- Proton transfer reaction - mass spectrometry
Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a very sensitive technique for online monitoring of volatile organic compounds (VOCs) in ambient air developed by scientists at the Institut für Ionenphysik at the Leopold-Franzens University in Innsbruck, Austria [A. Hansel, A. Jordan, R. Holzinger, P. Prazeller W. Vogel, W. Lindinger, Proton transfer reaction mass spectrometry: on-line trace gas analysis at ppb level, "Int. J. of Mass Spectrom. and Ion Proc.", 149/150, 609-619 (1995).] . A PTR-MS instrument consists of an
ion sourcethat is directly connected to a drift tube (in contrast to SIFT-MS no mass filter is interconnected) and an analyzing system ( Quadrupole mass analyzeror Time-of-flight mass spectrometer). Commercially available PTR-MS instruments have a response time of about 100ms and reach a detection limitin the single digit pptv region. Established fields of application are environmental research, food and flavour science, biological research, medicine, etc.http://www.ptrms.com/documentation/publications.html] ,http://www.uibk.ac.at/ionen-angewandte-physik/umwelt/publications/index.html] .
With H3O+ as the primary ion the proton transfer process is (with being the trace component): (1).Reaction (1) is only possible if energetically allowed, i.e. if the
proton affinityof is higher than the proton affinity of H2O (691 kJ/mol [http://webbook.nist.gov/cgi/cbook.cgi?ID=C7732185&Units=SI&Mask=20#Ion-Energetics] ). As most components of ambient air possess a lower proton affinity than H2O (e.g. N2, O2, Ar, CO2, etc.) the H3O+ ions only reacts with VOC trace components and the air itself acts as a buffer gas. Moreover due to the low number of trace components one can assume that the total number of H3O+ ions remains nearly unchanged, which leads to the equationW. Lindinger, A. Hansel and A. Jordan, 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, Review paper, "Int. J. Mass Spectrom. Ion Proc.", 173, 191-241 (1998).] : (2).In equation (2) is the density of product ions, is the density of primary ions in absence of reactant molecules in the buffer gas, is the reaction rate constantand is the average time the ions need to pass the reaction region. With a PTR-MS instrument the number of product and of primary ions can be measured, the reaction rate constant can be found in literature for most substances [Y. Ikezoe, S. Matsuoka and A. Viggiano, Gas Phase Ion-Molecule Reaction Rate Constants through 1986, "Maruzen Company Ltd.", Tokyo, (1987).] and the reaction time can be derived from the set instrument parameters. Therefore the absolute concentrationof trace constituents can be easily calculated without the need of calibrationor gas standards.
In commercial PTR-MS instruments water vapour is ionized in a hollow cathode discharge:::::.After the discharge a short drift tube is used to form very pure (>99.5%) H3O+ via ion-molecule reactions:::::.Due to the high purity of the primary ions a mass filter between the ion source and the reaction drift tube is not necessary and the H3O+ ions can be injected directly. The absence of this mass filter in turn greatly reduces losses of primary ions and leads eventually to an outstandingly low detection limit of the whole instrument. In the reaction drift tube a
vacuum pumpis continuously drawing through air containing the VOCs one wants to analyze. At the end of the drift tube the protonated molecules are mass analyzed ( Quadrupole mass analyzeror Time-of-flight mass spectrometer) and detected.
Advantages of PTR-MS
* "Low fragmentation:" Only a small amount of energy is transferred during the ionization process (compared to e.g. electron impact ionization), therefore fragmentation is suppressed and the obtained mass spectra are easily interpretable.
* "No sample preparation in necessary:" VOC containing air and fluids headspaces can be analyzed directly.
* "Real-time measurements:" With a typical response time of 100ms VOCs can be monitored on-line.
* "Real-time quantification:" Absolute concentrations are obtained directly without previous calibration measurements.
* "Compact and robust setup:" Due to the simple design and the low number of parts needed for a PTR-MS instrument, it can be built in into space saving and even mobile housings.
* "Easy to operate:" For the operation of a PTR-MS only
electric powerand a small amount of distilled water are needed. Unlike other techniques no gas cylinders are needed for buffer gas or calibration standards.
Disadvantages of PTR-MS
* "Not all molecules detectable:" Because only molecules with a proton affinity higher than water can be detected by PTR-MS, the technology is not suitable for all fields of application.
* "Maximum measurable concentration limited:" Equation (2) is based on the assumption that the decrease of primary ions is neglectable, therefore the total concentration of VOCs in air must not exceed 10ppmv.
The most common applications for the PTR-MS technique are:
* Environmental Research
* Waste Incineration
* Food and Flavour Science
* Biological Research
* Process Monitoring
Indoor Air Quality
In 2008 C. Lindinger et al. published an article [C. Lindinger, D. Labbe, P. Pollien, A. Rytz, M. A. Juillerat, C. Yeretzian, I. Blank, When Machine Tastes Coffee: Instrumental Approach To Predict the Sensory Profile of Espresso Coffee, "Anal. Chem.", 80 (5) 1574-1581, (2008). ] in "Analytical Chemistry" that found great response even in non-scientific media [http://www.msnbc.msn.com/id/23359908/] [http://www.nytimes.com/2008/02/19/science/19objava.html?ex=1361077200&en=393e1220ba7a4cf1&ei=5124&partner=permalink&exprod=permalink] . Lindinger et al. developed a method to convert "dry" data from a PTR-MS instrument that measured headspace air from different
coffeesamples into expressions of flavour (e.g. "woody", "winey", "flowery", etc.) and showed that the obtained flavour profiles matched nicely to the ones created by a panel of European coffee tasting experts.
An extensive review about PTR-MS and some of its applications was published in 2007 in "Mass Spectrometry Reviews" by Joost de Gouw et al. [J. de Gouw, C. Warneke, T. Karl, G. Eerdekens, C. van der Veen, R. Fall: Measurement of Volatile Organic Compounds in the Earth's Atmosphere using Proton-Transfer-Reaction Mass Spectrometry, "Mass Spectrometry Reviews", 26, 223-257, (2007).] .
* [http://www.ptrms.com Ionicon Analytik GmbH]
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