Corona Discharge Ionization Research Articles

Effect of ionic wind on the sample distribution in corona discharge ion mobility spectrometry

Ionic wind generated during corona discharge (CD) can significantly influence the airflow field within Ion Mobility Spectrometry (IMS), yet its impact is often overlooked. This study delves into the impact of ionic wind on sample distribution, emphasizing the need to balance reactant ion density and ionic wind intensity, which leads to sample dilution. To mitigate this issue, an axial injection mode employing a hollow needle was proposed, thereby improving the sensitivity and recovery performance of CD-IMS. As a result, the limit of detection of dimethyl methylphosphonate (DMMP) monomer is lowered from 15 ppbv to 5 ppbv. Furthermore, this technique was successfully applied to the detection of lithium battery electrolyte leaks, with carbonate concentrations as low as 10 mg/L or 1 nL being detected within 5 s. Such findings underscore the technique's applicability for swift and sensitive monitoring of battery safety.

Rapid evaluation of vegetable oil varieties and geographical origins by ambient corona discharge ionization mass spectrometry

The composition and ratio of unsaturated fatty acids in vegetable oils play a crucial role in determining their overall quality. In this study, we present a corona discharge ionization mass spectrometry (MS) method for the rapid differentiation of vegetable oil varieties and their geographical origins under environmental conditions. Abundant water dimer radical cations, (H2O)2+•, were generated by the ionization setup, which effectively activated carbon‑carbon double bonds (C=C) to form epoxidized products. These epoxidation products were analyzed using tandem MS, generating diagnostic fragment ions that precisely identified CC bond positions. Statistical analysis models were subsequently developed using the resulting MS fingerprint data, revealing significant differences between various vegetable oils and olive oils from different origins. Key advantages of this method include minimal sample preparation, rapid analysis, and easily interpretable spectra. This study provides a new MS-based strategy for food quality assessment and offers a promising tool for identifying CC positional isomers in complex systems.

A configuration for cooling assisted organic solvent coated thin film microextraction after dispersive liquid-liquid microextraction method: A microextraction method for ultra-trace analyzing of volatile sample

A combination of the dispersive liquid-liquid microextraction (DLLME) method based on the total vaporization procedure and cooling-assisted organic solvent-coated thin film microextraction (TFME) was applied for extracting chlorpyrifos (as the model compound). Based on the high thermal conductivity, a nickel foam thin film with the dimensions of 5.0 mm × 5.0 mm was used as a substrate for holding the organic solvent. Supporting thin film by organic solvent increases the thickness and contact area of the film relative to TFME or single drop microextraction (SDME) alone, resulting in a dramatic increase in the extraction efficiency. To protect the organic solvent and enhance the analyte distribution coefficient between the film and the vapor phase, a cooling system was applied. The proposed design was effective due to condensing the target analyte only on the uniform cooled thin film and not on the other regions in the extraction chamber. A corona discharge ionization source-ion mobility spectrometer was employed to identify the analyte. After optimizing the effective parameters, the limits of quantification (S/N = 10) and detection (S/N = 3) were calculated 0.1 and 0.03 μg L−1, respectively, and the dynamic range was measured between 0.1 and 7.0 μg L−1, with a determination coefficient of 0.9997. For three concentration levels of 0.1, 3.0, and 7.0 μg L−1, the relative standard deviations (n = 3) as the repeatability index were to be 6 %, 5 %, and 4 % for intra-day and 9 %, 6 %, and 5 % for inter-day, respectively. The enrichment factor was also calculated to be 3630 for the analyte concentration of 1.0 μg L−1. Well water, potato, and agricultural wastewater were analyzed as the real samples and the relative recovery values were measured between 92 % and 99 %. The accuracy of the proposed technique was validated by the European Standards EN 12393 method. In this approach, two steps of analyte extraction (DLLME and TFME) were used consecutively, resulting in better preconcentration and reduced matrix interference during cleaning-up.

Rapid Separation and Detection of Drugs in Complex Biological Matrix Using TD-CDI Mass Spectrometer.

The drug detection technology plays a pivotal role in the domains of pharmaceutical regulation and law enforcement. In this study, we introduce a method that combines thermal desorption corona discharge ionization (TD-CDI) with mass spectrometry for efficient drug detection. The TD-CDI module, characterized by its compact and simple design, enables the separation of analytes within seconds and real-time presentation of one or two analyte peaks on the mass spectrum most of the time, which reduces matrix interference and improves detection performance. Through experimental investigation, we studied the characteristics of TD-CDI for analyte separation and detection, even with the same mass number, and optimized the TD-CDI approach. TD-CDI-MS was employed for the rapid detection of drugs in various traditional medicine, food products, and human samples. Additionally, by utilizing TD-CDI for segmented hair direct analysis, it becomes possible to trace the drug usage cycle of individuals. This underscores the feasibility of the proposed analytical method within the realm of drug detection.

Rapid classification of coffee origin by combining mass spectrometry analysis of coffee aroma with deep learning

Mislabeling the geographical origin of coffee is a prevalent form of fraud. In this study, a rapid, nondestructive, and high-throughput method combining mass spectrometry (MS) analysis and intelligence algorithms to classify coffee origin was developed. Specifically, volatile compounds in coffee aroma were detected using self-aspiration corona discharge ionization mass spectrometry (SACDI–MS), and the acquired MS data were processed using a customized deep learning algorithm to perform origin authentication automatically. To facilitate high-throughput analysis, an air curtain sampling device was designed and coupled with SACDI–MS to prevent volatile mixing and signal overlap. An accuracy of 99.78% was achieved in the classification of coffee samples from six origins at a throughput of 1 s per sample. The proposed approach may be effective in preventing coffee fraud owing to its straightforward operation, rapidity, and high accuracy and thus benefit consumers.

Solid phase microextraction arrow-ion mobility spectrometry for determination of selected pesticides in water

Ion mobility spectrometry with corona discharge ion source was used for the measurements of selected pesticides cybutryne, terbutryn, dichlorvos, and quinoxyfen in water. The analyses were carried out by (i) direct injection of the aqueous solution of the pesticides and (ii) extraction using solid phase microextraction by commercial SPME arrows. The instrumental and the experimental extraction parameters including the drift tube temperature, injection port temperature, and the SPME fiber type were studied and optimized to achieve the maximum signal intensity. The limit of detections obtained by the direct injection were about 0.1–1.0 mg L−1. Using the SPME arrow-ion mobility spectrometry method, the detection limits were improved 7–50 times and obtained as 0.01, 0.015, 0.05, and 0.1 mg L−1 for terbutryn, dichlorvos, cybutryne, and quinoxyfen, respectively. The recovery rate for analysis in surface water (real samples) was approximately 90–110% for both the direct injection and solid phase microextraction method. The capability of ion mobility spectrometry for the simultaneous detection of a mixture of the studied pesticides was assessed, and it was found that terbutryn, dichlorvos, and quinoxyfen can be detected simultaneously without peak overlapping.

Synthesis and characterization of MoS2–COOH/gly/Mn nanocomposite as an efficient adsorbent for Ultra-trace determination of trifluralin herbicide

The world is confronting a severe water crisis. To clean up water from heavy metals, microorganisms, chemicals, and other types of pollutants, nanocomposites have been receiving great attention specifically due to the high surface area affording to work effectually even at low concentrations. In this research, we synthesized a new amino acid-modified MoS2 nanocomposite by chemically immobilizing Mn (II). The synthesized absorbent MoS2–COOH/gly/Mn was identified by thermogravimetric analysis (TGA), nitrogen adsorption measurement, X-ray diffraction (XRD), analysis of energy dispersive X-ray mapping (EDAX and MAP), field emission scanning electron microscopy (FE-SEM), and Fourier Transform Infrared spectrometry (FT-IR). The nanocomposite was employed as an adsorbent through the solid phase microextraction (SPME) method while trifluralin herbicide was chosen as a model compound. For the monitoring of trifluralin molecules, we employed an ion mobility spectrometry apparatus featuring a corona discharge ionization source. The SPME method's effectiveness was examined by investigating the stirring rate and extraction time as two crucial parameters, aiming to achieve trace analysis of trifluralin. Under the optimized condition of the trifluralin extraction, the coefficient (R2) and linear dynamic range (LDR) correlation were obtained at 0.9961 and 0.5–10 μg L−1, respectively. Relative recovery values the described approach were obtained in the span of 96–97% for agricultural wastewater samples. The quantification (LOQ) and limit of detection (LOD) were calculated at 0.5 and 0.15 μg L−1, respectively. The proposed nanocomposite absorbent has the capability to be applied as an efficient material for the extraction of trifluralin herbicide from different solutions.

Fe3O4@nitrogen-doped carbon core-double shell nanotubes as a novel and efficient nanosorbent for ultrasonic assisted dispersive magnetic solid phase extraction of heterocyclic pesticides from environmental soil and water samples.

Fe3O4@nitrogen-doped carbon core-double shell nanotubes (Fe3O4@N-C C-DSNTs) were successfully synthesized and applied as a novel nanosorbent in ultrasonic assisted dispersive magnetic solid phase extraction (UA-DMSPE) of tribenuron-methyl, fenpyroximate, and iprodione. Subsequently, corona discharge ion mobility spectrometry (CD-IMS) was employed for the detection of the extracted analytes. Effective parameters on theextraction recovery percentage (ER%) were systematically investigated and optimized. Under optimal conditions, UA-DMSPE-CD-IMS demonstrated remarkable linearity in different ranges within 1.0 - 700 ng mL-1 with correlation coefficients exceeding 0.993, repeatability values below 6.9%, limits of detection ranging from 0.30 to 0.90 ng mL-1, high preconcentration factors (418 - 435), and ER%values (83 - 87%). The potential of the proposed method was further demonstrated by effectively determining the targeted pesticides in various environmental soil and water samples, exhibiting relative recoveries in the range 92.1 - 102%.

Diverse thermal desorption combined with self-aspirating corona discharge ionization for direct mass spectrometry analysis of complex samples.

The thermal desorption (TD) technique is widely employed in modern mass spectrometry to facilitate the detection of non-volatile analytes. In this study, we developed a compact TD device based on a small resistance wire and coupled it with a self-aspirating corona discharge ionization (CDI) source to conduct direct MS analysis of various liquid and solid samples. Due to its small size and low heat capacity, the temperature of the TD module can be flexibly and rapidly modulated by controlling the power sequence. Multiple heating modes, including pulse heating (PH), isothermal heating, and step heating (SH), are realized and characterized, and then applied for the detection of different real samples. In particular, the PH mode is suitable for the simultaneous detection of multiple components in samples with relatively simple matrices, while the SH mode is capable of component separation. In addition, the sensitivity and quantitative capability of the TD-CDI system for DEP solutions were tested, showing acceptable stability with a relative standard deviation of about 6.7% and a detection limit of 0.088 ng. Overall, the developed TD-CDI system provides a simple, convenient, and versatile tool for direct mass spectrometry analysis of real samples.

Comments on "Identification of Negative Ion at m/z 20 Produced by Atmospheric Pressure Corona Discharge Ionization under Ambient Air".

Comments on "Identification of Negative Ion at m/z 20 Produced by Atmospheric Pressure Corona Discharge Ionization under Ambient Air".

Mass spectrometry analysis of drugs using an integrated thermal desorption corona discharge ionization device

In this study, we introduce the design, characterization, and application of an integrated thermal desorption corona discharge ionization (TD-CDI) device, which was developed for direct mass spectrometry (MS) analysis of drugs in solid or liquid samples. The structure and operational parameters of the TD module were optimized through simulation and experimental investigations. For the CDI module, a hollow needle was used as the discharge electrode and sample inlet, allowing self-aspiration and efficient ionization of the desorbed samples. The TD-CDI device was tested and characterized using different mass spectrometers, exhibiting satisfactory stability and quantitative performance. Owing to its compact structure, it can be coupled to a miniature MS instrument to implement rapid identification of various drugs in urine solutions.

Shake It Off! Acoustic Manipulation of Lipid Vesicles for Mass Spectrometric Analysis.

Analyzing lipid assemblies, including liposomes and extracellular vesicles (EVs), is challenging due to their size, diverse composition, and tendency to aggregate. Such vesicles form with a simple phospholipid bilayer membrane, and they play important roles in drug discovery and delivery. The use of mass spectrometry (MS) allows for broad analysis of lipids from different classes; however, their release from the higher order structural aggregates is typically achieved by chemical means. Mechanical disruption by high frequency surface acoustic waves (SAW) is presented as an appealing alternative to preparing lipid vesicles for MS sampling. In this work, SAWs used to disrupt liposomes allow for the direct analysis of their constituent lipids by employing SAW nebulization with corona discharge (CD) ionization. We explore the effects of duration, frequency, and incorporation of nonpolar lipids, including cholesterol, on the SAW's ability to disrupt the liposome. We also report on the successful MS analysis of liposome-derived lipids along with cytochrome C in solution, thus demonstrating applications to aqueous samples and native MS conditions.

Reducing ion diffusion at atmospheric pressure through intermingled positive and negative ions

Increasing ion molecule reaction times for ambient ionization techniques can increase sensitivity of detection. Longer reaction times result in an increase in analyte signal relative to the reactant ion signal, however with a subsequent decrease in the total ion intensity. This loss in the total number of ions reaching the detector limits the extent to which increased reaction time can improve detection in practical applications. In this study ion loss was measured using either electric fields or gas flow to control ion transit time. Ion transit times ranged from 40 ms to 8 s, which resulted in ion densities ranging from 5 × 106 to 2 × 104 ions/cm3, respectively. These results provide insights into practical reaction time limitations or experimental boundaries when exploring sensitivity enhancements in ambient ionization. When exploring longer reaction times with an atmospheric flow tube coupled to a mass spectrometer (AFT-MS), an additional corona discharge ionization source of the same polarity was added in an attempt to increase total ion signal, but no improvement in signal was observed. This observation suggested that there was a maximum ion density being reached by the corona discharge that could not be increased by adding more of the same polarity ions. A hypothesis was that intermingling both polarities of ions would reduce ion loss and increase the measured ion signal. When two corona discharge sources—one each of positive and negative polarity—were used simultaneously in an AFT-MS, the total ion signal of either polarity measured by the MS was approximately double the current from a single corona discharge source. An increase in the negative ion signal was also observed when ∼10 parts-per-trillion vapor levels of an explosive (RDX, also known as hexogen) were introduced. In this case both the nitrate reactant ions and the RDX signal more than doubled with the addition of a corona discharge source producing positive ions. When intermingling positive and negative ions, an increase in ion current was also observed when the AFT was coupled directly to a Faraday detector or to an ion mobility spectrometer (IMS). This was the first demonstration of interfacing the AFT to an IMS. The observations and developments from this work will help in creating more portable instruments with improved sensitivity for detection of chemicals.

Analysis of Volatile Esters and Alkanoic Acids by an Atmospheric Pressure Corona Discharge Ionization Collision-Induced Dissociation Mass Spectrometry in Positive-Ion Mode: Ionization, Fragmentation Patterns, and Discrimination between Isomeric Compounds.

The ionization and fragmentation patterns of 24 compounds with elemental composition of CmH2mO2, including isomeric esters and alkanoic acids, were investigated by atmospheric pressure corona discharge ionization collision-induced dissociation (CID) mass spectrometry in the positive-ion mode. All compounds were ionized as protonated molecules and NH4+ adducts. In addition, fragment ions were observed in mass spectra of esters other than methyl esters, which are owing to the dissociation of the alkyl group in the alcohol side from the protonated molecules. In CID spectra, protonated alkanoic acids/methyl esters split off H2O/CH3OH and CO or the alkyl group in the acid side, depending on the carbon chain length. Protonated esters (other than methyl esters) mainly fragmented the alkyl group in the alcohol side. These general rules on ionization and fragmentation patterns can provide relevant information on the discrimination of isomers.

Analysis of human skin sebum and animal meats by heat pulse desorption/mass spectrometry using proximity corona discharge ionization

Recently, we have developed heat pulse desorption/mass spectrometry (HPD/MS). In HPD/MS, a heated N2 gas pulse was directed to the sample surface and desorbed analytes were mass analyzed by corona discharge ionization/mass spectrometry using an Orbitrap mass spectrometer. In this work, HPD/MS was applied to the analysis of skin surface components sampled from the forehead, nose, and jaw of three volunteers. It was found that various kinds of biological compounds such as squalene, free fatty acids, wax esters, triacylglycerols, and amino acids were detected. The simultaneous detection of compounds with a wide range of proton affinities suggests that the occurrence of consecutive proton transfer reactions is less likely to occur in the present experimental system. This is mainly due to the short distance of 1.5 mm between the tip of the corona needle and the inlet of the mass spectrometer (i.e., proximity corona discharge ion source). Under this condition, the transition time of the primary reactant ions (e.g., H3O+) from the tip of the corona discharge needle to the ion sampling orifice is roughly estimated to be ∼20 μs. This value nearly corresponds to the reaction lifetime of exoergic proton transfer reactions with a rate constant: ∼10−9 cm3 s−1 for the analytes of 1 ppm. Accordingly, analytes with concentrations less than 1 ppm would be ionized semi-quantitatively by the present method, making this method highly suitable for the rapid analysis of samples composed of complex mixture of compounds, e.g., non-target lipidomics.

Protonation of gabapentin: Ion mobility spectrometry and computational study.

Protonation of gabapentin was studied using corona discharge ion mobility spectrometry with two types of reactant ions at temperature of 200°C. It was found that at elevated temperatures, ionization of gabapentin proceeds via two channels, including the protonation and reactant ion attachment, in the presence of both hydronium and ammonium reactant ions. The effect of the sample concentration on the relative intensity of product ion peaks was also studied. It turned out that in high concentrations, in addition to the protonation of gabapentin, binding of the reactant ion and the formation of proton-bound dimer also occurred, while in low concentrations, the only product of the ionization process is protonated gabapentin. Density functional theory (DFT) with B3LYP and M062X functionals employing the same basis set 6-311++G(d,p) was used to extend the experimental findings. The structures of the several conformers of neutral and protonated gabapentin were obtained. Based on them, topical proton affinity and topical gas-phase basicity of gabapentin were calculated for selected conformers. The attachment of reactant ions to neutral gabapentin and formation of proton-bound dimer were thermodynamically studied.

Identification of Negative Ion at m/z 20 Produced by Atmospheric Pressure Corona Discharge Ionization under Ambient Air.

The negative ion at m/z 20 observed at atmospheric pressure corona discharge ionization mass spectra has been identified by supplying the vapors of deuterium oxide (D2O) and H218O. From the mass shifts of the ion at m/z 20 observed with D2O and H218O, it was suggested that the chemical composition of the ion at m/z 20 is to be H4O. Further mass shift from m/z 20 to 22 was observed by supplying the vapor of perfluorokerocene, suggesting the chemical composition of H3F. The chemical compositions of the negative ions H4O- and H3F- were consistence with the dipole-bound complex states between hydrogen H2 and polar molecules such as H2O and hydrogen fluoride (HF) having dipole moments beyond a critical dipole moment of 1.625 D, theoretically proposed by Skurski and Simons. The ionic chemical compositions and structures of H4O- and H3F- obtained with density functional theory calculations implied that both dipole-bound complex H2O-…H2 and HF-…H2 can be formed by exothermic reactions by which H2 molecule is complexing with negative ions H2O- and HF-, respectively.

The new approach to determination of the combined isotopic composition of methane for its genetic characterization

A new approach to mass-spectrometric determination of the combined isotopic composition of methane has been put forward. The approach is based on the preliminary on-line conversion of methane to methanol in corona discharge and selective chemical ionization. The approach provides means to lower requirements for equipment, consumables, and operation conditions and offers a challenge to develop a new field method.

Corona discharge ionization ion mobility spectrometry for ultra-trace determination of methamphetamine extracted from urine and plasma samples by dispersive liquid–liquid microextraction

In this work, dispersive liquid-liquid microextraction (DLLME) based on high-density extraction solvent was applied as a simple, fast and sensitive method for extraction and preconcentration of methamphetamine from human plasma and urine samples. The efficiency of positive corona discharge ionization ion mobility spectrometry was investigated for direct analysis of the extracted analyte. Effective parameters on the extraction efficiency, such as type and volume of the extraction and disperser solvents, centrifugation time, and sample solution pH were optimized. Trichloromethane and isopropanol were selected as the extracting and disperser solvents, respectively. Under the optimized conditions, the linear dynamic range (R2 = 0.9969) was found to be 0.5-18µg/L, and 0.15µg/L was calculated as the limit of detection. The relative standard deviations of intra- and inter-day were obtained 4 and 10%, respectively, and finally, in the analysis of human plasma and urine samples, the extraction recovery was obtained 104%.

Effect of ion source polarity and dopants on the detection of auxin plant hormones by ion mobility-mass spectrometry.

Ion mobility spectrometry (IMS) equipped with a corona discharge (CD) ion source was used for measurement of three auxin plant hormones including indole-3-acetic acid (IAA), indole-3-propionic acid (IPA), and indole-3-butyric acid (IBA). The measurements were performed in both positive and negative polarities of the CD ion source. Dopant gases NH3, CCl4, and CHBr3 were used to modify the ionization mechanism. A time-of-flight mass spectrometer (TOFMS) orthogonal to the IMS cell was used for identification of the product ions. Density functional theory was used to rationalize formation of the ions, theoretically. The mixtures of the auxins were analyzed by CD-IMS. The separation performance depended on the ion polarity and the dopants. In the positive polarity without dopants, auxins were ionized via protonation and three distinguished peaks were observed. Application of NH3 dopant resulted in two ionization channels, protonation, and NH4+ attachment leading to peak overlapping. In the negative polarity, two ionization reactions were operative, via deprotonation and O2- attachment. The separation of the monomer peaks was not achieved while the peaks of anionic dimers [2M-H]- were separated well. The best LOD (4ng) was obtained in negative polarity with CCl4 dopant. Methylation (esterification) of IAA improved LODs by about one order.