Mass spectrum
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A mass spectrum is a
histogram A histogram is an approximate representation of the distribution of numerical data. The term was first introduced by Karl Pearson. To construct a histogram, the first step is to " bin" (or "bucket") the range of values—that is, divide the ent ...
plot of intensity vs. ''
mass-to-charge ratio The mass-to-charge ratio (''m''/''Q'') is a physical quantity relating the ''mass'' (quantity of matter) and the ''electric charge'' of a given particle, expressed in units of kilograms per coulomb (kg/C). It is most widely used in the electrody ...
'' (''m/z'') in a chemical sample, usually acquired using an instrument called a ''
mass spectrometer 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 ...
''. Not all mass spectra of a given substance are the same; for example, some mass spectrometers break the analyte molecules into '' fragments''; others observe the intact molecular masses with little fragmentation. A mass spectrum can represent many different types of information based on the type of mass spectrometer and the specific experiment applied. Common fragmentation processes for organic molecules are the ''
McLafferty rearrangement The McLafferty rearrangement is a reaction observed in mass spectrometry during the fragmentation or dissociation of organic molecules. It is sometimes found that a molecule containing a keto-group undergoes β-cleavage, with the gain of the γ-hyd ...
'' and ''
alpha cleavage Alpha-cleavage (α-cleavage) in organic chemistry refers to the act of breaking the carbon-carbon bond adjacent to the carbon bearing a specified functional group. Mass spectrometry Generally this topic is discussed when covering tandem mass spec ...
''. Straight chain alkanes and alkyl groups produce a typical series of peaks: 29 (CH3CH2+), 43 (CH3CH2CH2+), 57 (CH3CH2CH2CH2+), 71 (CH3CH2CH2CH2CH2+) etc.


X-axis: ''m/z'' (mass-to-charge ratio)

The
x-axis A Cartesian coordinate system (, ) in a plane is a coordinate system that specifies each point uniquely by a pair of numerical coordinates, which are the signed distances to the point from two fixed perpendicular oriented lines, measured in t ...
of a mass spectrum represents a relationship between the mass of a given ion and the number of elementary charges that it carries. This is written as the
IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
standard ''m/z'' to denote the quantity formed by dividing the mass of an ion by the
unified atomic mass unit The dalton or unified atomic mass unit (symbols: Da or u) is a non-SI unit of mass widely used in physics and chemistry. It is defined as of the mass of an unbound neutral atom of carbon-12 in its nuclear and electronic ground state and at ...
and by its charge number (positive absolute value). This has been referred to as a
mass-to-charge ratio The mass-to-charge ratio (''m''/''Q'') is a physical quantity relating the ''mass'' (quantity of matter) and the ''electric charge'' of a given particle, expressed in units of kilograms per coulomb (kg/C). It is most widely used in the electrody ...
, although in some ways it does not fit this description. The IUPAC Gold Book gives an example: "''for the ion C7H72+, m/z equals 45.5''". Since a mass spectrum ''x''-axis represents a relationship between the ion mass and the number of elementary charges that a given ion carries it contains mass information that may be extracted by a mass spectrometrist.


Alternative x-axis notations

There are several alternatives to the standard ''m/z'' notation that appear in the literature; however, these are not currently accepted by standards organizations and most journals. ''m/e'' appears in older historical literature. A label more consistent with the
IUPAC green book ''Quantities, Units and Symbols in Physical Chemistry'', also known as the ''Green Book'', is a compilation of terms and symbols widely used in the field of physical chemistry. It also includes a table of physical constants, tables listing the pr ...
and
ISO 31 ISO 31 (Quantities and units, International Organization for Standardization, 1992) is a superseded international standard concerning physical quantities, units of measurement, their interrrelationships and their presentation. It was revised and ...
conventions is ''m/Q'' or ''m/q'' where ''m'' is the symbol for mass and ''Q'' or ''q'' the symbol for charge with the units u/e or Da/e. This notation is not uncommon in the physics of mass spectrometry but is rarely used as the abscissa of a mass spectrum. It was also suggested to introduce a new unit
thomson Thomson may refer to: Names * Thomson (surname), a list of people with this name and a description of its origin * Thomson baronets, four baronetcies created for persons with the surname Thomson Businesses and organizations * SGS-Thomson Mic ...
(Th) as a unit of ''m/z'', where 1 Th = 1 u/e. According to this convention, mass spectra x axis could be labeled ''m/z'' (Th) and negative ions would have negative values. This notation is rare and not accepted by
IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
or any other standards organisation.


History of x-axis notation

In 1897 the mass-to-charge ratio m/e of the
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...
was first measured by
J. J. Thomson Sir Joseph John Thomson (18 December 1856 – 30 August 1940) was a British physicist and Nobel Laureate in Physics, credited with the discovery of the electron, the first subatomic particle to be discovered. In 1897, Thomson showed that ...
. By doing this he showed that the electron, which was postulated before in order to explain electricity, was in fact a particle with a mass and a charge and that its mass-to-charge ratio was much smaller than the one for the hydrogen ion H+. In 1913 he measured the mass-to-charge ratio of
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
s with an instrument he called a parabola spectrograph. Although this data was not represented as a modern mass spectrum, it was similar in meaning. Eventually there was a change to the notation as ''m/e'' giving way to the current standard of ''m/z''. Early in mass spectrometry research the
resolution Resolution(s) may refer to: Common meanings * Resolution (debate), the statement which is debated in policy debate * Resolution (law), a written motion adopted by a deliberative body * New Year's resolution, a commitment that an individual mak ...
of mass spectrometers did not allow for accurate mass determination.
Francis William Aston Francis William Aston FRS (1 September 1877 – 20 November 1945) was a British chemist and physicist who won the 1922 Nobel Prize in Chemistry for his discovery, by means of his mass spectrograph, of isotopes in many non-radioactive elements a ...
won the Nobel prize in Chemistry in 1922. "For his discovery, by means of his mass spectrograph, of isotopes, in a large number of non-radioactive elements, and for his enunciation of the
Whole Number Rule In chemistry, the whole number rule states that the masses of the isotopes are whole number multiples of the mass of the hydrogen atom. The rule is a modified version of Prout's hypothesis proposed in 1815, to the effect that atomic weights are mu ...
." In which he stated that all atoms (including isotopes) follow a whole-number rule This implied that the masses of atoms were not on a scale but could be expressed as integers (in fact multiple charged ions were rare, so for the most part the ratio was whole as well). There have been several suggestions (e.g. the unit thomson) to change the official mass spectrometry nomenclature m/z to be more internally consistent.


Y-axis: signal intensity

The ''y''-axis of a mass spectrum represents signal intensity of the ions. When using counting detectors the intensity is often measured in counts per second (cps). When using analog detection electronics the intensity is typically measured in volts. In FTICR and
Orbitrap 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 ...
s the
frequency domain In physics, electronics, control systems engineering, and statistics, the frequency domain refers to the analysis of mathematical functions or signals with respect to frequency, rather than time. Put simply, a time-domain graph shows how a signa ...
signal (the ''y''-axis) is related to the
power Power most often refers to: * Power (physics), meaning "rate of doing work" ** Engine power, the power put out by an engine ** Electric power * Power (social and political), the ability to influence people or events ** Abusive power Power may a ...
(~amplitude squared) of the signal
sine wave A sine wave, sinusoidal wave, or just sinusoid is a curve, mathematical curve defined in terms of the ''sine'' trigonometric function, of which it is the graph of a function, graph. It is a type of continuous wave and also a Smoothness, smooth p ...
(often reduced to an rms power); however, the axis is usually not labeled as such for many reasons. In most forms of mass spectrometry, the intensity of ion current measured by the spectrometer does not accurately represent relative abundance, but correlates loosely with it. Therefore, it is common to label the ''y''-axis with "arbitrary units".


Y-axis and relative abundance

Signal intensity may be dependent on many factors, especially the nature of the molecules being analyzed and how they ionize. The efficiency of ionization varies from molecule to molecule and from ion source to ion source. For example, in electrospray sources in positive ion mode a quaternary amine will ionize exceptionally well whereas a large hydrophobic alcohol will most likely not be seen no matter how concentrated. In an EI source these molecules will behave very differently. Additionally there may be factors that affect ion transmission disproportionally between ionization and detection. On the detection side there are many factors that can also affect signal intensity in a non-proportional way. The size of the ion will affect the velocity of impact and with certain detectors the velocity is proportional to the signal output. In other detection systems, such as FTICR, the number of charges on the ion are more important to signal intensity. In
Fourier transform ion cyclotron resonance Fourier-transform ion cyclotron resonance mass spectrometry is a type of mass analyzer (or mass spectrometer) for determining the mass-to-charge ratio (''m''/''z'') of ions based on the ion cyclotron resonance, cyclotron frequency of the ions in a ...
and
Orbitrap 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 ...
type mass spectrometers the signal intensity (Y-axis) is related to the amplitude of the
free induction decay In Fourier transform nuclear magnetic resonance spectroscopy, free induction decay (FID) is the observable NMR signal generated by non-equilibrium nuclear spin magnetization precessing about the magnetic field (conventionally along z). This non-e ...
signal. This is fundamentally a power relationship (amplitude squared) but often computed as an ms For decaying signals the rms is not equal to the average amplitude. Additionally the damping constant (decay rate of the signal in the fid) is not the same for all ions. In order to make conclusions about relative intensity a great deal of knowledge and care is required. A common way to get more quantitative information out of a mass spectrum is to create a standard curve to compare the sample to. This requires knowing what is to be quantitated ahead of time, having a standard available and designing the experiment specifically for this purpose. A more advanced variation on this is the use of an
internal standard An internal standard in analytical chemistry is a chemical substance that is added in a constant amount to samples, the blank and calibration standards in a chemical analysis. This substance can then be used for calibration by plotting the ratio of ...
which behaves very similarly to the analyte. This is often an isotopically labeled version of the analyte. There are forms of mass spectrometry, such as
accelerator mass spectrometry Accelerator mass spectrometry (AMS) is a form of mass spectrometry that accelerates ions to extraordinarily high kinetic energies before mass analysis. The special strength of AMS among the mass spectrometric methods is its power to separate a r ...
that are designed from the bottom up to be quantitative.


Spectral skewing

Spectral skewing is the change in relative intensity of mass spectral peaks due to the changes in concentration of the
analyte An analyte, component (in clinical chemistry), or chemical species is a substance or chemical constituent that is of interest in an analytical procedure. The purest substances are referred to as analytes, such as 24 karat gold, NaCl, water, etc. ...
in the
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 ...
as the mass spectrum is scanned. This situation occurs routinely as
chromatographic In chemical analysis, chromatography is a laboratory technique for the separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it through a system (a ...
components elute into a continuous ion source.Watson, J. THrock, Sparkman,O David.Introduction to Mass Spectrometry.John Wiley & Sons, Inc. 4th Edition,2007. Page:113 Spectral skewing is not observed in
ion trap An ion trap is a combination of electric and/or magnetic fields used to capture charged particles — known as ions — often in a system isolated from an external environment. Atomic and molecular ion traps have a number of applications in phy ...
(
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 ...
(this has been seen also in QMS) or magnetic) or
time-of-flight Time of flight (ToF) is the measurement of the time taken by an object, particle or wave (be it acoustic, electromagnetic, etc.) to travel a distance through a medium. This information can then be used to measure velocity or path length, or as a w ...
(TOF)
mass analyzer 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 ...
s because potentially all
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
s formed in operational cycle (a snapshot in time) of the instrument are available for detection.


See also

*
Kendrick mass The Kendrick mass is defined by setting the mass of a chosen molecular fragment, typically CH2, to an integer value in amu ( atomic mass units). It is different from the IUPAC definition, which is based on setting the mass of 12C isotope to exactly ...


References


External links

* Quantities, Units and Symbols in Physical Chemistry
IUPAC green book

An introductory video on Mass Spectrometry
The Royal Society of Chemistry *
NIST The National Institute of Standards and Technology (NIST) is an agency of the United States Department of Commerce whose mission is to promote American innovation and industrial competitiveness. NIST's activities are organized into physical sci ...
br>Standard Reference Database 1A v17
{{DEFAULTSORT:Mass Spectrum Mass spectrometry