Quadrupole mass analyzer

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Quadrupole
Quadrupole mass analyzer.svg

The quadrupole mass analyzer 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.[1] In a quadrupole mass spectrometer (acronym QMS) the quadrupole is the component of the instrument responsible for filtering 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.[1]

Principle of operation[edit]

Image from "Apparatus For Separating Charged Particles Of Different Specific Charges" Patent number: 2939952 [2]

The quadrupole consists of four parallel metal rods. Each opposing rod pair is connected together electrically, and a radio frequency (RF) voltage is applied between one pair of rods and the other. A direct current voltage is then superimposed on the RF voltage. Ions travel down the quadrupole between the rods. Only ions of a certain mass-to-charge ratio will reach the detector for a given ratio of voltages: other ions have unstable trajectories and will collide with the rods. This permits selection of an ion with a particular m/z or allows the operator to scan for a range of m/z-values by continuously varying the applied voltage.[1] Mathematically this can be modeled with the help of the Mathieu differential equation.[3]

Ideally, the rods are hyperbolic. Cylindrical rods with a specific ratio of rod diameter-to-spacing provide an easier-to-manufacture adequate approximation to hyperbolas. Small variations in the ratio have large effects on resolution and peak shape. Different manufacturers choose slightly different ratios to fine-tune operating characteristics in context of anticipated application requirements. In recent decades some manufacturers have produced quadrupole mass spectrometers with true hyperbolic rods.

Applications[edit]

These mass spectrometers excel at applications where particular ions of interest are being studied because they can stay tuned on a single ion for extended periods of time. One place where this is useful is in liquid chromatography-mass spectrometry or gas chromatography-mass spectrometry where they serve as exceptionally high specificity detectors. Quadrupole instruments are often reasonably priced and make good multi-purpose instruments.

Triple quadrupoles[edit]

A linear series of three quadrupoles can be used; known as a triple quadrupole mass spectrometer. The first (Q1) and third (Q3) quadrupoles act as mass filters, and the middle (q2) quadrupole is employed as a collision cell. This collision cell is an RF-only quadrupole (non-mass filtering) using Ar, He, or N gas (~10−3 Torr, ~30 eV) for collision induced dissociation of selected parent ion(s) from Q1. Subsequent fragments are passed through to Q3 where they may be filtered or fully scanned.

This process allows for the study of fragments (daughter ions) that are crucial in structural elucidation. For example, the Q1 may be set to 'filter' for a drug ion of known mass, which is fragmented in q2. The third quadrupole (Q3) can then be set to scan the entire m/z range, giving information on the intensities of the fragments made. Thus, the structure of the original ion can be deduced.

The arrangement of three quadrupoles was first developed by Jim Morrison of LaTrobe University, Australia for the purpose of studying the photodissociation of gas-phase ions.[4] The first triple-quadrupole mass spectrometer was developed at Michigan State University by Dr. Christie Enke and graduate student Richard Yost in the late 1970s.[5]

More recently, triple quadrupoles have had their final quadrupole replaced with a Time of Flight mass analyzer. This is known as Quadrupole-Time-of-Flight (QqTOF) and has been used commercially in the pharmaceutical industry on peptides and other large biological polymers.[6]

See also[edit]

References[edit]

  1. ^ a b c de Hoffmann, Edmond; Vincent Stroobant (2003). Mass Spectrometry: Principles and Applications (Second ed.). Toronto: John Wiley & Sons, Ltd. p. 65. ISBN 0-471-48566-7. 
  2. ^ US 2939952  Apparatus For Separating Charged Particles Of Different Specific Charges Jun 1960; Paul et al.
  3. ^ Teschl, Gerald (2012). Ordinary Differential Equations and Dynamical Systems. Providence: American Mathematical Society. ISBN 978-0-8218-8328-0. 
  4. ^ Morrison, J. D. (1991). "Personal reminiscences of forty years of mass spectrometry in Australia". Organic Mass Spectrometry 26 (4): 183. doi:10.1002/oms.1210260404. 
  5. ^ Yost, R. A.; Enke, C. G. (1978). "Selected ion fragmentation with a tandem quadrupole mass spectrometer". Journal of the American Chemical Society 100 (7): 2274. doi:10.1021/ja00475a072. 
  6. ^ Chernushevich, Igor V. (2001). "An introduction to quadrupole–time-of-flight mass spectrometry". Journal of Mass Spectrometry 36 (8): 849–865. 

External links[edit]