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Electrospray Ionization (ESI) Mass Spectrometry01:12

Electrospray Ionization (ESI) Mass Spectrometry

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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...
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Mass Spectrometry: Overview01:19

Mass Spectrometry: Overview

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Mass spectrometry is an analytical technique used to determine the molecular mass and molecular formula of a compound. The basic principle of mass spectrometry is to generate ions from the analyte molecule and measure these ion abundances against their molecular mass.  One common type of ionization, known as electrospray ionization or EI, bombards the analyte molecules in the gas phase with high-energy electron beams. The electron beams displace an electron from the molecule and leave...
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Mass Analyzers: Common Types01:19

Mass Analyzers: Common Types

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The quadrupole mass analyzer consists of four cylindrical metal rods arranged in a diamond carrying a DC voltage and a radio-frequency AC voltage. The motion of ions through the quadrupole depends on the field strength, causing only ions of a certain m/z to resonate successfully and strike the detector at a given field strength. Though the transmission rate for these analyzers is high, the exact elemental composition of the sample is not determined because of low resolution; however, they are...
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Mass Spectrometers01:16

Mass Spectrometers

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This lesson details the instrumentation of a mass spectrometer—a physical instrument to perform mass spectrometry on analyte molecules and record the characteristic mass spectra. This is achieved via three chief functions:
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Mass Analyzers: Overview01:13

Mass Analyzers: Overview

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The mass analyzer is a crucial component of the mass spectrometer. In the ionization chamber, the vaporized sample is bombarded with a high-energy electron beam to generate a radical cation and further fragment into neutral molecules, radicals, and cations. A series of negatively charged accelerator plates accelerate the cations into the mass analyzer. The mass analyzer separates ions according to their mass-to-charge (m/z) ratios and then directs them to the detector. The common types of mass...
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Mass Spectrometry: Complex Analysis01:21

Mass Spectrometry: Complex Analysis

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Mass spectrometry is an important technique for the identification of pure compounds. However, it has some limitations for the analysis of complex mixtures, often due to excessive fragmentation making the spectrum too complicated to decipher. Mass spectrometry can be combined with suitable separation methods in sequence, forming hyphenated methods, which are useful in the analysis of complex mixtures.
GC–MS is a powerful hyphenated method commonly used in forensics and environmental...
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A Strategy for Sensitive, Large Scale Quantitative Metabolomics
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Equilibration for Electrospray Ionization Mass Spectrometry in Quantitative Analysis.

Fulin Jiang1, Zihan Lu1, Chang Zhang1

  • 1Institute of Clinical Pharmacology, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510080, China.

Journal of the American Society for Mass Spectrometry
|June 1, 2022
PubMed
Summary

Achieving stable mass spectral signals in electrospray ionization mass spectrometry (ESI-MS) requires system equilibration. Most compounds stabilize within 60 minutes, but factors like compound properties and instrument type influence this crucial stabilization time.

Keywords:
electrospray ionization mass spectrometryequilibriumphysicochemical propertiesresponse stability

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Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry

Background:

  • Electrospray ionization mass spectrometry (ESI-MS) is vital in drug development and monitoring.
  • Unstable mass spectral signals, particularly early in instrument use, pose challenges for analysts.
  • Determining the necessary equilibration time for stable ESI-MS responses has been difficult.

Purpose of the Study:

  • To investigate the response stability of ESI-MS systems.
  • To identify factors influencing the time required for ESI-MS signals to stabilize.
  • To provide guidance on optimal equilibration times for quantitative analysis.

Main Methods:

  • Tested response stability using 72 diverse compounds across three ESI-MS systems.
  • Employed flow injection analysis in positive ion mode.
  • Evaluated stabilization using response stable factor (RSF) criteria of 5.00% and 2.00%.

Main Results:

  • Approximately 80% of compounds achieved stability within 60 minutes using a 5.00% RSF criterion.
  • A stricter 2.00% criterion resulted in significantly longer stabilization times.
  • Stabilization time is dependent on the specific instrument and compound physicochemical properties (Log P, molecular weight, molar volume).

Conclusions:

  • Balancing the ESI-MS system for an appropriate duration is essential before sample analysis.
  • Compounds with high hydrophilicity, small molecular weight, or small molar volume require careful consideration of equilibration time.
  • Understanding these factors optimizes quantitative accuracy in ESI-MS applications.