For wide class characterizations of volatile organic compounds (VOCs), conventional gas chromatography mass spectrometry (GC-MS)-based techniques are utilized. These GC-MS-based chemical identification approaches typically rely on library searches against ion fragmentation patterns of known compounds. Although MS library searches can often provide correct chemical identities, erroneous chemical assignments of structurally similar unknown compounds are also possible. Other detection systems, such as absorption spectrometers, have been used for VOC analysis and can provide complementary absorption data. Here, we demonstrate the analytical advantages of coupling vacuum ultraviolet (VUV) absorption spectroscopy and MS in tandem for the improved characterization of structurally similar VOCs. We also discuss technical considerations and limitations of coupling a VUV spectrometer to a quadrupole mass spectrometer. Moreover, we show that combining the isomer selectivity of VUV spectroscopy, as a nondestructive analyte detection approach, with the mass selectivity of MS in a VUV-MS detection system improves characterization of GC-eluting compounds. Utilizing GC/VUV-MS data, we demonstrate that orthogonal VUV and MS library searches improve identification of VOCs present in complex mixtures such as a mixed standard sample, a commercial perfume product, and an essential oil sample.
Mass spectrometry imaging (MSI) maps the spatial distributions of chemicals on surfaces. MSI requires improvements in throughput and spatial resolution, and often one is compromised for the other. In microprobe-mode MSI, improvements in spatial resolution increase the imaging time quadratically, thus limiting the use of high spatial resolution MSI for large areas or sample cohorts and time-sensitive measurements. Here, we bypass this quadratic relationship by combining a Timepix3 detector with a continuously sampling secondary ion mass spectrometry mass microscope. By reconstructing the data into large-field mass images, this new method, fast mass microscopy, enables orders of magnitude higher throughput than conventional MSI albeit yet at lower mass resolution. We acquired submicron, gigapixel images of fingerprints and rat tissue at acquisition speeds of 600,000 and 15,500 pixels s −1 , respectively. For the first image, a comparable microprobe-mode measurement would take more than 2 months, whereas our approach took 33.3 min.
Radical resection
for patients with oral cavity cancer remains
challenging. Rapid evaporative ionization mass spectrometry (REIMS)
of electrosurgical vapors has been reported for real-time classification
of normal and tumor tissues for numerous surgical applications. However,
the infiltrative pattern of invasion of oral squamous cell carcinomas
(OSCC) challenges the ability of REIMS to detect low amounts of tumor
cells. We evaluate REIMS sensitivity to determine the minimal amount
of detected tumors cells during oral cavity cancer surgery. A total
of 11 OSCC patients were included in this study. The tissue classification
based on 185 REIMS
ex vivo
metabolic profiles from
five patients was compared to histopathology classification using
multivariate analysis and leave-one-patient-out cross-validation.
Vapors were analyzed
in vivo
by REIMS during four
glossectomies. Complementary desorption electrospray ionization–mass
spectrometry imaging (DESI-MSI) was employed to map tissue heterogeneity
on six oral cavity sections to support REIMS findings. REIMS sensitivity
was assessed with a new cell-based assay consisting of mixtures of
cell lines (tumor, myoblasts, keratinocytes). Our results depict REIMS
classified tumor and soft tissues with 96.8% accuracy.
In
vivo
REIMS generated intense mass spectrometric signals.
REIMS detected 10% of tumor cells mixed with 90% myoblasts with 83%
sensitivity and 82% specificity. DESI-MSI underlined distinct metabolic
profiles of nerve features and a metabolic shift phosphatidylethanolamine
PE(O-16:1/18:2))/cholesterol sulfate common to both mucosal maturation
and OSCC differentiation. In conclusion, the assessment of tissue
heterogeneity with DESI-MSI and REIMS sensitivity with cell mixtures
characterized sensitive metabolic profiles toward
in vivo
tissue recognition during oral cavity cancer surgeries.
Time-of-flight (TOF) systems are one of the most widely used mass analyzers in native mass spectrometry (nMS) for the analysis of non-covalent multiply charged bio-macromolecular assemblies (MMAs). Typically, microchannel plates (MCPs) are employed for high mass native ion detection in TOF MS. MCPs are well known for their reduced detection efficiency when impinged by large slow moving ions. Here, a position-and time-sensitive Timepix (TPX) detector has been added to the back of a dual MCP stack to study the key factors that affect MCP performance for MMA ions generated by nMS. The footprint size of the secondary electron cloud generated by the MCP on the TPX for each individual ion event is analyzed as a measure of MCP performance at each mass-to-charge (m/z) value and resulted in a Poisson distribution. This allowed us to investigate the dependency of ion mass, ion charge, ion velocity, acceleration voltage, and MCP bias voltage on MCP response in the high mass low velocity regime. The study of measurement ranges; ion mass = 195 to 802,000 Da, ion velocity = 8.4 to 67.4 km/s, and ion charge = 1+ to 72+, extended the previously examined mass range and characterized MCP performance for multiply charged species. We derived a MCP performance equation based on two independent ion properties, ion mass and charge, from these results, which enables rapid MCP tuning for single MMA ion detection.
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