Recent developments of proton-transfer reaction mass spectrometry (PTR-MS) and its applications in medical research.

Proton-transfer reaction mass spectrometry (PTR-MS) allows for real-time, on-line determination of absolute concentrations of volatile organic compounds (VOCs) with a high sensitivity and low detection limits (in the pptv range). The technique utilizes H₃O⁺ ions for proton-transfer reactions with many common VOCs while having little to no reaction with any constituents commonly present in air. Over the past decades, research has greatly improved the applications and instrumental design of PTR-MS. In this article, we give an overview of the development of PTR-MS in recent years and its application in medical research. The theory of PTR-MS and various methods for discriminating isobaric VOCs are also described. We also show several specialized designs of sample inlet system, some of those may make PTR-MS suitable for the detection of aqueous solution and/or non-volatile samples.

[1]  Chengyin Shen,et al.  Thermal desorption extraction proton transfer reaction mass spectrometer (TDE-PTR-MS) for rapid determination of residual solvent and sterilant in disposable medical devices. , 2011, Journal of pharmaceutical and biomedical analysis.

[2]  Satoshi Inomata,et al.  High-resolution measurement of multiple volatile organic compounds dissolved in seawater using equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) , 2010 .

[3]  P. Shepson,et al.  Quantitative determination of biogenic volatile organic compounds in the atmosphere using proton-transfer reaction linear ion trap mass spectrometry. , 2010, Analytical chemistry.

[4]  A. Ostermann,et al.  Improved peak analysis of signals based on counting systems: Illustrated for proton-transfer-reaction time-of-flight mass spectrometry , 2010 .

[5]  A. Hansel,et al.  High resolution PTR-TOF: Quantification and formula confirmation of VOC in real time , 2010, Journal of the American Society for Mass Spectrometry.

[6]  Y. Lee,et al.  Ionizing nonvolatile samples using laser desorption–proton-transfer reaction with cluster reagent ions , 2010 .

[7]  I. Franke-Whittle,et al.  Substrate-induced volatile organic compound emissions from compost-amended soils , 2010, Biology and Fertility of Soils.

[8]  F. Biasioli,et al.  Improved mass accuracy in PTR-TOF-MS: Another step towards better compound identification in PTR-MS , 2010 .

[9]  T. Märk,et al.  Direct aqueous injection analysis of trace compounds in water with proton-transfer-reaction mass spectrometry (PTR-MS) , 2010 .

[10]  P. Shepson,et al.  MS/MS studies for the selective detection of isomeric biogenic VOCs using a Townsend Discharge triple quadrupole tandem MS and a PTR-Linear Ion Trap MS , 2009 .

[11]  Chengyin Shen,et al.  Control of solvent use in medical devices by proton transfer reaction mass spectrometry and ion molecule reaction mass spectrometry. , 2009, Journal of pharmaceutical and biomedical analysis.

[12]  Philipp Sulzer,et al.  An online ultra-high sensitivity Proton-transfer-reaction mass-spectrometer combined with switchable reagent ion capability (PTR + SRI − MS) , 2009 .

[13]  D. R. Hanson,et al.  Proton transfer mass spectrometry at 11 hPa with a circular glow discharge: Sensitivities and applications , 2009 .

[14]  P. Monks,et al.  Proton-transfer reaction mass spectrometry. , 2009, Chemical reviews.

[15]  S. Inomata,et al.  Aldehyde and ketone discrimination and quantification using two-stage proton transfer reaction mass spectrometry , 2008 .

[16]  P. Shepson,et al.  Development of a proton-transfer reaction-linear ion trap mass spectrometer for quantitative determination of volatile organic compounds. , 2008, Analytical Chemistry.

[17]  William B. Krantz,et al.  Arctic patterned-ground ecosystems: A synthesis of field studies and models along a North American Arctic Transect , 2008 .

[18]  C. Hoeschen,et al.  Effects of carbon dioxide in breath gas on proton transfer reaction-mass spectrometry (PTR-MS) measurements , 2008 .

[19]  S. Inomata,et al.  Differentiation of isomeric compounds by two-stage proton transfer reaction time-of-flight mass spectrometry , 2008, Journal of the American Society for Mass Spectrometry.

[20]  A. Wisthaler,et al.  Technical Note: Intercomparison of formaldehyde measurements at the atmosphere simulation chamber SAPHIR , 2007 .

[21]  Anton Amann,et al.  Lung cancer detection by proton transfer reaction mass-spectrometric analysis of human breath gas , 2007 .

[22]  S. Inomata,et al.  Development of a PTR-TOFMS instrument for real-time measurements of volatile organic compounds in air , 2007 .

[23]  S. Cristescu,et al.  Development of a proton-transfer reaction ion trap mass spectrometer , 2007 .

[24]  W. Cao,et al.  Current Status of Methods and Techniques for Breath Analysis , 2007 .

[25]  J. D. de Gouw,et al.  Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry. , 2007, Mass spectrometry reviews.

[26]  David P Wyon,et al.  PTR-MS assessment of photocatalytic and sorption-based purification of recirculated cabin air during simulated 7-h flights with high passenger density. , 2007, Environmental science & technology.

[27]  Simona M Cristescu,et al.  The suitability of Tedlar bags for breath sampling in medical diagnostic research , 2007, Physiological measurement.

[28]  P. Monks,et al.  Chemical ionization reaction time-of-flight mass spectrometry , 2006 .

[29]  P. Scheepers,et al.  On-line monitoring of UV-induced lipid peroxidation products from human skin in vivo using proton-transfer reaction mass spectrometry , 2006 .

[30]  W. Cao,et al.  Breath analysis: potential for clinical diagnosis and exposure assessment. , 2006, Clinical chemistry.

[31]  S. Inomata,et al.  A novel discharge source of hydronium ions for proton transfer reaction ionization: design, characterization, and performance. , 2006, Rapid communications in mass spectrometry : RCM.

[32]  H. Tilg,et al.  Analysis of Volatile Compounds Emitted by the Helicobacter pylori Reference Strain NCTC 11637 In Vitro , 2006, Helicobacter.

[33]  Jörg-Peter Schnitzler,et al.  Practical approaches to plant volatile analysis. , 2006, The Plant journal : for cell and molecular biology.

[34]  Bradford G. Stone,et al.  Effect of regulating cholesterol biosynthesis on breath isoprene excretion in men , 1993, Lipids.

[35]  S. Ruth,et al.  Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry , 2006 .

[36]  J. C. Reynolds,et al.  A hollow cathode proton transfer reaction time of flight mass spectrometer , 2005 .

[37]  P. Monks,et al.  Differentiation of isobaric compounds using chemical ionization reaction mass spectrometry. , 2005, Rapid communications in mass spectrometry : RCM.

[38]  D. Niederseer,et al.  H. pylori Infection Increases Levels of Exhaled Nitrate , 2005, Helicobacter.

[39]  David Smith,et al.  Selected ion flow tube mass spectrometry (SIFT-MS) for on-line trace gas analysis. , 2005, Mass spectrometry reviews.

[40]  Herbert Tilg,et al.  Headspace screening of fluid obtained from the gut during colonoscopy and breath analysis by proton transfer reaction-mass spectrometry: A novel approach in the diagnosis of gastro-intestinal diseases , 2005 .

[41]  D. Karall,et al.  BREATH GAS ANALYSIS IN PATIENTS SUFFERING FROM PROPIONIC ACIDAEMIA , 2005 .

[42]  R. Herwig,et al.  Urinary acetonitrile concentrations correlate with recent smoking behaviour , 2005, BJU international.

[43]  P. Lirk,et al.  Medical applications of proton transfer reaction-mass spectrometry: ambient air monitoring and breath analysis , 2004 .

[44]  T. Worthington,et al.  The proton transfer reaction mass spectrometer and its use in medical science: applications to drug assays and the monitoring of bacteria , 2004 .

[45]  S. Telser,et al.  Applications of breath gas analysis in medicine , 2004 .

[46]  D. Goebbert,et al.  Water Dimer Proton Affinity from the Kinetic Method: Dissociation Energy of the Water Dimer , 2004, European journal of mass spectrometry.

[47]  W. Miekisch,et al.  Diagnostic potential of breath analysis--focus on volatile organic compounds. , 2004, Clinica chimica acta; international journal of clinical chemistry.

[48]  Andrew M Ellis,et al.  Demonstration of proton-transfer reaction time-of-flight mass spectrometry for real-time analysis of trace volatile organic compounds. , 2004, Analytical chemistry.

[49]  James M. Roberts,et al.  Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in 2002 , 2003 .

[50]  David Smith,et al.  Quantification of acetonitrile in exhaled breath and urinary headspace using selected ion flow tube mass spectrometry , 2003 .

[51]  P. T. Palmer,et al.  Proton transfer reaction ion trap mass spectrometer. , 2003, Rapid communications in mass spectrometry : RCM.

[52]  A. Sharples.  Pollution*: just a whiff of gas?..... , 2003, Paediatric anaesthesia.

[53]  Karin Greiner,et al.  Elective haemodialysis increases exhaled isoprene. , 2003, Nephrology, dialysis, transplantation : official publication of the European Dialysis and Transplant Association - European Renal Association.

[54]  D. R. Hanson,et al.  Proton transfer reaction mass spectrometry at high drift tube pressure , 2003 .

[55]  M. L. Alexander,et al.  Membrane introduction proton-transfer reaction mass spectrometry , 2003 .

[56]  Franco Biasioli,et al.  Fingerprinting mass spectrometry by PTR-MS: heat treatment vs. pressure treatment of red orange juice—a case study , 2003 .

[57]  Timothy A. Su,et al.  Classical theories of the ion/linear quadrupole capture , 2002 .

[58]  C. J. Howard,et al.  Selective detection of gas-phase aldehydes and ketones using protonated hydrazine 3 3 Dedicated to P , 2001 .

[59]  R. Fall,et al.  Biogenic C5 VOCs : release from leaves after freeze-thaw wounding and occurrence in air at a high mountain observatory , 2001 .

[60]  C. Warneke,et al.  Measurements of benzene and toluene in ambient air using proton-transfer-reaction mass spectrometry: calibration, humidity dependence, and field intercomparison , 2001 .

[61]  Wouter Peters,et al.  Transport of biomass burning smoke to the upper troposphere by deep convection in the equatorial region , 2001 .

[62]  W. Lindinger,et al.  Analysis of volatile organic compounds: possible applications in metabolic disorders and cancer screening. , 2001, Wiener klinische Wochenschrift.

[63]  M. Boehler,et al.  Online monitoring of air quality at the postanesthetic care unit by proton-transfer-reaction mass spectrometry. , 2001, Anesthesia and analgesia.

[64]  H. Rüdiger,et al.  Waste anaesthetic gases induce sister chromatid exchanges in lymphocytes of operating room personnel. , 1999, British journal of anaesthesia.

[65]  T. Karl,et al.  Quantification of passive smoking using proton-transfer-reaction mass spectrometry , 1998 .

[66]  E. P. Hunter,et al.  Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update , 1998 .

[67]  A. Hansel,et al.  On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research , 1998 .

[68]  A. Hansel,et al.  Endogenous production of methanol after the consumption of fruit. , 1997, Alcoholism, clinical and experimental research.

[69]  J. Futrell,et al.  Detection of isoprene in expired air from human subjects using proton-transfer-reaction mass spectrometry. , 1997, Rapid communications in mass spectrometry : RCM.

[70]  Werner Lindinger,et al.  Analysis of Compounds in Human Breath after Ingestion of Garlic Using Proton-Transfer-Reaction Mass Spectrometry , 1996 .

[71]  Werner Lindinger,et al.  Proton transfer reaction mass spectrometry: on-line trace gas analysis at the ppb level , 1995 .

[72]  A. Lagg,et al.  Methanol in human breath. , 1995, Alcoholism, clinical and experimental research.

[73]  A. Hansel,et al.  Acetonitrile and benzene in the breath of smokers and non-smokers investigated by proton transfer reaction mass spectrometry (PTR-MS) , 1995 .

[74]  Timothy A. Su.  Parametrization of kinetic energy dependences of ion–polar molecule collision rate constants by trajectory calculations , 1994 .

[75]  W. Lindinger,et al.  Collision induced dissociation of the isometric ions H2COOH+ and HC(OH)+12 , 1993 .

[76]  J. Penner,et al.  Large contribution of organic aerosols to cloud-condensation-nuclei concentrations , 1993, Nature.

[77]  Timothy A. Su,et al.  Parametrization of the ion–polar molecule collision rate constant by trajectory calculations , 1982 .

[78]  Edward A. Mason,et al.  Transport Properties of Gaseous Ions over a Wide Energy Range , 1976 .

[79]  D. Albritton,et al.  Flow‐drift technique for ion mobility and ion‐molecule reaction rate constant measurements. II. Positive ion reactions of N+, O+, and H2+ with O2 and O+ with N2 from thermal to [inverted lazy s]2 eV , 1973 .

[80]  M. Bowers,et al.  Ion-Polar molecule collisions: the effect of ion size on ion-polar molecule rate constants; the parameterization of the average-dipole-orientation theory , 1973 .

[81]  M. Bowers,et al.  Theory of ion‐polar molecule collisions. Comparison with experimental charge transfer reactions of rare gas ions to geometric isomers of difluorobenzene and dichloroethylene , 1973 .

[82]  W. Lindinger.  Reaction-Rate Constants in Steady-State Hollow-Cathode Discharges: Ar + H 2 O Reactions , 1973 .

[83]  A. B. Robinson,et al.  Quantitative analysis of urine vapor and breath by gas-liquid partition chromatography. , 1971, Proceedings of the National Academy of Sciences of the United States of America.

[84]  F. Fehsenfeld,et al.  Flowing Afterglow Measurements of Ion-Neutral Reactions , 1969 .

[85]  F. H. Field,et al.  Chemical Ionization Mass Spectrometry. I. General Introduction , 1966 .