jet, the second plasma starts between the electrodes. During the negative voltage period, only the plasma in the capillary between the electrodes occurs.

Ambient diode laser desorption dielectric barrier discharge ionization mass spectrometry of nonvolatile chemicals.

In this work, the combined use of desorption by a continuous wave near-infrared diode laser and ionization by a dielectric barrier discharge-based probe (laser desorption dielectric barrier discharge ionization mass spectrometry (LD-DBDI-MS)) is presented as an ambient ionization method for the mass spectrometric detection of nonvolatile chemicals on surfaces. A separation of desorption and ionization processes could be verified. The use of the diode laser is motivated by its low cost, ease of use, and small size. To achieve an efficient desorption, the glass substrates are coated at the back side with a black point (target point, where the sample is deposited) in order to absorb the energy offered by the diode laser radiation. Subsequent ionization is accomplished by a helium plasmajet generated in the dielectric barrier discharge source. Examples on the application of this approach are shown in both positive and negative ionization modes. A wide variety of multiclass species with low vapor pressure were tested including pesticides, pharmaceuticals and explosives (reserpine, roxithromycin, propazine, prochloraz, spinosad, ampicillin, dicloxacillin, enrofloxacin, tetracycline, oxytetracycline, erythromycin, spinosad, cyclo-1,3,5,7-tetramethylene tetranitrate (HMX), and cyclo-1,3,5-trimethylene trinitramine (RDX)). A comparative evaluation revealed that the use of the laser is advantageous, compared to just heating the substrate surface.

A new interface to couple thin-layer chromatography with laser desorption/atmospheric pressure chemical ionization mass spectrometry for plate scanning.

An interface to allow on-line qualitative and quantitative full-plate detection and analysis of compounds separated by thin-layer chromatography (TLC) is presented. A continuous wave diode laser is employed as a desorption source. Atmospheric pressure chemical ionization mass spectrometry ionizes and subsequently identifies the desorbed sample molecules. Besides direct laser desorption on untreated TLC plates, graphite particles were used as a matrix to couple in the laser power and improve the efficiency of desorption.

Thin-layer chromatography combined with diode laser desorption/atmospheric pressure chemical ionization mass spectrometry.

The desorption of an analyte by a continuous wave diode laser from a porous surface of a thin-layer plate covered with a graphite suspension is presented. The thermally desorbed analyte molecules are ionized in the gas phase by a corona discharge at atmospheric pressure. Therefore, both essential processes--the desorption and the ionization of analyte molecules, which are often performed in one step--are separated. The target preparation is easy and fast since no additional extraction process is required. The mass spectrometric background signal was mostly limited to the low mass range showing no interference with typical compounds of interest. In this study, the calmative and antihypertensive drug reserpine was chosen as model analyte, which is often used for specification of mass spectrometers. No fragmentation was observed because of efficient collisional cooling under atmospheric pressure. The influence of diode laser power and the composition of the graphite suspension were investigated, and a primary optimization was performed.