ATMOSPHERIC PRESSURE CHEMICAL IONIZATION (MPHARM,BPHARM ,MSC,BSC,P.ANALYSIS)

ATMOSPHERIC PRESSURE CHEMICAL IONIZATION (MPHARM,BPHARM ,MSC,BSC,P.ANALYSIS)

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  jjjAT Presented by :Souparnika T Ist M.Pharm Pharmaceutical Chemistry PRINCIPLE AND INSTRUMENTATION OF APCI (ATMOSPHERIC PRESSURE CHEMICAL IONIZATION)
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  What is massspectroscopy Mass spectroscopy that charged particles passing through a magnetic field is deflected along circular path on a radius that is proportional to the mass to charge ratio M/Z. Principle A beam of electrons will be bombarded in the analyte compound and it will leads to removal of 1 electron from analyte. Due to removal of electron and molecules will be positively charged and known as molecular ion . 1
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  .M+ Molecular ion(unstable) M1 + , M 2 . M1 . M2 + M1 + + M2 + Stable ion Instrumentation of mass spectroscopy 1. Sample inlet 2. Ionization chamber 3. Ion separator/ mass analyser 4. Ion collector ,detector 5. Vaccum system 2
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  Ionization chamber Volatile samples 1.Electron impact ionization 2. Chemical ionization 3. GC inlets Non volatile sample 1. Fast atom bambartment 2. MALDI 3. Electrospary ionization 4. APCI 3
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  Atmospheric pressure chemicalionization (APCI) What is APCI  It is a type of soft ionization technique ,which is based upon the mechanism of evaporaton.  Actually it is a combination of chemical ionization and electrospray ionization with some deviation.  Generally APCI is coupled with chromatographic instruments like HPLC.  Analogous to chemical ionization  For compounds with MW about 1,500 Da  Produce monocharged ions  It is similar to ESI 4
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  Figure no 1:APCIDiagram 5 PRINCIPLE AND INSTRUMENTATION OF APCI
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  Sample will beinjected into the capillary supplied as a nebulizing gas, (It will helps to spray the sample and the analyte) Apart from this here to supply N2 gas as a dissolvation gas It will convert in the form of vapour ( Analyte vapour and Solvent vapour) It will be analyse by corona discharge electrode, Corona discharge electrode will ionize the solvent vapour molecule just like a primary ion in chemical ionization 1st step 2nd step 6
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  Analyte and solventvapour will pass through the corona discharge electrode The solvent will be ionized in the form of H⁺ and Due to collision and ion molecule charge transfer between solvent and analyte takes place, it will produce MH⁺ ions. A + S⁺ MH⁺ + S⁻ (Positive ions) (Quasi molecular ion) (M- - H⁻ ) A⁺ + S (MH)- + SH⁺ (Negative ions) (also called as (M-1)- ) 3rd step 7
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  Carbon Fiber IonizationMass Spectrometry for the Analysis of Analytes in Vapour, Liquid, and Solid Phase  In APCI using carbon fibre as a corona discharge ingredient. Figure no:2 carbon fibre ionization mass spectroscopy Eg . possibility of different chemical structure of aroma compound derived from the sesame oil = 23 type 8
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  APCI Consideration Solution chemistryparameters  Less sensitive to chemistry effects than ESI –ion suppresion not so important.  Best sensitivity at higher flow rates than ESI.  Accommodates some non polar solvents not compatilble with ESI (hexane , CH2CI2 Limitation for sample  Thermally labile ,polar and high mwt compounds due to the vapourization process.  Compounds of intermediates do not contain acidic or basic sites(eg. Hydrocarbons, steroids, alcohol,Ketons, esters) 9
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  APPLICATION  APCI workswell for small molecule that are moderately polar to non polar.  APCI works well for sample that contain heteroatoms.  Avoid sample that typically are charged in solution.  Avoid samples that are very thermally unstable or photosensitive. Figure no:3 Mass spectra of fatty acid Figure no:4 mass spectra of fatty esters 10
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  Figure no:5 massspectra of fatty amine Figure no:6 mass spectra of histamine Figure no:7 mass spectra of phenanthrene , and derivatives 11
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  Figure no:8 massspectra of cinnamic deviatives 12
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  REFERENCE:  Wu ML,Chen TY, Chen YC, Chen YC. Carbon fiber ionization mass spectrometry for the analysis of analytes in vapor, liquid, and solid phases. Analytical chemistry. 2017 Dec 19;89(24):13458-65.  Martínez-Vargas BL, Díaz-Real JA, Reyes-Vidal Y, Rodríguez-López JL, Ortega- Borges R, Ortiz-Frade L. Competition between the reaction medium and nanostructured ZnO in the photocatalytic degradation of anthracene. Toward an optimal process for polycyclic aromatic hydrocarbons remediation. Química Nova. 2017;40:6-16 13
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   Ji B,Zhao Y, Zhang Q, Wang P, Guan J, Rong R, Yu Z. Simultaneous determination of cinnamaldehyde, cinnamic acid, and 2-methoxy cinnamic acid in rat whole blood after oral administration of volatile oil of Cinnamoni Ramulus by UHPLC-MS/MS: An application for a pharmacokinetic study. Journal of Chromatography B. 2015 Sep 15;1001:107-13.  University of Bristol, High Performance Liquid Chromatography Mass Spectrometry (HPLC/MS). 14
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   Agilent TechnicalOverview: Making your LC method compatible with mass spectrometry, Edgar Naegale, Waldbronn, Germany.  Colizza K, Mahoney K E, et al., J. Am. Soc. Mass Spectrom. (2016)  Updated 17th June 2014 by Paul Gates | University of Bristol, School of Chemistry, Cantock's Close, Bristol BS8 1TS, United Kingdom.  Image from google. 15