Non-proximate mass spectrometry using a heated 1-m long PTFE tube and an air-tight APCI ion source.

Direct and rapid trace-level gas analysis is highly needed in various fields such as safety and security, quality control, food analysis, and forensic medicine. In many cases, the real samples are bulky and are not accessible to the space-limited ion source of the mass spectrometer. In order to circumvent this problem, we developed an airtight atmospheric-pressure chemical ionization (APCI) ion source equipped with a flexible 1-m-long, 2-mm-i.d. PTFE sniffing tube. The ambient air bearing sample gas was sucked into the heated PTFE tube (130 °C) and was transported to the air-tight ion source without using any extra pumping system or a Venturi device. Analytes were ionized by an ac corona discharge located at 1.5 mm from the inlet of the mass spectrometer. By using the airtight ion source, all the ionized gas in the ion source was introduced into the vacuum of the mass spectrometer via only the evacuation of the mass spectrometer (1.6 l min-1). Sub-pg limits of detection were obtained for carbaryl and trinitrotoluene. Owing to its flexibility and high sensitivity, the sniffing tube coupled with a mass spectrometer can be used as the stethoscope for the high-sensitive gas analysis. The experimental results obtained for drugs, hydrogen peroxide and small alkanes were discussed by DFT calculations.

[1]  Jentaie Shiea,et al.  Detecting large biomolecules from high-salt solutions by fused-droplet electrospray ionization mass spectrometry. , 2002, Analytical chemistry.

[2]  Dale G. Bottrell,et al.  Resurrecting the ghost of green revolutions past: The brown planthopper as a recurring threat to high-yielding rice production in tropical Asia , 2012 .

[3]  Shuiping Yang,et al.  Neutral desorption sampling of living objects for rapid analysis by extractive electrospray ionization mass spectrometry. , 2007, Angewandte Chemie.

[4]  K. Hiraoka,et al.  Development of ambient sampling chemi/chemical ion source with dielectric barrier discharge. , 2010, Journal of mass spectrometry : JMS.

[5]  J. Pawliszyn,et al.  Development of needle trap technology for on-site determinations: active and passive sampling. , 2014, Analytical chemistry.

[6]  Gurpur Rakesh D. Prabhu,et al.  The dawn of unmanned analytical laboratories , 2017 .

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

[8]  A. Vertes,et al.  Remote laser ablation electrospray ionization mass spectrometry for non-proximate analysis of biological tissues. , 2015, Rapid communications in mass spectrometry : RCM.

[9]  Joel F. Liebman,et al.  Evaluated Gas Phase Basicities and Proton Affinities of Molecules; Heats of Formation of Protonated Molecules , 1984 .

[10]  Z. Takáts,et al.  In vivo, in situ tissue analysis using rapid evaporative ionization mass spectrometry. , 2009, Angewandte Chemie.

[11]  R. Cooks,et al.  Non-proximate detection of explosives and chemical warfare agent simulants by desorption electrospray ionization mass spectrometry. , 2006, Chemical communications.

[12]  Huanwen Chen,et al.  Extractive electrospray ionization for direct analysis of undiluted urine, milk and other complex mixtures without sample preparation. , 2006, Chemical communications.

[13]  Bin Hu,et al.  Neutral desorption using a sealed enclosure to sample explosives on human skin for rapid detection by EESI-MS , 2009, Journal of the American Society for Mass Spectrometry.

[14]  M. Head‐Gordon,et al.  Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. , 2008, Physical chemistry chemical physics : PCCP.

[15]  C. E. Dykstra.  An examination of the Brueckner condition for the selection of molecular orbitals in correlated wavefunctions , 1977 .

[16]  D. B. Milligan,et al.  Application of selected ion flow tube mass spectrometry to real-time atmospheric monitoring. , 2010, Rapid communications in mass spectrometry : RCM.

[17]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[18]  朽津 耕三.  Dynamics of excited molecules , 1994 .

[19]  K. Fukui.  Formulation of the reaction coordinate , 1970 .

[20]  S. Sakaki,et al.  Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source. , 2015, Journal of mass spectrometry : JMS.

[21]  R. Cooks,et al.  Gas-flow assisted ion transfer for mass spectrometry. , 2012, Journal of mass spectrometry : JMS.

[22]  K. Hiraoka,et al.  Formation of the chelate bonds in the cluster O−2(CO2)n, CO−3(CO2)n, and NO−2(CO2)n , 1992 .

[23]  Marco Wellinger,et al.  Extraction kinetics of coffee aroma compounds using a semi-automatic machine : on-line analysis by PTR-ToF-MS , 2016 .

[24]  Shuiping Yang,et al.  Development of extractive electrospray ionization ion trap mass spectrometry for in vivo breath analysis. , 2009, The Analyst.

[25]  K. Hiraoka,et al.  Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source. , 2015, Journal of mass spectrometry : JMS.

[26]  K. Hiraoka,et al.  Trace level detection of explosives in solution using leidenfrost phenomenon assisted thermal desorption ambient mass spectrometry. , 2013, Mass spectrometry.

[27]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

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

[29]  R. Saxena,et al.  Role of plant volatiles in resistance of selected rice varieties to brown planthopper,Nilaparvata lugens (Stål) (Homoptera: Delphacidae) , 1985, Journal of Chemical Ecology.

[30]  Xiaohao Wang,et al.  Air flow assisted ionization for remote sampling of ambient mass spectrometry and its application. , 2011, Rapid communications in mass spectrometry : RCM.

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

[32]  Ambient aerodynamic ionization source for remote analyte sampling and mass spectrometric analysis. , 2008, Analytical chemistry.

[33]  R. Zenobi,et al.  Direct Coupling of Solid-Phase Microextraction with Mass Spectrometry: Sub-pg/g Sensitivity Achieved Using a Dielectric Barrier Discharge Ionization Source. , 2016, Analytical chemistry.

[34]  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 .

[35]  K. Hiraoka,et al.  Vapor phase detection of hydrogen peroxide with ambient sampling chemi/chemical ionization mass spectrometry , 2010 .

[36]  Yuichiro Hashimoto,et al.  Development of a portable mass spectrometer characterized by discontinuous sample gas introduction, a low-pressure dielectric barrier discharge ionization source, and a vacuumed headspace technique. , 2013, Analytical chemistry.

[37]  Michael Hirth,et al.  Ozone synthesis from oxygen in dielectric barrier discharges , 1987 .

[38]  R. Cooks,et al.  Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization , 2004, Science.

[39]  Zoltan Takats,et al.  In vivo endoscopic tissue identification by rapid evaporative ionization mass spectrometry (REIMS). , 2015, Angewandte Chemie.

[40]  H. Bernhard Schlegel,et al.  An improved algorithm for reaction path following , 1989 .

[41]  K. Hiraoka,et al.  Mass Spectrometric Detection of Gaseous Hydrogen Peroxide in Ambient Air Using Dielectric Barrier Discharge as an Excitation Source , 2009 .

[42]  E. Stashenko,et al.  Sampling flower scent for chromatographic analysis. , 2008, Journal of separation science.

[43]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[44]  Christopher C Mulligan,et al.  Non-proximate detection of small and large molecules by desorption electrospray ionization and desorption atmospheric pressure chemical ionization mass spectrometry: instrumentation and applications in forensics, chemistry, and biology. , 2007, Analytical chemistry.

[45]  G. Hanna,et al.  Selected ion flow tube mass spectrometry analysis of exhaled breath for volatile organic compound profiling of esophago-gastric cancer. , 2013, Analytical chemistry.

[46]  R. Winkler,et al.  Low-temperature plasma (LTP) jets for mass spectrometry (MS): Ion processes, instrumental set-ups, and application examples , 2017 .

[47]  K. Hiraoka,et al.  Mass spectrometric monitoring of oxidation of aliphatic C6-C8 hydrocarbons and ethanol in low pressure oxygen and air plasmas. , 2016, Journal of mass spectrometry : JMS.

[48]  Adam M. Hawkridge,et al.  Remote mass spectrometric sampling of electrospray- and desorption electrospray-generated ions using an air ejector , 2007, Journal of the American Society for Mass Spectrometry.

[49]  K. Hiraoka,et al.  Detection of explosives using a hollow cathode discharge ion source. , 2015, Rapid communications in mass spectrometry : RCM.

[50]  K. Hiraoka,et al.  Direct analysis of anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption-dielectric barrier discharge ionization mass spectrometry. , 2014, Analytica chimica acta.

[51]  A. Castleman,et al.  Thermochemical Data on Gas‐Phase Ion‐Molecule Association and Clustering Reactions , 1986 .

[52]  R. Zenobi,et al.  Capturing in Vivo Plant Metabolism by Real-Time Analysis of Low to High Molecular Weight Volatiles. , 2016, Analytical chemistry.

[53]  S. Jayaraj,et al.  Effect of steam distillate extract of resistant wild riceOryza officinalis on behavior of brown planthopperNilaparvata lugens (Stal) (Homoptera: Delphacidae) , 1990, Journal of Chemical Ecology.

[54]  Huanwen Chen,et al.  Neutral desorption sampling coupled to extractive electrospray ionization mass spectrometry for rapid differentiation of biosamples by metabolomic fingerprinting. , 2007, Journal of mass spectrometry : JMS.

[55]  Donald G Truhlar,et al.  Density functionals with broad applicability in chemistry. , 2008, Accounts of chemical research.