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Rapid, efficient, versatile, easy-to-use, and non-expensive analytical approaches are globally demanded for food analysis. Many ambient ionization approaches based on electrospray ionization (ESI) have been developed recently for the rapid molecular characterization of food products. However, those approaches mainly suffer from insufficient signal duration for comprehensive chemical characterization by tandem MS analysis. Here, a commercially available disposable gel loading tip is used as a low-cost emitter for the direct ionization of untreated food samples. The most important advantages of our approach include high stability, and durability of the signal (> 10 min), low cost (ca. 0.1 USD per run), low sample and solvent consumption, prevention of tip clogging and discharge, operational simplicity, and potential for automation. Quantitative analysis of sulfapyridine, HMF (hydroxymethylfurfural), and chloramphenicol in real sample shows the limit-of-detection 0.1 μg mL -1 , 0.005 μg mL -1 , 0.01 μg mL -1 ; the linearity range 0.1-5 μg mL -1 , 0.005-0.25 μg mL -1 , 0.01-1 μg mL -1 ; and the linear fits R 2  ≥ 0.980, 0.991, 0.986. Moreover, we show that tip-ESI can also afford sequential molecular ionization of untreated viscous samples, which is difficult to achieve by conventional ESI. We conclude that tip-ESI-MS is a versatile analytical approach for the rapid chemical analysis of untreated food samples., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

The growth and sustainable development of humanity is heavily dependent upon molecular nitrogen (N 2 ) fixation. Herein we discover ambient catalyst-free disproportionation of N 2 by water plasma which occurs via the distinctive HONH-HNOH +• intermediate to yield economically valuable nitroxyl (HNO) and hydroxylamine (NH 2 OH) products. Calculations suggest that the reaction is prompted by the coordination of electronically excited N 2 with water dimer radical cation, (H 2 O) 2 +• , in its two-center-three-electron configuration. The reaction products are collected in a 76-needle array discharge reactor with product yields of 1.14 μg cm -2 h -1 for NH 2 OH and 0.37 μg cm -2 h -1 for HNO. Potential applications of these compounds are demonstrated to make ammonia (for NH 2 OH), as well as to chemically react and convert cysteine, and serve as a neuroprotective agent (for HNO). The conversion of N 2 into HNO and NH 2 OH by water plasma could offer great profitability and reduction of polluting emissions, thus giving an entirely look and perspectives to the problem of green N 2 fixation., (© 2024. The Author(s).)

The positions of C═C bonds in unsaturated fatty acids (FAs) are one of the main factors determining the quality of food flavor. Herein, we developed an approach for the determination of C═C bonds of FAs by online epoxidation reaction with water dimer radical cations. The limit of detection for octenoic acid isomers was ∼9 μg/L. The positions of C═C bonds in trans -2/3-hexenoic acid, trans -2/3-octenoic acid, oleic acid, linoleic acid, and linolenic acid in black tea or olive oil samples were directly determined by the established method. These results indicate that the established method allows the rapid determination of unsaturated FAs in black tea and olive oil. The advantages of this approach include the analysis speed (∼1 min per sample), simple device, and no need for complex pretreatment. This study not only provides a strategy for the determination of C═C positions but also offers new possibilities for applications in the field of food chemistry.

The molecular composition of exhaled human breath can reflect various physiological and pathological conditions. Considerable progress has been achieved over the past decade in real-time analysis of exhaled human breath using direct mass spectrometry methods, including selected ion flow tube mass spectrometry, proton transfer reaction mass spectrometry, extractive electrospray ionization mass spectrometry, secondary electrospray ionization mass spectrometry, acetone-assisted negative photoionization mass spectrometry, atmospheric pressure photoionization mass spectrometry, and low-pressure photoionization mass spectrometry. Here, recent developments in direct mass spectrometry analysis of exhaled human breath are reviewed with regard to analytical performance (chemical sensitivity, selectivity, quantitative capabilities) and applications of the developed methods in disease diagnosis, targeted molecular detection, and real-time metabolic monitoring., (© 2023 John Wiley & Sons Ltd.)

The information regarding the occurrence and abundance of lead (Pb) in PM2.5 is useful for the evaluation of air pollution status and tracing the pollution source. Herein, electrochemical mass spectrometry (EC-MS) for sequential determination of Pb species in PM2.5 samples without sample pretreatment has been developed using the combination of online sequential extraction with mass spectrometry (MS) detection. Four kinds of Pb species including water-soluble Pb compounds, fat-soluble Pb compounds, water/fat-insoluble Pb compounds, and a water/fat-insoluble Pb element were sequentially extracted from PM2.5 samples, in which water-soluble Pb compounds, fat-soluble Pb compounds, and water/fat-insoluble Pb compounds were extracted sequentially by elution using H 2 O, CH 3 OH, and EDTA-2Na as the eluent respectively, while the water/fat-insoluble Pb element was extracted by electrolysis using EDTA-2Na as the electrolyte. The extracted water-soluble Pb compounds, water/fat-insoluble Pb compounds, and water/fat-insoluble Pb element were transformed into EDTA-Pb in real time for online electrospray ionization mass spectrometry analysis, while the extracted fat-soluble Pb compounds were directly detected by electrospray ionization mass spectrometry. The advantages of the reported method include the obviation of sample pretreatment, high speed of analysis (<60 min/sample), low detection limit (0.16 pg), low sample consumption (30 μg), and high accuracy (>90%), which indicates the potential of this method for the rapid quantitative species detection of metals in environmental particulate matter samples.

The molecular profile of a tumor is associated with its histological type and can be used both to study the mechanisms of tumor progression and to diagnose it. In this work, changes in the lipid profile of a malignant breast tumor and the adjacent tissue were studied. The potential possibility of determining the histological type of the tumor by its lipid profile was evaluated. Lipid profiling was performed by reverse-phase chromato-mass-spectrometric analysis the tissue of lipid extract with identification of lipids by characteristic fragments. Potential lipid markers of the histological type of tumor were determined using the Kruskal-Wallis test. Impact of lipid markers was calculated by MetaboAnalyst. Classification models were built by support vector machines with linear kernel and 1-vs-1 architecture. Models were validated by leave-one out cross-validation. Accuracy of models based on microenvironment tissue, were 99% and 75%, accuracy of models, based on tumor tissue, were 90% and 40% for the positive ion mode and negative ion mode respectively. The lipid profile of marginal (adjacent) tissue can be used for identification histological types of breast cancer. Glycerophospholipid metabolism pathway changes were statistically significant in the adjacent tissue and tumor tissue.

Research of cancer progression mechanisms and their impact on metabolism of tumor cells and tumor microenvironment cells is an important element in drug development for cancer target therapy. In this study, changes in tumor tissue and margin tissue lipid profiles, were associated with the following clinical and morphological characteristics: tumor size, cancer stage, multifocalite, tumor grade, number of lymph node metastasis, Nottingham prognostic index, total malignancy score, level of Ki67 protein. Lipid profiling was performed by reverse-phase chromato-mass spectrometry analysis of lipid tissue extract with lipid identification by characteristic fragments. In the lipid profile of tumor tissue 13 characteristic lipids were selected. Their levels significantly correlated with at least 5 clinical and morphological features. Eight of 13 belonged to phosphatidylcholines. In lipid profile of tumor microenviroment tissue 13 lipid features were selected. Their levels significantly correlated with at least 5 clinical and morphological features. Four of 13 belonged to oxidized lipids, 4 lipid features belonged to sphingomyelins, four of 13 belonged to phosphatidylethanolamines. The tumor microenvironment tissue lipid profile correlated with tumor size, cancer stage, tumor grade, number of axillary metastases, Nottingham prognostic index. The tumor tissue lipid profile correlated with tumor size, tumor grade, total malignant score, and number of axillary metastases.

Protonated water-hydrogen clusters [H + (H 2 O) n ·m(H 2 )] present an interesting model for fundamental water research, but their formation and isolation presents considerable experimental challenges. Here, we report the detection of [H + (H 2 O) n ·m(H 2 )] (2 ≤ n ≤ 3, m ≤ 2) clusters alongside protonated water clusters H + (H 2 O) n (2 ≤ n ≤ 3) in a linear ion trap mass spectrometer under two different experimental conditions: (1) when water vapor was ionized by +5.5 kV ambient corona discharge in front of the mass spectrometer inlet; (2) when isolated H + (H 2 O) n clusters were exposed to H 2 gas inside the linear trap. Chemical assignment of [H + (H 2 O) n ·m(H 2 )] clusters was confirmed using reference experiments with isotopically labeled water and deuterium. Also, the formation of H 2 gas in the corona discharge area was indicated by a flame test. Overall, our findings clearly indicate that [H + (H 2 O) n ·m(H 2 )] clusters can be produced at room temperature through the association of protonated water clusters H + (H 2 O) n with H 2 gas, without any cooling necessary. A mechanism for the formation of the protonated water-hydrogen complexes was proposed. Our results also suggest that the association of water ions with H 2 gas may play a notable role in corona discharge ionization processes, such as atmospheric pressure chemical ionization, and may be partially responsible for the stabilization of reactive radical species occasionally reported in corona discharge ionization experiments.

Sensitive analysis of metabolites in a single cell is of fundamental significance for the better understanding of biological variability, differential susceptibility in disease therapy, and cell-to-cell heterogeneity as well. Herein, polarity-specific profiling of metabolites in a single cell was implemented by probe electrophoresis mass spectrometry (PEMS), which combined electrophoresis sampling of metabolites from a single cell and nanoelectrospray ionization-mass spectrometry (nanoESI-MS) analysis of the sampled metabolites. Enhanced extraction of either negatively or positively charged metabolites from a single cell was achieved by applying a DC voltage offset of +2.0 and -2.0 V to the probe, respectively. The experimental data demonstrated that PEMS features high throughput (≥200 peaks) and high sensitivity (≥10-times signal enhancement for [Choline + H] + , [Glutamine + H] + , [Arginine + H] + , etc.) in comparison with direct nanoESI-MS analysis. The biological effects of CdSe quantum dots (QDs) and γ-radiation on Allium cepa cells were investigated by PEMS, which revealed that CdSe QDs lead to the increase of intracellular amines while γ-radiation causes the decrease of intracellular acids. Therefore, this work provides an alternative platform to probe novel insights of cells by sensitive analysis of polarity-specific metabolites in a single cell.

Panax notoginseng is a highly valuable and widely used herb in traditional Chinese medicine. The quality and efficacy of Panax notoginseng grown under different conditions can greatly vary due to the differences in chemical composition. The analysis of chemical composition in Panax notoginseng typically involves various experimental steps including extraction, chromatographic separation and characterization, which can be time- and labor-consuming. Therefore, the efficient quality assessment and control of Panax notoginseng requires the development of more rapid methods for the chemical characterization and classification of Panax notoginseng. In this study, a method based on internal extractive electrospray ionization mass spectrometry (iEESI-MS) was developed to characterize chemical components of Panax notoginseng samples under different growth conditions (e.g., place of origin, soil quality, growth season) at the speed of 0.5 min per sample, without sample pretreatment and chromatographic separation. A total of 35 chemical components, including sugars, saponins, organic acids, etc., were identified in Panax notoginseng samples. Clear separation was observed in the multivariate analysis of the iEESI-MS data from Panax notoginseng samples grown under different conditions. The difference in the content of sucrose, fructose, Rg1, Rf, Rb1, Noto-R1, malonyl-Rb1, malonyl-Rg1, malonyl-Rf, Rd, Re, linoleic acid, palmitic acid and malic acid can be used as key characteristic indicators to discriminate origin, commercial specifications, and cultivation conditions of Panax notoginseng samples. The results of our study indicate the high power of iEESI-MS for the rapid molecular characterization and classification of Panax notoginseng under different growth conditions, which can be used for the quality assessment of traditional herbal medicines as well as in pharmaceutical and clinical analysis., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Here, we report on the abundant formation of phenol and molecular hydrogen when benzene vapor was exposed to gas plasma generated by +5.5 kV corona discharge of water vapor in argon in the absence of oxygen. Systematic analysis using a series of isotopic standards ( d 6 -benzene, D 2 O, and H 2 18 O) and benzene derivatives (mono-, di-, trichlorobenzene, and N , N -dimethylaniline) indicated that the formation of phenol occurred through the reaction between neutral benzene and the radical cation of water dimer, (H 2 O) 2 +• . A two-step reaction mechanism was proposed based on the results of experiments and DFT calculations: (1) the formation of (C 6 H 6 ...H 2 O) +• intermediate through electrophilic addition; (2) the formation of C 6 H 5 OH +• through the release of H 2 from the (C 6 H 6 ...H 2 O) +• intermediate. Our findings offer a novel catalyst-free method to prepare phenol from benzene with phenol selectivity >90%.

An athlete's diet is influenced by external and internal factors that can reduce or exacerbate exercise-induced food intolerance/allergy symptoms. This review highlights many factors that influence food choices. However, it is important to remember that these food choices are dynamic, and their effectiveness varies with the time, location, and environmental factors in which the athlete chooses the food. Therefore, before training and competition, athletes should follow the recommendations of physicians and nutritionists. It is important to study and understand the nutritional strategies and trends that athletes use before and during training or competitions. This will identify future clinical trials that can be conducted to identify specific foods that athletes can consume to minimize negative symptoms associated with their consumption and optimize training outcomes.

Direct molecular analysis of tissue samples is a promising approach to increase the accuracy, speed and molecular specificity of cancer diagnosis. Herein, alterations of amino acids between human lung cancer tissues and matched adjacent normal tissues were profiled by internal extraction electrospray ionization mass spectrometry (iEESI-MS). The results indicated that the levels of 11 detected amino acids (including serine, proline, valine, threonine, asparagine, aspartic acid, methionine, histidine, phenylalanine, arginine and tyrosine) in the cancerous tissues were lower than that in the adjacent normal tissues. Based on the orthogonal partial least squares discriminant analysis (OPLS-DA) model, cancerous and adjacent normal tissues were clearly discriminated, and the amino acids that played the major role in the differentiation between cancerous and adjacent normal tissues were identified. Moreover, metabolic pathway analysis revealed alterations of differential amino acids in several metabolic pathways upon lung cancer. The current study extends the power of iEESI-MS as a promising tool for quantitative characterization of amino acids in tissues, and allows the study of alterations in amino acids metabolism associated with the development of lung cancer., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Ethnopharmacological Relevance: Aconitum carmichaelii Debeaux, a famous traditional medicinal herb for collapse, rheumatic fever, and painful joints, always raises global concerns about its fatal toxicity from toxic alkaloids when improperly processed. Therefore, it is urgent to clarify the internal molecular mechanism of processing detoxification on Aconitum and develop simple and reliable approaches for clinical application, which is also of great significance to the rational medicinal use of Aconitum., Aim of the Study: The study aimed at developing a complete molecular mechanism exploration strategy in complex medicinal herb decocting system, clarifying the internal molecular mechanism of processing detoxification on Aconitum, and exploring valid approaches for detoxification., Materials and Methods: Aconiti Lateralis Radix Praeparata (Fuzi) was selected as the model for exploring the complex Aconitum detoxification mechanism using an advanced online real-time platform based on extractive electrospray ionization mass spectrometry. The methods realized the sensitive capture of dynamic trace intermediates, accurate qualitative and quantitative analysis, and real-time and long-term monitoring of multi-components with satisfactory accuracy and resistance to complex matrices., Results: Components in the complex Aconitum decocting system were real-timely characterized and fat meat was discovered and verified to directionally detoxify Aconitum while reserving the therapy effect. More importantly, the dynamic detoxification mechanism in the chemically complex Aconitum decoction was molecularly profiled. A novel reaction pathway based on nucleophilic substitution reaction mechanism was proposed. As confirmed by the theoretic calculations at DFT B3LYP/6-31G (d) levels, fatty acids (e.g., palmitic acid) acted as a green, cheap, and high-performance catalyst and promote the decomposition of toxic diester alkaloids to non-toxic and active benzoyl-monoester alkaloids through the discovered mechanism., Conclusion: The study exposed a novel detoxification molecular mechanism of Aconitum and provided an effective method for the safe use of Aconitum, which could effectively guide the development of traditional processing technology and compatibility regulation of the toxic herb and had great value to the modernization and standardization development of traditional medicine., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The levels of acetone and other ketones in exhaled human breath can be associated with various metabolic conditions, e.g. ketosis, lung cancer, dietary fat loss and diabetes. In this study, ketones in breath samples were charged through the reaction with water radical cations to form [M + H 2 O]˙ + ions, which were detected by mass spectrometry. Our experimental data indicate that under the optimized experimental conditions, the limit of detection for acetone using our approach is 0.14 ng L -1 (∼0.06 ppb). The linear dynamic range of detection spans four orders of magnitude. The developed approach was applied to real-time semi-quantitative analysis of acetone in the exhaled breath of human volunteers, revealing significantly higher levels of acetone in the breath of smokers compared to non-smokers. The developed approach features the obviation of sample collection, easy operation, high speed of analysis (10 s per run), high sensitivity, and spectral interpretation, which indicates the potential of ambient corona discharge ionization mass spectrometry as a selective, sensitive and noninvasive technique for the determination of exhaled ketones in clinical diagnosis including lung cancer, diabetes, etc.

Uterine fibroids (UF) is the most common (about 70% cases) type of gynecological disease, with the recurrence rate varying from 11 to 40%. Because UF has no distinct symptomatology and is often asymptomatic, the specific and sensitive diagnosis of UF as well as the assessment for the probability of UF recurrence pose considerable challenge. The aim of this study was to characterize alterations in the lipid profile of tissues associated with the first-time diagnosed UF and recurrent uterine fibroids (RUF) and to explore the potential of mass spectrometry (MS) lipidomics analysis of blood plasma samples for the sensitive and specific determination of UF and RUF with low invasiveness of analysis. MS analysis of lipid levels in the myometrium tissues, fibroids tissues and blood plasma samples was carried out on 66 patients, including 35 patients with first-time diagnosed UF and 31 patients with RUF. The control group consisted of 15 patients who underwent surgical treatment for the intrauterine septum. Fibroids and myometrium tissue samples were analyzed using direct MS approach. Blood plasma samples were analyzed using high performance liquid chromatography hyphened with mass spectrometry (HPLC/MS). MS data were processed by discriminant analysis with projection into latent structures (OPLS-DA). Significant differences were found between the first-time UF, RUF and control group in the levels of lipids involved in the metabolism of glycerophospholipids, sphingolipids, lipids with an ether bond, triglycerides and fatty acids. Significant differences between the control group and the groups with UF and RUF were found in the blood plasma levels of cholesterol esters, triacylglycerols, (lyso) phosphatidylcholines and sphingomyelins. Significant differences between the UF and RUF groups were found in the blood plasma levels of cholesterol esters, phosphotidylcholines, sphingomyelins and triacylglycerols. Diagnostic models based on the selected differential lipids using logistic regression showed sensitivity and specificity of 88% and 86% for the diagnosis of first-time UF and 95% and 79% for RUF, accordingly. This study confirms the involvement of lipids in the pathogenesis of uterine fibroids. A diagnostically significant panel of differential lipid species has been identified for the diagnosis of UF and RUF by low-invasive blood plasma analysis. The developed diagnostic models demonstrated high potential for clinical use and further research in this direction.

Rationale: Direct analysis in real time (DART) combined with mass spectrometry (MS) detection has become one of the most broadly used analytical approaches for the direct molecular characterization of food samples with regard to their chemical quality, safety, origin, and authentication. The major advantages of DART-MS for food analysis include high chemical sensitivity and specificity, high speed and throughput of analysis, simplicity, and the obviation of tedious sample preparation and solvents., Methods: The recent applications of DART coupled with different mass analyzers, including quadrupole, ion trap, Orbitrap, and time of flight, are discussed. In addition, sample pretreatment methods that have been coupled with DART-MS are discussed., Results: We summarize the applications of DART-MS in food science and industry published in the period from 2005 to this date. The applications and analytical characteristics are systematically categorized across the three major types of foods: solid foods, liquid foods, and viscous foods., Conclusions: DART-MS has proved its high suitability for the direct, rapid, and high-throughput molecular analysis of very different food samples with minimal or no sample preparation, thus offering a high-speed alternative to liquid chromatography/mass spectrometry (LC/MS) and gas chromatography/mass spectrometry (GC/MS) approaches that are traditionally employed in food analysis., (© 2020 John Wiley & Sons Ltd.)

We present an approach for the elucidation of C=C bond position and cis/trans isomers, which is achieved by the reaction of ambient water radical cations and double bonds, followed by the fragmentation of epoxide radical cations to generate diagnostic ions in tandem mass spectrometry. Hexenol double bond positional isomers and cis/trans isomers which exhibit different properties and biological functions are characterized as a proof of concept. The merits of the approach include the simplicity of experimental setup, rapid derivatization (within seconds), the obviation of organic solvents, as well as easy spectral interpretation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Phospholipids in microvolume biofluid samples (≤0.5 μL), including human plasma and single cells, were selectively captured by dispersed magnetic Fe3O4@TiO2 nanocomposite particles (40 μg). A suspension containing Fe3O4@TiO2 nanoparticles was loaded into a glass capillary (i.d. 0.75 mm) by capillary force. The supernatant solution was discarded, while the Fe3O4@TiO2 particles were retained inside the capillary by using an external magnetic field (ca. 1.3 T). The phospholipids on the surface of Fe3O4@TiO2 nanoparticles were directly analyzed using internal extractive electrospray ionization mass spectrometry (iEESI-MS) by pumping ≤1 μL of extraction solution of methanol containing 1.5% ammonia (w/w) through the capillary tube toward the ESI tip. A single sample analysis was accomplished within 4 min. Phospholipids in blood plasma samples from 59 patients with ovarian cancer and 43 healthy controls, and 28 patients with pancreatic cancer and 23 healthy controls were studied. Based on the orthogonal partial least squares discriminant analysis (OPLS-DA), the cancer patients were confidently discriminated from the healthy controls. Phospholipids in single human cells (MV4-11 and NB4) were determined, showing the sensitivity for single cell analysis. Therefore the results demonstrated that rapid cancer differentiation is achieved using this approach through the detection of trace phospholipids in microvolume blood and cell samples with high sensitivity, high specificity, low sample consumption, and high throughput.

Comparative studies of molecular alterations upon cancer between mice and humans are of great importance in order to determine the relevance of research involving mouse cancer models to the development of diagnostic and therapeutic approaches in clinical practice as well as for the mechanistic studies of pathology in humans. Herein, using molecular fingerprinting by internal extractive electrospray ionization mass spectrometry (iEESI-MS), we identified 50 differential signals in mouse liver tissue and 62 differential signals in human liver tissue that undergo significant intensity alterations (variable importance in the project (VIP) >1.0) upon liver cancer, out of which only 27 were common in both mouse and human tissues. Out of the 27 common differential signals, six types of phospholipids were also identified to undergo significant alterations in human serum upon liver cancer, including PC(34:2), PC(36:4), PC(38:6), PC(36:2), PC(38:4) and PC(42:9). Statistical analysis of the relative intensity distribution of these six identified phospholipids in serum allowed confident determination of liver cancer in humans (sensitivity 91.0%, specificity 88.0%, and accuracy 90.0%). Our results indicate that, despite the significant difference in the overall alterations of phospholipid profiles upon liver cancer between humans and mice, the six identified 'core' differential phospholipids of liver cancer found in the liver tissues of both humans and mice as well as in human serum show high potential as a minimal panel for the rapid targeted diagnosis of liver cancer with high accuracy, sensitivity and specificity using direct mass spectrometry (MS) analysis.

Water radical cations, (H 2 O) n +• , are of great research interest in both fundamental and applied sciences. Fundamental studies of water radical reactions are important to better understand the mechanisms of natural processes, such as proton transfer in aqueous solutions, the formation of hydrogen bonds and DNA damage, as well as for the discovery of new gas-phase reactions and products. In applied science, the interest in water radicals is prompted by their potential in radiobiology and as a source of primary ions for selective and sensitive chemical ionization. However, in contrast to protonated water clusters, (H 2 O) n H + , which are relatively easy to generate and isolate in experiments, the generation and isolation of radical water clusters, (H 2 O) n +• , is tremendously difficult due to their ultra-high reactivity. This review focuses on the current knowledge and unknowns regarding (H 2 O) n +• species, including the methods and mechanisms of their formation, structure and chemical properties.

Current methods for the intraoperative determination of breast cancer margins commonly suffer from the insufficient accuracy, specificity and/or low speed of analysis, increasing the time and cost of operation as well the risk of cancer recurrence. The purpose of this study is to develop a method for the rapid and accurate determination of breast cancer margins using direct molecular profiling by mass spectrometry (MS). Direct molecular fingerprinting of tiny pieces of breast tissue (approximately 1 × 1 × 1 mm) is performed using a home-built tissue spray ionization source installed on a Maxis Impact quadrupole time-of-flight mass spectrometer (qTOF MS) (Bruker Daltonics, Hamburg, Germany). Statistical analysis of MS data from 50 samples of both normal and cancer tissue (from 25 patients) was performed using orthogonal projections onto latent structures discriminant analysis (OPLS-DA). Additionally, the results of OPLS classification of new 19 pieces of two tissue samples were compared with the results of histological analysis performed on the same tissues samples. The average time of analysis for one sample was about 5 min. Positive and negative ionization modes are used to provide complementary information and to find out the most informative method for a breast tissue classification. The analysis provides information on 11 lipid classes. OPLS-DA models are created for the classification of normal and cancer tissue based on the various datasets: All mass spectrometric peaks over 300 counts; peaks with a statistically significant difference of intensity determined by the Mann-Whitney U-test ( p < 0.05); peaks identified as lipids; both identified and significantly different peaks. The highest values of Q2 have models built on all MS peaks and on significantly different peaks. While such models are useful for classification itself, they are of less value for building explanatory mechanisms of pathophysiology and providing a pathway analysis. Models based on identified peaks are preferable from this point of view. Results obtained by OPLS-DA classification of the tissue spray MS data of a new sample set ( n = 19) revealed 100% sensitivity and specificity when compared to histological analysis, the "gold" standard for tissue classification. "All peaks" and "significantly different peaks" datasets in the positive ion mode were ideal for breast cancer tissue classification. Our results indicate the potential of tissue spray mass spectrometry for rapid, accurate and intraoperative diagnostics of breast cancer tissue as a means to reduce surgical intervention.

Rationale: Floral volatiles are commonly present only at trace amounts and can be degraded or lost during vapor collection, which is often challenging from the analytical standpoint. Osmanthus fragrans Lour. is a widely cultivated plant known for the highly distinct fragrance of its flowers. The identification of specific volatile organic compounds (VOCs) and molecular differentiation of O. fragrans without any chemical pretreatment and VOC collection are important., Methods: Twenty-eight VOCs released by the flowers from ten different cultivars of O. fragrans were identified using neutral desorption extractive atmospheric pressure chemical ionization mass spectrometry (ND-EAPCI-MS) without any chemical pretreatment or VOC collection. Chemical identification was performed by high-resolution MS n analysis and whenever possible was confirmed by the analysis of standards., Results: According to our literature search, nine of the identified VOCs, 3-buten-2-one, cyclohexadiene, 2-methylfuran, 3-allylcyclohexene, cuminyl alcohol, hotrienol oxide, epoxy-linalool oxide, N-(2-hydroxyethyl) octanamide, and 3-hydroxy-dihydro-β-ionone, have not been reported in O. fragrans in earlier studies. Confident differentiation between ten different cultivars of O. fragrans was achieved by the principal component analysis of the mass spectrometric results., Conclusions: The results of our ND-EAPCI-MS analysis substantially increase our knowledge about the chemistry of the O. fragrans floral fragrance and demonstrate the power of this technique for direct molecular profiling for plant recognition or in biotechnological applications., (© 2019 John Wiley & Sons, Ltd.)

Salt stress is one of the most common factors limiting plant cultivation. In this study, metabolic responses to salt stress in Arabidopsis thaliana ( A. thaliana ) leaves were analyzed in situ by neutral desorption-extractive electrospray ionization mass spectrometry (ND-EESI-MS) without any sample pretreatment. Metabolic changes of A. thaliana leaves were observed in response to salt stress conditions, including the levels of serine, glutamic acid, arginine, cinnamic acid, ferulic acid, caffeic acid, protocatechuic acid, epicatechin, morin, myricetin, apigravin, and β-cotonefuran. The content of serine increased under 50, 100, and 200 mM NaCl salt stress, reaching the highest level at 200 mM NaCl, but decreased under the maximum concentration of 300 mM NaCl. A similar phenomenon was observed for arginine, glutamic acid, cinnamic acid, caffeic acid, ferulic acid, and epicatechin, respectively, involved in the metabolic pathway of shikimate-phenylpropanoid. Both principal component analysis (PCA) and partial least-squares discrimination analysis (PLS-DA) showed that the salt stress treatment groups of the higher concentrations (200 and 300 mM) could be well distinguished from those of the lower concentrations (50 and 100 mM) and the control. Marker metabolites, like m / z 261 (apigravin) and m / z 305 (β-cotonefuran), were assistantly selected from the fingerprints by variable importance for the projection (VIP). Our results indicated the potential of the ND-EESI-MS method for the rapid recognition of metabolic conditions in plant leaves under salt stress.

The deployment of mini mass spectrometers on the field strongly demands efficient ionization sources that are easy-to-operate. Nano-electrospray (nESI) ion source has been widely used in the field of chemistry, biology, medicine, pharmaceutical industry, clinical assessment and forensic science. In this study, a high ohmic resistor hyphenated gel loading tip nESI source was coupled with our home developed mini mass spectrometer. This ionization source has the advantages of simple-in-design, disposable and low-in-cost, therefore it could be frequently used for analysis of aqueous samples without leading to cross contamination. Performances of the gel loading tip nESI emitter were similar to pulled glass capillary, and highly compatible for the analysis of biomolecule in aqueous solution. Different peptide and small molecules have been confirmed with a continuous atmospheric pressure-interfaced (CAPI) mini mass spectrometer. The corona discharge, which was usually observed at nESI emitter tip under high aqueous solvent conditions, resulting in low ion intensity, has been successfully quenched using a 10 GΩ resistor in both a pulled glass capillary and a gel loading tip as nESI emitter in this study. Compared with conventional ESI, the metal wire assisted gel loading tip facilitated loading and direct analysis of biological samples without sample pretreatment., (Copyright © 2019. Published by Elsevier B.V.)

Traditionally, molecular information on metabolites, lipids, and proteins is collected from separate individual tissue samples using different analytical approaches. Herein a novel strategy to minimize the potential material losses and the mismatch between metabolomics, lipidomics, and proteomics data has been demonstrated based on internal extractive electrospray ionization mass spectrometry (iEESI-MS). Sequential detection of lipids, metabolites, and proteins from the same tissue sample was achieved without sample reloading and hardware alteration to MS instrument by sequentially using extraction solutions with different chemical compositions. With respect to the individual compound class analysis, the sensitivity, specificity, and accuracy obtained with the integrative information on metabolites, lipids, and proteins from 57 samples of 13 patients for lung cancer prediction was substantially improved from 54.0%, 51.0%, and 76.0% to 100.0%, respectively. The established method is featured by low sample consumption (ca. 2.0 mg) and easy operation, which is important to minimize systematic errors in precision molecular diagnosis and systems biology studies.

Real-time molecular navigation of tissue surgeries is an important goal at present. Combination of electrosurgical units and mass spectrometry (MS) to perform accurate molecular visualization of biological tissues has been pursued by many research groups. Determination of molecular tissue composition at a particular location by surgical smoke analysis is now of increasing interest for clinical use. However, molecular analysis of surgical smoke is commonly lacking molecular specificity and is associated with significant carbonization and chemical contamination, which are mainly related to the high temperature of smoke at which many molecules become unstable. Unlike traditional electrosurgical tools, low-temperature electrosurgical units allow tissue dissection without substantial heating. Here, we show that low-temperature electrosurgical units can be used for desorption of molecules from biological tissues without thermal degradation. The use of extractive electrospray ionization technique for the ionization of desorbed molecules allowed us to obtain mass spectra of healthy and pathological tissues with high degree of differentiation. Overall, the data indicate that the described approach has potential for intraoperative use.

The metal salts ubiquitously present in biological samples cause serious ion suppression, capillary clogging and signal fluctuation in ESI/nESI. Herein, a current-limited high voltage polarity reversing approach was applied for the online separation of intrinsic metal ions in biological samples, resulting in the generation of protonated analytes at the nESI tip for mass analysis without interference from salt cations. Stable and durable signals (∼30-60 s) were observed for protonated proteins, peptides and metabolites in complex biological samples, including liquids, solids and viscous samples, even with very high salt concentration (100 mM NaCl), allowing comprehensive tandem MS analysis with on average ca. 5-times higher analyte signal intensities compared to the conventional nESI analysis. Therefore this approach offers improved performance of nESI/ESI for the sensitive molecular analysis of untreated biological samples, opening new possibilities in various disciplines, including biology, medicine, chemistry, life sciences, etc.

Micro-electrochemical probe mass spectrometry (μECP-MS) is demonstrated as a method for the direct profiling of chemical composition of bulk alloy samples without tedious sample pretreatment. The spatial distribution of Zn and Cu components of a Cu/Zn alloy sample was successively identified by scanning the electrolysis potential from -0.6 V to 0.6 V. The lateral resolution of alloy chemical profiling was ≤10 μm, and the depth resolution was ≤0.5 nm. Besides metal components, the method also allows the simultaneous detection of organic molecules on the sample surface. The limit of detection for Rhodamine B, Zn, and Cu depositions was 4.47, 9.58, and 24.25 ag per μm 2 , respectively. The method is particularly useful for high-throughput (<2 min per single run) quality monitoring of industrial parts and conductive materials of irregular geometries, such as alloy, microchips, solder side, etc.

Knowledge about the chemical composition of floral volatile organic compounds (VOCs) is valuable in biological studies as well as for the flavor, cosmetic, and fragrance industries. The flowers of Chinese chestnut (Castanea mollissima) emit a distinctive semen-like odor; however, the chemical composition and biological role for the semen-like odor of chestnut flowers remain scarcely studied. Herein, we report the floral VOCs and the pollinators of chestnut flowers. A fast method based on a neutral desorption (ND) device coupled to extractive atmospheric pressure chemical ionization mass spectrometry (EAPCI-MS) was developed for the rapid identification of VOCs from freshly collected chestnut flowers without any chemical pretreatment. Chemical identification was performed using high-resolution MS analysis in combination with tandem MS analysis and whenever possible was confirmed by the analysis of standard reference compounds. Twenty volatiles were identified, most of which are nitrogen-containing. Out of the identified volatiles, 1-pyrroline is known to have a semen-like odor and is probably also responsible for the semen-like odor of the chestnut flowers. Four nitrogenous VOCs of chestnut flowers, including 1-pyrroline, 1-piperideine, 2-pyrrolidone, and phenethylamine, were also common in other semen-like odor flowers such as Photinia serrulata, Castanopsis sclerophylla, and Stemona japonica, suggesting similar chemical origin. The main visitors of chestnut flowers were dipteran species, such as Eristalis tenax, Eristalis arvorum, Episyrphus balteatus, Lucilia sericata, Chrysomya megacephala, Chrysochus asclepiadeus, and Adalia bipunctata. Our results suggest that the chestnut flowers and other semen-like odor flowers may present a new type of sapromyophily. This study also indicates that ND-EAPCI-MS provides more sensitive and simpler detection of many VOCs (particularly nitrogen-containing VOCs) than GC-MS and therefore can be used to complement traditional approaches for the higher chemical coverage of VOCs analysis. Graphical abstract ᅟ.

Endometriosis is a recurrent and benign gynecological disorder, defined by the ectopic presence of endometrium. About 10% of reproductive-aged women suffer from endometriosis. There are no non-invasive or minimally invasive tests available in clinical practice to accurately diagnose endometriosis today. Here, we present our efforts to determine the diagnostic accuracy of biomarkers in peritoneal fluid and blood plasma using flow injection analysis with electrospray ionization tandem mass spectrometry (ESI-MS/MS) in 70 women with endometriosis and 20 women from a control group. The presence of endometriosis was confirmed by surgical findings and post-operative pathological examination. A qualitative and quantitative evaluation of the lipids in peritoneal fluids and blood plasma was carried out using electrospray ionization mass spectrometry (ESI-MS). The analysis revealed more than 140 molecular species of lipids, most of which pertained to five classes: phosphatidylcholines, phosphatidylethanolamines, sphingomyelins, di- and triglycerides. The data were analyzed using a statistical multifactorial method (i.e., PLS-DA). It was found that 9 potential biomarkers of endometriosis (LPC 16:0, PE O-20:0, PE O 34:1, PC 36:2, PC 36:4, PC 36:5, PC 38:4, PC 38:6 and SM 34:1) are common in blood plasma and peritoneal fluid, supporting connection with the pathological process. The sensitivity of the method developed for plasma was 93% with a specificity of 95%; for peritoneal fluid, the sensitivity was 90% and the specificity 95%. Accordingly, plasma is the most suitable biological fluid for clinical diagnostics of endometriosis. Further validation of these lipids as serologic biomarkers may enhance non-invasive diagnostic tools for patients with suspected endometriosis and reduce the frequency of diagnostic laparoscopy., Competing Interests: All authors have nothing to disclose., (© 2019 The Association for Mass Spectrometry: Applications to the Clinical Lab (MSACL). Published by Elsevier B.V.)

New approaches are demanded in daily life and industry for the rapid inspection of chemical impurities on various objects, particularly those with irregular shapes. Herein, an analytical strategy combining electrochemistry (EC) and mass spectrometry (MS) has been developed for the direct inspection of metal impurities on various objects which are commonly used in daily life and industry. An intact object (e.g., necklace, bearing, ring) was immersed in an electrolytic cell containing EDTA/acetonitrile/water solution at appropriate potentials to form metal ions. The formed metal ions were instantly chelated with specific ligands (e.g. ethylenediaminetetraacetic acid) and sampled for online electrospray ionization (ESI) with high-resolution MS detection. The unique feature of the method is that metal speciation information can be obtained even when just a metal impurity (e.g., Pb, Ni) is localized on a hard-to-reach tiny spot on the inner surface of objects with extremely irregular shapes. A single sample analysis requires less than 10 minutes, regardless of the object shape. The limit of detection is 0.05 ppb with sample consumption on the nanogram level. The experimental results demonstrate that the method is promising for the non-destructive quality and safety inspection of metal impurities on virtually any kinds of objects with high chemical sensitivity.

Commercially available disposable plastic pipette tip with the inner diameter of ca. 120 μm in series with a high-ohmic resistor (10 GΩ) was adapted as a low-cost alternative ion source for high-throughput nanoelectrospray mass spectrometry (nESI-MS) analysis of a variety of samples, especially aqueous solutions, without sample pretreatment. The use of high-ohmic resistor enabled the formation of stable electrospray of aqueous solutions at ambient conditions. In addition, corona discharge was avoided even with a high voltage applied. Quantitative analysis of vitamin B in water was successfully conducted by tip-ESI. The results exhibited a good linearity (R ˃ 0.9983), a low detection limit (0.25 ng/mL), and a wide dynamic response range (0.25-1000 ng/mL). Our study revealed that tip-ESI not only performed equally well to capillary nESI in terms of flow rate (˂ 100 nL/min), signal sensitivity, and sample consumption, but also offered a number of additional advantages, including better signal duration, tolerance to high analyte concentration (> 100 μg/mL) and high ionizing voltage (up to 6 kV), and obviation of tip clogging and corona discharge. High compatibility of tip-ESI with various kinds of samples (aqueous, viscous, solid, or bulk biological samples) makes it a promising tool for direct MS analysis.

Supercharged protein ions produced by electrospray ionization are extremely efficient proton donors for secondary ionization. Here, by electrospraying the protein solutions containing 5% 1,2-butylene carbonate, the supercharged protein ions with unusually high proton density were produced as the primary ions for the ionization of exhaled breath samples in the extractive electrospray ionization mass spectrometry (EESI-MS), which resulted in the enhanced ionization efficiency for the breath analytes even with relatively low gas phase basicity. Moreover, the total number of metabolites detected in breath increased by about 260% in the mass range of 200-500 Da, owing to the substantial signal enhancement for breath metabolites, providing complementary and additional information to conventional SESI.

Rapid chemical decoding of bulk alloys to obtain both organic and elemental composition is of sustainable interest in multiple disciplines. Herein, an analytical strategy inherited from electrochemistry and mass spectrometry (MS) was developed for direct molecular characterization of alloys. While the organics on the alloy surface were simply extracted into the solvent for ESI-MS analysis, the components in the bulk alloy were successively converted into metal ions at appropriate electrolysis potentials, which were online chelated with specific ligands for ESI-MS analysis. A single sample analysis took only a few seconds since no other sample pretreatment was required, and a detection limit of 0.1 ppb was achieved for a component in alloy with low sample consumption (<1.0 mg). Proof-of-concept application indicated that the presented method has unique capability for successive analysis of organic and metallic components in liquids (e.g., engine oil), solids (e.g., alloy), and tunable spatial resolution (∼1.0 to (1.0 × 10 -5 ) cm 2 ) for molecular characterization of bulk alloys.

Rapid analysis of phosphopeptides and phospholipids in biological matrixes is of significant interest in multiple disciplines of life sciences. Herein, trace phospholipids in human plasma, whole blood, and undiluted human urine as well as phosphopeptides in protein digest were selectively captured on a homemade array of TiO 2 nanowires for sensitive characterization by internal extractive electrospray ionization mass spectrometry (TiO 2 -iEESI-MS). Sequential release of captured chemicals from TiO 2 array was achieved by tuning pH of the extraction solvent. A single sample analysis, including sample loading, chemical extraction and MS detection, was accomplished within 3 min. As far as the quantification of phospholipids, acceptable linearity ( R 2 ≥ 0.9985) and relative standard deviations (RSDs ≤ 8.9%) were obtained within the range of 0.1-500 μg L -1 for LysoPC(14:0) and LysoPC(16:0) in raw urine samples. Limit of detection (LOD) ≤ 0.025 μg L -1 and recovery rates of 94.8-101.6% were obtained for these phospholipids. As far as the quantification of phosphopeptides, R 2 ≥ 0.9994 and RSDs ≤ 9.2% within the range of 0.3-200 μg L -1 were obtained for two phosphopeptides in nonphosphopeptides mixtures. LODs ≤ 0.09 μg L -1 and recovery rates of 83.4-107.0% were obtained for these phosphopeptides. On the basis of the orthogonal partial least-squares discriminant analysis, TiO 2 -iEESI-MS patterns from the blood of 46 patients with ovarian cancer were confidently discriminated from the MS patterns of 46 healthy volunteers. Our results indicate the strong potential of TiO 2 -iEESI-MS approach for the selective detection of trace phosphopeptides and phospholipids in various biological matrixes with high sensitivity, high specificity, low sample consumption, and high throughput.

The pronounced enrichment of surface-active compounds in the aerosols produced by bubble bursting plays a central role in the chemical transfer from the ocean into the atmosphere and has an important impact on the global Earth's climate. However, the mechanism of chemical enrichment in bursting bubble aerosols remains poorly understood and controversial due to the high complexity and diversity of experimental behaviors. Contrary to the common belief, here we show that the major share of surfactants in the jet droplets produced by individually bursting bubbles at a calm solution surface is released directly from the bubble surface rather than from the solution surface or subsurface microlayer. We reveal that surfactants are accumulated at the surface of a rising bubble in solution following three successive stages with strongly distinct adsorption profiles: linear kinetic, mixed kinetic, and equilibrium. The magnitude of surfactant enrichment in the aerosol is directly determined by which adsorption mode is in control by the moment of the bubble bursting at solution surface. Our mechanistic description explains the diversity of experimental observations regarding the surfactant enrichment in aerosol droplets and lays the ground for understanding the more complex behaviors associated with collective effects at the solution surface (e.g., breaking waves)., Competing Interests: The authors declare no competing financial interest.

Native electrospray ionization mass spectrometry (ESI-MS) is nowadays widely used for the direct and sensitive determination of protein complex stoichiometry and binding affinity constants ( K a ). A common yet poorly understood phenomenon in native ESI-MS is the difference between the charge-state distributions (CSDs) of the bound protein-ligand complex (PL) and unbound protein (P) signals. This phenomenon is typically attributed to experimental artifacts such as nonspecific binding or in-source dissociation and is considered highly undesirable, because the determined K a values display strong variation with charge state. This situation raises serious concerns regarding the reliability of ESI-MS for the analysis of protein complexes. Here we demonstrate that, contrary to the common belief, the CSD difference between P and PL ions can occur without any loss of complex integrity, simply due to a change in the solvent-accessible surface area (ΔSASA) of the protein upon ligand binding in solution. The experimental CSD shifts for PL and P ions in ESI-MS are explained in relation to the magnitude of ΔSASA for diverse protein-ligand systems using a simple model based on the charged residue mechanism. Our analysis shows that the revealed ΔSASA factor should be considered rather general and be given attention for the correct spectral interpretation of protein complexes.

Study Objective: To introduce a method for the rapid assessment of endometriotic tissues using direct mass spectrometry (MS)-based lipidomics., Design: A prospective observational cohort study (Canadian Task Force classification II2)., Setting: Department of Operative Gynecology of the Research Centre for Obstetrics, Gynecology and Perinatology., Patients: Fifty patients with ovarian cysts and peritoneal endometriosis who underwent laparoscopic surgery between 2014 and 2016., Intervention: Differences in mass spectrometric profiles of ectopic endometria (endometriosis) and eutopic endometria were analyzed for each patient in combination with morphohistologic evaluation. The lipidomic approach was applied using a direct high-resolution MS method., Measurements and Main Results: Of 148 metabolites, 15 showed significant differences between endometriotic tissue and a healthy endometrium of the same patient, considered as a control in this study. The main lipids prevalent in endometriotic tissues were phosphoethanolamine (PE O-20:0), sphingomyelin (SM 34:1), diglycerides (DG 44:9), phosphatidylcholines (PC 32:1, PC O-36:3, PC 38:7, PC 38:6, PC 40:8, PC 40:7, PC 40:6, PC 40:9, and PC O-42:1), and triglycerides (TG 41:2, TG 49:4, and TG 52:3). Using partial least squares discriminant analysis models, MS showed that the lipidomic profile of endometriotic tissue (peritoneal endometriosis and ovarian endometriomas) was clearly separated from the eutopic endometrium, indicating tissue-type differentiation., Conclusion: Our results suggest that direct MS may play an important role for endometriotic tissue identification. Such an approach has potential usefulness for real-time tissue determination and differentiation during surgical treatment. Lipids of 3 important classes, sphingolipids, phospholipids, and the fatty acids (di- and triglycerides), were identified. Validation is required to determine whether these lipids can be used to discriminate between patients with endometriosis and those with other gynecologic diseases., (Copyright © 2017 American Association of Gynecologic Laparoscopists. Published by Elsevier Inc. All rights reserved.)

Recent research revealed that tissue spray mass spectrometry enables rapid molecular profiling of biological tissues, which is of great importance for the search of disease biomarkers as well as for online surgery control. However, the payback for the high speed of analysis in tissue spray analysis is the generally lower chemical sensitivity compared with the traditional approach based on the offline chemical extraction and electrospray ionization mass spectrometry detection. In this study, high resolution mass spectrometry analysis of endometrium tissues of different localizations obtained using direct tissue spray mass spectrometry in positive ion mode is compared with the results of electrospray ionization analysis of lipid extracts. Identified features in both cases belong to three lipid classes: phosphatidylcholines, phosphoethanolamines, and sphingomyelins. Lipids coverage is validated by hydrophilic interaction liquid chromatography with mass spectrometry of lipid extracts. Multivariate analysis of data from both methods reveals satisfactory differentiation of eutopic and ectopic endometrium tissues. Overall, our results indicate that the chemical information provided by tissue spray ionization is sufficient to allow differentiation of endometrial tissues by localization with similar reliability but higher speed than in the traditional approach relying on offline extraction. Graphical Abstract ᅟ.

The chemical origin and biological role of distinct semen-like odor occasionally found in some flowers are very curious but remain scarcely studied. Here, we used direct ambient corona discharge ionization mass spectrometry (MS) to study the volatile chemical composition behind the semen-like odor emitted by the fresh flowers of Photinia serrulata, Castanopsis sclerophylla and Stemona japonica without any chemical pretreatment. Chemical identification was performed using high-resolution MS analysis in combination with tandem MS analysis and whenever possible was confirmed by the analysis of standard reference compounds. A total of 19 compounds, mostly belonging to nitrogenous volatiles, were identified in P. serrulata, C. sclerophylla, and S. japonica flowers, 1-pyrroline, 1-piperideine, 2-pyrrolidone, and phenethylamine being common in all the three studied species. Several lines of evidence indicate that the major component responsible for the semen-like odor is most likely 1-pyrroline. 1-Pyrroline is most probably formed via the oxidative deamination of putrescine, as indicated by the observation of signal from 4-amino-butanal intermediate. Flower visitation observations suggest that the released volatiles serve to attract dipterans, including Syrphidae, Calliphoridae, and Muscidae. On the analytical side, the comparison of our results to earlier studies also indicate that compared to the traditional GC-MS approach the direct corona discharge ionization mass spectrometry provides more sensitive detection of VOCs with high proton affinity, in particular volatile amines, and therefore can be used to complement traditional GC-MS approach for the highest chemical coverage of VOC analysis., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Rapid quantitative determination of bulk molecular concentration in solid samples without sample pretreatment is demonstrated using the internal extractive electrospray ionization-mass spectrometry (iEESI-MS) analysis of six β-agonists, including salbutamol (Sal), clenbuterol (Cle), ractopamine (Rac), terbutaline (Ter), tulobuterol (Tul), brombuterol (Bro), in pork tissue samples. Single sample analysis only required 1 min. The linear range of detection was about 0.01-1000 μg/kg (R 2 > 0.9994). The limit-of-detection (LOD) varied from 0.002 μg/kg for Sal to 0.006 μg/kg for Tul. Relative standard deviation (RSD) of quantitation was in the range 6.5-11.3%. The analytical results were validated by gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography-mass spectrometry (LC-MS), showing the accuracy rates of 92-105%. The current study extends the power of ambient MS as a method for the quantification of molecules at the surface of solid samples (e.g., in μg/cm 2 units) toward the quantification of molecules in bulk sample volume (i.e., in μg/kg units), which is commonly required in food safety control, biomedical analysis, public security, and many other disciplines.

Hemoglobin (Hb) present in the blood and meat juice samples was selectively adsorbed by graphene oxide (GO) particles functionalized with amylopectin (AP) and was sensitively detected by direct internal extractive electrospray ionization mass spectrometry (iEESI-MS) analysis for the identification of meat type. Various samples including the whole blood samples of chicken, duck, sheep, mouse, pigeon, turtledove, and meat juice mixtures were successfully identified based on the difference in molecular composition of Hb reflected in MS. The adulteration of sheep blood with only 2% chicken blood could be detected, which demonstrated the high chemical specificity of the approach. The established method is featured by the high speed of analysis (4 min per sample, including the analyte extraction and sample loading), high sensitivity, minimal sample preparation, and low sample consumption (0.9 μL of whole blood or 300 mg of raw meat). In perspective, the reported method can be extended for the sensitive detection of trace analytes in complex matrices in broad molecular range by using the selective enrichment on functionalized graphene oxide particles followed by iEESI-MS analysis.

1-Pyrroline has a highly characteristic odor, which is employed by living organisms for chemical signaling and other purposes, but the mechanism whereby this odor is formed remains poorly understood. Here we used a combination of ambient mass spectrometry (AMS) and nuclear magnetic resonance (NMR) spectroscopy to experimentally address the mechanistic aspects of 1-pyrroline volatility and other controversies regarding the chemistry of this compound. Our results indicate that in solution the volatility of the monomer species is significantly higher than that of the trimer species, and 1-pyrroline is evaporated mainly in its monomer state. Neat 1-pyrroline is essentially the pure trimer and displays ca. 100-fold lower evaporation rate than the monomer state in solution. In the gas-phase the trimer species is irreversibly decomposed into monomer species. Under equilibrium conditions the vapor of 1-pyrroline entirely consists of monomer species. The evaporation rate of 1-pyrroline in water has a step-wise dependence on the solution pH, the abrupt increase in volatility (>1,000-fold) occurring around the pKa value of 1-pyrroline (6.8). The pronounced step-wise dependence of 1-pyrroline volatility around neutral pH may also be an important evolutionary factor allowing living systems to regulate the odor strength from very weak to very strong with minimal efforts.