Proton-transfer-reaction mass spectrometry
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Proton-transfer-reaction mass spectrometry (PTR-MS) is an
analytical chemistry Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separati ...
technique that uses gas phase
hydronium In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the aqueous cation , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is d ...
reagent ions which are produced in an
ion source An ion source is a device that creates atomic and molecular ions. Ion sources are used to form ions for mass spectrometers, optical emission spectrometers, particle accelerators, ion implanters and ion engines. Electron ionization Electron ...
. PTR-MS is used for online monitoring of volatile organic compounds (VOCs) in ambient air and was developed in 1995 by scientists at the Institut für Ionenphysik at the Leopold-Franzens University in Innsbruck, Austria. A PTR-MS instrument consists of an ion source that is directly connected to a
drift tube A wire chamber or multi-wire proportional chamber is a type of proportional counter that detects charged particles and photons and can give positional information on their trajectory, by tracking the trails of gaseous ionization. was located via ...
(in contrast to
SIFT-MS Selected-ion flow-tube mass spectrometry (SIFT-MS) is a quantitative mass spectrometry technique for trace gas analysis which involves the chemical ionization of trace volatile compounds by selected positive precursor ions during a well-defined t ...
no mass filter is interconnected) and an analyzing system (
quadrupole mass analyzer The quadrupole mass analyzer, originally conceived by Nobel Laureate Wolfgang Paul and his student Helmut Steinwedel, also known as quadrupole mass filter, is one type of mass analyzer used in mass spectrometry. As the name implies, it consists of ...
or
time-of-flight mass spectrometer Time-of-flight mass spectrometry (TOFMS) is a method of mass spectrometry in which an ion's mass-to-charge ratio is determined by a time of flight measurement. Ions are accelerated by an electric field of known strength. This acceleration resul ...
). Commercially available PTR-MS instruments have a
response time Response time may refer to: *The time lag between an electronic input and the output signal which depends upon the value of passive components used. * Responsiveness, how quickly an interactive system responds to user input * Response time (biolog ...
of about 100 ms and reach a
detection limit The limit of detection (LOD or LoD) is the lowest signal, or the lowest corresponding quantity to be determined (or extracted) from the signal, that can be observed with a sufficient degree of confidence or statistical significance. However, the ...
in the single digit
pptv PPTV () is a Chinese video streaming website. Its predecessor, PPLive, was peer-to-peer streaming video freeware created at the Huazhong University of Science and Technology in Wuhan, Hubei Province. The group of companies that runs the websi ...
or even ppqv region. Established fields of application are environmental research, food and flavor science, biological research, medicine, security, cleanroom monitoring, etc.


Theory

With H3O+ as the reagent ion the proton transfer process is (with being the trace component) Reaction () is only possible if energetically allowed, i.e. if the
proton affinity The proton affinity (PA, ''E''pa) of an anion or of a neutral atom or molecule is the negative of the enthalpy change in the reaction between the chemical species concerned and a proton in the gas phase: ::: A- + H+ -> HA ::: B + H+ -> BH+ ...
of is higher than the proton affinity of H2O (691 kJ/mol). As most components of
ambient air Ambient or Ambiance or Ambience may refer to: Music and sound * Ambience (sound recording), also known as atmospheres or backgrounds * Ambient music, a genre of music that puts an emphasis on tone and atmosphere * Ambient (album), ''Ambient'' (alb ...
possess a lower proton affinity than H2O (e.g. N2, O2, Ar, CO2, etc.) the H3O+ ions only react with VOC trace components and the air itself acts as a
buffer gas A buffer gas is an inert or nonflammable gas. In the Earth's atmosphere, nitrogen acts as a buffer gas. A buffer gas adds pressure to a system and controls the speed of combustion with any oxygen present. Any inert gas such as helium, neon, or ar ...
. Moreover, due to the low concentrations of trace components one can assume that the total number of H3O+ ions remains nearly unchanged, which leads to the equation In equation () H+/chem> is the density of product ions, 3O+ is the density of reagent ions in absence of reactant molecules in the buffer gas, is the
reaction rate constant In chemical kinetics a reaction rate constant or reaction rate coefficient, ''k'', quantifies the rate and direction of a chemical reaction. For a reaction between reactants A and B to form product C the reaction rate is often found to have the ...
and is the average time the ions need to pass the reaction region. With a PTR-MS instrument the number of product and of reagent ions can be measured, the reaction rate constant can be found in literature for most substances and the reaction time can be derived from the set instrument parameters. Therefore, the absolute
concentration In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', ''molar concentration'', ''number concentration'', an ...
of trace constituents /chem> can be easily calculated without the need of
calibration In measurement technology and metrology, calibration is the comparison of measurement values delivered by a device under test with those of a calibration standard of known accuracy. Such a standard could be another measurement device of know ...
or gas standards. Furthermore, it gets obvious that the overall sensitivity of a PTR-MS instrument is dependent on the reagent ion yield. Fig. 1 gives an overview of several published (in
peer-reviewed journals An academic journal or scholarly journal is a periodical publication in which scholarship relating to a particular academic discipline is published. Academic journals serve as permanent and transparent forums for the presentation, scrutiny, and d ...
) reagent ion yields during the last decades and the corresponding sensitivities.


Technology

In commercial PTR-MS instruments water vapor is ionized in a hollow cathode discharge: :e^- + H2O -> H2O+ + 2e^- :e^- + H2O -> H2+ + O + 2e^- :e^- + H2O -> H+ + OH + 2e^- :e^- + H2O -> O+ + H2 + 2e^-. After the discharge a short drift tube is used to form very pure (>99.5%) H3O+ via ion-molecule reactions: :H2+ + H2O -> H2O+ + H2 :H+ + H2O -> H2O+ + H :O+ + H2O -> H2O+ + O :H2O+ + H2O -> H3O+ + OH. Due to the high purity of the reagent ions a mass filter between the ion source and the reaction drift tube is not necessary and H3O+ can be injected directly. The absence of this mass filter in turn greatly reduces losses of reagent ions and leads eventually to an outstandingly low detection limit of the whole instrument. In the reaction drift tube a
vacuum pump A vacuum pump is a device that draws gas molecules from a sealed volume in order to leave behind a partial vacuum. The job of a vacuum pump is to generate a relative vacuum within a capacity. The first vacuum pump was invented in 1650 by Otto v ...
is 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 analyzer The quadrupole mass analyzer, originally conceived by Nobel Laureate Wolfgang Paul and his student Helmut Steinwedel, also known as quadrupole mass filter, is one type of mass analyzer used in mass spectrometry. As the name implies, it consists of ...
or
time-of-flight mass spectrometer Time-of-flight mass spectrometry (TOFMS) is a method of mass spectrometry in which an ion's mass-to-charge ratio is determined by a time of flight measurement. Ions are accelerated by an electric field of known strength. This acceleration resul ...
) and detected. As an alternative to H3O+ already in early PTR-MS related publications the use of NH4+ reagent ions has been suggested.
Ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
has a proton affinity of 853.6 kJ/mol. For compounds that have a higher proton affinity than ammonia proton transfer can take place similar to the process described above for hydronium: :NH4+ + R -> RH+ + NH3. Additionally, for compounds with higher, but also for some with lower proton affinities than ammonia a clustering reaction can be observed :NH4+ + R -> R.NH4+* where the cluster needs a third body to get collisionally stabilized. The main advantage of using NH4+ reagent ions is that fragmentation of analytes upon chemical ionization is strongly suppressed, leading to straightforward
mass spectra A mass spectrum is a histogram plot of intensity vs. ''mass-to-charge ratio'' (''m/z'') in a chemical sample, usually acquired using an instrument called a ''mass spectrometer''. Not all mass spectra of a given substance are the same; for example ...
even for complex mixtures. The reason why during the first 20 years after the invention of PTR-MS NH4+ reagent ions have only been used in a very limited number of studies is most probably because the NH4+ production required
toxic Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a subst ...
and
corrosive A corrosive substance is one that will damage or destroy other substances with which it comes into contact by means of a chemical reaction. Etymology The word ''corrosive'' is derived from the Latin verb ''corrodere'', which means ''to gnaw'', ...
ammonia as a source gas. This led to problems with handling the instrument and its exhaust gas, as well as to increased wear of vacuum components. In 2017 a patent application was submitted where the inventors introduced a novel method of NH4+ production without the need of any form of ammonia. In this method N2 and water vapor are introduced into the hollow cathode ion source and by adjusting electric fields and pressures NH4+ can be produced at the same or even higher purity levels than H3O+. It is expected that this invention, which eliminates the problems connected to the use of NH4+ so far, will lead to a widespread use of NH4+ reagent ions in the near future.


Advantages

Advantages include low fragmentation – only a small amount of energy is transferred during the ionization process (compared to e.g.
electron ionization Electron ionization (EI, formerly known as electron impact ionization and electron bombardment ionization) is an ionization method in which energetic electrons interact with solid or gas phase atoms or molecules to produce ions. EI was one of th ...
), therefore fragmentation is suppressed and the obtained mass spectra are easily interpretable, no sample preparation is necessary – VOC containing air and liquids' headspaces can be analyzed directly, real-time measurements – with a typical response time of 100 ms 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 power Electric power is the rate at which electrical energy is transferred by an electric circuit. The SI unit of power is the watt, one joule per second. Standard prefixes apply to watts as with other SI units: thousands, millions and billions o ...
and a small amount of
distilled water Distilled water is water that has been boiled into vapor and condensed back into liquid in a separate container. Impurities in the original water that do not boil below or near the boiling point of water remain in the original container. Thus, di ...
are needed. Unlike other techniques no
gas cylinder A gas cylinder is a pressure vessel for storage and containment of gases at above atmospheric pressure. High-pressure gas cylinders are also called ''bottles''. Inside the cylinder the stored contents may be in a state of compressed gas, vapor ...
s are needed for buffer gas or calibration standards.


Disadvantages

One disadvantage is that not all molecules are detectable. Because only molecules with a proton affinity higher than water can be detected by PTR-MS, proton transfer from H3O+ is not suitable for all fields of application. Therefore, in 2009 first PTR-MS instruments were presented, which are capable of switching between H3O+ and O2+ (and NO+) as reagent ions. This enhances the number of detectable substances to important compounds like
ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene i ...
,
acetylene Acetylene (systematic name: ethyne) is the chemical compound with the formula and structure . It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is unstable in its pure ...
, most
halocarbon Halocarbon compounds are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms (fluorine, chlorine, bromine or iodine â€“ ) resulting in the formation of organofluorine compounds, organochlori ...
s, etc. Furthermore, particularly with NO+ it is possible to separate and independently quantifiy some
isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Iso ...
s. In 2012 a PTR-MS instrument was introduced which extends the selectable reagent ions to Kr+ and Xe+; this should allow for the detection of nearly all possible substances (up to the ionization energy of krypton (14 eV)). Although the ionization method for these additional reagent ions is charge-exchange rather than proton-transfer ionization the instruments can still be considered as "classic" PTR-MS instruments, i.e. no mass filter between the ion source and the drift tube and only some minor modifications on the ion source and vacuum design. The maximum measurable concentration is limited. Equation (2) is based on the assumption that the decrease of reagent ions is negligible, therefore the total concentration of VOCs in air must not exceed about 10 ppmv. Otherwise the instrument's response will not be linear anymore and the concentration calculation will be incorrect. This limitation can be overcome easily by diluting the sample with a well-defined amount of pure air.


Sensitivity enhancing measures

As it is the case for most analytical instruments, also in PTR-MS there has always been a quest for sensitivity improvement and for lowering the detection limit. However, until 2012 these improvements were limited to optimizations of the conventional setup, i.e. ion source, DC drift tube, transfer lens system, mass spectrometer (compare above). The reason for this conservative approach was that the addition of any RF ion focusing device negatively affects the well-defined PTR-MS ion chemistry, which makes quantification complicated and considerably limits comparability of measurement results obtained with different instruments. Only in 2016 a patent application providing a solution to this problem was submitted.


Ion funnel

Ion funnel in mass spectrometry, an ion funnel is a device used to focus a beam of ions using a series of stacked ring electrodes with decreasing inner diameter. A combined radio frequency and fixed electrical potential is applied to the grids. In electrosp ...
s are RF devices which have been used for decades to focus ion currents into narrow beams. In PTR-MS they have been introduced in 2012 by Barber et al. when they presented a PTR-MS setup with a PTR reaction region incorporating an ion funnel. Although the focusing properties of the ion funnel improved the sensitivity of the setup by a factor of >200 (compared to operating in DC only mode, i.e. with the ion funnel turned off) for some compounds, the sensitivities of other compounds were only improved by a factor of <10. That is, because of the highly compound dependent instrumental response one of the main advantages of PTR-MS, namely that concentration values can be directly calculated, is lost and a calibration measurement is needed for each analyte of interest. Furthermore, with this approach unusual fragmentation of analytes has been observed which complicates interpretation of measurement results and comparison between different types of instruments even more. A different concept has been introduced by the company IONICON Analytik GmbH. (Innsbruck, AT) where the ion funnel is not predominantly part of the reaction region but mainly for focusing the ions into the transfer region to the TOF mass spectrometer. In combination with the above-mentioned method of controlling the ion chemistry this enables a considerable increase in sensitivity and thus also an improvement of the detection limit, while keeping the ion chemistry well-defined and thus avoiding problems with quantification and interpretation of the results.


Ion guide

Quadrupole A quadrupole or quadrapole is one of a sequence of configurations of things like electric charge or current, or gravitational mass that can exist in ideal form, but it is usually just part of a multipole expansion of a more complex structure refl ...
, hexapole and other multipole ion guides can be used to transfer ions between different parts of an instrument with high efficiency. In PTR-MS they are particularly suitable for being installed in the differentially pumped interface between the reaction region and the mass spectrometer. In 2014 Sulzer et al. published an article about a PTR-MS instrument which utilizes a quadrupole ion guide between the drift tube and the TOF mass spectrometer. They reported an increase in sensitivity by a factor of 25 compared to a similar instrument without an ion guide. Quadrupole ion guides are known to have high focusing power, but also rather narrow ''m/z'' transmission bands. Hexapole ion guides on the other hand have focusing capabilities over a broader ''m/z'' band. Additionally, less energy is put into the transmitted ions, i.e. fragmentation and other adverse effects are less likely to occur. Consequently, some latest high-end PTR-MS instruments are equipped with hexapole ion guides for considerably improved performance or even with a sequential arrangement of an ion funnel followed by a hexapole ion guide for even higher sensitivity and lower detection limit.


Add-Ons

As a real-time trace gas analysis method based on mass spectrometry PTR-MS has two obvious limitations: Isomers cannot be easily separated (for some it is possible by switching the reagent ions and/or by changing the reduced electric field strength in the drift tube) and the sample has to be in the gas
phase Phase or phases may refer to: Science *State of matter, or phase, one of the distinct forms in which matter can exist *Phase (matter), a region of space throughout which all physical properties are essentially uniform * Phase space, a mathematic ...
. Countermeasures against these limitations have been developed in the form of add-ons, which can either be installed into the PTR-MS instrument or operated as external devices.


FastGC

Gas chromatography (GC) in combination with mass spectrometry ( GC-MS) is capable of separating isomeric compounds. Although GC has been successfully coupled to PTR-MS in the past, this approach annihilates the real-time capability of the PTR-MS technology, because a single GC analysis run typically takes between 30 min and 1 h. Thus, state-of-the-art GC add-ons for PTR-MS are based on fastGC technology. Materic et al. utilized an early version of a commercially available fastGC addon in order to distinguish various
monoterpene Monoterpenes are a class of terpenes that consist of two isoprene units and have the molecular formula C10H16. Monoterpenes may be linear (acyclic) or contain rings (monocyclic and bicyclic). Modified terpenes, such as those containing oxygen funct ...
isomers. Within a fastGC run of about 70 s they were able to separate and identify: ''alpha''-pinene, ''beta''-pinene,
camphene Camphene is a bicyclic organic compound. It is one of the most pervasive monoterpenes. As for other terpenes, it is insoluble in water, flammable, colorless, and has a pungent smell. It is a minor constituent of many essential oils such as tur ...
,
myrcene Myrcene, or β-myrcene, is a monoterpene. A colorless oil, it occurs widely in essential oils. It is produced mainly semi-synthetically from '' Myrcia'', from which it gets its name. It is an intermediate in the production of several fragrances. Π...
,
3-carene 3-Carene is a bicyclic monoterpene consisting of fused cyclohexene and cyclopropane rings. It occurs as a constituent of turpentine, with a content as high as 42% depending on the source. Carene has a sweet and pungent odor, best described as a ...
and
limonene Limonene is a colorless liquid aliphatic hydrocarbon classified as a cyclic monoterpene, and is the major component in the oil of citrus fruit peels. The -isomer, occurring more commonly in nature as the fragrance of oranges, is a flavoring ag ...
in a standard mixture,
Norway spruce ''Picea abies'', the Norway spruce or European spruce, is a species of spruce native to Northern, Central and Eastern Europe. It has branchlets that typically hang downwards, and the largest cones of any spruce, 9–17 cm long. It is very close ...
,
Scots pine ''Pinus sylvestris'', the Scots pine (UK), Scotch pine (US) or Baltic pine, is a species of tree in the pine family Pinaceae that is native to Eurasia. It can readily be identified by its combination of fairly short, blue-green leaves and orang ...
and black pine samples, respectively. Particularly, if the operation mode of a PTR-MS instrument equipped with fastGC is continuously switched between fastGC and direct injection (dependent on the application, e.g. a loop sequence of one fastGC run followed by 10 min of direct injection measurement), real-time capability is preserved, while at the same time valuable information on substance identification and isomer separation is acquired.


Aerosol and particulate matter inlet

Researchers at the Leopold-Franzens University in Innsbruck invented a dedicated PTR-MS inlet system for the analysis of
aerosol An aerosol is a suspension (chemistry), suspension of fine solid particles or liquid Drop (liquid), droplets in air or another gas. Aerosols can be natural or Human impact on the environment, anthropogenic. Examples of natural aerosols are fog o ...
s and
particulate matter Particulates – also known as atmospheric aerosol particles, atmospheric particulate matter, particulate matter (PM) or suspended particulate matter (SPM) – are microscopic particles of solid or liquid matter suspended in the air. The ter ...
, which they called "CHemical Analysis of aeRosol ON-line (CHARON)". After further development work in collaboration with a PTR-MS manufacturer, CHARON has become readily available as an add-on for PTR-MS instruments in 2017. The add-on consists of a honeycomb
activated charcoal "Activated" is a song by English singer Cher Lloyd. It was released on 22 July 2016 through Vixen Records. The song was made available to stream exclusively on ''Rolling Stone'' a day before to release (on 21 July 2016). Background In an interv ...
denuder which adsorbs organic gases but transmits particles, an aerodynamic lens system that collimates sub-µm particles, and a thermo-desorber that evaporates non-refractory organic particulate matter at moderate temperatures of 100-160 Â°C and reduced pressures of a few mbar. So far, CHARON has predominantly being utilized within studies in the field of
atmospheric chemistry Atmospheric chemistry is a branch of atmospheric science in which the chemistry of the Earth's atmosphere and that of other planets is studied. It is a multidisciplinary approach of research and draws on environmental chemistry, physics, meteoro ...
, e.g. for airborne measurements of particulate organic matter and bulk organic aerosol analysis.


Inlet for liquids

A now well established setup for the controlled
evaporation Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. High concentration of the evaporating substance in the surrounding gas significantly slows down evaporation, such as when humidi ...
and subsequent analysis of
liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, a ...
s with PTR-MS has been published in 2013 by Fischer et al. As the authors saw the main application of their setup in the calibration of PTR-MS instruments via
aqueous An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), in water would be rep ...
standards, they named it "Liquid Calibration Unit (LCU)". The LCU sprays a liquid standard into a gas stream at well-defined flow rates via a purpose-built nebulizer (optimized for reduced probability of clogging and high tolerance to salts in the liquid). The resulting micro-droplets are injected into a heated (> 100 Â°C) evaporation chamber. This concept offers two main advantages: (i) the evaporation of compounds is enhanced by the enlarged surface area of the droplets and (ii) compounds which are dissociated in water, such as
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
s (or bases), experience a shift in
pH value In chemistry, pH (), historically denoting "potential of hydrogen" (or "power of hydrogen"), is a scale used to specify the acidity or basicity of an aqueous solution. Acidic solutions (solutions with higher concentrations of ions) are mea ...
when the water evaporates from a droplet. This in turn reduces dissociation and supports total evaporation of the compound. The resulting continuous gas flow containing the analytes can be directly introduced into a PTR-MS instrument for analysis.


Applications

The most common applications for the PTR-MS technique are
environmental research Environmental science is an interdisciplinary academic field that integrates physics, biology, and geography (including ecology, chemistry, plant science, zoology, mineralogy, oceanography, limnology, soil science, geology and physical geo ...
,
waste incineration Incineration is a waste treatment process that involves the combustion of substances contained in waste materials. Industrial plants for waste incineration are commonly referred to as waste-to-energy facilities. Incineration and other high ...
,
food science Food science is the basic science and applied science of food; its scope starts at overlap with agricultural science and nutritional science and leads through the scientific aspects of food safety and food processing, informing the developm ...
,
biological research Biology is the scientific study of life. It is a natural science with a broad scope but has several unifying themes that tie it together as a single, coherent field. For instance, all organisms are made up of cells that process hereditary in ...
, process monitoring,
indoor air quality Indoor air quality (IAQ) is the air quality within and around buildings and structures. IAQ is known to affect the health, comfort, and well-being of building occupants. Poor indoor air quality has been linked to sick building syndrome, reduced ...
,
medicine Medicine is the science and practice of caring for a patient, managing the diagnosis, prognosis, prevention, treatment, palliation of their injury or disease, and promoting their health. Medicine encompasses a variety of health care pract ...
and
biotechnology Biotechnology is the integration of natural sciences and engineering sciences in order to achieve the application of organisms, cells, parts thereof and molecular analogues for products and services. The term ''biotechnology'' was first used b ...
and
Homeland security Homeland security is an American national security term for "the national effort to ensure a homeland that is safe, secure, and resilient against terrorism and other hazards where American interests, aspirations, and ways of life can thrive" to ...
. Trace gas analysis is another common application. Some other techniques are
Secondary electrospray ionization Secondary electro-spray ionization (SESI) is an ambient ionization technique for the analysis of trace concentrations of vapors, where a nano-electrospray produces charging agents that collide with the analyte molecules directly in gas-phase. In t ...
(SESI),
Electrospray ionization Electrospray ionization (ESI) is a technique used in mass spectrometry to produce ions using an electrospray in which a high voltage is applied to a liquid to create an aerosol. It is especially useful in producing ions from macromolecules becaus ...
(ESI), and
Selected-ion flow-tube mass spectrometry Selected-ion flow-tube mass spectrometry (SIFT-MS) is a quantitative mass spectrometry technique for trace gas analysis which involves the chemical ionization of trace volatile compounds by selected positive precursor ions during a well-defined ...
(SIFT).


Food science

Fig. 2 shows a typical PTR-MS measurement performed in food and flavor research. The test person swallows a sip of a
vanillin Vanillin is an organic compound with the molecular formula . It is a phenolic aldehyde. Its functional groups include aldehyde, hydroxyl, and ether. It is the primary component of the extract of the vanilla bean. Synthetic vanillin is now used ...
flavored drink and breathes via his nose into a heated inlet device coupled to a PTR-MS instrument. Due to the high time resolution and sensitivity of the instrument used here, the development of vanillin in the person's breath can be monitored in real-time (please note that
isoprene Isoprene, or 2-methyl-1,3-butadiene, is a common volatile organic compound with the formula CH2=C(CH3)−CH=CH2. In its pure form it is a colorless volatile liquid. Isoprene is an unsaturated hydrocarbon. It is produced by many plants and animals ...
is shown in this figure because it is a product of human metabolism and therefore acts as an indicator for the breath cycles). The data can be used for food design, i.e. for adjusting the intensity and duration of vanillin flavor tasted by the consumer. Another example for the application of PTR-MS in food science was published in 2008 by C. Lindinger et al. in ''
Analytical Chemistry Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separati ...
''. This publication found great response even in non-scientific media. Lindinger et al. developed a method to convert "dry" data from a PTR-MS instrument that measured headspace air from different
coffee Coffee is a drink prepared from roasted coffee beans. Darkly colored, bitter, and slightly acidic, coffee has a stimulant, stimulating effect on humans, primarily due to its caffeine content. It is the most popular hot drink in the world. S ...
samples into expressions of
flavor Flavor or flavour is either the sensory perception of taste or smell, or a flavoring in food that produces such perception. Flavor or flavour may also refer to: Science *Flavors (programming language), an early object-oriented extension to Lis ...
(e.g. "woody", "winey", "flowery", etc.) and showed that the obtained flavor profiles matched nicely to the ones created by a panel of European coffee tasting experts.


Air quality analysis

In Fig. 3 a mass spectrum of air inside a laboratory (obtained with a time-of-flight (TOF) based PTR-MS instrument), is shown. The
peaks Peak or The Peak may refer to: Basic meanings Geology * Mountain peak ** Pyramidal peak, a mountaintop that has been sculpted by erosion to form a point Mathematics * Peak hour or rush hour, in traffic congestion * Peak (geometry), an (''n''-3)-di ...
on ''m/z'' 19, 37 and 55 (and their
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numbers) ...
s) represent the reagent ions (H3O+) and their clusters. On ''m/z'' 30 and 32 NO+ and O2+, which are both impurities originating from the ion source, appear. All other peaks correspond to compounds present in typical laboratory air (e.g. high intensity of protonated
acetone Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour. Acetone is miscib ...
on ''m/z'' 59). If one takes into account that virtually all peaks visible in Fig. 3 are in fact double, triple or multiple peaks ( isobaric compounds) it becomes obvious that for PTR-MS instruments selectivity is at least as important as sensitivity, especially when complex samples / compositions are analyzed. One methods for improving the selectivity is high mass resolution. When the PTR source is coupled to a
high resolution Image resolution is the detail an image holds. The term applies to digital images, film images, and other types of images. "Higher resolution" means more image detail. Image resolution can be measured in various ways. Resolution quantifies how cl ...
mass spectrometer isobaric compounds can be distinguished and substances can be identified via their exact mass.A. Jordan, S. Haidacher, G. Hanel, E. Hartungen, L. Märk, H. Seehauser, R. Schottkowsky, P. Sulzer, T.D. Märk: A high resolution and high sensitivity time-of-flight proton-transfer-reaction mass spectrometer (PTR-TOF-MS), International Journal of Mass Spectrometry, 286, 122–128, (2009). Some PTR-MS instruments are despite of the lack of a mass filter between the ion source and the drift tube capable of switching the reagent ions (e.g. to NO+ or O2+). With the additional information obtained by using different reagent ions a much higher level of selectivity can be reached, e.g. some
isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Iso ...
ic molecules can be distinguished.


See also

*
Chemical ionization Chemical ionization (CI) is a soft ionization technique used in mass spectrometry. This was first introduced by Burnaby Munson and Frank H. Field in 1966. This technique is a branch of gaseous ion-molecule chemistry. Reagent gas molecules (often ...
* Gas analysis *
Mass Spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...
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Selected-ion flow-tube mass spectrometry Selected-ion flow-tube mass spectrometry (SIFT-MS) is a quantitative mass spectrometry technique for trace gas analysis which involves the chemical ionization of trace volatile compounds by selected positive precursor ions during a well-defined ...
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Secondary electrospray ionization Secondary electro-spray ionization (SESI) is an ambient ionization technique for the analysis of trace concentrations of vapors, where a nano-electrospray produces charging agents that collide with the analyte molecules directly in gas-phase. In t ...


References


External links


Kore Technology – Principles of PTR
* {{YouTube, id=y6BfTfo2_Ko, title=IONICON webinar: Introduction to PTR-MS Mass spectrometry Measuring instruments Proton