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Related Concept Videos

Electrospray Ionization (ESI) Mass Spectrometry01:12

Electrospray Ionization (ESI) Mass Spectrometry

Higher molecular weight biomolecules are nonvolatile compounds that may decompose before ionizing or vaporizing during mass analysis with conventional electron impact ionization methods. Accordingly, electrospray ionization (ESI) is the favored method for vaporizing and ionizing biomolecules as it circumvents rapid fragmentation and enables the recording of mass signals for the entire biomolecule.
ESI utilizes electrical energy to transfer ions from the liquid phase of the sample into the...
Chemical Ionization (CI) Mass Spectrometry01:21

Chemical Ionization (CI) Mass Spectrometry

The molecular ion peak of a molecule in the mass spectrum provides vital information for molecular identification. However, conventional electron impact ionization can lead to the rapid dissociation of some molecular ions before they reach the detector. A milder ionization method is required to increase the lifetime of such ionized analyte molecules. Chemical ionization (CI) is a gas-phase protonation reaction useful for mass-analyzing analyte molecules that are easily protonated to yield the...
Inductively Coupled Plasma Atomic Emission Spectroscopy: Principle01:19

Inductively Coupled Plasma Atomic Emission Spectroscopy: Principle

Inductively coupled plasma (ICP) is the most widely used plasma source in atomic emission spectroscopy (AES), also known as Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). The ICP source, or torch, consists of three concentric quartz tubes with argon gas flowing through them. A spark from a Tesla coil initiates the ionization of argon, generating a high-temperature plasma.
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Inductively Coupled Plasma–Mass Spectrometry (ICP–MS): Overview01:19

Inductively Coupled Plasma–Mass Spectrometry (ICP–MS): Overview

In inductively coupled plasma–mass spectrometry (ICP–MS), an inductively coupled plasma (ICP) torch is used as an atomizer and ionizer. Solid samples are dissolved and volatilized before being introduced into the high-temperature argon plasma, while solution samples are nebulized and passed through the high-temperature argon plasma. Plasma dissociates the analytes and ionizes their component atoms to form a mixture of positive ions and molecular species. The positive ions are then passed on to...
Atomic Emission Spectroscopy: Instrumentation01:22

Atomic Emission Spectroscopy: Instrumentation

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Imaging of Biological Tissues by Desorption Electrospray Ionization Mass Spectrometry
06:21

Imaging of Biological Tissues by Desorption Electrospray Ionization Mass Spectrometry

Published on: July 12, 2013

Does electrospray ionization produce gas-phase or liquid-phase structures?

Zhixin Tian1, Steven R Kass

  • 1Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.

Journal of the American Chemical Society
|July 30, 2008
PubMed
Summary
This summary is machine-generated.

Electrospray ionization of tyrosine yields different ion structures based on the solvent. Methanol/water mixtures favor gas-phase equilibrium, while acetonitrile solutions produce primarily carboxylate ions.

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Area of Science:

  • Analytical Chemistry
  • Physical Chemistry
  • Mass Spectrometry

Background:

  • Electrospray ionization (ESI) is a crucial technique for analyzing biomolecules.
  • The structure of ions generated by ESI can be influenced by solvent composition.
  • Understanding ion formation mechanisms is vital for accurate mass spectrometry analysis.

Purpose of the Study:

  • To investigate the impact of solvent systems on the gas-phase isomeric composition of tyrosine deprotonated ions generated by electrospray ionization.
  • To determine whether the observed ion ratios reflect liquid-phase or gas-phase equilibria.

Main Methods:

  • Electrospray ionization mass spectrometry (ESI-MS) was employed.
  • Tyrosine was dissolved in various solvent mixtures, including methanol/water and acetonitrile/water.
  • The deprotonated ions ([M-H]-) of tyrosine were analyzed to determine their isomeric structures.

Main Results:

  • ESI of tyrosine in a 3:1 methanol/water mixture produced a deprotonated ion ([M-H]-) composed of 70% phenoxide and 30% carboxylate ions, reflecting gas-phase equilibrium.
  • In contrast, anhydrous acetonitrile and acetonitrile/water mixtures yielded predominantly carboxylate ions (approx. 95%).
  • Addition of small amounts of methanol to acetonitrile-based solvents shifted the ion composition back towards the gas-phase equilibrium ratio.

Conclusions:

  • The isomeric structure of electrosprayed tyrosine ions is highly dependent on the solvent system used.
  • Solvent choice in ESI-MS can significantly influence the observed ion composition, potentially reflecting gas-phase equilibria rather than liquid-phase distributions.
  • This finding has implications for interpreting mass spectrometry data and optimizing ESI conditions for specific analytes.