Analysis of human breath samples using a modified thermal desorption: gas chromatography electrospray ionization interface
James C Reynolds, Modupe A Jimoh, Cristina Guallar-Hoyas, Colin S Creaser, Salman Siddiqui and C L Paul Thomas
A two-stage thermal desorption/secondary electrospray ionization/time-of-flight mass spectrometry for faster targeted breath profiling has been studied. A new secondary electrospray ionization (SESI) source was devised to constrain the thermal desorption plume and promote efficient mixing in the ionization region. Further, a chromatographic preseparation stage was introduced to suppress interferences from siloxanes associated with thermal desorption profiles of exhaled breath samples…
Fingerprinting Breast Cancer vs. Normal Mammary Cells by Mass Spectrometric Analysis of Volatiles
Jingjing He, P. M-L Sinues, M. Hollmén, Xue Li, M. Detmar & R. Zenobi
There is increasing interest in the development of noninvasive diagnostic methods for early cancer detection, to improve the survival rate and quality of life of cancer patients. Identification of volatile metabolic compounds may provide an approach for noninvasive early diagnosis of malignant diseases.
High throughput volatile fatty acid skin metabolite profiling by thermal desorption secondary electrospray ionisation mass spectrometry
Helen J. Martin,a James C. Reynolds,a Svetlana Riazanskaiab and C. L. Paul Thomas*a
The non-invasive nature of volatile organic compound (VOC) sampling from skin makes this a priority in the development of new screening and diagnostic assays. Evaluation of recent literature highlights the tension between the analytical utility of ambient ionisation approaches for skin profiling and the practicality of undertaking larger campaigns (higher statistical power), or undertaking research in remote locations. This study describes how VOC may be sampled from skin and recovered from a polydimethylsilicone sampling coupon and analysed by thermal desorption (TD) interfaced to secondary electrospray ionisation (SESI) time-of-flight mass spectrometry (MS) for the high throughput screening of volatile fatty acids (VFAs) from human skin…
Rapid identification of bacteria in blood cultures by mass-spectrometric analysis of volatiles
C. Ballabio, S. Cristoni, G. Puccio, M. Kohler, M. R. Sala, P. Brambilla, P. M-L Sinues
Blood cultures are routine tests to determine whether micro-organisms have entered the patient’s bloodstream. Automated systems, based on the detection of CO2 increase in the culture media, have considerably improved the screening efficiency for the detection of bacteria. However, further identification of bacteria still requires time consuming culturing procedures.
Breath Analysis in Real Time by Mass Spectrometry in Chronic Obstructive Pulmonary Disease
P. M-L Sinues, L. Meier, C. Berchtold, M.Ivanov, N. Sievi, G. Camen, M. Kohler, R. Zenobi
Background: It has been suggested that exhaled breath contains relevant information on health status. Objectives: We hypothesized that a novel mass spectrometry (MS) technique to analyze breath in real time could be useful to differentiate breathprints from chronic obstructive pulmonary disease (COPD) patients and controls (smokers and nonsmokers) …
Direct Determination of Urinary Creatinine by Reactive-Thermal Desorption-Extractive Electrospray-Ion Mobility-Tandem Mass Spectrometry
Neil A. Devenport, Daniel J. Blenkhorn, Daniel J. Weston, James C. Reynolds, and Colin S. Creaser
A direct, ambient ionization method has been developed for the determination of creatinine in urine that combines derivatization and thermal desorption with extractive electrospray ionization and ion mobility-mass spectrometry. The volatility of creatinine was enhanced by a rapid on-probe aqueous acylation reaction, using a custom-made thermal desorption probe, allowing thermal desorption and ionization of the monoacylated derivative..
Analysis of the Exhalome A Diagnostic Tool of the Future
P. M-L Sinues, R. Zenobi, M. Kohler
Investigations on breath analysis have provided preliminary data on its potential in the noninvasive diagnosis of lung diseases. Although the conventional comparisons of exhaled breath in study populations (ie, diseased vs healthy) may help to identify patients with various lung diseases, we believe that the analysis of exhaled breath holds promise beyond this scenario …
Robust detection of P. aeruginosa and S. aureus acute lung infections by secondary electrospray ionization-mass spectrometry (SESI-MS) breathprinting: from initial infection to clearance
J. Zhu, J. Jimenez-Díaz, H. D. Bean, N. A. Daphtary, M. I. Aliyeva, L. K. A. Lundblad and J. E. Hill
Before breath-based diagnostics for lung infections can be implemented in the clinic, it is necessary to understand how the breath volatiles change during the course of infection, and ideally, to identify a core set of breath markers that can be used to diagnose the pathogen at any point during the infection …
A new strategy based on real-time secondary electrospray ionization and high-resolution mass spectrometry to discriminate endogenous and exogenous compounds in exhaled breath
C. Berchtold, L. Meier, R. Steinhoff, R. Zenobi
Breath is considered to be an easily accessible matrix, whose chemical composition relates to compounds present in blood. Therefore many metabolites are expected in exhaled breath, which may be used in the future for the development of diagnostic methods. In this article, a new strategy to discriminate between exhaled endogenous metabolites and exhaled exogenous contaminants by direct high-resolution mass spectrometry is introduced.
Direct Detection of a Sulfonate Ester Genotoxic Impurity by Atmospheric-Pressure Thermal Desorption–Extractive Electrospray–Mass Spectrometry
Neil A. Devenport, Laura C. Sealey, Faisal H. Alruways, Daniel J. Weston, James C. Reynolds, and Colin S. Creaser.
A direct, ambient ionization method has been developed using atmospheric pressure thermal desorption–extractive electrospray–mass spectrometry (AP/TD-EESI-MS) for the detection of the genotoxic impurity (GTI) methyl p-toluenesulfonate (MTS) in a surrogate pharmaceutical matrix. A custom-made thermal desorption probe was used to the desorb and vaporize MTS from the solid state, by rapid heating to 200 °C then cooling to ambient temperature, with a cycle time of 6 min…
Human Breath Analysis May Support the Existence of Individual Metabolic Phenotypes
P. M.-L. Sinues, M. Kohler, R. Zenobi
The metabolic phenotype varies widely due to external factors such as diet and gut microbiome composition, among others. Urine metabolite profiling studies have suggested that there are highly individual phenotypes that persist over extended periods of time. This hypothesis was tested by analyzing the exhaled breath of a group of subjects during nine days by mass spectrometry.
Secondary electrospray ionization-mass spectrometry (SESI-MS) breathprinting of multiple bacterial lung pathogens, a mouse model study
J. Zhu, H. D. Bean, J. Jiménez-Díaz, and J. E. Hill
Bacterial pneumonia is one of the leading causes of disease-related morbidity and mortality in the world, in part because the diagnostic tools for pneumonia are slow and ineffective. To improve the diagnosis success rates and treatment outcomes for bacterial lung infections, we are exploring the use of SESI-MS breath analysis as a rapid, noninvasive method for determining …
In situ detection of hydroxybutyrate and butyrolactone in drinks by secondary electrospray ionization
Christian Berchtold; Stefan Schmid; Lukas Meiera and Renato Zenobi.
γ-Hydroxybutyrate (GHB) and γ-butyrolactone (GBL) are used as “date rape drugs” since they cause catalepsy and memory loss. A new application of secondary electrospray ionization (SESI) mass spectrometry for in situ detection of GHB and GBL in drinks and body fluids is introduced.
Detection of Escherichia coli via VOC Profiling using Secondary Electrospray Ionization-Mass Spectrometry (SESI-MS)
J. Zhu, J. E. Hill
Escherichia coli O157:H7 (EC O157:H7), as well as its recently emerging non-O157 relatives, are a notorious group of pathogenic bacteria associated with foodborne outbreaks. In this study, we demonstrated that secondary electrospray ionization mass spectrometry (SESI-MS) could be a rapid and accurate detection technology for foodborne pathogens …
Monitoring Diurnal Changes in Exhaled Human Breath
P. M-L Sinues, M. Kohler and R. Zenobi
The development of noninvasive analytical techniques is of interest to the field of chronobiology, in order to reveal the human metabolome that seems to show temporal patterns and to predict internal body time. We report on the real-time mass spectrometric analysis of human breath as a potential method to be used in this field.
High mass resolution breath analysis using secondary electrospray ionization mass spectrometry assisted by an ion funnel
L. Meier, C. Berchtold, S. Schmid and R. Zenobi
In this study, we used secondary electrospray ionization mass spectrometry assisted by an ion funnel (IF) operating at ambient pressure to find compounds in the mass range of 100–500 m/z in online breath fingerprinting experiments. In low-resolution experiments conducted on an ion trap instrument, we found that pyridin is present in breath of individuals long after drinking coffee …
Low-Sample Flow Secondary Electrospray Ionization: Improving Vapor Ionization Efficiency
G. Vidal-de-Miguel, M. Macía, P. Pinacho, and J. Blanco
In secondary electrospray ionization (SESI) systems, gaseous analytes exposed to an elecrospray plume become ionized after charge is transferred from the charging electrosprayed particles to the sample species. Current SESI systems have shown a certain potential. However, their ionization efficiency is limited by …
Secondary Electrospray Ionization of Complex Vapor Mixtures. Theoretical and Experimental Approach
G. Vidal-de-Miguel, A. Herrero
In secondary electrospray ionization (SESI) systems, gaseous analytes exposed to an electrospray plume become ionized after charge is transferred from the charging electrosprayed particles (the charging agent) to the vapor species. Currently available SESI models are valid for simplified systems having only one type of electrosprayed species …
Sensitive detection of drug vapors using an ion funnel interface for secondary electrospray ionization mass spectrometry
L. Meier, C. Berchtold, S. Schmid and R. Zenobi
In this study, we use an ion funnel (IF) at ambient pressure to enhance the sensitivity of secondary electrospray ionization (SESI). Atenolol, salbutamol and cocaine as test compounds are delivered to the SESI interface in the gas phase and are charged with three nano electrosprays …
Mechanistic study on the ionization of trace gases by an electrospray plume
P. M-L Sinues, E. Criado, G. Vidal-de-Miguel
The fact that electrosprays of pure solvents can efficiently ionize gas-phase analytes has been known for decades, although this method has not been widely exploited. With the advent of ambient mass spectrometry, this approach is becoming increasingly popular. However, the mechanism by which vapors become ionized remains largely unknown …