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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 used in many different fields and is applied to pure samples as well as complex mixtures.
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.
Secondary-ion mass spectrometry (SIMS) is a technique used to analyze the composition of solid surfaces and thin films by sputtering the surface of the specimen with a focused primary ion beam and collecting and analyzing ejected secondary ions. The mass/charge ratios of these secondary ions are measured with a mass spectrometer to determine the elemental, isotopic, or molecular composition of the surface to a depth of 1 to 2 nm. Due to the large variation in ionization probabilities among elements sputtered from different materials, comparison against well-calibrated standards is necessary to achieve accurate quantitative results. SIMS is the most sensitive surface analysis technique, with elemental detection limits ranging from parts per million to parts per billion.
Tandem mass spectrometry, also known as MS/MS or MS2, is a technique in instrumental analysis where two or more mass analyzers are coupled together using an additional reaction step to increase their abilities to analyse chemical samples. A common use of tandem MS is the analysis of biomolecules, such as proteins and peptides.
Gas chromatography–mass spectrometry (GC-MS) is an analytical method that combines the features of gas-chromatography and mass spectrometry to identify different substances within a test sample. Applications of GC-MS include drug detection, fire investigation, environmental analysis, explosives investigation, and identification of unknown samples, including that of material samples obtained from planet Mars during probe missions as early as the 1970s. GC-MS can also be used in airport security to detect substances in luggage or on human beings. Additionally, it can identify trace elements in materials that were previously thought to have disintegrated beyond identification. Like liquid chromatography–mass spectrometry, it allows analysis and detection even of tiny amounts of a substance.
An ion trap is a combination of electric or magnetic fields used to capture charged particles — known as ions — often in a system isolated from an external environment. Ion traps have a number of scientific uses such as mass spectrometry, basic physics research, and controlling quantum states. The two most common types of ion trap are the Penning trap, which forms a potential via a combination of electric and magnetic fields, and the Paul trap which forms a potential via a combination of static and oscillating electric fields.
The quadrupole mass analyzer (QMS), originally conceived by Nobel Laureate Wolfgang Paul and his student Helmut Steinwedel, also known as a transmission quadrupole mass spectrometer, quadrupole mass filter, or quadrupole mass spectrometer, is one type of mass analyzer used in mass spectrometry. As the name implies, it consists of four cylindrical rods, set parallel to each other. In a quadrupole mass spectrometer the quadrupole is the mass analyzer - the component of the instrument responsible for selecting sample ions based on their mass-to-charge ratio (m/z). Ions are separated in a quadrupole based on the stability of their trajectories in the oscillating electric fields that are applied to the rods.
In mass spectrometry, matrix-assisted laser desorption/ionization (MALDI) is an ionization technique that uses a laser energy absorbing matrix to create ions from large molecules with minimal fragmentation. It has been applied to the analysis of biomolecules and various organic molecules, which tend to be fragile and fragment when ionized by more conventional ionization methods. It is similar in character to electrospray ionization (ESI) in that both techniques are relatively soft ways of obtaining ions of large molecules in the gas phase, though MALDI typically produces far fewer multi-charged ions.
Atmospheric pressure chemical ionization (APCI) is an ionization method used in mass spectrometry which utilizes gas-phase ion-molecule reactions at atmospheric pressure (105 Pa), commonly coupled with high-performance liquid chromatography (HPLC). APCI is a soft ionization method similar to chemical ionization where primary ions are produced on a solvent spray. The main usage of APCI is for polar and relatively less polar thermally stable compounds with molecular weight less than 1500 Da. The application of APCI with HPLC has gained a large popularity in trace analysis detection such as steroids, pesticides and also in pharmacology for drug metabolites.
The history of mass spectrometry has its roots in physical and chemical studies regarding the nature of matter. The study of gas discharges in the mid 19th century led to the discovery of anode and cathode rays, which turned out to be positive ions and electrons. Improved capabilities in the separation of these positive ions enabled the discovery of stable isotopes of the elements. The first such discovery was with the element neon, which was shown by mass spectrometry to have at least two stable isotopes: 20Ne and 22Ne. Mass spectrometers were used in the Manhattan Project for the separation of isotopes of uranium necessary to create the atomic bomb.
In mass spectrometry, Orbitrap is an ion trap mass analyzer consisting of an outer barrel-like electrode and a coaxial inner spindle-like electrode that traps ions in an orbital motion around the spindle. The image current from the trapped ions is detected and converted to a mass spectrum using the Fourier transform of the frequency signal.
Penning ionization is a form of chemi-ionization, an ionization process involving reactions between neutral atoms or molecules. The Penning effect is put to practical use in applications such as gas-discharge neon lamps and fluorescent lamps, where the lamp is filled with a Penning mixture to improve the electrical characteristics of the lamps.
A Bradbury–Nielsen shutter is a type of electrical ion gate, which was first proposed in an article by Norris Bradbury and Russel A. Nielsen, where they used it as an electron filter. Today they are used in the field of mass spectrometry where they are used in both TOF mass spectrometers and in ion mobility spectrometers , as well as Hadamard transform mass spectrometers. The Bradbury–Nielsen shutter is ideal for injecting short pulses of ions and can be used to improve the mass resolution of TOF instruments by reducing the initial pulse size as compared to other methods of ion injection.
Electron-transfer dissociation (ETD) is a method of fragmenting multiply-charged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry (MS/MS). Similar to electron-capture dissociation, ETD induces fragmentation of large, multiply-charged cations by transferring electrons to them. ETD is used extensively with polymers and biological molecules such as proteins and peptides for sequence analysis. Transferring an electron causes peptide backbone cleavage into c- and z-ions while leaving labile post translational modifications (PTM) intact. The technique only works well for higher charge state peptide or polymer ions (z>2). However, relative to collision-induced dissociation (CID), ETD is advantageous for the fragmentation of longer peptides or even entire proteins. This makes the technique important for top-down proteomics. The method was developed by Hunt and coworkers at the University of Virginia.
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 results in an ion having the same kinetic energy as any other ion that has the same charge. The velocity of the ion depends on the mass-to-charge ratio. The time that it subsequently takes for the ion to reach a detector at a known distance is measured. This time will depend on the velocity of the ion, and therefore is a measure of its mass-to-charge ratio. From this ratio and known experimental parameters, one can identify the ion.
Proton-transfer-reaction mass spectrometry (PTR-MS) is an analytical chemistry technique that uses gas phase hydronium reagent ions which are produced in an ion source. 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 and an analyzing system. Commercially available PTR-MS instruments have a response time of about 100 ms and reach a detection limit in the single digit pptv or even ppqv region. Established fields of application are environmental research, food and flavor science, biological research, medicine, security, cleanroom monitoring, etc.
Ion mobility spectrometry–mass spectrometry (IMS-MS) is an analytical chemistry method that separates gas phase ions based on their interaction with a collision gas and their masses. In the first step, the ions are separated according to their mobility through a buffer gas on a millisecond timescale using an ion mobility spectrometer. The separated ions are then introduced into a mass analyzer in a second step where their mass-to-charge ratios can be determined on a microsecond timescale. The effective separation of analytes achieved with this method makes it widely applicable in the analysis of complex samples such as in proteomics and metabolomics.
Delayed extraction is a method used with a time-of-flight mass spectrometer in which the accelerating voltage is applied after some short time delay following pulsed laser desorption/ionization from a flat surface of target plate or, in other implementation, pulsed electron ionization or Resonance enhanced multiphoton ionization in some narrow space between two plates of the ion extraction system. The extraction delay can produce time-of-flight compensation for ion energy spread and improve mass resolution.
A hybrid mass spectrometer is a device for tandem mass spectrometry that consists of a combination of two or more m/z separation devices of different types.
In mass spectrometry, fragmentation is the dissociation of energetically unstable molecular ions formed from passing the molecules in the ionization chamber of a mass spectrometer. The fragments of a molecule cause a unique pattern in the mass spectrum. These reactions are well documented over the decades and fragmentation pattern is useful to determine the molar weight and structural information of the unknown molecule. Fragmentation that occurs in tandem mass spectrometry experiments has been a recent focus of research, because this data helps facilitate the identification of molecules.
References
- ↑ Bleakney, Walker; John A. Hipple Jr. (1938). "A New Mass Spectrometer with Improved Focusing Properties". Phys. Rev. 53 (7): 521–529. Bibcode:1938PhRv...53..521B. doi:10.1103/PhysRev.53.521 . Retrieved 2007-10-02.
- ↑ IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) " Prolate trochoidal mass spectrometer ". doi : 10.1351/goldbook.P04874
- ↑ Adamczyk B, Bederski K, Wójcik L (1988). "Mass spectrometric investigation of dissociative ionization of toxic gases by electrons at 20-1000 eV". Biomed. Environ. Mass Spectrom. 16 (1–12): 415–7. doi:10.1002/bms.1200160181. PMID 3149538.
- ↑ Laramée JA, Deinzer ML (1994). "Capillary gas chromatographic introduction of environmental compounds into a trochoidal electron monochromator/mass spectrometer". Anal. Chem. 66 (5): 719–24. doi:10.1021/ac00077a022. PMID 8154592.
- ↑ Voinov VG, Vasil'ev YV, Morré J, Barofsky DF, Deinzer ML, Gonin M, Egan TF, Führer K (2003). "A resonant electron capture time-of-flight MS with trochoidal electron monochromator". Anal. Chem. 75 (13): 3001–9. doi:10.1021/ac030019v. PMID 12964744.