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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.

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.

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.