
Dushyant Patel LC-MS/MS Method
S.K.P.C.P.E.R., Kherva 23 M .Pharm. Thesis
molecules form negative ions in solution, and basic molecules form positive ions. The
ejection of sample ions from droplets is facilitated if the ionic charge and surface charge
of the droplet are of the same polarity. Thus, a positively charged needle is used to
analyze positive ions and a negatively charged needle is used to analyze negative ions.
¾ Sample ions can carry a single charge or multiple charges. The number of charges
carried by the sample ion depends on the structure of the analyte of interest and the
carrier solvent. The ESI process is affected by droplet size, surface charge, liquid surface
tension, solvent volatility, and ion solvation strength. Large droplets with high surface
tension, low volatility, strong ion solvation, low surface charge, and high conductivity
prevent good electrospray.
Figure 4.2 ESI process in the positive ion polarity mode
¾ Organic solvents such as methanol, acetonitrile, and isopropyl alcohol are superior to
water for ESI. Volatile acids and bases are good, but salts above 10 mM concentration
and strong acids and bases are extremely detrimental.
Atmospheric pressure chemical ionization:
¾ Atmospheric pressure chemical ionization (APCI) is a soft ionization technique, but not
as soft as ESI. APCI is used to analyze compounds of medium polarity that have some
volatility.
¾ In APCI, ions are produced and analyzed as follows:
• The APCI nozzle sprays the sample solution into a fine mist of droplets.
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