Laser spray ionization refers to one of several methods for creating ions using a laser interacting with a spray of neutral particles or ablating material to create a plume of charged particles. The ions thus formed can be separated by m/z with

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 ...

. Laser spray is one of several ion sources that can be coupled with

liquid chromatography-mass spectrometry 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, an ...

for the detection of larger molecules.

Types of laser spray ionization

Neutral spray

In one version of the laser spray interface, explosive vaporization and

mist Mist is a phenomenon caused by small droplets of water suspended in the cold air, usually by condensation. Physically, it is an example of a dispersion. It is most commonly seen where water vapor in warm, moist air meets sudden cooling, such a ...

formation occur when an

aqueous solution 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 re ...

effusing from the tip of the

stainless steel Stainless steel is an alloy of iron that is resistant to rusting and corrosion. It contains at least 11% chromium and may contain elements such as carbon, other nonmetals and metals to obtain other desired properties. Stainless steel's corros ...

capillary A capillary is a small blood vessel from 5 to 10 micrometres (μm) in diameter. Capillaries are composed of only the tunica intima, consisting of a thin wall of simple squamous endothelial cells. They are the smallest blood vessels in the body: ...

is irradiated from the opposite side of the capillary by a 10.6 μm infrared

laser A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word "laser" is an acronym for "light amplification by stimulated emission of radiation". The fir ...

. Weak ion signals could be detected when the plume was sampled through the ion sampling orifice. When a high

voltage Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a static electric field, it corresponds to the work needed per unit of charge to m ...

(3–4 kV) was applied to the stainless-steel capillary, strong ion signals appeared. The ion abundances were found to be orders of magnitude greater than those obtained by conventional

electrospray The name electrospray is used for an apparatus that employs electricity to disperse a liquid or for the fine aerosol resulting from this process. High voltage is applied to a liquid supplied through an emitter (usually a glass or metallic capilla ...

ionization in the case of aqueous solutions. This approach to laser spray ionization is a hybrid of three basic techniques for the generation of gaseous ions from the condensed phase, i.e., energy-sudden activation, nebulization and the action of an electric field. Laser spray mass spectrometry can faithfully reflect the solution-phase characteristics of

biomolecules A biomolecule or biological molecule is a loosely used term for molecules present in organisms that are essential to one or more typically biological processes, such as cell division, morphogenesis, or development. Biomolecules include large ...

. It has been successfully applied to evaluate the binding affinities of

protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respo ...

- DNA. Laser spray has better ionization efficiency than conventional electrospray

ionization Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule i ...

(ESI). In particular, the sensitivity became more than one order of magnitude higher in negative ion modes. It was also found that this technique has a potential benefit for the low concentration samples due to condensation effect of the formed droplet by the irradiation of laser. Higher the solvation energies of triply charged metal ions, stronger are the signals for ions.

Laserspray ionization

Laserspray Ionization (LSI) is a newer mass spectrometric technique commonly used with biomolecules, such as proteins. This method is similar to

matrix-assisted laser desorption/ionization 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 ...

(MALDI) at atmospheric pressure in that it involves an

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. ...

and

matrix Matrix most commonly refers to: * ''The Matrix'' (franchise), an American media franchise ** ''The Matrix'', a 1999 science-fiction action film ** "The Matrix", a fictional setting, a virtual reality environment, within ''The Matrix'' (franchis ...

mixture. It also contains features from electrospray ionization, in which it produces a similar mass spectra. The mechanism was initially thought to involve laser induced production of highly charge matrix/analyte clusters that upon evaporation of the matrix produces ions by the same mechanism as ESI. LSI's ability to ablate proteins at atmospheric pressure in order to form a multiple of charged ions with a mass resolution of 100,000 when coupled with a

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 ...

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 ...

mass spectrometer. The advantages of using LSI includes a solvent-free ionization technique, fast data acquisition, simply to use, and the improved fragmentation through multiple charging.

Laser spray ionization inlet

Due to recent innovations to the laser spray technique, a new method of laser ablation using the spray method has surfaced. Laserspray inlet ionization (LSII) involves a matrix/analyte sample at atmospheric pressure being ablated, and the ionization process will take place in an ion transfer capillary tube located in the mass spectrometer

inlet An inlet is a (usually long and narrow) indentation of a shoreline, such as a small arm, bay, sound, fjord, lagoon or marsh, that leads to an enclosed larger body of water such as a lake, estuary, gulf or marginal sea. Overview In marine geogra ...

. The LSII method is also known as laserspray ionization vacuum (LSIV).

Applications

Matrix-assisted inlet ionization (MAII) has shown that the laser is not necessary for the ionization process. Ions are formed when matrix-analyte is introduced to the vacuum of a mass spectrometer through an inlet aperture. LSI is a subset of MAII and is now called laserspray inlet ionization (LSII). Laser spray inlet ionization and matrix-assisted inlet ionization can be coupled to a

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 cyclotron frequency of the ions in a fixed magnetic field. Th ...

(FT-ICR) mass analyzer to improve detection of

peptides Peptides (, ) are short chains of amino acids linked by peptide bonds. Long chains of amino acids are called proteins. Chains of fewer than twenty amino acids are called oligopeptides, and include dipeptides, tripeptides, and tetrapeptides. A p ...

and

proteins Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respo ...

References

{{Reflist Chromatography Ion source