Application Of Ambient Mass Spectrometry Research Articles

Authentication of Edible Insects' Powders by the Combination of DART-HRMS Signatures: The First Application of Ambient Mass Spectrometry to Screening of Novel Food.

This feasibility study reports the use of direct analysis in real-time high-resolution mass spectrometry (DART-HRMS) in profiling the powders from edible insects, as well as the potential for the identification of different insect species by classification modeling. The basis of this study is the revolution that has occurred in the field of analytical chemistry, with the improved capability of ambient mass spectrometry to authenticate food matrices. In this study, we applied DART-HRMS, coupled with mid-level data fusion and a learning method, to discriminate between Acheta domesticus (house cricket), Tenebrio molitor (yellow mealworm), Locusta migratoria (migratory locust), and Bombyx mori (silk moth). A distinct metabolic fingerprint was observed for each edible insect species, while the Bombyx mori fingerprint was characterized by highly abundant linolenic acid and quinic acid; palmitic and oleic acids are the statistically predominant fatty acids in black soldier fly (Hermetia illucens). Our chemometrics also revealed that the amino acid proline is a discriminant molecule in Tenebrio molitor, whereas palmitic and linoleic acids are the most informative molecular features of the house cricket (Acheta domesticus). Good separation between the four different insect species was achieved, and cross-validation gave 100% correct identification for all training samples. The performance of the random forest classifier was examined on a test set and produced excellent results, in terms of overall accuracy, sensitivity, and specificity. These results demonstrate the reliability of the DART-HRMS as a screening method in a future quality control scenario to detect complete substitution of insect powders.

Authentication of organically grown vegetables by the application of ambient mass spectrometry and inductively coupled plasma (ICP) mass spectrometry; The leek case study

Health conscious and environmentally aware consumers are purchasing more organically produced foods. They prefer organic fruits and leafy vegetables as these are much less likely to have been exposed to contaminants such as pesticides.The detection of fraudulent activity in this area is difficult to undertake, because many chemical plant protection treatments degrade very quickly or can be washed off to remove evidence of their existence.It was found that when combining DART-MS with a compact, inexpensive and robust single quadrupole mass spectrometer, it was possible to differentiate organic from conventional leeks with 93.8% to 100% accuracy. ICP-MS results showed similar performance, with an ability to differentiate conventional from organic leeks with 92.5% to 98.1% accuracy.This study has paved the way for the certification of vegetables as being organically produced. The next step is to create data libraries to support the roll out of the methodologies described.

Oregano authentication by mid-level data fusion of chemical fingerprint signatures acquired by ambient mass spectrometry

Economically motivated adulteration (EMA) of herbs and spices is very frequent and a major cause of concern to consumers, manufacturers and legislators. Rapid, non-targeted methods capable of distinguishing authentic herbs from those mixed with low cost materials are desirable. To this aim, ambient mass spectrometry (AMS) was applied to authenticate dried oregano leaves. Authentic and adulterated oregano samples were submitted to two extraction procedures and analysed in positive and negative ion modes by direct analysis in real time-high resolution mass spectrometry (DART-HRMS). Mid-level data fusion of the four blocks of DART-HRMS data was performed, and the resultant unique dataset was submitted to supervised statistical analysis to ascertain the signals that discriminate authentic from adulterated oregano. The fourteen most informative signals of authenticity were tentatively assigned and validated by support vector machine (SVM). In the final model, accuracy, sensitivity and specificity of >90% were obtained. Independent authentic and adulterated oregano samples were used to validate the discriminative m/z values and evaluate the classification capability of the model. To the best of our knowledge this is the first application of AMS coupled to mid-level data fusion for oregano authentication.

Synergetic effect of laser and micro-fabricated glow discharge plasma in a new ion source for ambient mass spectrometry

A new ambient ionization technique named laser ablation micro-fabricated glow discharge plasma (LA-MFGDP) was developed for mass spectrometry in this study. This technique used low energy laser for sample ablation and ionized sample aerosol with MFGDP in sequence. The combination of laser ablation and MFGDP exhibited a synergetic effect that significantly improved the performance of MFGDP. Experimental results showed that MFGDP dominated the ionization process while laser played the role of desorption in LA-MFGDP. [M+H]+ and M+ proved that proton transfer reactions and charge transfer reactions were involved in the ionization process, respectively, indicating that the ionization character was the same as MFGDP. LA-MFGDP could analyze less volatile samples that were unable to be detected by MFGDP because laser significantly improved the ionization capability of MFGDP. Strong ion signals were obtained by LA-MFGDP with low sample consumption. The limits of detection (LODs) of LA-MFGDP was as low as three orders of magnitude than that of MFGDP, which demonstrated that LA-MFGDP possessed an outstanding advantage in detecting trace substances. LA-MFGDP was successfully applied to detect pharmaceutical tablets without any pretreatment. Benefited from the excellent performance, LA-MFGDP offers great potential in broadening the application of ambient mass spectrometry.

Ambient mass spectrometry for the molecular diagnosis of lung cancer.

Lung cancer is one of the most common malignancies and the leading cause of cancer-related death worldwide. Among the technologies suitable for the rapid and accurate molecular diagnosis of lung cancer, ambient mass spectrometry (AMS) has gained increasing interest as it allows the direct profiling of molecular information from various biological samples (e.g., tissue, serum, urine and sputum) in real-time and with minimal or no sample pretreatment. This minireview summarizes the applications of AMS in lung cancer studies (including tissue molecular identification, the discovery of potential biomarkers, and surgical margin assessment), and discusses the challenges and perspectives of AMS in the clinical precision molecular diagnosis of lung cancer.

Applications of ambient mass spectrometry of natural products in the fields of food safety, phytochemistry and forensics

Applications of ambient mass spectrometry of natural products in the fields of food safety, phytochemistry and forensics

Substrate-Mediated Laser Ablation under Ambient Conditions for Spatially-Resolved Tissue Proteomics.

Numerous applications of ambient Mass Spectrometry (MS) have been demonstrated over the past decade. They promoted the emergence of various micro-sampling techniques such as Laser Ablation/Droplet Capture (LADC). LADC consists in the ablation of analytes from a surface and their subsequent capture in a solvent droplet which can then be analyzed by MS. LADC is thus generally performed in the UV or IR range, using a wavelength at which analytes or the matrix absorb. In this work, we explore the potential of visible range LADC (532 nm) as a micro-sampling technology for large-scale proteomics analyses. We demonstrate that biomolecule analyses using 532 nm LADC are possible, despite the low absorbance of biomolecules at this wavelength. This is due to the preponderance of an indirect substrate-mediated ablation mechanism at low laser energy which contrasts with the conventional direct ablation driven by sample absorption. Using our custom LADC system and taking advantage of this substrate-mediated ablation mechanism, we were able to perform large-scale proteomic analyses of micro-sampled tissue sections and demonstrated the possible identification of proteins with relevant biological functions. Consequently, the 532 nm LADC technique offers a new tool for biological and clinical applications.

Determining fatty acids by desorption/ionization mass spectrometry using thin-layer chromatography substrates

In this study, we demonstrate the application of ambient mass spectrometry for measuring fatty acids from various biological sample matrices such as olive oil, fish oil, salmon, and human serum. Optimum performance was obtained after spotting samples onto thin-layer chromatography (TLC) plates as sample substrates for a custom-built solvent-assisted desorption/ionization mass spectrometry (DI-MS) interface. Good to excellent linearities (coefficients of determination, 0.9856 to 0.9977) and reproducibilities (average 6% relative standard deviation (RSD) using syringe deposition) were obtained after application of an internal standard. Signal suppression phenomena were minimized by separating the analytes by TLC to some extent prior to DI-MS, leading to a fourfold increase of signal-to-noise ratios as compared to single spot mixture analysis without TLC separation. Graphical Abstract Solvent-assisted desorption/ionization-mass spectrometry.

Desorption/ionization efficiencies of triacylglycerols and phospholipids via EASI‐MS

Knowledge of the major effects governing desorption/ionization efficiency is required for the development and application of ambient mass spectrometry. Although all triacylglycerols (TAG) have the same favorable protonation and cationization sites, their desorption/ionization efficiencies can vary dramatically during easy ambient sonic-spray ionization because of structural differences in the carbon chain. To quantify this somewhat surprising and drastic effect, we have performed a systematic investigation of desorption/ionization efficiencies as a function of unsaturation and length for TAG as well as for diacylglycerols, monoacylglycerols and several phospholipids (PL). Affinities for Na(+) as a function of unsaturation level have also been assayed via comprehensive metadynamics calculations to understand the influence of this phenomenon on the ionization efficiency. The results suggest that dipole-dipole interactions within a carbon chain tuned by unsaturation sites govern ionization efficiency of TAG and PL.

Applications of ambient mass spectrometry in high-throughput screening

The development of rapid screening and identification techniques is of great importance for drug discovery, doping control, forensic identification, food safety and quality control. Ambient mass spectrometry (AMS) allows rapid and direct analysis of various samples in open air with little sample preparation. Recently, its applications in high-throughput screening have been in rapid progress. During the past decade, various ambient ionization techniques have been developed and applied in high-throughput screening. This review discusses typical applications of AMS, including DESI (desorption electrospray ionization), DART (direct analysis in real time), EESI (extractive electrospray ionization), etc., in high-throughput screening (HTS).

Active capillary plasma source for ambient mass spectrometry

Imaging mass spectrometry with high spatial resolution has become a rapidly developing area of mass spectrometric research. Many scientific and industrial problems deal with mass spectrometric analysis at ambient pressures. This requires efficient transport and ionization of small amounts of substance. An active sampling capillary based on a dielectric barrier discharge was constructed for ambient mass spectrometry. The capillary serves as an ionization source as well as an atmospheric interface of the mass spectrometer. The analyzed samples are transported through the sampling capillary due to the pressure difference between the atmospheric environment and the vacuum in the mass spectrometer. Ionization of the transported samples is provided by a low-temperature dielectric barrier discharge. This active capillary was shown to work in a robust fashion for ionizing both gas-phase and laser-ablated solid-phase samples. The geometry of the electrodes was found to play a crucial role in ionization efficiency. The capillary was optimized in order to perform surface analysis of solid samples. Sensitivity tests were carried out to characterize different active capillary constructions. The sensitivity of the constructed active capillary was 0.1 ppb (relative concentration of a gaseous sample in ambient air). The active capillary was able to detect samples evaporated from a solid surface. With the active capillary source, it was possible to detect anthracene traces evaporated from a surface located 3 cm from the capillary inlet. A plasma-based active capillary ionization source was constructed. This concept of an active sample inlet should broaden the range of applications of ambient mass spectrometry.

Principle and Application of Ambient Mass Spectrometry for Direct Analysis of Complex Samples

Abstract Ambient mass spectrometry allows the in situ, real-time, online, high throughput, and low sample-consumption analysis to be performed with no/minimal sample pretreatment. Consequently, ambient mass spectrometry featured by direct ionization techniques is of increasing interest for the detection of trace analytes in complex matrix. The application of ambient mass spectrometry has greatly improved the efficiency of mass spectrometry method, and renders fast mass spectrometry analysis of practical samples possible. In this tutorial paper, the fundamental principles, operating modes, the instrumentation, and application of typical ambient ionization techniques have been reviewed, giving emphasis on the theoretical modes to illustrate the working mechanism of various ionization techniques. The important progresses in food analysis, pharmaceutical analysis, environmental analysis, in vivo analysis, metabolomics studies, proteomics studies, and ambient mass spectrometry imaging have been systematically discussed, showing a clear trend that the development of ambient mass spectrometry has been accelerated by the urgently practical need of detecting trace compounds in complex matrices with high analysis speed. The perspectives on the development and application of ambient mass spectrometry have been discussed in the present article.